Patent Application
20220169931
There is a well-known global issue with waste disposal, particularly of large volume consumer products such as mixed plastic waste, textiles and other polymers that are not considered biodegradable within acceptable temporal limits. There is a public desire to incorporate these types of wastes into new products through recycling, reuse, or otherwise reducing the amount of waste in circulation or in landfills.
A variety of means for the recycle, reuse, or reduction of waste stocks such as biomass, solid municipal waste, mixed plastic waste, and paper have been articulated, among which is the gasification of such waste stocks. In such proposals, waste gasifiers, which are typically air supplied fluidized bed gasifiers fed with a variety of component sizes and mixed stock types, have been proposed. Such waste gasifiers typically operate at low to medium temperatures in the range of 500° C. to 1000° C. using air as an oxidizer, and given the lower operating temperature, incomplete oxidation reactions occur resulting the generating of high quantities of residues that can appear in both the gas phase (syngas stream) and bottoms solid phase; e.g. tarry substances. The types of residues and their quantity will vary depending on the feedstock composition. Further, while waste gasifiers have the advantage of accepting a highly variable sizes and compositions of feedstocks, the resulting syngas compositions are also widely variable over time rendering them unusable for making chemicals without installation of expensive post treatments systems to clean up and purify the syngas streams exiting the gasifier vessel. Even with purification processes, the hydrogen/carbon monoxide/carbon dioxide ratios can remain highly variable. As a result of the expense to install systems to purify the syngas stream exiting the gasifier vessel suitable for chemicals synthesis, or their compositional variability, or their low throughput, or by reason of a combination of these factors, waste gasifier generated syngas streams are typically used to generate energy, e.g. steam or electricity or are used as fuel stocks.
Separated portions of mixed solid municipal wastes (MSW) have been investigated as a feed to a gasifier. MSW compositions contain a variety of solids, including bottles, sheets, films, paper, rubber, cardboard, cups, trays, wood, leather, textiles, glass, metal, etc. After separation of combustibles from non-combustibles (e.g. glass, metal, dirt), the mix of combustibles nevertheless remains highly variable in time from hour to hour, day to day, week to week, month to month, season to season, and by the source location. The variability lies both in form, e.g. bottles, garments, other textiles, personal care items, sheets, films, paper, cardboard, cups, trays, etc., and variability in compositional mix, e.g. polycarbonate, polyethylene, polypropylene, polyethylene terephthalate, polyamides, epoxy resins, acrylonitrilebutadiene, acrylics, alkyds, nylons, polyacetals, polystyrene, polyurethanes, vinyls, styrene acrylonitriles, ureas and melamines, wood, cellulosics, leather, food wastes, etc., variability in source location, and variability in the large variety of mechanical handling processes commercially practiced which employ different physical and chemical separation methods. In fixed bed and fluidized bed gasifiers, this can result in an unacceptable syngas composition variability over time, particularly when the syngas is needed to synthesize chemicals which require a very consistent rate and quality of syngas or syngas ingredients.
Additionally, plastics and textiles have a fixed carbon content that is lower than solid fossil fuel sources such as coal or petcoke. As a result, feeding textiles to a gasifier will combust and generate the syngas components at a more rapid rate than, for example, coal. Carbon monoxide generated from mixed plastic wastes or textiles will, therefore, have a longer residence time to convert to carbon dioxide under gasification conditions, relative to coal. While mixed plastic wastes and textiles have a high heat value (“HHV”), even in some cases equal to or exceeding coal, its use can also result in the generation of undesirable amounts of carbon dioxide in the raw syngas stream, particularly at high temperatures and pressures, along with a reduction in the amount of carbon monoxide that could have been produced by feeding only a fossil fuel. In addition, mixed plastic wastes and textiles have a higher hydrogen content that does, for example, solid fossil fuels, which can lead to the production of higher amounts of hydrogen in the raw syngas stream and affect the carbon monoxide/hydrogen ratio. These issues are not a concern when syngas is used for generating electricity or burned for heat value, but become a concern when making chemicals since the manufacture of chemicals relies on consistent output, ratio of carbon monoxide and/or hydrogen as raw materials for chemicals, and impurity types and profile in the syngas stream, particularly the lack of tarry residues or concentration of soot.
We desire to employ a method for providing a circular life cycle of fibers in textiles that includes recycling post-consumer or post-industrial textiles back to a molecular form suitable for making chemicals. The fixed bed waste gasifiers employed to accept combustible MSW streams are not an attractive alternative for generating a syngas stream for making chemicals for the reasons stated above. Many large-scale commercial gasifiers used to make pure consistent syngas streams at high output have a variety of constraints against accepting MSW or the components of MSW, such constraints depending on the type of gasifier employed. For example, entrained flow gasifiers employing feed injectors are not amenable to injecting the textiles in the form found in MSW. Even if the textiles are reduced to a very small size, their variable composition between natural and synthetic fibers, and different types of synthetic fibers, can cause screening or filtration plugging if co-ground with other solid fuels, or may lead to unstable slurries. The configuration of updraft fixed bed or updraft moving bed gasifiers that have a countercurrent flow of gas through the bed make it difficult to handle fines. For example, fine fibers introduced at the top of a fixed or moving downdraft gasifier may not uniformly settle onto the lower bed to form a fine char and gasify.
Further, textiles introduced into liquid or slurry fed gasifiers may not homogeneously disperse into the slurry, dispersion, or solution fed to the gasifier.
It would be desirable to incorporate textiles into a feedstock to a gasifier producing a syngas stream suitable for making chemicals. We also desire to employ a method of gasification of textiles stream that would generate a syngas stream suitable for chemicals synthesis in which more complete oxidation of waste feedstocks occurs to reduce the quantity of incomplete oxidation residues. It would also be desirable to generate a syngas stream suitable for chemicals synthesis in at least a portion of a product is the use of the recycled product to make the raw materials fit for making the same types of products as what was recycled. There remains a need to continue the development of circularity in a variety of products.
We have discovered a method to incorporate torrefied textile into a gasifier feedstock to producing a torrefied textile derived syngas stream suitable for making chemicals. It would also be desirable to generate a torrefied textile derived syngas stream suitable for chemicals synthesis in which more carbon monoxide is formed in the torrefied textile derived syngas using feedstocks containing textiles relative to lower temperature and/or lower pressure MSW fed fixed bed waste gasifiers, and to reduce the quantity of incomplete oxidation residues (e.g. tar, char, etc.). We also desire to generate a derived syngas stream output from a gasifier vessel which is sufficiently compositionally consistent over time and suitable for making chemicals, and particularly without the need for blending syngas streams. It is also desirably to conduct the operations efficiently, in a stable manner, and on a commercial scale. From the textile derived syngas made by such a process, chemicals can be made which ultimately will form a raw material to make a variety of polymers or articles, including textile derived cellulose esters.
There is now provided a process for the production of syngas comprising:
There is also provided a process for the production of syngas comprising:
There is further provided a composition comprising:
There is also provided a composition comprising:
There is also provided a feedstock slurry composition comprising torrefied textile, a solid fossil fuel, and water, wherein torrefied textile has a particle size of not more than 2 mm, and the solid fossil fuel in the feedstock composition has a particle size of less than 2 mm, the solids content in the slurry is at least 62 wt. % (or at least 65 wt. %, or at least 68 wt. %, or at least 69 wt. %, or at least 70 wt. %), the amount of torrefied textile present in the feedstock stream slurry composition is 0.1 wt. % to less than 5 wt. % based on the weight of all solids, and the water is at least 20 wt. % based on the weight of the feedstock slurry composition, and wherein either:
There is also provided a syngas composition discharged from a gasifier and obtained by gasifying a feedstock composition comprising torrefied textile, and said syngas stream contains no tar or less than 4 wt. % (or less than 3 wt. %, or not more than 2 wt. %, or not more than 1 wt. %, or not more than 0.5 wt. %, or not more than 0.2 wt. %, or not more than 0.1 wt. %, or not more than 0.08 wt. %, or not more than 0.05 wt. %, or not more than 0.02 wt. %, or not more than 0.01 wt. %, or nor more than 0.005 wt. %) tar, based on the weight of all condensable solids in the syngas composition.
There is further provided a syngas stream composition produced by gasifying in a gasifier, as well as a process for making a syngas stream by gasifying in a gasifier, a feedstock comprising torrefied textile wherein said syngas stream has a compositional variability that is 5% or less measured over a time period that is the lesser of 12 days or the time period the feedstock is fed to the gasifier, said syngas compositional variability satisfied against at least one of the following gaseous compounds (in moles):
There is also provided a syngas composition stream having a switching variability that is negative, zero, or not more than 15%, wherein the switching frequency is at least 1 time every two years, and the switching variability is determined by the following equation:
where % SV is percent syngas switching variability on one or more measured ingredients in the syngas composition; and
Vt is the syngas compositional variability of a gaseous compound(s) using a feedstock comprising torrefied textile and a second fuel source; and
Vb is the syngas compositional variability of the gaseous compound(s) using the same second fuel source without the torrefied textile, and where the feedstocks have the same solids concentration and mass fed to the gasifier and are gasified under the same conditions, other than temperature fluctuations which may autogeneously differ as a result of having torrefied textile in the feedstock, and the variabilities are measured and satisfied against at least one of the following gaseous compounds (in moles):
Ideally, a torrefied textile includes the residues of thermoplastic polymers or a combination of thermoplastic polymer residues and natural fiber residues.
There is also provided a torrefied textile derived cellulose ester reactant, a torrefied textile derived cellulose ester, a torrefied textile derived acetic acid, a torrefied textile derived acetic anhydride, a torrefied textile derived methanol, a torrefied textile derived methyl acetate, a torrefied textile derived cellulose ester fiber, a torrefied textile derived textile, and/or a torrefied textile derived nonwoven web.
There is further provided a torrefied textile derived cellulose ester reactant, and a process for making a cellulose ester reactant, by reacting at least two reactants, at least one of said reactants indirectly obtained from a torrefied textile derived syngas obtained by gasifying torrefied textiles.
A torrefied textile derived cellulose ester is also provided, and a process for making cellulose ester by reacting at least two reactants, at least one of said reactants indirectly obtained from a torrefied textile derived syngas obtained by gasifying torrefied textiles.
There is also provide a torrefied textile derived cellulose ester fiber, and a process for making cellulose ester fiber by spinning a cellulose ester to make a fiber, said cellulose ester obtained by reacting at least two reactants, at least one of said reactants indirectly obtained from a torrefied textile derived syngas obtained by gasifying torrefied textiles.
There is also provided a torrefied textile derived textile, and a process for making a textile by weaving or knitting fibers comprising polymers, at least one of said polymers obtained by reacting at least two reactants, at least one of said reactants indirectly obtained from a torrefied textile derived syngas obtained by gasifying torrefied textiles.
There is also provided a torrefied textile derived nonwoven web, and a process for making a nonwoven web by dry laying or melt spinning fibers, said fibers comprising polymers, at least one of said polymers obtained by reacting at least two reactants, at least one of said reactants indirectly obtained from a torrefied textile derived syngas obtained by gasifying torrefied textiles.
There is also provided a process of making a torrefied textile derived polymer reactant, comprising making a torrefied textile derived syngas, and reacting said torrefied textile derived syngas to make the torrefied textile derived polymer reactant through one or more torrefied textile derived chemical intermediates.
There is further provided a process of making a torrefied textile derived polymer by reacting a torrefied textile derived polymer reactant with a second reactant to make said polymer.
There is also provided a process for preparing a polymer by:
There is further provided a process of making a torrefied textile fiber, comprising making a torrefied textile derived polymer and spinning said polymer into the fiber.
There is also provided a circular manufacturing process comprising:
There is also provided a torrefied textile derived cellulose ester that is synthesized from (i) a raw material that is sustainable, and (ii) a raw material at least a portion of which is obtained, through one or more intermediate steps, from torrefied textiles, wherein the torrefied textile derived cellulose ester is biodegradable.
Further, there is provided an integrated process for preparing a torrefied textile derived cellulose ester comprising:
Unless otherwise stated, reference the weight of the feedstock composition or stream includes all solids, and if present liquids, fed to the gasifier, and unless otherwise stated, does not include the weight of any gases in the feedstock composition as fed to the injector or gasifier. A composition or a stream are used interchangeably.
Reference made throughout to a torrefied textile derived syngas, a torrefied textile derived chemical intermediate, torrefied textile derived cellulose ester reactants, torrefied textile derived cellulose ester polymers, their fibers, articles made from the fibers including nonwoven webs, yarns, cloth, fabric, and textiles includes, in each case, that at least a portion are torrefied textile derived.
By a “torrefied textile derived” gas, chemical compound, intermediate, reactant, polymer, fiber, nonwoven web, sheet, film, textile, or any other product (collectively a “material”) or a material “obtained by,” is meant that at least a portion of the material either a) finds its immediate source, or its ultimate source through one or more intermediate materials, from a syngas that is obtained by gasifying a fuel that contains torrefied textiles, or b) an allotment is associated with a material where the allotment is generated from a torrefied textile that is gasified or destined to be gasified. In one embodiment, at least a portion of each material finds its ultimate source throughout the chain of materials in torrefied textiles that are gasified. Any material downstream of a gasifier is deemed to be derived from or obtained by a torrefied textile if the material is in fluid and/or gaseous communication with the torrefied textile derived syngas, such as with integrated processes, whether or not a particular syngas molecule of CO or hydrogen can be traced to the material. A torrefied textile derived syngas that is completely contained, isolated, and diverted from the streams that are in fluid and/or gaseous communication with the material of interest can be regarded as not forming a part of such materials, but will form part of other materials to which such contained, isolated, and diverted syngas stream is dedicated.
Throughout the description, reference can be made to one or more products derived from or obtained by a torrefied textile derived syngas. It is to be understood that such derivation or sourcing is not limited to employing both hydrogen and carbon monoxide in the syngas stream, but rather, such a product is considered to have its origin in a torrefied textile derived syngas stream if any part of the torrefied textile derived syngas stream is reacted or used in a reaction, including hydrogen alone, carbon monoxide alone, or any ratio of hydrogen and carbon monoxide in combination.
A PIA or PIA reactant or composition or compound is associated with, or originates from, a torrefied textile that is gasified, regardless of when the allotment is taken, realized, or consumed. For example, a PIA can be associated with a torrefied textile that is gasified even though the allotment is taken and deposited into a recycle inventory or transferred to a PIA when torrefied textiles are received or possessed or owned by a syngas manufacturer and even though the torrefied textile is not gasified at the time the allotment is taken or generated. If the torrefaction process is performed by the same owner or Family of Entities along with the gasification process, or on the same Site, an allotment can be taken when the feedstock recycle textiles are received or inventoried provided that the torrefied textiles made from the feedstock recycle textiles are used in a gasification process to generate a torrefied textile derived syngas. Further, an allotment that is associated with or originates from gasifying a torrefied textile does not limit the timing of taking or recognizing the allotment or depositing the allotment into a recycle inventory. An allotment generated or taken when a torrefied textile, or a recycle textile that will be torrefied into a torrefied textile for feeding to a gasifier, is owned, possessed, or receiving and deposited into a recycle inventory is an allotment that is associated with or originates from gasifying a torrefied textile even though, at the time of taking or depositing the allotment, the torrefied textile has not yet been gasified or even though the recycle textile has not yet been torrefied and subsequently gasified.
As used throughout, the phrase “originates” or “origin” is synonymous to “associated with.”
By gasifying a torrefied textile in a gasifier that makes torrefied textile derived syngas of a quantity and quality suitable for making chemicals, a variety of chemicals a polymer can now be made containing the molecular components of the torrefied textile derived syngas.
There is now provided a torrefied textile derived cellulose ester reactant, a torrefied textile derived cellulose ester, a torrefied textile derived acetic acid, a torrefied textile derived acetic anhydride, a torrefied textile derived methanol, a torrefied textile derived methyl acetate, a torrefied textile derived cellulose ester fiber, a torrefied textile derived textile, and/or a torrefied textile derived nonwoven web.
As an example, reference is made to making a cellulose ester. In one embodiment or in combination with any of the mentioned embodiments, a torrefied textile derived cellulose ester composition is provided comprising at least one torrefied textile derived cellulose ester having at least one substituent on an anhydroglucose unit (AU) derived from torrefied textile derived syngas.
In embodiments, the torrefied textile derived cellulose ester utilized in this invention can be any that is known in the art. Torrefied textile derived cellulose esters that can be used for the present invention generally comprise repeating units of the structure:
wherein R1, R2, and R3 are selected independently from the group consisting of hydrogen or straight chain alkanoyl having from 2 to 10 carbon atoms. For torrefied textile derived cellulose esters, the substitution level is usually express in terms of degree of substitution (DS), which is the average number of non-OH substituents per anhydroglucose unit (AGU). Generally, conventional cellulose contains three hydroxyl groups in each AGU unit that can be substituted; therefore, DS can have a value between zero and three. However, low molecular weight cellulose mixed esters can have a total degree of substitution slightly above 3, due to end group contributions. Native cellulose is a large polysaccharide with a degree of polymerization from 250-5,000 even after pulping and purification, and thus the assumption that the maximum DS is 3.0 is approximately correct. However, as the degree of polymerization is lowered, as in low molecular weight cellulose mixed esters, the end groups of the polysaccharide backbone become relatively more significant, thereby resulting in a DS that can range in excess of 3.0. Low molecular weight cellulose mixed esters are discussed in more detail subsequently in this disclosure. Because DS is a statistical mean value, a value of 1 does not assure that every AGU has a single substituent. In some cases, there can be unsubstituted anhydroglucose units, some with two and some with three substituents, and typically the value will be a non-integer. Total DS is defined as the average number of all of substituents per anhydroglucose unit. The degree of substitution per AGU can also refer to a particular substituent, such as, for example, hydroxyl, acetyl, butyryl, or propionyl.
In embodiments, the torrefied textile derived cellulose ester utilized can be a cellulose triester or a secondary torrefied textile derived cellulose ester. Examples of cellulose triesters include, but are not limited to, cellulose triacetate, cellulose tripropionate, or cellulose tributyrate. Examples of secondary torrefied textile derived cellulose esters include cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate.
In one embodiment or in combination with any of the mentioned embodiments, the torrefied textile derived cellulose ester can be chosen from cellulose acetate (CA), cellulose propionate (CP), cellulose butyrate (CB), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose propionate butyrate (CPB), and the like, or combinations thereof. Examples of such torrefied textile derived cellulose esters are described in U.S. Pat. Nos. 1,698,049; 1,683,347; 1,880,808; 1,880,560; 1,984,147, 2,129,052; and 3,617,201, incorporated herein by reference in their entirety to the extent that they do not contradict the statements herein.
In embodiments, the torrefied textile derived cellulose esters have at least 2 anhydroglucose rings and can have between at least 50 and up to 5,000 anhydroglucose rings. The number of anhydroglucose units per molecule is defined as the degree of polymerization (DP) of the torrefied textile derived cellulose ester. In embodiments, torrefied textile derived cellulose esters can have an inherent viscosity (IV) of about 0.2 to about 3.0 deciliters/gram, or about 0.5 to about 1.8, or about 1 to about 1.5, as measured at a temperature of 25° C. for a 0.25-gram sample in 100 ml of a 60/40 by weight solution of phenol/tetrachloroethane. Examples of torrefied textile derived cellulose esters include, but are not limited to, cellulose acetate, cellulose diacetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose propionate butyrate, and the like. In embodiments, torrefied textile derived cellulose esters useful herein can have a DS/AGU of about 2 to about 2.99, and the substituting ester can comprise acetyl, propionyl, butyryl, or any combinations of these. In another embodiment, the total DS/AGU ranges from about 2 to about 2.99 and the DS/AGU of acetyl ranges from about 0 to 2.2, with the remainder of the ester groups comprising propionyl, butyryl or combinations thereof.
Cellulose esters can be produced by any method known in the art. Examples of processes for producing cellulose esters are taught in Kirk-Othmer, Encyclopedia of Chemical Technology, 5th Edition, Vol. 5, Wiley-Interscience, New York (2004), pp. 394-444. Cellulose, the starting material for producing torrefied textile derived cellulose esters, can be obtained in different grades and sources such as from cotton linters, softwood pulp, hardwood pulp, corn fiber and other agricultural sources, and bacterial cellulose, among others.
One method of producing torrefied textile derived cellulose esters is esterification of the cellulose by mixing cellulose with the appropriate torrefied textile derived organic acids, torrefied textile derived acid anhydrides, and catalysts. Cellulose is then converted to a cellulose triester. Ester hydrolysis is then performed by adding a water-acid mixture to the cellulose triester, which can then be filtered to remove any gel particles or fibers. Water is then added to the mixture to precipitate the torrefied textile derived cellulose ester. The torrefied textile derived cellulose ester can then be washed with water to remove reaction by-products followed by dewatering and drying.
The cellulose triesters to be hydrolyzed can have three substituents selected independently from alkanoyls having from 2 to 10 carbon atoms. Examples of cellulose triesters include cellulose triacetate, cellulose tripropionate, and cellulose tributyrate or mixed triesters of cellulose such as cellulose acetate propionate, and cellulose acetate butyrate. These torrefied textiles derived cellulose esters can be prepared by a number of methods known to those skilled in the art. For example, torrefied textile derived cellulose esters can be prepared by heterogeneous acylation of cellulose in a mixture of carboxylic acid and anhydride, at least one of which and at least a portion of which are a torrefied textile derived cellulose reactant, in the presence of a catalyst such as H2SO4. Cellulose triesters can also be prepared by the homogeneous acylation of cellulose dissolved in an appropriate solvent such as LiCl/DMAc or LiCl/NMP.
Those skilled in the art will understand that the commercial term of cellulose triesters also encompasses torrefied textile derived cellulose esters that are not completely substituted with acyl groups. For example, cellulose triacetate commercially available from Eastman Chemical Company, Kingsport, Tenn., U.S.A., typically has a DS from about 2.85 to about 2.99.
After esterification of the cellulose to the triester, part of the acyl substituents can be removed by hydrolysis or by alcoholysis to give a secondary torrefied textile derived cellulose ester. As noted previously, depending on the particular method employed, the distribution of the acyl substituents can be random or non-random. Secondary torrefied textile derived cellulose esters can also be prepared directly with no hydrolysis by using a limiting amount of acylating reagent. This process is particularly useful when the reaction is conducted in a solvent that will dissolve cellulose. All of these methods yield torrefied textile derived cellulose esters that are useful in this invention.
In one embodiment or in combination with any of the mentioned embodiments, the secondary torrefied textile derived cellulose esters useful in the present invention have an absolute weight average molecular weight (Mw) from about 5,000 to about 400,000 as measured by gel permeation chromatography (GPC) according to ASTM D6474. The following method is used to calculate the absolute weight average molecular weight values (Mw) for CE. The solvent is THF stabilized with BHT Preservative. The instrumentation for the THF/torrefied textile derived cellulose ester procedure consists of the following Agilent 1200 series components: degasser, isocratic pump, auto-sampler, column oven, UV/Vis detector and a refractive index detector. The test temperature is 30° C. and flow rate is 1.0 ml/min. A sample solution of 25 mg torrefied textile derived cellulose ester in 10 ml THF with BHT preservative and 10 μl toluene flow rate marker is made. The injection volume is 50 μl. The column set is Polymer Laboratories 5 μm PLgel, Guard+Mixed C+Oligopore. The detection is by refractive index. The calibrants are monodisperse polystyrene standards, Mw=580 to 3,220,000 from Polymer Laboratories. The universal calibration parameters are as follows: PS (K=0.0001280 and a=0.7120) and CE (K=0.00007572 and a=0.8424). The universal calibration parameters above were determined by light scattering and viscometry to yield the correct weight average molecular weights. In a further embodiment, the Mw is from about 15,000 to about 300,000. In yet further embodiments, the Mw ranges from about 10,000 to about 250,000; from about 15000 to 200000; from about 20,000 to about 150,000; from about 50,000 to about 150,000, or from about 70,000 to about 120,000.
The most common commercial secondary torrefied textile derived cellulose esters are prepared by initial acid catalyzed heterogeneous acylation of cellulose to form the cellulose triester. After a homogeneous solution in the corresponding carboxylic acid of the cellulose triester is obtained, the cellulose triester is then subjected to hydrolysis until the desired degree of substitution is obtained. After isolation, a random secondary torrefied textile derived cellulose ester is obtained. That is, the relative degree of substitution (RDS) at each hydroxyl is roughly equal.
In embodiments, the torrefied textile derived cellulose esters can contain chemical functionality and are described herein as either derivatized, modified, or functionalized torrefied textile derived cellulose esters. Functionalized torrefied textile derived cellulose esters can be produced by reacting the free hydroxyl groups of torrefied textile derived cellulose esters with a bifunctional reactant that has one linking group for grafting to the torrefied textile derived cellulose ester and one functional group to provide a new chemical group to the torrefied textile derived cellulose ester. Examples of such bifunctional reactants include succinic anhydride which links through an ester bond and provides acid functionality; mercaptosilanes which links through alkoxysilane bonds and provides mercapto functionality; and isocyanotoethyl methacrylate which links through a urethane bond and gives methacrylate functionality.
In embodiments, the torrefied textile derived cellulose esters can be prepared by converting cellulose to torrefied textile derived cellulose esters with reactants that are obtained, through one or more intermediate steps, from a torrefied textile derived syngas source. In embodiments, such reactants can be torrefied textile derived cellulose reactants that include organic acids and/or acid anhydrides, at least one of which is torrefied textile derived, used in the esterification or acylation reactions of the cellulose, e.g., as discussed herein.
By “torrefied textile derived syngas” is meant torrefied textile derived syngas obtained from a synthesis gas obtained by gasifying a torrefied textile, as described in the various embodiments more fully herein below. In embodiments, the feedstock (for the synthesis gas operation) can be in the form of a combination of one or more particulated fossil fuel sources and torrefied textiles.
At least a portion of a torrefied textile derived syngas chemicals can be used to make chemicals or polymers. For example, a torrefied textile derived cellulose ester reactant used to make a torrefied textile derived cellulose ester does not imply that the entire amount of the reactant used to make the torrefied textile derived cellulose ester is derived from a torrefied textile derived cellulose ester reactant, but rather that at least a portion of the batch or stream of the reactant contains a torrefied textile derived cellulose ester reactant, or put another way, at least a portion of the acyl groups on the torrefied textile derived cellulose ester were obtained from reactants, that through one or more intermediate steps, were obtained from a torrefied textile derived syngas.
In embodiments, the torrefied textile derived syngas is utilized to make at least one torrefied textile derived chemical intermediate in a reaction scheme to make a torrefied textile derived cellulose ester (CE intermediate). In embodiments, the torrefied textile derived syngas can be a component of feedstock (used to make at least one CE intermediate) that includes other sources of torrefied textile derived syngas, hydrogen, carbon monoxide, or combinations thereof. In one embodiment or in combination with any of the mentioned embodiments, the only source of torrefied textile derived syngas used to make the CE intermediates is obtained from entrained flow gasifiers, at least one of which gasifies torrefied textiles intermittently or continuously.
Reference to a reaction scheme means reacting a reactant to make one or more intermediates that are used to make the desired end chemical or polymer, and all the reaction process to accomplish the manufacture of the chemical or polymer
In embodiments, the torrefied textile derived intermediates made directly from, or through one or more intermediate steps from, torrefied textile derived syngas can include methanol, acetic acid, methyl acetate, acetic anhydride and combinations thereof. In embodiments, the torrefied textile derived chemical intermediates can be derived from at least one reactant or made into at least one product in one or more of the following reactions: (1) torrefied textile derived syngas conversion to methanol; (2) torrefied textile derived syngas conversion to acetic acid; (3) methanol conversion to acetic acid, e.g., carbonylation of methanol to produce acetic acid; (4) producing methyl acetate from methanol and acetic acid; and (5) conversion of methyl acetate to acetic anhydride, e.g., carbonylation of methyl acetate and methanol to acetic acid and acetic anhydride, where in each case, the final product is a torrefied textile derived product.
In embodiments, torrefied textile derived syngas is used to produce at least one torrefied textile derived cellulose reactant. In embodiments, the torrefied textile derived syngas is used to produce one or more torrefied textile derived chemical compounds or a torrefied textile derived cellulose ester via one or more reaction schemes.
In embodiments, the torrefied textile derived syngas is utilized to make torrefied textile derived acetic anhydride. In embodiments, torrefied textile derived syngas is first converted to torrefied textile derived methanol and this methanol is then used in a reaction scheme to make torrefied textile derived acetic anhydride, which is an acetic anhydride that is directly derived from torrefied textile derived syngas. Directly derived from means that at least some of the feedstock source material that is used in any reaction scheme to make a product, intermediate or CE intermediate, or polymer such as a CE polymer has some content of syngas obtained from gasifying a feedstock comprising torrefied textiles.
In one embodiment or in combination with any mentioned embodiments, the torrefied textile derived syngas is a reactant to make torrefied textile derived methanol. Torrefied textile derived syngas comprised of hydrogen and carbon monoxide in a ratio of approximately 2:1 H2:CO is fed to a methanol production plant. The torrefied textile derived syngas is typically supplied to a methanol reactor at the pressure of about 25 to about 140 bara, depending upon the process employed. It is then contacted with a catalyst to affect the conversion of 2 equivalents of H2 and 1 equivalent of CO into 1 equivalent of methanol. The produced methanol can be purified by distillation.
The methanol process can operate in the gas phase at a pressure range of about 25 to about 140 bara using various catalyst systems well known in the art. A number of different state-of-the-art technologies are known for synthesizing methanol such as, for example, the ICI (Imperial Chemical Industries) process, the Lurgi process, the Haldor-Topsoe process, and the Mitsubishi process. Liquid phase processes are also well known in the art. Thus, the methanol process may comprise a fixed bed methanol reactor, containing a solid or supported catalyst, or liquid slurry phase methanol reactor, which utilizes a slurried catalyst in which metal or supported catalyst particles are slurried in an unreactive liquid medium such as, for example, mineral oil.
Examples of suitable methanol synthesis catalysts include, but are not limited to, oxides of zinc and chromium; oxides of zinc, copper and chromium; and oxides of zinc, copper, and aluminum; as well as zinc, copper, and aluminum; as well as zinc-copper-chromium-lanthanum oxides.
The reaction is exothermic; therefore, heat removal is ordinarily required. The raw or impure methanol is then condensed and may be purified to remove impurities such as higher alcohols including ethanol, propanol, and the like or, burned without purification as fuel. The uncondensed vapor phase comprising unreacted torrefied textile derived syngas can be recycled to the methanol process feed.
Torrefied textile derived methanol produced from torrefied textile derived syngas synthesis gas can be used to produce torrefied textile derived acetic acid when methanol is reacted with carbon monoxide. Torrefied textile derived acetic acid can also be produced by reacting methanol from any source with carbon monoxide obtained from torrefied textile derived syngas. Torrefied textile derived acetic acid can also be produced by reacting both torrefied textile derived methanol carbon monoxide obtained from torrefied textile derived syngas.
Any method known in the art can be used to produce the torrefied textile derived acetic acid. In one embodiment, an acetic acid product containing one or a combination of acetic acid, acetic anhydride and/or methyl acetate can be prepared by converting torrefied textile derived syngas to methanol and dimethyl ether in a first step at a pressure of 5-200 bar and a temperature of 150° C. to 400° C. in the presence of one or more catalysts which together catalyze the reactions and then passing the entire effluent from the first reactor to a second reactor in which methanol and dimethyl ether at a pressure of 1-800 bar and a temperature of 100° C. to 500° C. are carbonylated to one or more of acetic acid, acetic anhydride and/or methyl acetate in the following reaction schemes:
CH3OH+CO→CH3COOH (acetic acid) (1)
CH3OCH3 (dimethyl ether)+CO→CH3COOCH3 (methyl acetate) (2)
optionally
CH3OCH3+2CO→(CH3CO)2O (acetic anhydride) (3)
and
CH3COOCH3+CO→(CH3CO)2O (acetic anhydride) (4)
and optionally hydrolysis to acetic acid:
CH3COOCH3+H2O→CH3COOH+CH3OH (5)
In each of these reactions schemes, the end products can be torrefied textile derived products obtained at least in part from at least a portion of a torrefied textile derived syngas.
The torrefied textile derived methanol composition containing dimethyl ether can be utilized for the synthesis of methyl acetate. Also, torrefied textile derived acetic acid and methanol can be contacted in the presence of a catalytic amount of sulfuric acid in a distillation column to make methyl acetate. In this reaction scheme, the methanol, acetic acid, or both can be torrefied textile derived reactants. The resulting torrefied textile derived methyl acetate is removed by distillation out the top of the column and the resulting water and sulfuric acid are removed from the bottom of the column.
The torrefied textile derived methyl acetate can be fed into a carbonylation plant where it is contacted with carbon monoxide, optionally torrefied textile derived carbon monoxide, and a small amount of hydrogen (<5%), optionally torrefied textile derived hydrogen obtained from a torrefied textile derived syngas stream. Methyl acetate and carbon monoxide react to form acetic anhydride. This reaction takes place in acetic acid solvent and is catalyzed by [Li][Rh(CO)2(I)2] and Li cocatalysts. Optionally, methanol can be added to the reactor which will contact acetic anhydride and react to form methyl acetate, which is subsequently carbonylated to acetic anhydride and acetic acid. In this way, torrefied textile derived acetic anhydride and torrefied textile derived acetic acid can be produced as co-products and can be recovered in high purity by distillation.
In embodiments, the torrefied textile derived acetic anhydride is utilized as a CE intermediate reactant for the esterification of cellulose to prepare a torrefied textile derived cellulose ester, as discussed more fully above. In embodiments, the torrefied textile derived acetic acid is utilized as a reactant to prepare cellulose acetate or cellulose diacetate.
In embodiments, the torrefied textile derived acetic anhydride is utilized to make a biodegradable torrefied textile derived cellulose ester.
In one aspect, a torrefied textile derived cellulose ester composition is provided that comprises at least one torrefied textile derived cellulose ester having at least one substituent on an anhydroglucose unit (AGU) derived from torrefied textile derived syngas. In embodiments, the substituent is a combination of acetyl and propionyl functional groups. In embodiments, the substituent is a combination of acetyl and butyryl functional groups. In embodiments, the substituent is any combination of organic acid functional groups. In one embodiment or in combination with any of the mentioned embodiments, the at least one substituent is an acetyl functional group.
In embodiments, the torrefied textile derived cellulose ester is cellulose di-acetate (CDA). In one embodiment or in combination with any of the mentioned embodiments, the torrefied textile derived cellulose ester is cellulose tri-acetate (CTA).
In embodiments, the torrefied textile derived cellulose ester is prepared from a torrefied textile derived cellulose reactant that comprises acetic anhydride that is derived from torrefied textile derived syngas.
In embodiments, the torrefied textile derived syngas comprises gasification products from a gasification feedstock. In one embodiment or in combination with any of the mentioned embodiments, the gasification products are produced by a gasification process using a gasification feedstock that comprises torrefied textiles. In embodiments, the gasification feedstock comprises coal.
In embodiments, the gasification feedstock comprises a liquid slurry that comprises coal and torrefied textiles. In embodiments, the gasification process comprises gasifying said gasification feedstock in the presence of oxygen.
In one aspect, a torrefied textile derived cellulose ester composition is provided that comprises at least one torrefied textile derived cellulose ester having at least one substituent on an anhydroglucose unit (AGU) derived from one or more torrefied textile derived chemical compounds, at least one of which is obtained at least in part from torrefied textile derived syngas.
In aspects, an article is provided that comprises the torrefied textile derived cellulose ester compositions, as described herein. In embodiments, the article is a textile fabric. In embodiments, the article is biodegradable and/or compostable. In embodiments, a staple fiber is provided that comprises a torrefied textile derived cellulose ester composition that comprises cellulose acetate, as described herein.
In embodiments, the torrefied textile derived cellulose ester, fibers made therefrom, nonwoven webs made therefrom, and yarns and textiles made therefrom, is biodegradable. In embodiments, the torrefied textile derived cellulose ester is biodegradable and contains content derived from a renewable source, e.g., cellulose from wood or cotton linter, and content derived from a recycled material source, e.g., torrefied textiles. Thus, in embodiments, a thermoplastic material is provided that is biodegradable and contains both renewable or sustainable sources and recycled content, i.e., made from renewable or sustainable sources and recycled sources.
In one aspect, the invention is directed to a fiber comprising at least one torrefied textile derived cellulose ester, as described herein. In embodiments, sheets, webs or fabrics are provided that comprise such fibers. In embodiments, the sheets, webs or fabrics can be woven or non-woven. In embodiments, the sheets, webs or fabrics can be wet laid or dry laid.
In one embodiment or in combination with any of the mentioned embodiments, the invention is directed to a spun yarn that comprises at least one torrefied textile derived cellulose ester, as described herein. In embodiments, fibers comprising at least one torrefied textile derived cellulose ester can be prepared by spinning fibers. The fibers can be spun as a continuous fiber or can be cut to a desired length.
In embodiments, the invention can include fibers, filaments, yarns and nonwoven fabrics as described in WO2018/160588 A1, published on Sep. 7, 2018 (Applicant: Eastman Chemical Company), the contents of which is incorporated herein by reference, with the proviso that the fibers, filaments, yarns or nonwoven fabrics comprise at least one torrefied textile derived cellulose ester having torrefied textile content, as described more fully herein.
In one embodiment or in combination with any of the mentioned embodiments, the invention is directed to a textile fabric comprising fibers that comprise at least one torrefied textile derived cellulose ester, as described herein. In embodiments, the textile fabric can be prepared from fibers made with such torrefied textile derived cellulose esters. Such fibers can be used to make slivers, spun yarns, nonwoven webs, cloth, fabric, whether woven, knitted, or made from dry laid nonwovens or melt spun method. Dry laid nonwovens can be made by carding or air laid methods. The fibers can be filaments or staple fibers.
It has been found that slivers can be successfully formed from CA staple fibers and further processed successfully to spun yarns to make textile fabric. CA staple fibers may be environmentally friendly, exhibit thermoplastic behavior, have a soft feel similar to that of cotton, and can be processed using both new and existing processing equipment. A CA staple fiber means a cellulose acetate staple fiber, and a “staple fiber” refers to a fiber cut from a continuous filament or tow band of continuous filaments. A carded sliver, spun yarn, or textile fabric “obtained from” a described element includes any number and type of intervening steps or process operations.
Staple fibers and filaments as described herein may be formed from one or more torrefied textile derived cellulose esters including, but not limited to, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate formate, cellulose acetate propionate, cellulose acetate butyrate, cellulose propionate butyrate, and mixtures thereof. Although described herein with reference to “cellulose acetate,” it should be understood that one or more of the above cellulose acid esters or mixed esters may also be used to form the fibers, nonwovens, and articles as described herein. Various types of torrefied textile derived cellulose esters are described, for example, in U.S. Pat. Nos. 1,698,049; 1,683,347; 1,880,808; 1,880,560; 1,984,147, 2,129,052; and 3,617,201, each of which is incorporated herein by reference to the extent not inconsistent with the present disclosure. In some cases, other types of treated or regenerated cellulose (e.g., viscose, rayon, or lyocell) may or may not be used in forming staple fibers as described herein.
When the staple fiber or filament is formed from cellulose acetate, it may be formed from cellulose diacetate, cellulose triacetate, or mixtures thereof. The cellulose acetate (or other torrefied textile derived cellulose ester) useful in embodiments of the present invention can have a degree of substitution in the range of from 1.9 to 2.9. As used herein, the term “degree of substitution” or “DS” refers to the average number of acyl substituents per anhydroglucose ring of the cellulose polymer, wherein the maximum degree of substitution is 3.0, as described above. In some cases, the cellulose acetate used to form fibers as described herein may have an average degree of substitution of at least about 1.95, or at least 2.0, or at least 2.05, or at least 2.1, or at least 2.15, or at least 2.2, or at least 2.25, or at least 2.3 and/or not more than about 2.9, 2.85, 2.8, 2.75, 2.7, 2.65, 2.6, 2.55, 2.5, 2.45, 2.4, or 2.35, with greater than 90, or at least 91, or at least 92, or at least 93, or at least 94, or at least 95, or at least 96, or at least 97, or at least 98, or at least 99 percent of the cellulose acetate having a degree of substitution greater than 2.15, or at least 2.2, or at least 2.25. In some cases, greater than 90 percent of the cellulose acetate can have a degree of substitution greater than 2.2, or at least 2.25, or at least 2.3, or at least 2.35. Typically, acetyl groups can make up at least about 1, or at least 5, or at least 10, or at least 15, or at least 20, or at least 25, or at least 30, or at least 35, or at least 40, or at least 45, or at least 50, or at least 55, or at least 60 percent and/or not more than about 99, 95, 90, 85, 80, 75, or 70 percent of the total acyl substituents.
In embodiments, the cellulose acetate may have a weight-average molecular weight (Mw) of not more than 90,000, measured using gel permeation chromatography with N-methyl-2-pyrrolidone (NMP) as the solvent. In some cases, the cellulose acetate may have a molecular weight of at least about 10,000, at least about 20,000, 25,000, 30,000, 35,000, 40,000, or 45,000 and/or not more than about 100,000, 95,000, 90,000, 85,000, 80,000, 75,000, 70,000, 65,000, 60,000, or 50,000.
In one embodiment or in combination with any of the mentioned embodiments, the invention is directed to a staple fiber or filament formed from cellulose acetate, as described herein. In embodiments, the fiber is at least partially coated with at least one finish. In embodiments, the fiber has a denier per filament of less than about 3.0 and a crimp frequency of less than 22 crimps per inch (CPI). In embodiments, a plurality of the fibers exhibits a fiber-to-fiber staple pad coefficient of friction of not more than about 0.70.
In aspects, a carded nonwoven web or a carded sliver is provided comprising CA staple fibers that comprise cellulose acetate prepared according to the methods described herein. A carded sliver is a continuous bundle or strand of loose untwisted fibers that are aligned generally relatively parallel to each other. This alignment is conducted by subjecting the fibers to a carding process.
Other types of fibers suitable for use in a blend with torrefied textile derived cellulose ester staple fibers and filament can include natural and/or synthetic fibers including, but not limited to, cotton, rayon, viscose) or other types of regenerated cellulose such as Cupro, Tencel, Modal, and Lyocell cellulose, acetates such as polyvinylacetate, wool, glass, polyamides including nylon, polyesters such as polyethylene terephthalate (PET), polycyclohexylenedimethylene terephthalate (PCT) and other copolymers, olefinic polymers such as polypropylene and polyethylene, polycarbonates, poly sulfates, poly sulfones, polyethers, acrylics, acrylonitrile copolymers, polyvinylchloride (PVC), poly lactic acid, poly glycolic acid and combinations thereof.
In embodiments, the fibers, and yarns and nonwovens and cloths, fabrics and textiles formed therefrom can be biodegradable, meaning that such fibers are expected to decompose under certain environmental conditions. The degree of degradation can be characterized by the weight loss of a sample over a given period of exposure to certain environmental conditions. In some cases, the material used to form the staple fibers, the fibers, or the nonwoven webs or articles produced from the fibers can exhibit a weight loss of at least about 5, or at least 10, or at least 15, or at least 20 percent after burial in soil for 60 days and/or a weight loss of at least about 15, or at least 20, or at least 25, or at least 30, or at least 35 percent after 15 days of exposure to a typical municipal composter. However, the rate of degradation may vary depending on the particular end use of the fibers, as well as the composition of the remaining article, and the specific test. Exemplary test conditions are provided in U.S. Pat. Nos. 5,970,988 and 6,571,802.
In some embodiments, the torrefied textile derived cellulose ester fibers may be biodegradable fibers and such fibers may be used to form fibrous articles such as textiles, nonwoven fabrics, filters, and yarns. The torrefied textile derived cellulose ester fibers as described herein can exhibit enhanced levels of environmental non-persistence, characterized by better-than-expected degradation under various environmental conditions. Fibers and fibrous articles described herein may meet or exceed passing standards set by international test methods and authorities for industrial compostability, home compostability, and/or soil biodegradability.
To be considered “compostable,” a material must meet the following four criteria: (1) the material must be biodegradable; (2) the material must be disintegrable; (3) the material must not contain more than a maximum amount of heavy metals; and (4) the material must not be ecotoxic. As used herein, the term “biodegradable” generally refers to the tendency of a material to chemically decompose under certain environmental conditions. Biodegradability is an intrinsic property of the material itself, and the material can exhibit different degrees of biodegradability, depending on the specific conditions to which it is exposed. The term “disintegrable” refers to the tendency of a material to physically decompose into smaller fragments when exposed to certain conditions. Disintegration depends both on the material itself, as well as the physical size and configuration of the article being tested. Ecotoxicity measures the impact of the material on plant life, and the heavy metal content of the material is determined according to the procedures laid out in the standard test method.
The torrefied textile derived cellulose ester fibers can exhibit a biodegradation of at least 70 percent in a period of not more than 50 days, when tested under aerobic composting conditions at ambient temperature (28° C.±2° C.) according to ISO 14855-1 (2012). In some cases, the torrefied textile derived cellulose esters and fibers can exhibit a biodegradation of at least 70 percent in a period of not more than 49, or not more than 48, or not more than 47, or not more than 46, or not more than 45, or not more than 44, or not more than 43, or not more than 42, or not more than 41, or not more than 40, or not more than 39, or not more than 38, or not more than 37 days when tested under these conditions, also called “home composting conditions.” These conditions may not be aqueous or anaerobic. In some cases, the torrefied textile derived cellulose esters and fibers can exhibit a total biodegradation of at least about 71, or at least 72, or at least 73, or at least 74, or at least 75, or at least 76, or at least 77, or at least 78, or at least 79, or at least 80, or at least 81, or at least 82, or at least 83, or at least 84, or at least 85, or at least 86, or at least 87, or at least 88 percent, when tested under according to ISO 14855-1 (2012) for a period of 50 days under home composting conditions. This may represent a relative biodegradation of at least about 95, or at least 97, or at least 99, or at least 100, or at least 101, or at least 102, or at least 103 percent, when compared to cellulose subjected to identical test conditions.
To be considered “biodegradable,” under home composting conditions according to the French norm NF T 51-800 and the Australian standard AS 5810, a material must exhibit a biodegradation of at least 90 percent in total (e.g., as compared to the initial sample), or a biodegradation of at least 90 percent of the maximum degradation of a suitable reference material after a plateau has been reached for both the reference and test item. The maximum test duration for biodegradation under home compositing conditions is 1 year. The torrefied textile derived cellulose esters and fibers as described herein may exhibit a biodegradation of at least 90 percent within not more than 1 year, measured according 14855-1 (2012) under home composting conditions. In some cases, the torrefied textile derived cellulose esters and fibers may exhibit a biodegradation of at least about 91, or at least 92, or at least 93, or at least 94, or at least 95, or at least 96, or at least 97, or at least 98, or at least 99, or at least 99.5 percent within not more than 1 year, or the fibers may exhibit 100 percent biodegradation within not more than 1 year, measured according 14855-1 (2012) under home composting conditions.
Additionally, or in the alternative, the fibers described herein may exhibit a biodegradation of at least 90 percent within not more than about 350, or not more than 325, or not more than 300, or not more than 275, or not more than 250, or not more than 225, or not more than 220, or not more than 210, or not more than 200, or not more than 190, or not more than 180, or not more than 170, or not more than 160, or not more than 150, or not more than 140, or not more than 130, or not more than 120, or not more than 110, or not more than 100, or not more than 90, or not more than 80, or not more than 70, or not more than 60, or not more than 50 days, measured according 14855-1 (2012) under home composting conditions. In some cases, the fibers can be at least about 97, or at least 98, or at least 99, or at least 99.5 percent biodegradable within not more than about 70, or not more than 65, or not more than 60, or not more than 50 days of testing according to ISO 14855-1 (2012) under home composting conditions. As a result, the torrefied textile derived cellulose esters and fibers may be considered biodegradable according to, for example, French Standard NF T 51-800 and Australian Standard AS 5810 when tested under home composting conditions.
The torrefied textile derived cellulose esters and fibers can exhibit a biodegradation of at least 60 percent in a period of not more than 45 days, when tested under aerobic composting conditions at a temperature of 58° C. (±2° C.) according to ISO 14855-1 (2012). In some cases, the fibers can exhibit a biodegradation of at least 60 percent in a period of not more than 44, or not more than 43, or not more than 42, or not more than 41, or not more than 40, or not more than 39, or not more than 38, or not more than 37, or not more than 36, or not more than 35, or not more than 34, or not more than 33, or not more than 32, or not more than 31, or not more than 30, or not more than 29, or not more than 28, or not more than 27 days when tested under these conditions, also called “industrial composting conditions.” These may not be aqueous or anaerobic conditions. In some cases, the fibers can exhibit a total biodegradation of at least about 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 87, or at least 88, or at least 89, or at least 90, or at least 91, or at least 92, or at least 93, or at least 94, or at least 95 percent, when tested under according to ISO 14855-1 (2012) for a period of 45 days under industrial composting conditions. This may represent a relative biodegradation of at least about 95, or at least 97, or at least 99, or at least 100, or at least 102, or at least 105, or at least 107, or at least 110, or at least 112, or at least 115, or at least 117, or at least 119 percent, when compared to cellulose fibers subjected to identical test conditions.
To be considered “biodegradable,” under industrial composting conditions according to ASTM D6400 and ISO 17088, at least 90 percent of the organic carbon in the whole item (or for each constituent present in an amount of more than 1% by dry mass) must be converted to carbon dioxide by the end of the test period when compared to the control or in absolute. According to European standard ED 13432 (2000), a material must exhibit a biodegradation of at least 90 percent in total, or a biodegradation of at least 90 percent of the maximum degradation of a suitable reference material after a plateau has been reached for both the reference and test item. The maximum test duration for biodegradability under industrial compositing conditions is 180 days. The torrefied textile derived cellulose esters and fibers described herein may exhibit a biodegradation of at least 90 percent within not more than 180 days, measured according 14855-1 (2012) under industrial composting conditions. In some cases, the torrefied textile derived cellulose esters and fibers may exhibit a biodegradation of at least about 91, or at least 92, or at least 93, or at least 94, or at least 95, or at least 96, or at least 97, or at least 98, or at least 99, or at least 99.5 percent within not more than 180 days, or the fibers may exhibit 100 percent biodegradation within not more than 180 days, measured according 14855-1 (2012) under industrial composting conditions.
Additionally, or in the alternative, torrefied textile derived cellulose esters and fibers described herein may exhibit a biodegradation of least 90 percent within not more than about 175, or not more than 170, or not more than 165, or not more than 160, or not more than 155, or not more than 150, or not more than 145, or not more than 140, or not more than 135, or not more than 130, or not more than 125, or not more than 120, or not more than 115, or not more than 110, or not more than 105, or not more than 100, or not more than 95, or not more than 90, or not more than 85, or not more than 80, or not more than 75, or not more than 70, or not more than 65, or not more than 60, or not more than 55, or not more than 50, or not more than 45 days, measured according 14855-1 (2012) under industrial composting conditions. In some cases, the torrefied textile derived cellulose esters and fibers can be at least about 97, or at least 98, or at least 99, or at least 99.5 percent biodegradable within not more than about 65, 60, 55, 50, or 45 days of testing according to ISO 14855-1 (2012) under industrial composting conditions. As a result, the torrefied textile derived cellulose esters and fibers described herein may be considered biodegradable according ASTM D6400 and ISO 17088 when tested under industrial composting conditions.
The fibers or fibrous articles may exhibit a biodegradation in soil of at least 60 percent within not more than 130 days, measured according to ISO 17556 (2012) under aerobic conditions at ambient temperature. In some cases, the fibers can exhibit a biodegradation of at least 60 percent in a period of not more than 130, or not more than 120, or not more than 110, or not more than 100, or not more than 90, or not more than 80, or not more than 75 days when tested under these conditions, also called “soil composting conditions.” These may not be aqueous or anaerobic conditions. In some cases, the fibers can exhibit a total biodegradation of at least about 65, or at least 70, or at least 72, or at least 75, or at least 77, or at least 80, or at least 82, or at least 85 percent, when tested under according to ISO 17556 (2012) for a period of 195 days under soil composting conditions. This may represent a relative biodegradation of at least about 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95 percent, when compared to cellulose fibers subjected to identical test conditions.
In order to be considered “biodegradable,” under soil composting conditions according the OK biodegradable SOIL conformity mark of Vinçotte and the DIN Geprüft Biodegradable in soil certification scheme of DIN CERTCO, a material must exhibit a biodegradation of at least 90 percent in total (e.g., as compared to the initial sample), or a biodegradation of at least 90 percent of the maximum degradation of a suitable reference material after a plateau has been reached for both the reference and test item. The maximum test duration for biodegradability under soil compositing conditions is 2 years. The torrefied textile derived cellulose esters and fibers as described herein may exhibit a biodegradation of at least 90 percent within not more than 2 years, 1.75 years, 1 year, 9 months, or 6 months measured according ISO 17556 (2012) under soil composting conditions. In some cases, the torrefied textile derived cellulose esters and fibers may exhibit a biodegradation of at least about 91, or at least 92, or at least 93, or at least 94, or at least 95, or at least 96, or at least 97, or at least 98, or at least 99, or at least 99.5 percent within not more than 2 years, or the fibers may exhibit 100 percent biodegradation within not more than 2 years, measured according ISO 17556 (2012) under soil composting conditions.
Additionally, or in the alternative, torrefied textile derived cellulose esters and fibers described herein may exhibit a biodegradation of at least 90 percent within not more than about 700, or not more than 650, or not more than 600, or not more than 550, or not more than 500, or not more than 450, or not more than 400, or not more than 350, or not more than 300, or not more than 275, or not more than 250, or not more than 240, or not more than 230, or not more than 220, or not more than 210, or not more than 200, or not more than 195 days, measured according 17556 (2012) under soil composting conditions. In some cases, the torrefied textile derived cellulose esters and fibers can be at least about 97, or at least 98, or at least 99, or at least 99.5 percent biodegradable within not more than about 225, or not more than 220, or not more than 215, or not more than 210, or not more than 205, or not more than 200, or not more than 195 days of testing according to ISO 17556 (2012) under soil composting conditions. As a result, the torrefied textile derived cellulose esters and fibers described herein may meet the requirements to receive The OK biodegradable SOIL conformity mark of Vinçotte and to meet the standards of the DIN Geprüft Biodegradable in soil certification scheme of DIN CERTCO.
In some embodiments, torrefied textile derived cellulose esters and fibers (or fibrous articles) of the present invention may include less than 1, or not more than 0.75, or not more than 0.50, or not more than 0.25 weight percent of components of unknown biodegradability. In some cases, the fibers or fibrous articles described herein may include no components of unknown biodegradability.
In addition to being biodegradable under industrial and/or home composting conditions, torrefied textile derived cellulose esters and fibers or fibrous articles as described herein may also be compostable under home and/or industrial conditions. As described previously, a material is considered compostable if it meets or exceeds the requirements set forth in EN 13432 for biodegradability, ability to disintegrate, heavy metal content, and ecotoxicity. The torrefied textile derived cellulose ester fibers or fibrous articles described herein may exhibit sufficient compostability under home and/or industrial composting conditions to meet the requirements to receive the OK compost and OK compost HOME conformity marks from Vinçotte.
In some cases, the torrefied textile derived cellulose ester and fibers and fibrous articles described herein may have a volatile solids concentration, heavy metals and fluorine content that fulfill all of the requirements laid out by EN 13432 (2000). Additionally, the torrefied textile derived cellulose esters and fibers may not cause a negative effect on compost quality (including chemical parameters and ecotoxicity tests).
In some cases, the torrefied textile derived cellulose esters and fibers or fibrous articles can exhibit a disintegration of at least 90 percent within not more than 26 weeks, measured according to ISO 16929 (2013) under industrial composting conditions. In some cases, the fibers or fibrous articles may exhibit a disintegration of at least about 91, or at least 92, or at least 93, or at least 94, or at least 95, or at least 96, or at least 97, or at least 98, or at least 99, or at least 99.5 percent under industrial composting conditions within not more than 26 weeks, or the fibers or articles may be 100 percent disintegrated under industrial composting conditions within not more than 26 weeks. Alternatively, or in addition, the fibers or articles may exhibit a disintegration of at least 90 percent under industrial compositing conditions within not more than about 26, or not more than 25, or not more than 24, or not more than 23, or not more than 22, or not more than 21, or not more than 20, or not more than 19, or not more than 18, or not more than 17, or not more than 16, or not more than 15, or not more than 14, or not more than 13, or not more than 12, or not more than 11, or not more than 10 weeks, measured according to ISO 16929 (2013). In some cases, the torrefied textile derived cellulose esters and fibers or fibrous articles described herein may be at least 97, or at least 98, or at least 99, or at least 99.5 percent disintegrated within not more than 12, or not more than 11, or not more than 10, or not more than 9, or not more than 8 weeks under industrial composting conditions, measured according to ISO 16929 (2013).
In some cases, the torrefied textile derived cellulose esters and fibers or fibrous articles can exhibit a disintegration of at least 90 percent within not more than 26 weeks, measured according to ISO 16929 (2013) under home composting conditions. In some cases, the fibers or fibrous articles may exhibit a disintegration of at least about 91, or at least 92, or at least 93, or at least 94, or at least 95, or at least 96, or at least 97, or at least 98, or at least 99, or at least 99.5 percent under home composting conditions within not more than 26 weeks, or the fibers or articles may be 100 percent disintegrated under home composting conditions within not more than 26 weeks. Alternatively, or in addition, the fibers or articles may exhibit a disintegration of at least 90 percent within not more than about 26, or not more than 25, or not more than 24, or not more than 23, or not more than 22, or not more than 21, or not more than 20, or not more than 19, or not more than 18, or not more than 17, or not more than 16, or not more than 15 weeks under home composting conditions, measured according to ISO 16929 (2013). In some cases, the torrefied textile derived cellulose esters and fibers or fibrous articles described herein may be at least 97, or at least 98, or at least 99, or at least 99.5 percent disintegrated within not more than 20, or not more than 19, or not more than 18, or not more than 17, or not more than 16, or not more than 15, or not more than 14, or not more than 13, or not more than 12 weeks, measured under home composting conditions according to ISO 16929 (2013).
In embodiments, cellulose acetate fibers are provided that comprise torrefied textile content and are biodegradable and/or compostable. It is believed that the cellulose acetate fibers can achieve higher levels of biodegradability and/or compostability without use of additives that have traditionally been used to facilitate environmental non-persistence of similar fibers. Such additives can include, for example, photodegradation agents, biodegradation agents, decomposition accelerating agents, and various types of other additives. Despite being substantially free of these types of additives, in embodiments, the cellulose acetate fibers and articles can be provided that exhibit enhanced biodegradability and compostability when tested under industrial, home, and/or soil conditions, as discussed herein.
In some embodiments, the cellulose acetate fibers described herein may be substantially free of photodegradation agents. For example, the fibers may include not more than about 1, or not more than 0.75, or not more than 0.50, or not more than 0.25, or not more than 0.10, or not more than 0.05, or not more than 0.025, or not more than 0.01, or not more than 0.005, or not more than 0.0025, or not more than 0.001 weight percent of photodegradation agent, based on the total weight of the fiber, or the fibers may include no photodegradation agents. Examples of such photodegradation agents include, but are not limited to, pigments which act as photooxidation catalysts and are optionally augmented by the presence of one or more metal salts, oxidizable promoters, and combinations thereof. Pigments can include coated or uncoated anatase or rutile titanium dioxide, which may be present alone or in combination with one or more of the augmenting components such as, for example, various types of metals. Other examples of photodegradation agents include benzoins, benzoin alkyl ethers, benzophenone and its derivatives, acetophenone and its derivatives, quinones, thioxanthones, phthalocyanine and other photosensitizers, ethylene-carbon monoxide copolymer, aromatic ketone-metal salt sensitizers, and combinations thereof.
In some embodiments, the cellulose acetate fibers described herein may be substantially free of biodegradation agents and/or decomposition agents. For example, the fibers may include not more than about 1, 0.75, or not more than 0.50, or not more than 0.25, or not more than 0.10, or not more than 0.05, or not more than 0.025, or not more than 0.01, or not more than 0.005, or not more than 0.0025, or not more than 0.0020, or not more than 0.0015, or not more than 0.001, or not more than 0.0005 weight percent of biodegradation agents and/or decomposition agents, based on the total weight of the fiber, or the fibers may include no biodegradation and/or decomposition agents. Examples of such biodegradation and decomposition agents include, but are not limited to, salts of oxygen acid of phosphorus, esters of oxygen acid of phosphorus or salts thereof, carbonic acids or salts thereof, oxygen acids of phosphorus, oxygen acids of sulfur, oxygen acids of nitrogen, partial esters or hydrogen salts of these oxygen acids, carbonic acid and its hydrogen salt, sulfonic acids, and carboxylic acids.
Other examples of such biodegradation and decomposition agents include an organic acid selected from the group consisting of oxo acids having 2 to 6 carbon atoms per molecule, saturated dicarboxylic acids having 2 to 6 carbon atoms per molecule, and lower alkyl esters of the oxo acids or the saturated dicarboxylic acids with alcohols having from 1 to 4 carbon atoms. Biodegradation agents may also comprise enzymes such as, for example, a lipase, a cellulase, an esterase, and combinations thereof. Other types of biodegradation and decomposition agents can include cellulose phosphate, starch phosphate, calcium secondary phosphate, calcium tertiary phosphate, calcium phosphate hydroxide, glycolic acid, lactic acid, citric acid, tartaric acid, malic acid, oxalic acid, malonic acid, succinic acid, succinic anhydride, glutaric acid, acetic acid, and combinations thereof.
Cellulose acetate fibers described herein may also be substantially free of several other types of additives that have been added to other fibers to encourage environmental non-persistence. Examples of these additives can include, but are not limited to, polyesters, including aliphatic and low molecular weight (e.g., less than 5000) polyesters, enzymes, microorganisms, water soluble polymers, modified cellulose acetate, water-dispersible additives, nitrogen-containing compounds, hydroxy-functional compounds, oxygen-containing heterocyclic compounds, sulfur-containing heterocyclic compounds, anhydrides, monoepoxides, and combinations thereof. In some cases, the fibers described herein may include not more than about 0.5, or not more than 0.4, or not more than 0.3, or not more than 0.25, or not more than 0.1, or not more than 0.075, or not more than 0.05, or not more than 0.025, or not more than 0.01, or not more than 0.0075, or not more than 0.005, or not more than 0.0025, or not more than 0.001 weight percent of these types of additives, or the cellulose acetate fibers may not include any of these types of additives.
In one embodiment or in combination with any of the mentioned embodiments, durable articles are provided that comprise the torrefied textile derived cellulose esters, as described herein. In embodiments, the durable articles are made from moldable thermoplastic material comprising the torrefied textile derived cellulose esters, as described herein. In embodiments, the moldable thermoplastic material comprises torrefied textile derived cellulose esters chosen from cellulose acetate propionate, cellulose acetate butyrate, or combinations thereof.
In one embodiment or in combination with any of the mentioned embodiments, an integrated process for preparing a torrefied textile derived cellulose ester is provide which comprises the processing steps of: (1) preparing a torrefied textile derived syngas obtained by gasifying a solid fossil fuel source and torrefied textiles; (2) preparing at least one torrefied textile derived chemical intermediate from said torrefied textile derived syngas; (3) reacting said torrefied textile derived chemical intermediate in a reaction scheme to prepare at least one torrefied textile derived cellulose reactant for preparing a torrefied textile derived cellulose ester, and/or selecting said torrefied textile derived chemical intermediate to be at least one torrefied textile derived cellulose reactant for preparing a torrefied textile derived cellulose ester; and (4) reacting said at least one torrefied textile derived cellulose reactant to prepare said torrefied textile derived cellulose ester; wherein said torrefied textile derived cellulose ester comprises at least one substituent on an anhydroglucose unit (AGU) derived from torrefied textile derived syngas.
In embodiments, the processing steps (1) to (4) are carried out in a system that is in fluid and/or gaseous communication (i.e., including the possibility of a combination of fluid and gaseous communication). It should be understood that the torrefied textile derived chemical compounds, in one or more of the reaction schemes for producing torrefied textile derived cellulose esters starting from torrefied textile derived syngas, may be temporarily stored in storage vessels and later reintroduced to the integrated process system, or at time are sealed off through valves, and are nevertheless considered to be in fluid communication upstream and downstream. Further, the entire process need not be in gaseous and/or fluid communication simultaneously to be considered in gaseous communication provided that piping can be traced from one vessel to another to close the loop.
In one embodiment, an integrated process for preparing a torrefied textile derived cellulose ester is provide which comprises the processing steps of: (1) preparing a torrefied textile derived syngas obtained by gasifying a solid fossil fuel source and torrefied textiles; (2) preparing at least one torrefied textile derived chemical compound from said torrefied textile derived syngas; (3) reacting said torrefied textile derived chemical compound in a reaction scheme to prepare at least one torrefied textile derived cellulose reactant for preparing a torrefied textile derived cellulose ester, and/or selecting said torrefied textile derived chemical compound to be at least one torrefied textile derived cellulose reactant for preparing a torrefied textile derived cellulose ester; and (4) reacting said at least one torrefied textile derived cellulose reactant to prepare said torrefied textile derived cellulose ester; wherein said torrefied textile derived cellulose ester comprises at least one substituent on an anhydroglucose unit (AGU) derived from torrefied textile derived syngas.
In embodiments, the at least one torrefied textile derived chemical compound is chosen from methanol, methyl acetate, acetic anhydride, acetic acid, or combinations thereof. In embodiments, one torrefied textile derived chemical intermediate is methanol, and the methanol is used in a reaction scheme to make a second torrefied textile derived chemical intermediate that is acetic anhydride. In embodiments, the torrefied textile derived cellulose reactant is acetic anhydride.
There is also provided an integrated process for preparing a torrefied textile derived cellulose ester. The process includes the (i) preparation of a textile derived syngas obtained by gasifying a torrefied textiles, and (ii) preparing at least one torrefied textile derived chemical compound from said torrefied textile derived syngas, and (iii) reacting said torrefied textile derived chemical compound in a reaction scheme to prepare at least one torrefied textile derived cellulose reactant as a raw material for preparing a torrefied textile derived cellulose ester, and/or selecting said torrefied textile derived chemical compound to be at least one torrefied textile derived cellulose reactant for preparing a torrefied textile derived cellulose ester; and (iv) reacting said at least one torrefied textile derived cellulose reactant to prepare said torrefied textile derived cellulose ester. For example, the:
In one embodiment or additional to any of the mentioned embodiments, the steps (1)-(4) can be in gaseous or liquid communication with at least one preceding step, or at least two preceding steps, or at least 3 preceding steps, or all four steps with each other, with an option that liquid chemicals in steps (2)-(4) can be stored as liquids before their use with cutoff valves isolating the liquids in vessels provided at least a portion of the liquid are fed from such vessel through a series of pipes and/or vessels, directly or indirectly, to the next reaction step and not shipped by rail, ship, or truck.
In one embodiment, the torrefied textile derived syngas is a reactant to at least two of the 4 steps, or to 3 of the 4 steps.
The processes also allow for a complete circular manufacturing process by providing a first textile, torrefying that textile to make a torrefied textile, gasifying the torrefied textile to make a torrefied textile derived syngas, reacting the torrefied textile derived syngas to make a torrefied textile derived textile through chemical compounds, polymer reactants, polymers, and fibers, all of which have a part of their origin in the torrefied textile derived syngas. By a “part of their origin” is meant that the chain of chemicals or materials used to make the element under consideration have their origin in and can be traced back to one or more sources of a torrefied textile derived syngas. The textile to be torrefied is desirably a post-consumer textile. Once the first cycle is complete, it becomes possible that the post-consumer textile to be torrefied is actually a torrefied textile derived textile. The polymer reactants can be cellulose ester reactants, and the polymer can be a cellulose ester.
In one embodiment or in any of the mentioned embodiments, the polymer reactants can be adipic acid made by carbonylation of butadiene with the torrefied textile derived syngas, and such reactant can then be reacted to make nylon 6,6, spun into a fiber to make a textile. The conventional process for making nylon 6,6 by oxidizing a mixture of cyclohexanol and cyclohexanone can also find its origin in a torrefied textile derived syngas in that the hydrogen component from such gas can be employed to hydrogenate phenol to make the torrefied textile derived chemical compound cyclohexanol, which is in turn oxidized with cyclohexanone to make a torrefied polymer reactant adipic acid, which is reacted with hexamethylenediamine to make nylon 6,6, a torrefied textile derived polymer. Likewise, cyclohexane can be hydrogenated using the torrefied textile derived syngas hydrogen component to make cyclohexanone used in the manufacture of nylon 6 and nylon 6,6.
Turning to the gasification process for making the torrefied derived syngas, at least a torrefied textile is fed to the gasifier, and optionally solid fossil fuels are also fed to the gasifier. For purposes of classifying materials in the feedstock composition, a fossil fuel can include coal, petcoke, any other solid at 25° C. and 1 atmosphere that is a byproduct from refining oil or petroleum, or liquid hydrocarbons or streams obtained from refining crude oil, or waste streams from chemical synthetic processes. The fossil fuel portion of the feedstock composition is to be distinguished from finished articles made from fossil fuel derivatives or from such finished articles that are processed, such as torrefied textiles, even if the torrefied textiles are carbonaceous or if they are derived in part from raw materials obtained from refining crude oil
Generally, in a synthesis gas operation one or more feedstock composition(s) comprised of torrefied textiles and fossil fuel sources (e.g. coal, petcoke) or liquid fuel sources, or a combination of solid and liquid fuel sources, fed as an individual stream or combined with the fossil fuel source streams, and optionally water and other chemical additives, are fed or injected along with an oxidizer gas into a gasification reaction zone or chamber of a synthesis gas generator (gasifier) and gasified in the presence of an oxidizer such as oxygen, also fed to the gasifier. A hot gas stream is produced in the gasification zone, optionally refractory lined, at high temperature and high pressure generating a molten slag, soot, ash and gases including hydrogen, carbon monoxide, carbon dioxide and can include other gases such as methane, hydrogen sulfide and nitrogen depending on the fuel source and reaction conditions. The hot gas stream is produced in the reaction zone is cooled using a syngas cooler or in a quench water bath at the base of the gasifier which also solidifies ash and slag and separates solids from the gases. The quench water bath also acts as a seal to maintain the internal temperature and pressure in the gasifier while the slag, soot and ash are removed into a lock hopper. The cooled product gas stream removed from the gasifier (the raw torrefied textile derived syngas stream) can be further treated with water to remove remaining solids such as soot, and then further treated to remove acid gas (e.g. hydrogen sulfide) after optionally further cooling and shifting the ratio of carbon monoxide to hydrogen.
The torrefied textiles employed in the feedstock stream to the gasifier are solid at 25° C. at 1 atm. The torrefied textiles are a collection of torrefied textile particles, briquettes, agglomerates, pellets, or rods, or any other shape or size that different from the native shape of the textile from which the torrefied textile is made. The torrefied textiles are obtained by subjecting a recycle feedstock containing textiles to a torrefaction process. The recycle feedstock to be torrefied contains at least textiles. Textiles as used herein are natural and/or synthetic fibers, rovings, yarns, nonwoven webs, cloth, fabrics and products made from or containing any of the aforementioned items, provided that the textiles are either post-consumer or post-industrial textiles. Even though textiles can contain natural fibers obtained from plants or wood, textiles are not a biomass feedstock or a wood feedstock since the textiles to be torrefied are post-consumer or postindustrial articles used or intended for use as articles in finished form or components to make the finished articles (e.g. yarn, rovings, cloth, etc.).
Textiles can be woven, knitted, knotted, stitched, tufted, pressing of fibers together such as would be done in a felting operation, embroidered, laced, crocheted, braided, or nonwoven webs and materials. Textiles as used herein include fabrics, and fibers separated from a textile or other product containing fibers, scrap or off spec fibers or yarns or fabrics, or any other source of loose fibers and yarns. A textile also includes staple fibers, continuous fibers, threads, tow bands, twisted and/or spun yarns, grey fabrics made from yarns, finished fabrics produced by wet processing gray fabrics, and garments made from the finished fabrics or any other fabrics. Textiles include apparels, interior furnishings, and industrial types of textiles.
Examples of textiles in the apparel category (things humans wear or made for the body) include sports coats, suits, trousers and casual or work pants, shirts, socks, sportswear, dresses, intimate apparel, outerwear such as rain jackets, cold temperature jackets and coats, sweaters, protective clothing, uniforms, and accessories such as scarves, hats, and gloves. Examples of textiles in the interior furnishing category include furniture upholstery and slipcovers, carpets and rugs, curtains, bedding such as sheets, pillow covers, duvets, comforters, mattress covers; linens, tablecloths, towels, washcloths, and blankets. Examples of industrial textiles include transportation (auto, airplanes, trains, buses) seats, floor mats, trunk liners, and headliners; outdoor furniture and cushions, tents, backpacks, luggage, ropes, conveyor belts, calendar roll felts, polishing cloths, rags, soil erosion fabrics and geotextiles, agricultural mats and screens, personal protective equipment, bullet proof vests, medical bandages, sutures, tapes, and the like.
The nonwoven webs that are classified as textiles do not include the category of wet laid nonwoven webs and articles made therefrom. While a variety of articles having the same function can be made from a dry or wet laid process, the article made from the dry laid nonwoven web is classified as a textile. Examples of suitable articles that may be formed from dry laid nonwoven webs as described herein can include those for personal, consumer, industrial, food service, medical, and other types of end uses. Specific examples can include, but are not limited to, baby wipes, flushable wipes, disposable diapers, training pants, feminine hygiene products such as sanitary napkins and tampons, adult incontinence pads, underwear, or briefs, and pet training pads. Other examples include a variety of different dry or wet wipes, including those for consumer (such as personal care or household) and industrial (such as food service, health care, or specialty) use. Nonwoven webs can also be used as padding for pillows, mattresses, and upholstery, batting for quilts and comforters. In the medical and industrial fields, nonwoven webs of the present invention may be used for medical and industrial face masks, protective clothing, caps, and shoe covers, disposable sheets, surgical gowns, drapes, bandages, and medical dressings. Additionally, nonwoven webs as described herein may be used for environmental fabrics such as geotextiles and tarps, oil and chemical absorbent pads, as well as building materials such as acoustic or thermal insulation, tents, lumber and soil covers and sheeting. Nonwoven webs may also be used for other consumer end use applications, such as for, carpet backing, packaging for consumer, industrial, and agricultural goods, thermal or acoustic insulation, and in various types of apparel. The dry laid nonwoven webs as described herein may also be used for a variety of filtration applications, including transportation (e.g., automotive or aeronautical), commercial, residential, industrial, or other specialty applications. Examples can include filter elements for consumer or industrial air or liquid filters (e.g., gasoline, oil, water), including nanofiber webs used for microfiltration, as well as end uses like tea bags, coffee filters, and dryer sheets. Further, nonwoven webs as described herein may be used to form a variety of components for use in automobiles, including, but not limited to, brake pads, trunk liners, carpet tufting, and under padding.
The textiles can include single type or multiple type of natural fibers and/or single type or multiple type of synthetic fibers. Examples of textile fiber combinations include all natural, all synthetic, two or more type of natural fibers, two or more types of synthetic fibers, one type of natural fiber and one type of synthetic fiber, one type of natural fibers and two or more types of synthetic fibers, two or more types of natural fibers and one type of synthetic fibers, and two or more types of natural fibers and two or more types of synthetic fibers.
Polymers used to make the synthetic fibers can be thermoplastic or thermosetting polymers. The polymer number average molecular weight can be at least 300, or at least 500, or at least 1000, or at least 5,000, or at least 10,000, or at least 20,000, or at least 30,000, or at least 50,000 or at least 70,000 or at least 90,000 or at least 100,000 or at least 130,000. The weight average molecular weight of the polymers can be at least 300, or at least 500, or at least 1000, or at least 5,000, or at least 10,000, or at least 20,000, or at least 30,000 or at least 50,000, or at least 70,000, or at least 90,000, or at least 100,000, or at least 130,000, or at least 150,000, or at least 300,000.
Natural fibers include those that are plant derived or animal derived. Natural fibers can be cellulosics, hemicellulosics, and lignins. Examples of plant derived natural fibers include hardwood pulp, softwood pulp, and wood flour; and other plant fibers including those in wheat straw, rice straw, abaca, coir, cotton, flax, hemp, jute, bagasse, kapok, papyrus, ramie, rattan, vine, kenaf, abaca, henequen, sisal, soy, cereal straw, bamboo, reeds, esparto grass, bagasse, Sabai grass, milkweed floss fibers, pineapple leaf fibers, switch grass, lignin-containing plants, and the like. Examples of animal derived fibers include wool, silk, mohair, cashmere, goat hair, horsehair, avian fibers, camel hair, angora wool, and alpaca wool.
Synthetic fibers are those fibers that are, at least in part, synthesized or derivatized through chemical reactions, or regenerated, and include, but are not limited to, rayon, viscose, mercerized fibers or other types of regenerated cellulose (conversion of natural cellulose to a soluble cellulosic derivative and subsequent regeneration) such as lyocell (also known as Tencel), Cupro, Modal, acetates such as polyvinylacetate, polyamides including nylon, polyesters such as those polyethylene terephthalate (PET), copolyesters including those made with IPA, CHDM and/or 2,2,4,4-tetramethyl-1,3-cyclobutanediol, polycyclohexylenedimethylene terephthalate (PCT) and other copolymers, olefinic polymers such as polypropylene and polyethylene, polycarbonates, poly sulfates, poly sulfones, polyethers such as polyether-urea known as Spandex or elastane, polyacrylates, acrylonitrile copolymers, polyvinylchloride (PVC), polylactic acid, polyglycolic acid, sulfopolyester fibers, and combinations thereof.
At least a portion of the textiles in the recycle feedstock, and at least a portion of the torrefied textiles are obtained from post-consumer textiles and/or post-industrial textiles (also commonly known as pre-consumer textiles). Post-consumer textiles are those that have been used at least once for its intended application for any duration of time regardless of wear. Post-industrial torrefied textile include rework, regrind, scrap, trim, out of specification textiles (e.g. fibers, yarns, webs, cloths, fabrics, finished textiles) that have not been used for their intended application, or any textiles that have not been used by the end consumer.
The form of the textiles useful to make torrefied textile is not limited, and can include any of the forms of articles or materials used to make textiles described above; e.g. fibers, yarns, fabrics, cloths, finished article forms, or pieces thereof. The textiles and the torrefied textile can be of varying age and composition.
The source of the post-consumer or postindustrial textiles is not limited, and can include textiles present in and separated from municipal solid waste streams (“MSW”). For example, an MSW stream can be processed and sorted to several discrete components, including textiles, fibers, papers, wood, glass, metals, etc. Other sources of textiles include those obtained by collection agencies, or by or for or on behalf of textile brand owners or consortiums or organizations, or from brokers, or from postindustrial sources such as scrap from mills or commercial production facilities, unsold fabrics from wholesalers or dealers, from mechanical and/or chemical sorting or separation facilities, from landfills, or stranded on docks or ships.
To obtain a torrefied textile (and in all instance mention of a torrefied textile provides support for an embodiment of a torrefied textile char, and mention of a torrefied textile char provides support for a torrefied textile), the feedstock containing at least textiles (textile feedstock) is torrefied. A torrefication process devolatizes and degrades (or depolymerizes) the textiles in an oxygen starved environment under mild temperatures (below carbonization temperatures) to generate a char that can be densified to produce an energy dense, hydrophobic and more homogeneous fuel source, optionally that can have a closer resemblance to coal than the textile feedstock. Torrefaction of textiles reduces their H/C and O/C ratios, and increases the relative concentration of carbon, which is an advantage for the production of syngas made from solid fossil fuels, particularly when such syngas is used to make chemicals in that chemical synthetic processes are sensitive to and require consistency: in both the ratio and amount of H/CO.
Prior to entering the torrefication chamber, the textiles are typically size reduced to accommodate them in the chamber. The textiles can be cut, confricated, chopped, shredded, or subjected to any conventional size reduction process.
Suitable temperatures for torrefying textiles can occur at any temperature from 180° C. to 325° C., desirably from 200° C. to 300° C., or from 220° C. to 300° C. If wet torrefaction is used, the temperature can be lowered, even down to 180° C. For dry torrefaction, the temperature is desirably at least 200° C.
The torrefaction process can be oxidative or nonoxidative. If oxidative, the torrefaction occurs in the presence of a substoichiometric amount of oxygen needed to form CO2, or in the absence of any added oxygen enriched gas but in the presence of air, or in the absence of any added oxygen but without purging the reactor of oxygen. A nonoxidative process will occur in the substantial absence added oxygen and is typically accompanied by a purge and/or blanket of an inert gas, the combination accomplishing the torrefaction process in the substantial absence of free oxygen. Depending on the torrefaction temperature employed, some amount of oxygen will not affect the quality of the torrefied char. Thus, to save on inert gas costs and separation equipment and energy, the torrefaction process can be conducted at lower temperatures (e.g. lower than 275° C.) with some oxygen present (e.g. less than 20% oxygen at the conclusion of the torrefaction residence time), or no fresh air feed, while still enhancing the energy density of the char after densification.
In one embodiment or in any of the mentioned embodiments, the atomic ratio in moles of total free oxygen to carbon under torrefaction conditions can be from 0 to less than 2, or from 0 to 1.5, or from 0 to 1.2, or from 0 to 1, or from 0 to 0.7, or from 0 to 0.5, or from 0 to 0.3, or from 0 to 0.2, or from 0 to 0.1 or from 0 to 0.05 or from 0 to 0.01 or from 0 to 0.005 or from 0 to 0.001 or from 0 to 0.0005 or from 0 to 0.0001 or from or from 0 to 0.00005 or from 0 to 0.00001 or from 0 to 0.000005 or from 0 to 0.000001, in each case per mole of carbon subjected to torrefaction.
In one embodiment or in any of the mentioned embodiments, the torrefaction chamber is purged with an inert gas or torrefaction is conducted in an inert gas blanket or atmosphere, and no oxygen (whether enriched or air) is added during torrefaction chamber during the torrefaction process. Suitable inert gases do not participate in the reaction or decomposition of the textiles or create a combustion environment. Examples of suitable inert gases include helium, neon, argon, xenon, and nitrogen.
In one embodiment or in any of the mentioned embodiments, the torrefaction is an oxidative torrefaction. The torrefaction process is conducted in a substoichiometric amount of oxygen necessary to convert all carbon atoms in the textiles to carbon dioxide. This process has the advantage of cost reduction for the supply and separation energy and equipment of the inert gas, helps with heat supply to the reaction since oxidative reactions are exothermic, and can reduce the residence time if one is willing to also generate a torrefied textile char with a lower HHV.
The pressure condition in the torrefaction chamber is not limited, and is desirably conducted at atmospheric pressure or without application of pressure to the reactor vessel, and this method is suitable for dry torrefaction. In a wet torrefaction method utilizing pressurized steam, the torrefaction reaction can be conducted at a pressure exceeding 1 atmosphere, or at 10 psig, or at least 50 psig, or at least 100 psig, or at least 130 psig, or at least 200 psig, or at least 400 psig, or at least 500 psig, or at least 700 psig, or at least 1000 psig, or at least 1400 psig, and in addition or in the alternative up to the pressure limit to keep the reactor condition sub-critical, or up to 30,000 psig, or up to 10,000 psig, or up to 5000 psig, or up to 2000 psig. The steam feed to the torrefaction chamber can be 200 lb to 1750 lb saturated steam.
Suitable torrefaction residence times can range from 5 minutes minutes to 5 hours, depending on the degree of mass reduction desired, the torrefaction temperature applied, and whether wet or dry torrefaction is applied. Typically, from 30 minutes to 3 hours are sufficient for dry torrefaction, while the residence time in wet torrefaction processes can be faster, e.g. from 5 minutes to 2 hours. In one embodiment or in any of the mentioned embodiments, the temperature and/or residence time of torrefaction are on the high end (e.g. 2.5 to 4 hours and 250-320° C.) to enhance the flowability and compactability of the char into a densified form. The torrefaction residence time can be reduced at higher temperatures while obtaining similar mass reduction. In one embodiment or in any of the mentioned embodiments, the torrefaction temperature is at least 270° C., or at least 280° C., or at least 290° C., and in each case the residence time can be not more than 2 hours, or
not more than 1.5 hours. Suitable upper torrefaction temperatures can be up to 320° C., or up to 310° C.
The torrefaction of the textiles can be wet or dry. In one embodiment or in any of the mentioned embodiments, the torrefied textiles are obtained by a wet torrefaction method. In such a process, steam is injected into the torrefication chamber. A steam process can decrease the residence time and/or torrefication temperature. As noted above, from 200 lb to 1750 lb saturated steam can be injected into the torrefaction chamber, or the torrefaction chamber can be heated with water to generate steam within the chamber at a pressure below supercritical steam conditions. Wet torrefaction can advantageously increase the energy density, carbon concentration, and reduce ash content relative to dry torrefaction methods.
In one embodiment or in any of the mentioned embodiments, the torrefaction of the textiles is a dry torrefaction method, meaning that no water or steam is added to the torrefaction chamber. In a dry torrefaction method, the textile feedstock can optionally be dried before torrefying conditions are applied.
The torrefaction temperature, pressure, residence time, and oxygen conditions are effective to prevent combustion of the textiles. The torrefaction process conditions are also effective to drive volatile compounds from the textiles into the gas phase at the torrefaction temperatures. The combustible gases from the volatile compounds can be used as a fuel to heat the torrefaction process, thus becomes self-sustaining after start-up. A portion or all of the polymers in the textiles, such as some thermoplastic polymer or natural polymers containing cellulose, hemicellulose, and lignin, will partly decompose and release volatiles organic compounds. The resulting mass is the torrefied textile char that has a mass less than that of the textiles from which they were derived on a solid/solid basis. The textiles subjected to torrefaction can lose at least 10%, or at least 15%, or at least 20%, or at least 25%, or at least 30%, or at least 35% of their mass, on a bone-dry weight basis.
In one embodiment or in any of the mentioned embodiments, the torrefaction reaction process is conducted such that the percentage of energy reduction from textiles to char is less than the percentage of mass reduction or in other words, the rate of energy loss is not as high as the rate of mass loss over the course of the residence time. Since the energy reduction as a percentage is less than the percentage of mass reduction, the energy density (a function of energy/unit mass) of the char is increased, resulting in an increase of the HHV. In this embodiment, the torrefied textile char has a higher energy density and higher HHV than the textiles from which the char is derived.
In one embodiment or in any of the mentioned embodiments, the HHV, or the energy density, of the torrefied textile char is at least 5%, or at least 8%, or at least 10%, or at least 13%, or at least 15%, or at least 18%, or at least 20%, or at least 23%, or at least 25% greater than the HHV, or the energy density, of the textile raw material form which the char is derived. This can be achieved when the torrefied textile char is densified. Densification can take the form of making a powder, particles, briquettes, pellets, or any other shape resulting from the application of a densification process that increases the density of the char, via pressure or agglomeration with or without pressure.
In one embodiment or in any of the mentioned embodiments, the ash content of the torrefied textile char is not more than the ash content of the solid fossil fuel to be gasified. For example, the ash content of the torrefied textile char can be not more than 6 wt. %, or not more than 5 wt. %, or not more than 4 wt %, or not more than 3 wt. %, or not more than 2 wt. %, or not more than 1.5 wt. %.
By subjecting textiles to torrefaction, their elemental composition can become similar to that of coal depending on the torrefaction conditions employed. In one embodiment or in any of the mentioned embodiments, the torrefied textile char has a similar fixed carbon content to that of the solid fossil fuel fed to the gasifier. For example, the fixed carbon content in the torrefied textile char can be within 25%, or within 20%, or within 15%, or within 10%, or within 8%, or within 5%, or within 3%, or within 2%, or within 1.5% less than the fixed carbon content in the solid fossil fuel gasified, or equal to it, or even greater than the fixed carbon content of the solid fossil fuel gasified.
In one embodiment or in any of the mentioned embodiments, the torrefied textile char has a similar (relative to textiles) oxygen content to that of the solid fossil fuel fed to the gasifier. For example, the oxygen content in the torrefied textile char can be within 40%, or within 30%, or within 25%, or within 20%, or within 15%, or within 13%, or within 10% greater than the oxygen content in the solid fossil fuel gasified.
In one embodiment or in any of the mentioned embodiments, the torrefied textile char has a similar hydrogen content to that of the solid fossil fuel fed to the gasifier. For example, the hydrogen content in the torrefied textile char can be within 40%, or within 30%, or within 25%, or within 20%, or within 15%, or within 13%, or within 10% greater than hydrogen content in the solid fossil fuel gasified, or equal to it, or even less hydrogen content that contained in the solid fossil fuel gasified.
The torrefied textile is a char that is a solid at room temperature and 1 atm. The char is the solid residue of torrefying the textiles.
In one embodiment or in any of the mentioned embodiments, the loose bulk density of a raw terrified textile char (the immediate product of the torrefication process) is lower than the loose bulk density of the textiles in the textile feedstock. This is as a result of releasing volatiles from the textiles at the torrefaction temperatures and residence time.
The torrefied textile char can be of any shape: friable flakes, random shaped lumps, briquettes, powder, particles, or pellets. The torrefied textile char is desirably densified, particularly when the torrefied textile char is transported by truck, rail, ocean going vessels, or by air, in order to increase its mass and energy density on a volume basis. Densification will not increase the energy density of the torrefied textile char on a mass basis, but will increase its energy density on a volume basis, making densification an attractive option if it needs to be transported or stored, and for ease of handling.
The torrefied textile char can be stored in humid or moist conditions, or be added to a slurry, without substantially changing its moisture content or HHV, unlike the textiles from which they are derived. The torrefaction process can render the char hydrophobic or have similar hygroscopic characteristics to coal, even in particle or powder form. As such, they are an attractive co-feed with dry coal fed gasifiers. They are also attractive feedstocks in slurry fed solid fossil fuel fed gasifiers because they can remain in free-flowing pourable form, even in moist conditions, for feeding into a coal mill or slurry. Whether fed dry or in a slurry, the torrefied textile char is more stable, easier to store and handle, remain drier, and are more resistant to rot or decomposition than textiles stored on a gasification site.
In one embodiment or in any of the mentioned embodiments, the torrefied textile char absorbs an amount of water than is less than the weight of the char, or absorbs not more than 20%, or not more than 15% or not more than 10%, or not more than 8% of the weight of the char, when measured by taking a sample of char and immersing it in water at room temperature for 1 hour. This feature also makes them attractive as co-feeds with fossil fuels fed a dry fed gasifier as the torrefied textile char, even in particle form, will not be hydrophilic and have similar hygroscopic characteristics to coal.
The torrefied textile char, before densification, is brittle and friable. Although the densification of the char increases its density to provide transport, storage, and handling advantages, the densified char is also easily pulverized or ground, thereby also providing the advantage of not consuming more energy than would be consumed to grind coal. Accordingly, the torrefied textile char, whether or not densified, can be added to any coal Mill or grinder used to size reduce a solid fossil fuel fed to the gasifier. In one embodiment or in any of the mentioned embodiments, the energy consumption to co-grind coal and the torrefied textile char is no greater than, and is advantageously less than, the energy consumption to grind only coal at the same weight.
In one embodiment or in any of the mentioned embodiments, the torrefied textile char has a higher homogeneity in N, O, H, and C content than does the textile from which it is derived. For example, the variation in oxygen O concentration (or oxygen content) from a random sample taken from one batch of torrefied textile char produced on a first day and a sample taken from a batch of torrefied textile produced on a different day (second day) is less than the variation in O concentration (or content) between the textile feeds to make char on the first and second days, and can be less by 5%, or less by 10%, or less by 20%, or less by 25%, or less by 30%. The variation in nitrogen N concentration (or nitrogen content) from a random sample taken from one batch of torrefied textile char produced on a first day and a sample taken from a batch of torrefied textile produced on a different day (second day) is less than the variation in N concentration (or content) between the textile feeds to make char on the first and second days, and can be less by 5%, or less by 10%, or less by 20%, or less by 25%, or less by 30%. The variation in hydrogen H concentration (or hydrogen content) from a random sample taken from one batch of torrefied textile char produced on a first day and a sample taken from a batch of torrefied textile produced on a different day (second day) is less than the variation in H concentration (or content) between the textile feeds to make char on the first and second days, and can be less by 5%, or less by 10%, or less by 20%, or less by 25%, or less by 30%.
In one embodiment or in any of the mentioned embodiments, the torrefaction process does not occur in the same vessel as gasification, and the gasification vessel does not include a zone for torrefaction or pyrolysis. In one embodiment or in any of the mentioned embodiments, torrefied textile char is isolated as a char (or densified char) outside of any vessel and fed to a gasification vessel.
In one embodiment, the textiles used to make the torrefied textiles are within one of the components or streams that are separated from an MSW source.
The torrefied textile char, whether in the form or size of a raw char, briquette, pellet, or any other densified material, can be reduced in size. This can be accomplished by chopping, grinding, shredding, harrowing, confrication, or cutting a feed of torrefied textile char to make size reduced char. Optionally, the size reduced char can continue to be ground to obtain the desired average particle size if one desires to obtain particles. Fluidized bed granulators can be used, optionally with a drying gas, as well as tumbling granulators of disc or drum design connected to high speed mixers having cutting blades on a horizontal or vertical shaft. Examples of different kinds of suitable size reducing processes and equipment as stand-alone or coupled together include air swept mills, knife cutting, fine grinders that can have multiple grinding zones with internal classification systems, choppers with finer knives at the end, disintegrators that can handle shredding of textile char even high moisture feeds and then optional fine cutting or milling into smaller size such as a powder, high speed cutting blades that can have multiple zones for moving coarser material to finer material. The size reducing equipment can also include drying before cutting or simultaneous with drying.
The form of the size reduced char will depend on the desired method of densification. For example, the size reduced char can be in the form of particles (of any shape other than the original shape of the raw torrefied textile char). Any number of steps or no steps can occur between the formation of the raw torrefied textile char and size reduction prior to feeding the size reduced char to the gasifier. For example, the raw torrefied textile char (the char product of the torrefication process) can be ground to particles, densified (e.g. to pellets), transported and/or stored, and the densified char is size reduced to particles by milling, grinding or pulverizing the pellets. Alternatively, the raw torrefied char can be size reduced by grinding the raw char to particles and those particles are fed to the gasifier.
If desired, the torrefied textile char can be densified. The densification process increases the loose bulk density of the raw char. In one embodiment or in any of the mentioned embodiments, the loose bulk density of the torrefied textile char fed to the gasifier is higher than the loose bulk density of the raw torrefied textile char. In one embodiment or in any of the mentioned embodiments, a torrefied textile char is made that has a loose bulk density higher than the loose bulk density of the raw torrefied textile char and the torrefied textile char fed to the gasifier.
Any densification process can be employed. For example, the densification process can be accomplished by forming agglomerates without application of external heat source (the “agglomeration process”), or by applying external heat energy in a process for forming particles (“heat treated process”). In one embodiment or in any of the mentioned embodiments, the densified torrefied textiles are obtained by an agglomeration process that includes pressure. In one embodiment or in any of the mentioned embodiments, the densified torrefied textiles are obtained by an agglomeration process that does not include application of pressure. In one embodiment or in any of the mentioned embodiments, the densified torrefied textile char can be obtained by a heat-treated process that includes that application of pressure.
Examples of pressure agglomeration include compactors (roll, roll press, double roll press). Compactors roll the material into a sheet, and then feed the material to a flake breaker and granulator. The process is generally a dry process. Another example of pressure agglomeration includes briquetters which produce pillow shape agglomerates in the roll press or double roll press. Another example of pressure agglomeration are pelletizers which produce cylindrical shaped pellets from ½ inch to 4 or 5 inches.
Examples of non-pressure agglomeration processes include forming agglomerates with disc pelletizers (also called pan pelletizers or granulators), agglomeration drums, pin mixers, and paddle mixers (pug mills).
Generally, the size of the agglomerates is higher than the size of the size reduced char by, for examples, combining or consolidating smaller particles into larger particles to make granules, tablets, briquettes, pellets, or the like. Since agglomerates are consolidated or pressure compacted rather than fused, they can break apart into smaller sizes more easily than extrudates in grinding or milling equipment, such as those used in a coal or petcoke grinder or mill. Agglomerates also produce fewer fines and dust and can easily flow.
The agglomerates, after formed, can be cured, dried, or fired by application of external heat sources.
In one embodiment or in any of the mentioned embodiments, a portion of the densified torrefied textile char contains thermoplastic polymer. Thermoplastic polymers assist to retain the shape and particle integrity. The amount of thermoplastic polymer can be at least 1 wt. %, or at least 2 wt. %, or at least 5 wt. %, based on the weight of the densified torrefied textile char. In one embodiment or in any of the mentioned embodiments, the thermoplastic polymer is obtained from recycle plastics.
In one embodiment or in any of the mentioned embodiments, the densification step includes the application of heat or are processed by a heat-treated process. The size reduced char is subjected to an external source of heat energy at or above the Tg of the thermoplastic polymer added to the torrefied textile char, causing the softened or melted thermoplastic textiles to flow around and bind the char.
In one embodiment or in combination with any of the mentioned embodiments, at least a portion or all of the torrefied textiles in the feedstock composition or stream, or the feedstock composition or stream fed to a gasifier or into the gasification zone, are obtained from torrefied textiles. In one embodiment or in combination with any of the mentioned embodiments, the torrefied textile char fed to the gasifier contain at least 10 wt. %, or at least 15 wt. %, or at least 20 wt. %, or at least 25 wt. %, or at least 30 wt. %, or at least 35 wt. %, or at least 40 wt. %, or at least 45 wt. %, or at least 50 wt. %, or at least 55 wt. %, or at least 60 wt. %, or at least 65 wt. %, or at least 70 wt. %, or at least 75 wt. %, or at least 80 wt. %, or at least 85 wt. %, or at least 90 wt. %, or at least 95 wt. % or at least 97 wt. % or at least 98 wt. % or at least 99 wt. % or at least 99.5 wt. % material obtained from textiles or textile fibers, based on the weight of the torrefied textile char and not including any additives added after torrefication, such as thermoplastic resin.
Non-combustible inorganic matter such as metals and minerals may be contained in the torrefied textile char for gasification. Examples include tin, cobalt, manganese, antimony, titanium, sodium, calcium, sulfur, zinc, and aluminum, their oxides and other compounds thereof. Advantageously, titanium and calcium that may be present in the torrefied textile char can be slag modifiers.
In one embodiment or in any of the mentioned embodiments, the amount of calcium compounds present in the ash of torrefied textile char is at least 30 wt. %, or at least 40 wt. %, or at least 50 wt. %, or at least 55 wt. %, or at least 60 wt. %, or at least 63 wt. %, based on the weight of the ash obtained by carbonizing a sample of the torrefied textile char. The upper amount is desirably not more than 90 wt. %, or not more than 80 wt. %, or not more than 75 wt. %, based on the weight of the ash resulting from carbonizing a sample of the torrefied textile char.
In another embodiment, the amount of sodium compounds present in the ash of torrefied textile char is at least 2 wt. %, or at least 3 wt. %, or at least 4 wt. %, or at least 5 wt. %, or at least 6 wt. %, or at least 7 wt. %, based on the weight of the ash resulting from carbonizing a sample of the torrefied textile char. The upper amount is desirably not more than 20 wt. %, or not more than 17 wt. %, or not more than 15 wt. %, based on the weight of the ash resulting from carbonizing a sample of the torrefied textile char.
In another embodiment, the amount of titanium compounds present in the ash of torrefied textile char is at least 30 wt. %, or at least 40 wt. %, or at least 50 wt. %, or at least 60 wt. %, or at least 70 wt. %, or at least 75 wt. %, based on the weight of the ash resulting from carbonizing a sample of the torrefied textile char. The upper amount is desirably not more than 96 wt. %, or not more than 90 wt. %, or not more than 86 wt. %, based on the weight of the ash resulting from carbonizing a sample of the torrefied textile char.
In another embodiment, the amount of iron compounds present in the ash of torrefied textile char used in the feedstock is not more than 5 wt. %, or not more than 3 wt. %, or not more than 2 wt. %, or not more than 1.5 wt. %, based on the weight of the ash resulting from carbonizing a sample of the torrefied textile char.
In another embodiment, the amount of aluminum compounds present in the ash of torrefied textile char used in the feedstock is not more than 20 wt. %, or not more than 15 wt. %, or not more than 10 wt. %, or not more than 5 wt. %, or not more than 3 wt. %, or not more than 2 wt. %, or not more than 1.5 wt. %, based on the weight of the ash resulting from carbonizing a sample of the torrefied textile char.
In another embodiment, the amount of silicon compounds present in the ash of torrefied textile char used in the feedstock is not more than 20 wt. %, or not more than 15 wt. %, or not more than 10 wt. %, or not more than 8 wt. %, or not more than 6 wt. %, based on the weight of the ash resulting from carbonizing a sample of the torrefied textile char.
Desirably, the torrefied textile char contains low levels or no halide containing polymers, in particular polyvinyl chloride, polyvinyl fluoride, polyvinylidene fluoride, and polytetrafluoroethane, and other fluorinated or chlorinated polymers, especially if the torrefied textile char is fed to a refractory line gasifier. The release of chlorine or fluorine elements or radicals over time can impact the longevity of refractory lining on gasifiers operating at high temperature and pressure. In one embodiment or in any of the mentioned embodiments, the torrefied textile char contains less than 10 wt. %, or not more than 8 wt. %, or not more than 6 wt. %, or not more than 5 wt. %, or not more than 4 wt. %, or not more than 3.5 wt. %, or not more than 3 wt. %, or not more than 2.5 wt. %, or not more than 2 wt. %, or not more than 1.5 wt. %, or not more than 1 wt. %, or not more than 0.5 wt. %, or not more than 0.25 wt. %, or not more than 0.1 wt. %, or not more than 0.05 wt. %, or not more than 0.01 wt. % halide containing polymers, based on the weight of the torrefied textile char. In one embodiment or in any of the mentioned embodiments, the torrefied textile char contains less than 0.1 wt. %, or not more than 0.05 wt. %, or not more than 0.01 wt. %, or not more than 0.005 wt. %, or not more than 0.001 wt. %, or not more than 0.0005 wt. %, or not more than 0.0001 wt. %, or not more than 0.00005 wt. %, or not more than 0.00001 wt. %, or not more than 0.000005 wt. %, or not more than 0.000001 wt. % halide, based on the weight of the torrefied textile char.
The polymers, intermediates &chemicals, and articles such as fibers and textiles having a recycle content are broadly named as Recycle PIA (recycle polymers, intermediates or articles). The polymers, intermediates and articles are as described throughout this description. Recycle PIA can be obtained in a reaction scheme as described herein, or can be obtained by way of a recycle content allotment, provided that the allotment has its origin in, or withdrawn from an inventory of allotments containing at least one allotment having its origin in, gasifying a feedstock containing a solid fossil fuel and torrefied textiles. The “recycle content allotment” is a recycle content value that is transferred from an originating composition, compound or polymer at least a portion of which is obtained by or with the gasification of feedstock a feedstock containing a solid fossil fuel and torrefied textiles, to a receiving composition, compound, or polymer (referred to herein as a “composition” for brevity) receiving the allotment.
There is also provided a circular manufacturing process comprising:
In the above described process, an entirely circular or closed loop process is provided in which textiles can be recycled multiple times to make the same family or classification of textiles.
Examples of articles that are included in PIA are fibers, yarns, tow, continuous filaments, staple fibers, rovings, fabrics, textiles, flake, sheet, compounded sheet, and consumer articles.
In this or in combination with any of the mentioned embodiments, the allotment can be assigned to an intermediate, polymer, or article to produce a Recycle PIA directly from a recycle content value taken from the torrefied textile or torrefied textiles or from the step of gasifying a feedstock containing a fossil fuel and torrefied textiles, or the allotment can be assigned to the intermediate, polymer, or article to product a recycle PIA indirectly by assigning the recycle content value taken from a recycle inventory into which recycle content value is deposited from the recycle content present in the torrefied textile or in the torrefied textiles or the step of gasifying a feedstock containing a fossil fuel and torrefied textiles.
In one embodiment, the Recycle PIA is a polymer or article (e.g fiber) of the same family or classification of polymers or articles (e.g. fibers) contained in or one the torrefied textile used in step (i).
In one embodiment, a Recycle PIA can be made by a process in which torrefied textiles are gasified according to any of the processes described herein.
There is also provided a circular manufacturing process comprising:
In this or in combination with any of the mentioned embodiments, the allotment can be assigned to an intermediate, polymer, or article to produce a Recycle PIA directly from a recycle content value taken from the torrefied textile or torrefied textiles or from the step of gasifying a feedstock containing a fossil fuel and torrefied textile or torrefied textiles, or the allotment can be assigned to the intermediate, polymer, or article to product a recycle PIA indirectly by assigning the recycle content value taken from a recycle inventory into which recycle content value is deposited from the recycle content present in the torrefied textile or in the torrefied textiles or the step of gasifying a feedstock containing a fossil fuel and torrefied textiles.
In the above described process, an entirely circular or closed loop process is provided in which textiles can be recycled multiple times to make the same family or classification of textiles. The industrial supplier may furnish a processor entity with the torrefied textiles to process them into a form suitable or more suitable for gasification as further described herein, and in turn, the processor entity supplies the processes torrefied textiles to the manufacturer of syngas or one among its Family of Entities who can either feed to torrefied textiles as such to a feedstock stream to a gasifier, or can further process the torrefied textiles into a final size suitable for gasification by any suitable process, such as pulverization or grinding. The gasification processes, equipment, and designs used can be any of those mentioned herein. The torrefied textile derived syngas made using feedstocks containing the torrefied textiles can then either by converted through a reaction scheme to make Recycle PIA, or the allotments created by such gasification step or obtained from the torrefied textile or torrefied textiles can be stored in an inventory of allotments, and from the inventory of allotments from any source, a portion thereof can be withdrawn and assigned to an intermediate, polymer or article to make Recycle PIA. To close the circularity of the textile, at least a portion of the Recycle PIA can by furnished to the supplier of the textiles, or it can be supplied to any entity contracted with the supplier to process the Recycle PIA into a different form, different size, or to combine with other ingredients or textiles (e.g. compounders and/or sheet extruders), or to make articles containing the PIA, for supply to or on behalf of the supplier. The Recycle PIA furnished to the industrial supplier or one of its contracted entities is desirably in the same family or type of textile as the textile or article containing the textile was supplied by the industrial supplier to the Recipient.
A “recycle content allotment” or “allotment” means a recycle content value that is:
An allotment can be an allocation or a credit. A recycle textile waste is any one of textile streams identified throughout this disclosure, including the recycle textiles obtained for torrefaction, size reduced textiles made ready for torrefaction, torrefied textiles, or the feedstock composition to a gasifier containing the torrefied textile char.
A “recycle content value” is a unit of measure representative of a quantity of material having its origin in torrefied textile or torrefied textiles. The recycle content value can have its origin in any type of recycled textile or any torrefied textile processed in any type of process before being gasified.
The particular recycle content value can be determined by a mass balance approach or a mass ratio or percentage or any other unit of measure and can be determined according to any system for tracking, allocating, and/or crediting recycle content among various compositions. A recycle content value can be deducted from a recycle inventory and applied to a product or composition to attribute recycle content to the product or composition. A recycle content value does not have to originate from gasifying torrefied textile, and can be a unit of measure having its known or unknown origin in any technology used to process torrefied textile. In one embodiment, at least a portion of the torrefied textile from which an allotment is obtained is also gasified as described throughout the one or more embodiments herein; e.g. combined with a fossil fuel and subjected to gasification.
In one embodiment, at least a portion of the recycle content allotment or allotment or recycle value deposited into a recycle content inventory is obtained from textiles for use in torrefaction or from torrefied textiles. Desirably, at least 60%, or at least 70%, or at least 80%, or at least 90% or at least 95%, or up to 100% of the:
A recycle content allotment can include an allocation or a credit obtained with the transfer or use of a raw material. In one embodiment or in combination with any of the mentioned embodiments, the polymer, intermediate, composition, article or stream receiving the recycle content allotment can be or contain a portion of a non-recycle composition (e.g., compound, polymer, feedstock, product, or stream). “Non-recycle” means a composition, compound or polymer none of which was directly or indirectly derived from a torrefied textile derived syngas stream. As used herein, a “non-recycle feed” in the context of a feed to the gasifier means a feed that does not contain a recycle waste stream of any kind. Once a non-recycle feed, composition, compound, polymer, or article obtains a recycle content allotment (e.g. either through a credit or allocation), it becomes a recycle content feed, composition, compound, polymer or article, or in this case, a Recycle PIA.
As used herein, the term “recycle content allocation” is a type of recycle content allotment, where the entity or person supplying the composition sells or transfers the composition to the receiving person or entity, and the person or entity that made the composition has an allotment at least a portion of which can be associated with the composition sold or transferred by the supplying person or entity to the receiving person or entity. The supplying entity or person can be controlled by the same entity or person(s) or a variety of affiliates that are ultimately controlled or owned at least in part by a parent entity (“Family of Entities”), or they can be from a different Family of Entities. Generally, a recycle content allocation travels with a composition and with the downstream derivates of the composition. An allocation may be deposited into a recycle inventory and withdrawn from the recycle inventory as an allocation and applied to a composition to make a Recycle PIA.
A “recycle content credit” and “credit” mean a type of recycle content allotment and may or may not contain a physical component that is traceable to a torrefied textile derived syngas stream. For example, the (i) manufacturer of the product can operate within a legal framework, or an association framework, or an industry recognized framework for making a claim to a recycle content through, for example, a system of credits transferred to the product manufacturer regardless of where or from whom the torrefied textile derived syngas stream, or downstream products made thereby, or reactant feedstocks to make the polymer and/or article, is purchased or transferred, or (ii) a supplier of the torrefied textile derived syngas stream or downstream products made thereby (“supplier”) operates within an allocation framework that allows for allocating a recycle content value to a portion or all of the torrefied textile derived syngas stream or downstream products made thereby and to transfer the allotment to the manufacturer A credit is available for sale or transfer or use, or is sold or transferred or used, either:
In one embodiment or in combination with any of torrefied textile derived syngas stream, the mentioned embodiments, an allotment may be deposited into a recycle inventory, and a credit may be withdrawn from the inventory and applied to a composition to make a Recycle PIA. This would be the case where an allotment is created from a torrefied textile and deposited into a recycle inventory, and deducting a recycle content value from the recycle inventory and applying it to a composition to make a Recycle PIA that either has no portion originating from syngas or does have a portion originating from syngas but such syngas making up the portion of the composition was not a torrefied textile derived syngas. In this system, one need not trace the source of a reactant compound or composition back to the manufacture of torrefied textile derived syngas stream or back to any atoms contained in the torrefied textile derived syngas stream, but rather can use any reactant compound or composition made by any process and have associated with such reactant compound or composition, or have associated with the Recycle PIA, a recycle content allotment. In an embodiment, the Recycle PIA reactants (the compositions used to make Recycle PIA or the compositions to which an allotment is applied) do not contain recycle content.
In one embodiment, the composition receiving an allotment to make a Recycle PIA originates in part from a syngas stream obtained by any gasification process. The feedstock to the gasification process may optionally contain fossil fuel such as coal. The feedstock may optionally also contain a combination of fossil fuel and torrefied textile or torrefied textiles. In one embodiment, there is provided a process in which:
The steps b. and c. do not have to occur simultaneously. In one embodiment, they occur within a year of each other, or within six (6) months of each other, or within three (3) months of each other, or within one (1) month of each other, or within two (2) weeks of each other, or within one (1) week of each other, or within three (3) days of each other. The process allows for a time lapse between the time an entity or person receiving the textile or torrefied textile and creating the allotment (which can occur upon receipt or ownership of the torrefied textile) and the actual processing of the torrefied textile in a gasifier.
As used herein, “recycle inventory” and “inventory” mean a group or collection of allotments (allocations or credits) from which deposits and deductions of allotments in any units can be tracked. The inventory can be in any form (electronic or paper), using any or multiple software programs, or using a variety of modules or applications that together as a whole tracks the deposits and deductions. Desirably, the total amount of recycle content withdrawn (or applied to the Recycle PIA) does not exceed the total amount of recycle content allotments or credits on deposit in the recycle inventory (from any source, not only from gasification of torrefied textile). However, if a deficit of recycle content value is realized, the recycle content inventory is rebalanced to achieve a zero or positive recycle content value available. The timing for rebalancing can be either determined and managed in accordance with the rules of a particular system of accreditation adopted by the torrefied textile derived syngas manufacturer or by one among its Family of Entities, or alternatively, is rebalanced within one (1) year, or within six (6) months, or within three (3) months, or within one (1) month of realizing the deficit. The timing for depositing an allotment into the recycle inventory, applying an allotment (or credit) to a composition to make a Recycle PIA, and gasifying a torrefied textile, need not be simultaneous or in any particular order. In one embodiment, the step of gasifying a particular volume of torrefied textile occurs after the recycle content value or allotment from that volume of torrefied textile is deposited into a recycle inventory. Further, the allotments or recycle content values withdrawn from the recycle inventory need not be traceable to torrefied textile or gasifying torrefied textile, but rather can be obtained from the textiles used to make torrefied textiles. Desirably, at least a portion of the recycle content value in the recycle inventory is obtained from recycle textile for use in torrefaction or from a torrefied textile, and optionally at least a portion of torrefied textile are processed in the one or more gasification processes as described herein, optionally within a year of each other and optionally at least a portion of the volume of torrefied textile from which a recycle content value is deposited into the recycle inventory is also processed by any or more of the gasification processes described herein.
The determination of whether a Recycle PIA is derived directly or indirectly from recycled waste is not on the basis of whether intermediate steps or entities do or do not exist in the supply chain, but rather whether at least a portion of the torrefied textile molecules fed to the gasifier can be traced into a Recycle PIA. The Recycle PIA is considered to be directly derived from torrefied textile or have direct contact with torrefied textile if at least a portion of the molecules in the Recycle PIA can be traced back, optionally through one or more intermediate steps or entities, to at least a portion of the torrefied textile derived syngas molecules. Any number of intermediaries and intermediate derivates can be made before the Recycle PIA is made.
A Recycle PIA can be indirectly derived from recycled textiles if no portion of its molecules are obtained from torrefied textile derived syngas molecules or some portion of is molecules are obtained from torrefied textile derived syngas molecules but the Recycle PIA has a recycle content value that exceeds the recycle content value associated with the torrefied textile derived syngas molecules, and in this latter case, a Recycle PIA can be both directly and indirectly derived from torrefied textile.
In one embodiment or in combination with any of the mentioned embodiments, the Recycle PIA is indirectly derived from torrefied textile or torrefied textile derived syngas. In another embodiment, the Recycle PIA is directly derived from torrefied textile or torrefied textile derived syngas. In another embodiment, the Recycle PIA is indirectly derived from recycle textile for use in a torrefaction process or from a torrefied textile or torrefied textile derived syngas and no portion of the Recycle PIA is directly derived from the a torrefied textile or torrefied textile derived syngas.
In another embodiment, there is provided a variety of methods for apportioning the recycle content among the various Recycle PIA compositions made by any one entity or a combination of entities among the Family of Entities of which the torrefied textile derived syngas manufacturer is a part. For example, the torrefied textile derived syngas manufacturer, of any combination or the entirety of its Family of Entities, or a Site, can:
Both the symmetric distribution and the asymmetric distribution of recycle content can be proportional on a Site wide basis, or on a multi-Site basis. In one embodiment or in combination with any of the mentioned embodiments, the recycle content input (torrefied textile or allotments) can be within a Site, and recycle content values from said inputs are applied to one or more compositions made at the same Site to make Recycle PIA. The recycle content values can be applied symmetrically or asymmetrically to one or more different compositions made at the Site.
In one embodiment or in combination with any of the mentioned embodiments, the recycle content input or creation (recycle content feedstock or allotments) can be to or at a first Site, and recycle content values from said inputs are transferred to a second Site and applied to one or more compositions made at a second Site. The recycle content values can be applied symmetrically or asymmetrically to the compositions at the second Site.
In an embodiment, the Recycle PIA has associated with it, or contains, or is labelled, advertised, or certified as containing recycle content in an amount of at least 0.01 wt. %, or at least 0.05 wt. %, or at least 0.1 wt. %, or at least 0.5 wt. %, or at least 0.75 wt. %, or at least 1 wt. %, or at least 1.25 wt. %, or at least 1.5 wt. %, or at least 1.75 wt. %, or at least 2 wt. %, or at least 2.25 wt. %, or at least 2.5 wt. %, or at least 2.75 wt. %, or at least 3 wt. %, or at least 3.5 wt. %, or at least 4 wt. %, or at least 4.5 wt. %, or at least 5 wt. %, or at least 6 wt. %, or at least 7 wt. %, or at least 10 wt. %, or at least 15 wt. %, or at least 20 wt. %, or at least 25 wt. %, or at least 30 wt. %, or at least 35 wt. %, or at least 40 wt. %, or at least 45 wt. %, or at least 50 wt. %, or at least 55 wt. %, or at least 60 wt. %, or at least 65 wt. % and/or the amount can be up to 100 wt. %, or up to 95 wt. %, or up to 90 wt. %, or up to 80 wt. %, or up to 70 wt. %, or up to 60 wt. %, or up to 50 wt. %, or up to 40 wt. %, or up to 30 wt. %, or up to 25 wt. %, or up to 22 wt. %, or up to 20 wt. %, or up to 18 wt. %, or up to 16 wt. %, or up to 15 wt. %, or up to 14 wt. %, or up to 13 wt. %, or up to 11 wt. %, or up to 10 wt. %, or up to 8 wt. %, or up to 6 wt. %, or up to 5 wt. %, or up to 4 wt. %, or up to 3 wt. %, or up to 2 wt. %, or up to 1 wt. %, or up to 0.9 wt. %, or up to 0.8 wt. %, or up to 0.7 wt. %. The recycle content associated with the Recycle PIA can be associated by applying an allotment (credit or allocation) to any polymer and/or article made or sold. The allotment can be contained in an inventory of allotments created, maintained or operated by or for the Recycle PIA manufacturer. The allotment can be obtained from any source along any manufacturing chain of products provided that its origin is in gasifying a feedstock containing a fossil fuel and torrefied textiles.
The amount of recycle content in a polymer/article reactant, or the amount of recycle content applied to the Recycle PIA, or the amount of recycle content polymer/article reactant (r-reactant) needed to feed the gasifier to claim a desired amount of recycle content in the Recycle PIA in the event that all the recycle content from the torrefied textile feedstock is applied to the Recycle PIA, can be determined or calculated by any of the following methods:
In one embodiment, the Recycle PIA manufacturer can make Recycle PIA, or process a polymer/article reactant and make a Recycle PIA, or make Recycle PIA by obtaining any source of a reactant compound or composition from a supplier, whether or not such reactant compound or composition has any recycle content, and either:
The allotment in (i) is obtained from a polymer/article reactant supplier, and the polymer/article reactant supplier also supplies polymer/article reactant to the Recycle PIA manufacturer or within its Family of Entities. The circumstance described in (i) allows a Recycle PIA manufacturer to obtain a supply of a reactant compound or composition that is a non-recycle content polymer/article reactant, yet obtain a recycle content allotment from the polymer/article reactant supplier. In one embodiment, the polymer/article reactant supplier transfers a recycle content allotment to the Recycle PIA manufacturer and a supply of polymer/article reactant to the Recycle PIA manufacturer, where the recycle content allotment is not associated with the polymer/article reactant supplied, or even not associated with any polymer/article reactant made by the polymer/article reactant supplier. The recycle content allotment does not have to be tied to an amount of recycle content in a reactant compound or composition or to any monomer used to make Recycle PIA, but rather the recycle content allotment transferred by the polymer/article reactant supplier can be associated with other products having their origin in torrefied textile derived syngas stream other than those in a reaction scheme to make polymer and/or articles. This allows flexibility among the reactant compound or composition supplier and Recycle PIA manufacturer to apportion a recycle content among the variety of products they each make. In each of these cases, however, the recycle content allotment is associated with gasifying torrefied textile.
In one embodiment, the polymer/article reactant supplier transfers a recycle content allotment to the Recycle PIA manufacturer and a supply of polymer/article reactant to the Recycle PIA manufacturer, where the recycle content allotment is associated with polymer/article reactant. Optionally, the polymer/article reactant being supplied can be derived from torrefied textile feedstock and at least a portion of the recycle content allotment being transferred can be the recycle content in the reactant to make an r-reactant. The recycle content allotment transferred to the Recycle PIA manufacturer can be up front with the polymer/article reactant supplied, optionally in installments, or with each polymer/article reactant installment, or apportioned as desired among the parties.
The allotment in (ii) is obtained by the Recycle PIA manufacturer (or its Family of Entities) from any person or entity without obtaining a supply of polymer/article reactant from the person or entity. The person or entity can be a polymer/article reactant manufacturer that does not supply polymer/article reactant to the Recycle PIA manufacturer or its Family of Entities, or the person or entity can be a manufacturer that does not make polymer/article reactant. In either case, the circumstances of (ii) allows a Recycle PIA manufacturer to obtain a recycle content allotment without having to purchase any polymer/article reactant from the entity supplying the recycle content allotment. For example, the person or entity may transfer a recycle content allotment through a buy/sell model or contract to the Recycle PIA manufacturer or its Family of Entities without requiring purchase or sale of an allotment (e.g. as a product swap of products that are not polymer/article reactant), or the person or entity may outright sell the allotment to the Recycle PIA manufacturer or one among its Family of Entities. Alternatively, the person or entity may transfer a product, other than a polymer/article reactant, along with its associated recycle content allotment to the Recycle PIA manufacturer. This can be attractive to a Recycle PIA manufacturer that has a diversified business making a variety of products other than Recycle PIA requiring raw materials other than a polymer/article reactant that the person or entity can supply to the Recycle PIA manufacturer.
The allotment can be deposited into a recycle inventory (e.g. an inventory of allotments). In one embodiment, the allotment is created by the manufacturer of the torrefied textile derived syngas stream. The Recycle PIA manufacturer (who may be the same as the can also make a polymer and/or article, whether or not a recycle content is applied to the polymer and/or article and whether or not recycle content, if applied to the polymer and/or article, is drawn from the inventory. For example, either the torrefied textile derived syngas stream manufacturer and/or the Recycle PIA manufacturer may:
If desired, however, from that inventory, any recycle content allotment can be deducted in any amount and applied to a polymer and/or article to make a Recycle PIA. For example, a Recycle inventory of allotments can be generated having a variety of sources for creating the allotments. Some recycle content allotments (credits) can have their origin in methanolysis of recycle waste, or from gasification of other types of recycle waste, or from mechanical recycling of waste plastic or metal recycling, and/or from pyrolyzing recycle waste, or from any other chemical or mechanical recycling technology. The recycle inventory may or may not track the origin or basis of obtaining a recycle content value, or the inventory may not allow one to associate the origin or basis of an allocation to the allocation applied to Recycle PIA. It is sufficient that an allocation is deducted from an allocation inventory and applied to Recycle PIA regardless of the source or origin of the allocation, provided that a recycle content allotment derived from a torrefied textile feedstock containing a fossil fuel and torrefied textiles is present in the allotment inventory as the time of withdrawal, or a recycle content allotment is obtained by the Recycle PIA manufacturer as specified in step (i) or step (ii), whether or not that recycle content allotment is actually deposited into the inventory. In one embodiment, the recycle content allotment obtained in step (i) or (ii) is deposited into an inventory of allotments. In one embodiment, the recycle content allotment deducted from the inventory and applied to the Recycle PIA originates from torrefied textile or torrefied textiles, whereby the torrefied textiles are ultimately gasified with a fossil fuel.
As used throughout, the inventory of allotments can be owned by the torrefied textile derived syngas manufacturer, or by the Recycle PIA manufacturer, or operated by either of them, or owned or operated by neither but at least in part for the benefit of either of them, or licensed by either of them. Also, as used throughout, the torrefied textile derived syngas manufacturer or the Recycle PIA manufacturer may also include either of their Family of Entities. For example, while either of them may not own or operate the inventory, one among its Family of Entities may own such a platform, or license it from an independent vendor, or operate it for either of them. Alternatively, an independent entity may own and/or operate the inventory and for a service fee operate and/or manage at least a portion of the inventory for either of them.
In one embodiment, the Recycle PIA manufacturer obtains a supply of polymer/article reactant from a supplier, and also obtains an allotment from the supplier, where such allotment is derived from gasifying a feedstock containing a fossil fuel and torrefied textiles, and optionally the allotment is associated with the polymer/article reactant supplied by the supplier. In one embodiment, at least a portion of the allotment obtained by the Recycle PIA manufacturer is either:
It is not necessary in all embodiments that r-reactant is used to make Recycle PIA composition or that the Recycle PIA was obtained from a recycle content allotment associated with a polymer/article reactant composition. Further, it is not necessary that an allotment be applied to the feedstock for making the Recycle PIA to which recycle content is applied. Rather, as noted above, the allotment, even if associated with a reactant compound or composition when the reactant compound or composition is obtained, can be deposited into an electronic inventory. In one embodiment, however, r-reactant associated with the allotment is used to make the Recycle PIA composition. In one embodiment, the Recycle PIA is obtained from a recycle content allotment associated with an r-reactant, or with torrefied textiles, or with gasifying torrefied textiles. In one embodiment, at least a portion of the allotments obtained from textile received (and optionally classified as inventory) for dedicated for making torrefied textiles, or the torrefied textiles, or gasifying torrefied textiles are applied to Recycle PIA to make a Recycle PIA.
In one embodiment, an allotment is generated from a textile dedicated for torrefaction, or the torrefied textiles, or from the torrefied textile derived syngas stream obtained by gasifying a combination of a fossil fuel and torrefied textiles, and either:
In any of the embodiments described throughout, the timing for taking the allotment, or depositing the allotment into a recycle inventory, can be as early as when a recycle textile is received or owned or submitted into inventory to a manufacturer of torrefied textiles, or by a Recipient or one among its Family of Entities, or when it is converted to a torrefied textiles, or when a Recipient or one among its Family of Entities receives or owns torrefied textiles, or when they are combined with a fossil fuel, or when gasified, or when a torrefied textile derived syngas is made. For clarification, an allotment is deemed generated or obtained by or originating from gasifying torrefied textiles even though the timing of taking or recognizing the allotment is earlier or later than the actual time the torrefied textiles are gasified, provided that the torrefied textiles are subjected to gasification.
There is now also be provided a package or a combination of a Recycle PIA and a recycle content identifier associated with Recycle PIA, where the identifier is or contains a representation that the Recycle PIA contains, or is sourced from or associated with a recycle content. The package can be any suitable package for containing a polymer and/or article, such as a plastic or metal drum, railroad car, isotainer, totes, polytote, bale, IBC totes, bottles, compressed bales, jerricans, and polybags, spools, roving, winding, or cardboard packaging. The identifier can be a certificate document, a product specification stating the recycle content, a label, a logo or certification mark from a certification agency representing that the article or package contains contents or the Recycle PIA contains, or is made from sources or associated with recycle content, or it can be electronic statements by the Recycle PIA manufacturer that accompany a purchase order or the product, or posted on a website as a statement, representation, or a logo representing that the Recycle PIA contains or is made from sources that are associated with or contain recycle content, or it can be an advertisement transmitted electronically, by or in a website, by email, or by television, or through a tradeshow, in each case that is associated with Recycle PIA. The identifier need not state or represent that the recycle content is derived from gasifying a feedstock containing a fossil fuel and torrefied textiles. Rather, the identifier can merely convey or communicate that the Recycle PIA has or is sourced from a recycle content, regardless of the source. However, the Recycle PIA has a recycle content allotment that, at least in part, associated with gasifying torrefied textiles.
In one embodiment, one may communicate recycle content information about the Recycle PIA to a third party where such recycle content information is based on or derived from at least a portion of the allocation or credit. The third party may be a customer of the torrefied textile derived syngas manufacturer or Recycle PIA manufacturer or supplier, or may be any other person or entity or governmental organization other than the entity owning the either of them. The communication may electronic, by document, by advertisement, or any other means of communication.
In one embodiment, there is provided a system or package comprising:
The system can be a physical combination, such as package having at least Recycle PIA as its contents and the package has a label, such as a logo, that the contents such as the Recycle PIA has or is sourced from a recycle content. Alternatively, the label or certification can be issued to a third party or customer as part of a standard operating procedure of an entity whenever it transfers or sells Recycle PIA having or sourced from recycle content. The identifier does not have to be physically on the Recycle PIA or on a package, and does not have to be on any physical document that accompanies or is associated with the Recycle PIA. For example, the identifier can be an electronic credit transferred electronically by the Recycle PIA manufacturer to a customer in connection with the sale or transfer of the Recycle PIA product, and by sole virtue of being a credit, it is a representation that the Recycle PIA has recycle content. The identifier itself need only convey or communicate that the Recycle PIA has or is sourced from a recycle content, regardless of the source. In one embodiment, articles made from the Recycle PIA may have the identifier, such as a stamp or logo embedded or adhered to the article. In one embodiment, the identifier is an electronic recycle content credit from any source. In one embodiment, the identifier is an electronic recycle content credit having its origin in gasifying a feedstock containing a fossil fuel and torrefied textiles.
The Recycle PIA is made from a reactant compound or composition, whether or not the reactant is a recycle content reactant (r-reactant). Once a Recycle PIA composition is made, it can be designated as having recycle content based on and derived from at least a portion of the allotment, again whether or not the r-reactant is used to make the Recycle PIA composition. The allocation can be withdrawn or deducted from inventory. The amount of the deduction and/or applied to the Recycle PIA can correspond to any of the methods described above, e.g. a mass balance approach.
In an embodiment, a Recycle PIA composition can be made by having an inventory of allocations, and reacting a reactant compound or composition a synthetic process to make a Recycle PIA, and applying a recycle content to that Recycle PIA to thereby obtain a Recycle PIA by deducting an amount of allocation from an inventory of allocations. A Recycle PIA manufacturer may have an inventory of allocations by itself or one among its Family of Entities owning, possessing, or operating the inventory, or a third party operating at least a portion of the inventory for the Recycle PIA manufacturer or its Family of Entities or as a service provided to the Recycle PIA manufacturer or one among its Family of Entities. The amount of allocation deducted from inventory is flexible and will depend on the amount of recycle content applied to the Recycle PIA. It should be at least sufficient to correspond with at least a portion if not the entire amount of recycle content applied to the Recycle PIA. The method of calculation can be a mass balance approach, or the methods of calculation described above. The inventory of allocations can be established on any basis and may be a mix of basis, provided that at least some amount of allocation in the inventory is attributable to gasifying a feedstock containing a fossil fuel and torrefied textiles. The recycle content allotment applied to the Recycle PIA does not have to have its origin in gasifying a feedstock containing a fossil fuel and torrefied textiles, and instead can have its origin in any other method of generating allocations from recycle waste, such as through methanolysis or gasification of recycle waste, provided that the inventory of allotments also contains an allotment or has an allotment deposit having its origin in gasifying a feedstock containing a fossil fuel and torrefied textiles. In one embodiment, however, the recycle content applied to the Recycle PIA is an allotment obtained from gasifying a feedstock containing at least torrefied textiles.
The following are examples of designating or declaring a recycle content to Recycle PIA or a recycle content to a reactant compound or composition:
In one embodiment, the Recycle PIA, or articles made thereby, can be offered for sale or sold as Recycle PIA containing or obtained with recycle content. The sale or offer for sale can be accompanied with a certification or representation of the recycle content claim made in association with the Recycle PIA or article made with the Recycle PIA.
The obtaining of an allocation and designating (whether internally such as through a bookkeeping or an inventory tracking software program or externally by way of declaration, certification, advertising, representing, etc.) can be by the Recycle PIA manufacturer or within the Recycle PIA manufacturer Family of Entities. The designation of at least a portion of the Recycle PIA as corresponding to at least a portion of the allotment (e.g. allocation or credit) can occur through a variety of means and according to the system employed by the Recycle PIA manufacturer, which can vary from manufacturer to manufacturer. For example, the designation can occur internally merely through a log entry in the books or files of the Recycle PIA manufacturer or other inventory software program, or through an advertisement or statement on a specification, on a package, on the product, by way of a logo associated with the product, by way of a certification declaration sheet associated with a product sold, or through formulas that compute the amount deducted from inventory relative to the amount of recycle content applied to a product.
Optionally, the Recycle PIA can be sold. In one embodiment, there is provided a method of offering to sell or selling polymer and/or articles by:
The steps described need not be sequential, and can be independent from each other. For example, the step a) of obtaining an allocation and the step of making Recycle PIA from a reactant compound or composition can be simultaneous.
As used throughout, the step of deducting an allocation from an inventory of allocations does not require its application to a Recycle PIA product. The deduction also does not mean that the quantity disappears or is removed from the inventory logs. A deduction can be an adjustment of an entry, a withdrawal, an addition of an entry as a debit, or any other algorithm that adjusts inputs and outputs based on an amount recycle content associated with a product and one or a cumulative amount of allocations on deposit in the inventory. For example, a deduction can be a simple step of a reducing/debit entry from one column and an addition/credit to another column within the same program or books, or an algorithm that automates the deductions and entries/additions and/or applications or designations to a product slate. The step of applying an allocation to a Recycle PIA product where such allocation was deducted from inventory also does not require the allocation to be applied physically to a Recycle PIA product or to any document issued in association with the Recycle PIA product sold. For example, a Recycle PIA manufacturer may ship Recycle PIA product to a customer and satisfy the “application” of the allocation to the Recycle PIA product by electronically transferring a recycle content credit to the customer.
In one embodiment, the amount of recycle content in the torrefied textile feedstock or in the Recycle PIA will be based on the allocation or credit obtained by the manufacturer of the Recycle PIA composition or the amount available in the Recycle PIA manufacturer's inventory of allotments. A portion or all of the allocation or credit obtained by or in the possession of a manufacturer of Recycle PIA can be designated and assigned to a recycle textile dedicated or to be used for or actually used for torrefaction, or the torrefied textiles, or from the torrefied textile derived syngas stream, or the gasification of a feedstock containing torrefied textiles or Recycle PIA on a mass balance basis. The assigned value of the recycle content to the torrefied textile feedstock or Recycle PIA should not exceed the total amount of all allocations and/or credits available to the manufacturer of the Recycle PIA or other entity authorized to assign a recycle content value to the Recycle PIA on an annual basis, or on a quarterly basis.
There is now also provided a method of introducing or establishing a recycle content in a compound, composition, polymer and/or article without necessarily using an r-polymer/article reactant feedstock. In this method,
In this method, the polymer and/or article manufacturer need not purchase a recycle reactant compound or composition from a particular source or supplier, and does not require the polymer and/or article manufacturer to use or purchase a reactant compound or composition having recycle content in order to successfully establish a recycle content in the polymer and/or article composition. The polymer/article reactant manufacturer may use any source of polymer/article reactant and apply at least a portion of the allocation or credit to at least a portion of the polymer/article reactant feedstock or to at least a portion of the polymer and/or article product. The association by the polymer and/or article manufacturer may come in any form, whether by on in its inventory, internal accounting methods, or declarations or claims made to a third party or the public.
There is also provided a use for a recycle textile dedicated or to be used for or actually used for torrefaction, or the torrefied textiles, or from the torrefied textile derived syngas stream, or the gasification of a feedstock containing torrefied textiles, the use including converting torrefied textiles in any synthetic process, such as gasification, to make torrefied textile derived syngas and/or Recycle PIA.
There is also provided a use for a recycle torrefied textiles that includes converting a polymer/article reactant in a synthetic process to make polymer and/or articles and applying at least a portion of an allotment to the polymer and/or article to the polymer/article reactant, where the allotment is associated with recycle textile dedicated or to be used for or actually used for torrefaction, or the torrefied textiles, or from the torrefied textile derived syngas stream, or the gasification of a feedstock containing torrefied textiles, or gasifying a feedstock containing a fossil fuel and torrefied textiles or has its origin in an inventory of allotments where at least one deposit made into the inventory is associated with the aforementioned.
In one embodiment, there is provided a polymer and/or article composition that is obtained by any of the methods described above.
The reactant compound or composition, such a reactant compound or composition can be stored in a storage vessel and transferred to a Recycle PIA manufacturing facility by way of truck, pipe, or ship, or as further described below, the reactant compound or composition production facility can be integrated with the Recycle PIA facility. The reactant compound or composition may be shipped or transferred to the operator or facility that makes the polymer and/or article.
In an embodiment, the process for making Recycle PIA can be an integrated process. One such example is a process to make Recycle PIA by:
In one embodiment, one may integrate two or more facilities and make Recycle PIA. The facilities to make Recycle PIA, the polymer/article reactant, or the syngas can be stand-alone facilities or facilities integrated to each other. For example, one may establish a system of producing and consuming a polymer/article reactant composition, as follows:
The Recycle PIA manufacturing facility can make Recycle PIA by accepting any reactant compound or composition from the polymer/article reactant manufacturing facility and applying a recycle content to Recycle PIA made with the reactant compound or composition by deducting allotments from its inventory and applying them to the Recycle PIA, optionally in amounts using the methods described above. The allotments obtained and stored in inventory can be obtained by any of the methods described above. The allotments withdrawn from inventory and applied can be allotments obtained by any source of recycle content, and need not necessarily be allotments associated with gasifying torrefied textiles.
In one embodiment, there is also provided a system for producing Recycle PIA as follows:
The Recycle PIA manufacturing facility can make Recycle PIA. In this system, the gasification manufacturing facility can have its output in fluid communication with the polymer/article reactant manufacturing facility which in turn can have its output in fluid communication with the Recycle PIA manufacturing facility. Alternatively, the manufacturing facilities of a) and b) alone can be in fluid communication, or only b) and c). In the latter case, the Recycle PIA manufacturing facility can make Recycle PIA directly by having the torrefied textile derived syngas produced in the gasification manufacturing facility converted all the way to Recycle PIA, or indirectly by accepting any reactant compound or composition from the polymer/article reactant manufacturing facility and applying a recycle content to Recycle PIA by deducting allotments from its inventory and applying them to the Recycle PIA, optionally in amounts using the methods described above. The allotments obtained and stored in inventory can be obtained by any of the methods described above,
The fluid communication can be gaseous or liquid or both. The fluid communication need not be continuous and can be interrupted by storage tanks, valves, or other purification or treatment facilities, so long as the fluid can be transported from the manufacturing facility to the subsequent facility through an interconnecting pipe network and without the use of truck, train, ship, or airplane. Further, the facilities may share the same site, or in other words, one site may contain two or more of the facilities. Additionally, the facilities may also share storage tank sites, or storage tanks for ancillary chemicals, or may also share utilities, steam or other heat sources, etc., yet also be considered as discrete facilities since their unit operations are separate. A facility will typically be bounded by a battery limit.
In one embodiment, the integrated process includes at least two facilities co-located within 5, or within 3, or within 2, or within 1 mile of each other (measured as a straight line). In one embodiment, at least two facilities are owned by the same Family of Entities.
In an embodiment, there is also provided an integrated Recycle PIA generating and consumption system. This system includes:
The system does not necessarily require a fluid communication between the two facilities, although fluid communication is desirable. For example, the torrefied textile derived syngas can be delivered to the reactant compound or composition facility through the interconnecting piping network that can be interrupted by other processing equipment, such as treatment, purification, pumps, compression, or equipment adapted to combine streams, or storage facilities, all containing optional metering, valving, or interlock equipment. The equipment can be a fixed to the ground or fixed to structures that are fixed to the ground. The interconnecting piping does not need to connect to the reactant compound or composition reactor or the cracker, but rather to a delivery and receiving point at the respective facilities. The interconnecting pipework need not connect all three facilities to each other, but rather the interconnecting pipework can be between facilities a)-b), or b)-c), or between a)-b)-c).
In one embodiment or in combination with any of the mentioned embodiments, the total amount of carbon in the torrefied textile is at least 60 wt. %, or at least 65 wt. %, or at least 70 wt. %, or at least 75 wt. %, or at least 80 wt. %, or at least 85 wt. %, or at least 90 wt. %, and desirably at least 92 wt. %, or at least 95 wt. %, or at least 97 wt. %.
Desirably, the halide minimized or excluded is chlorine.
In another embodiment, the torrefied textile char, once made, is not thereafter melted, extruded, or pyrolyzed prior to their entry into the gasifier. In an embodiment, the total amount of fixed carbon in the torrefied textile char is at least 50 wt. %, or at least 55 wt. %, or at least 60 wt. %, or at least 65 wt. %, or at least 70 wt. %, or at least 75 wt. %, or at least 80 wt. %, or at least 85 wt. %, or at least 90 wt. %, and desirably at least 92 wt. %, or at least 95 wt. %, or at least 97 wt. %, based on the weight of the torrefied textile char. The fixed carbon content is the combustible solids remaining (other than ash) after the material is heated and volatiles removed. It can be determined by subtracting the percentages of moisture, volatile matter, and ash from a sample.
The amount of torrefied textile char present in the feedstock composition to the gasifier can range from 0.1 wt. % to 100 wt. % based on the weight of all solids. Since torrefied textile char can have, on average, fixed carbon content similar to that of solid fossil fuels, and the H/C ratio is also lowered by torrefaction, the amount of torrefied textile char added to a feedstock containing coal or supplied to the gasifier can be higher than the same mass of textiles fed to the feedstock or gasifier, and can even entirely replace the solid fossil fuel fed to a gasifier. Thus, the cost factor aside, solid fossil fuel supplied entrained flow gasifier can be fed with from 0.5 wt. % to 100 wt. % torrefied textile char, based on the weight of all solid fuel fed to the gasifier. In one embodiment or in any of the mentioned embodiments, the amount of torrefied textile char fed to the gasifier is not more than 20 wt. %, or not more than 15 wt. %, or not more than 10 wt. %, or not more than 7 wt. %, or not more than 5 wt. %, or not more than 3 wt %, or not more than 2 wt %, based on the weight of all fuel fed to the gasifier (and fuel does not include the oxidizer, steam, water, or carbon dioxide). In one embodiment or in any of the mentioned embodiments, the amount of torrefied textile char fed to the gasifier is more than 20 wt. %, or more than 25 wt. %, or more than 30 wt %, or more than 35 wt. %, or more than 40 wt. %, or more than 50 wt. %, based on the weight of all fuel fed to the gasifier (and fuel does not include the oxidizer, steam, water, or carbon dioxide).
The torrefied textile char can have an average sulfur content that is fairly sizable and successfully gasify since high temperature or slagging gasifiers are well equipped to handle sulfur. The torrefied textile char fed to the gasifier can have an average sulfur content of up to 20 wt. %, or up to 15 wt. %, or up to 10 wt. %, or up to 5 wt. %, or up to 4 wt. %, or up to 3.5 wt. %, or up to 3 wt. %, or up to 2.5 wt. %, or up to 2 wt. %, or up to 1.5 wt. %, based on the weight of the torrefied textile char fed to the gasifier. In addition or in the alternative, the torrefied textile char fed to the gasifier can have an average sulfur content of at least 0.01 wt. %, or at least 0.1 wt. %, or at least 0.5 wt. %, or at least 1 wt. %, or at least 1.5 wt. %, or at least 2 wt. %, or at least 2.5 wt. %, or at least 2.75 wt. %, or at least 3 wt. %, or at least 3.25 wt. %, or at least 3.5 wt. %, or at least 3.75 wt. %, or at least 5 wt. %, based on the weight of the torrefied textile char fed to the gasifier.
The particle size of the torrefied textile char fed to the gasifier is not larger than the maximum size the gasifier in use can accept. Many coal fed gasifiers can grind or mill the coal to a desired size before feeding them to the gasifier or gasification zone. In one embodiment or in any of the mentioned embodiments, densified torrefied textile char (e.g. agglomerates), or the raw torrefied textile char, or any form of the torrefied textile char, can be size reduced before introducing them into the gasification zone by a pulverizer, hammermill, rod mill, ball mills, or grinder, whether conducted wet or dry. In one embodiment or in any of the mentioned embodiments, densified torrefied textile char (e.g. agglomerates) can be size reduced concurrent with a solid fossil fuel by any of these methods to reduce the size of the densified char and solid fossil fuel simultaneously. Existing grinding equipment in the traditional solid fed process to co-grind the torrefied textile char with the solid fossil fuel. An example would be a dry feed coal pulverizer. An additional example would be a slurry-fed coal gasifier utilizing a water-based rod mill or ball mill. A densified char without further size reduction could be co-fed with the coal and water and reduced in size together.
The torrefied textile char is optionally sieved, and then combined with one or more fossil fuel components of the feedstock composition at any location prior to introducing the feedstock composition into a gasification zone within the gasifier. The coal milling or grinding equipment will provide an excellent source of energy for mixing torrefied textile char with the fossil fuel while reducing the size of the coal particles. Therefore, one of the desirable locations for combining torrefied textile char having a target size for feeding into the gasifier is into the equipment used for milling or grinding the other carbonaceous fossil fuel sources (e.g. coal, pet-coke). This location is particularly attractive in a slurry fed gasifier because it is desirable to use a gasifier feedstock having the highest stable solids concentration possible, and at higher solids concentration, the viscosity of the slurry is also high. The torque and shear forces employed in fossil fuel milling or grinding equipment is high, and coupled with the shear thinning behavior of a coal slurry, good mixing of the torrefied textile char with the ground fossil fuel can be obtained in the fossil fuel milling or grinding equipment.
Other locations for combining torrefied textile char with fossil fuel sources can be onto the fossil fuel loaded on the main fossil fuel belt feeding a mill or grinder, or onto the main fossil fuel belt feeding a mill or grinder before the fossil fuel is loaded onto the belt, or into a fossil fuel slurry storage tank containing a slurry of fossil fuel ground to the final size, particularly if the storage tank is agitated. The torrefied textile char in the form of small particles or powder can also be blown into a pneumatically conveyed stream of size reduced solid fossil fuels for a dry fed entrained flow gasifier, or the torrefied textile char can be pneumatically conveyed with or without a solid fossil fuel, to the gasifier.
In one embodiment or in any of the mentioned embodiments, the torrefied textile char is fed as a separate stream to the gasifier to an injection location on the gasifier that is separate from the feedstock stream containing the solid fossil fuel and separate from the injection point for feeding the solid fossil fuel stream. The torrefied textile char can be pneumatically conveyed as a separate stream to the gasifier, or can be mixed with water or an organic liquid as a slurry fed to the gasifier. In one embodiment or in any of the mentioned embodiments, the two separate streams of solid fossil fuel and torrefied textile char can converge as a single feed to a single injection location on the gasifier, or can converge into a single injector on the gasifier.
The fossil fuel (coal or petcoke) and the torrefied textile char is size reduced for multiple purposes. The torrefied textile char is of a small size or must be ground to a small size as does the fossil fuel source to (i) allow for faster reaction once inside the gasifier due to mass transfer limitations, (ii) to create a slurry that is stable, fluid and flowable at high concentrations of solids to water in slurry fed gasifiers, (iii) to pass through processing equipment such as high-pressure pumps, valves, and feed injectors that have tight clearances, (iv) to flow through screens between the mills or grinders and the gasifier, or (v) to be conveyed with gases used for conveying solid fossil fuels to dry fed gasifiers.
In one embodiment or in any of the mentioned embodiments, the torrefied textile char particle sizes are desirably not more than 5 inches, or not more than 4 inches, or not more than 1 inch, or not more than ¼ inch, or not more than 2 mm. The larger sizes are useful for addition to a fixed bed or moving bed gasifier, particularly in updraft gasifiers to provide sufficient density to allow them to contact the bed as a solid that has not fully charred or be converted to ash.
In one embodiment or in any of the mentioned embodiments, the solids in the gasifier feedstock, including the torrefied textile char, have a particle size of 2 mm or smaller. This embodiment is particularly applicable to entrained flow gasifiers. As used throughout, unless a different basis is expressed (e.g. a mean), a stated particle size means that at least 90 wt. % of the particles have a largest dimension in the stated size, or alternatively that 90 wt. % passes through sieve designated for that particle size. Either conditions satisfy the particle size designation. Larger size torrefied textile char has the potential for being blown through the gasification zone of entrained flow gasifiers without completely gasifying, particularly when the gasification conditions are established to gasify solid fossil fuel having a particle dimension of 2 mm or smaller.
In one embodiment or in any of the mentioned embodiments, the size of the torrefied textile char combined with the solid fossil fuel, or as fed to the gasifier, is 2 mm or smaller or constitute those particles passing through a 10 mesh, or 1.7 mm or smaller (those particles passing through a 12 mesh), or 1.4 mm or smaller (those particles passing through a 14 mesh), or 1.2 mm or smaller (those particles passing through a 16 mesh), or 1 mm or smaller (those particles passing through a 18 mesh), or 0.85 mm or smaller (those particles passing through a 20 mesh), or 0.7 mm or smaller (those particles passing through a 25 mesh) or 0.6 mm or smaller (those particles passing through a 30 mesh), or 0.5 mm or smaller (those particles passing through a 35 mesh), or 0.4 mm or smaller (those particles passing through a 40 mesh), or 0.35 mm or smaller (those particles passing through a 45 mesh), or 0.3 mm or smaller (those particles passing through a 50 mesh), or 0.25 mm or smaller (those particles passing through a 60 mesh), or 0.15 mm or smaller (those particles passing through a 100 mesh), or 0.1 mm or smaller (those particles passing through a 140 mesh), or 0.07 mm or smaller (those particles passing through a 200 mesh), or 0.044 mm or smaller (those particles passing through a 325 mesh), or 0.037 mm or smaller (those particles passing through a 400 mesh). In another embodiment, the size of the torrefied textile char particles is at least 0.037 mm (or 90% retained on a 400 mesh).
In one embodiment or in any of the mentioned embodiments, the torrefied textile char has a particle size that, after optional sieving, is acceptable for gasifying within the design parameters of the type of gasifier used. The particle sizes of torrefied textile char and the solid fossil fuels can be sufficiently matched to retain the stability of the slurry and avoid a coal/torrefied textile char separation at high solids concentrations prior to entering the gasification zone in the gasifier. A feedstock composition that phase separates, whether between solids/liquid or solid/solids in a slurry, or solids/solids in a dry feed, or solid/liquid in a liquid feedstock, can plug lines, created localized zones of gasified torrefied textile char, create inconsistent ratios of fossil fuel/torrefied textile char, and can impact the consistency of the syngas composition. Variables to consider for determining the stability of the feedstock composition include setting an optimal particle size of the torrefied textile char, and variables for determining the optimal particle sizes include the loose bulk density of the ground coal, the concentration of all solids in the slurry if a slurry is used or the solid/solid concentration in a dry feed, the effectiveness of any additives employed such as surfactants/stabilizers/viscosity modifiers, and the velocity and turbulence of the feedstock composition to the gasifier and through the injector nozzles.
In one embodiment or in any of the mentioned embodiments, the loose bulk density of the torrefied textile char after final grinding is within 150%, or within 110%, or within 100%, or within 75%, or within 60%, or within 55%, or within 50%, or within 45%, or within 40%, or within 35% of the loose bulk density of the ground fossil fuel in the gasifier feedstock. For example, if the granulated coal has a loose bulk density of 40 lbs/ft3 and the torrefied textile char has a loose bulk density of 33 lbs/ft3, the loose bulk density of the torrefied textile char would be within 21% of the ground coal. For measurement purposes, the loose bulk density of the torrefied textile char and the fossil fuel is determined on a dry basis (excluding water) even if they are ultimately used in a slurry.
In one embodiment or in any of the mentioned embodiments, the particle size of the torrefied textile char is selected to be similar (below or above) to the maximum particle size of the ground solid fossil fuel. The maximum particle size of the torrefied textile char used in the gasifier feedstock can be not more than 50% larger than the maximum solid fossil fuel size in the gasifier feedstock, or not more than 45%, or not more than 40%, or not more than 35%, or not more than 30%, or not more than 25%, or not more than 20%, or not more than 15%, or not more than 10%, or not more than 5%, or not more than 3%, or not more than 2%, or not more than 1% larger than the maximum solid fossil fuel size in the gasifier feedstock, or not larger than, or smaller than the maximum solid fossil fuel size in the gasifier feedstock. Optionally, the maximum particle size of the torrefied textile char used in the gasifier feedstock as stated above can be within (meaning not larger than and not smaller than) the stated values. The maximum particle size is not determined as the maximum size of the particle distribution but rather by sieving through meshes. The maximum particle size is determined as the first mesh which allows at least 90 volume % of a sample of the particles to pass. For example, if less than 90 volume % of a sample passes through a 300 mesh, then a 100 mesh, a 50 mesh, a 30 mesh, a 16 mesh, but succeeds at a 14 mesh, then the maximum particle size of that sample is deemed to correspond to the first mesh size that allowed at least 90 volume % to pass through, and in this case, a 14 mesh corresponding to a maximum particle size of 1.4 mm.
The torrefied textile char is desirably isolated as a torrefied textile char feed for ultimate destination to be mixed with one or more components of the feedstock composition. In one embodiment or in any of the mentioned embodiments, at least 80 wt. %, or at least 85 wt. %, or at least 90 wt. %, or at least 95 wt. %, or at least 96 wt. %, or at least 97 wt. %, or at least 98 wt. %, or at least 99 wt. %, or at least 99.5 wt. %, or 100 wt. % of all solid feedstock other than solid fossil fuels fed to the gasifier is torrefied textile char, based on the cumulative weight of all streams containing solids fed to the gasifier.
In one embodiment or in any of the mentioned embodiments, both torrefied textile char and recycle plastic particles are fed to the gasifier. For example, a single feedstock composition can contain the torrefied textile char and recycle plastic particles, or they may be contained in separate streams fed to the gasifier. In one embodiment or in any of the mentioned embodiments, at least 80 wt. %, or at least 85 wt. %, or at least 90 wt. %, or at least 95 wt. %, or at least 96 wt. %, or at least 97 wt. %, or at least 98 wt. %, or at least 99 wt. %, or at least 99.5 wt. %, or 100 wt. % of all solid feedstock, other than solid fossil fuels, fed to the gasifier is torrefied textile char and recycle plastic particles, based on the cumulative weight of all streams containing solids fed to the gasifier.
In one embodiment or in any of the mentioned embodiments, the torrefied textile char fed to a gasifier is obtained by densifying a combination of a torrefied textile char and recycle plastics. Such an aggregate can be made by combining, blending including melt blending or otherwise together densifying the recycle plastics and torrefied textile char in one chamber. The densified torrefied textile char can contain a recycle plastic in an amount of at least 1 wt. %, or at least 3 wt. %, or at least 5 wt. %, or at least 10 wt. %.
The torrefied textiles are combined with one or more fossil fuel components of the feedstock stream at any location prior to introducing the feedstock stream into gasification zone within the gasifier. Solid fossil fuel grinding equipment will provide an excellent source of energy for mixing torrefied textiles with the solid fossil fuel while reducing the size of the solid fossil fuel particles. Therefore, one of the desirable locations for combining torrefied textiles having a target size for feeding into the gasifier is into the equipment used for grinding the other solid fossil fuel sources (e.g. coal, pet-coke). This location is particularly attractive in a slurry fed gasifier because it is desirable to use a feed having the highest stable solids concentration possible, and at higher solids concentration, the viscosity of the slurry is also high. The torque and shear forces employed in fossil fuel grinding equipment is high, and coupled with the shear thinning behavior of a solid fossil fuel (e.g. coal) slurry, good mixing of the torrefied textiles with the ground fossil fuel can be obtained in the fossil fuel grinding equipment.
Other locations for combining torrefied textiles with fossil fuel sources can be onto the fossil fuel loaded on the main fossil fuel belt feeding a mill or grinder, or onto the main fossil fuel before the fossil fuel is loaded onto the belt to the mill or grinder, or into a fossil fuel slurry storage tank containing a slurry of fossil fuel ground to the final size, particularly if the storage tank is agitated.
More particularly, there are several locations that provide a safe, economic and effective way to introduce torrefied textiles to a slurry fed coal gasifier. In additional embodiments of the invention,
In an embodiment of the invention shown in
In another embodiment of the invention, torrefied textiles can be introduced as shown in
In another embodiment the invention, the torrefied textiles can be added at location number 120, the grinding mill. The existing equipment, coal, water and viscosity modifiers are already added to the grinding mill to reduce the particle size of the coal or petcoke and produce a viscous slurry high in solids. The torrefied textiles can be independently conveyed to the entry point of the mill and added directly to the mill in the proper ratio. The mill will then grind the solid fossil fuel, produce the slurry and thoroughly mix in the torrefied textiles in the process. This avoids wind and weather effects on the coal, recycled material mixture.
In yet another embodiment of the invention the torrefied textiles can be introduced at location number 130, the slurry storage tank. Since the torrefied textiles are pre-ground to the proper particle size for introduction into the gasifier, it can be added to the slurry storage tank directly after the grinding/slurry operation. Alternatively, torrefied textiles can be added to the tank through a separate screen or the screen used by the slurry to ensure no excessively large torrefied textiles are passed to the tank. This is the last low-pressure addition point before the slurry is pumped at pressure to the gasifier. This will minimize the amount of material in process that is mixed together. The agitation in the slurry tanks will mix in the torrefied textiles torrefied textiles to ensure they are evenly distributed.
Granulators can be used to obtain the desired size reduction. These can include systems for shredding the textiles using high capacity shredders, and if necessary, a fine/powder granulator can be used in a last step. For the last step, the fine/powder granulators can be in communication with a conveying system to transport the torrefied textiles to a storage vessel from which the torrefied textiles particles can be fed to any location for making the feedstock stream, or the particles can be fed continuously from the fine granulator to the desired location for making the feedstock stream. The feed of granulated torrefied textiles particles from a storage vessel can be in a batch mode or in a continuous mode.
In one embodiment or in combination with any mentioned embodiments, the feedstock materials, e.g. fossil fuel and torrefied textiles are advantageously loose and not densified by mechanical or chemical means after the torrefied textiles are combined with the solid fossil fuel such as coal (other than natural compaction that may result from storage under its own weight). For example, once torrefied textiles are contacted with coal, the combination is not densified.
The solid fossil fuel is typically ground to a size of 2 mm or less, and can be ground to any of the sizes noted above with respect to the torrefied textiles of less than 2 mm. The small size of the coal and torrefied textiles particles is advantageous to enhance a uniform suspension in the liquid vehicle which will not settle out, to allow sufficient motion relative to the gaseous reactants, to assure substantially complete gasification, and to provide pumpable slurries of high solids content with a minimum of grinding.
In one embodiment or in combination with any of the mentioned embodiments, both torrefied textiles and recycle plastic particles are fed to the gasifier. For example, a single feedstock composition can contain the torrefied textiles and recycle plastic particles, or they may be contained in separate streams fed to the gasifier. In one embodiment or in combination with any of the mentioned embodiments, at least 80 wt. %, or at least 85 wt. %, or at least 90 wt. %, or at least 95 wt. %, or at least 96 wt. %, or at least 97 wt. %, or at least 98 wt. %, or at least 99 wt. %, or at least 99.5 wt. %, or 100 wt. % of all solid feedstock, other than solid fossil fuels, fed to the gasifier is torrefied textiles and recycle plastic particles, based on the cumulative weight of all streams containing solids fed to the gasifier.
In one embodiment or in any of the mentioned embodiments, the solids fed to the gasifier include a combination of torrefied textile char and recycle plastic particles as a solid/solid combination, and desirably also solid fossil fuel particles. The weight ratio of torrefied textiles to recycle plastic particles can be from 1:99 to 99:1, or 10:90 to 90:10, or 20:80 to 80:20, or from 30:70 to 70:30.
If recycle plastic particles are used in combination with the torrefied textile char, the recycle plastic particles are desirably not more than 5 inches, or not more than 4 inches, or not more than 1 inch, or not more than ¼ inch, or not more than 2 mm, or not more than any of the sizes mentioned above applicable to the torrefied textile char.
The solids in the feedstock composition to the gasifier desirably do not contain sewage sludge, wastepaper not already embedded in a thermoplastic matrix, or biomass. In one embodiment or in combination with any of the mentioned embodiments, the feedstock composition contains not more than 10 wt. %, or not more than 6 wt. %, or not more than 5 wt. %, or not more than 4 wt. %, or not more than 3 wt. %, or not more than 2 wt. %, or not more than 1 wt. %, or not more than 0.5 wt. %, or not more than 0.25 wt. %, or not more than 0.1 wt. % of any one of sewage sludge, waste paper not embedded in a thermoplastic matrix, biomass, or a combination of two or more, each based on the weight of the solids in the feedstock composition.
In one embodiment or in any of the mentioned embodiments, the feedstock used to make the torrefied textile char contains not more than 10 wt. % biomass, or not more than 8 wt. %, or not more than 6 wt. %, or not more than 5 wt. %, or not more than 4 wt. %, or not more than 3 wt. %, or not more than 2 wt. %, or not more than 1 wt. %, or not more than 0.5 wt. %, or no biomass, based on the weight of the feedstock used to make the torrefied textile char. In one embodiment or in any of the mentioned embodiments, the torrefied textile char fed to the gasifier vessel is obtained from a feedstock containing not more than 10 wt. % biomass, or not more than 8 wt. %, or not more than 6 wt. %, or not more than 5 wt. %, or not more than 4 wt. %, or not more than 3 wt. %, or not more than 2 wt. %, or not more than 1 wt. %, or not more than 0.5 wt. %, or no biomass, based on the weight of the feedstock used to make the torrefied textile char.
In one embodiment or in any of the mentioned embodiments, the feedstock used to make the torrefied textile char contains not more than 10 wt. % wood, or not more than 8 wt. %, or not more than 6 wt. %, or not more than 5 wt. %, or not more than 4 wt. %, or not more than 3 wt. %, or not more than 2 wt. %, or not more than 1 wt. %, or not more than 0.5 wt. %, or no wood, based on the weight of the feedstock used to make the torrefied textile char. In one embodiment or in any of the mentioned embodiments, the torrefied textile char fed to the gasifier vessel is obtained from a feedstock containing not more than 10 wt. % wood, or not more than 8 wt. %, or not more than 6 wt. %, or not more than 5 wt. %, or not more than 4 wt. %, or not more than 3 wt. %, or not more than 2 wt. %, or not more than 1 wt. %, or not more than 0.5 wt. %, or no wood, based on the weight of the feedstock used to make the torrefied textile char.
In one embodiment or in any of the mentioned embodiments, the feedstock used to make the torrefied textile char contains not more than 10 wt. % grain, or not more than 8 wt. %, or not more than 6 wt. %, or not more than 5 wt. %, or not more than 4 wt. %, or not more than 3 wt. %, or not more than 2 wt. %, or not more than 1 wt. %, or not more than 0.5 wt. %, or no grain, based on the weight of the feedstock used to make the torrefied textile char. In one embodiment or in any of the mentioned embodiments, the torrefied textile char fed to the gasifier vessel is obtained from a feedstock containing not more than 10 wt. % grain, or not more than 8 wt. %, or not more than 6 wt. %, or not more than 5 wt. %, or not more than 4 wt. %, or not more than 3 wt. %, or not more than 2 wt. %, or not more than 1 wt. %, or not more than 0.5 wt. %, or no grain, based on the weight of the feedstock used to make the torrefied textile char.
The torrefied textile char may contain some level of inorganic materials other polymer, such as metals, glass (whether in the form of fibers or particles), mineral fillers, and other inorganic materials. The quantity of such materials in the torrefied textile char that feed into the feedstock composition, is desirably less than 8 wt. %, or not more than 6 wt. %, or not more than 5 wt. %, or not more than 4 wt. %, or not more than 3.5 wt. %, or not more than 2 wt. %, or not more than 1.5 wt. %, or not more than 1 wt. %, or not more than 0.75 wt. %, or not more than 0.5 wt. %, based on the weight of the torrefied textile char.
The amount of solid fossil fuel, such as coal, in the feedstock or fed to the gasifier can be at least 10 wt. %, or at least 80 wt. %, or at least 85 wt. %, or at least 90 wt. %, or at least 93 wt. %, or at least 95 wt. %, or at least 97 wt. %, or at least 98 wt. %, or at least 98.5 wt. %, or at least 99 wt. %, and less than 100 wt. %, or less than 99.5 wt. %, based on the weight of solids in the feedstock.
Coal contains a quantity of ash that also contains elements other than carbon, oxygen, and hydrogen. The quantity of elements other than carbon, hydrogen, oxygen, and sulfur in the fossil fuel, or in the feedstock composition, is desirably not more than 15 wt. %, or not more than 13 wt. %, or not more than 10 wt. %, or not more than 9 wt. %, or not more than 8.5 wt. %, or not more than 8 wt. %, or not more than 7.5 wt. %, or not more than 7 wt. %, or not more than 7.5 wt. %, or not more than 7 wt. %, or not more than 6.5 wt. %, or not more than 6 wt. %, or not more than 5.5 wt. %, or not more than 5 wt. %, or not more than 4.5 wt. %, based on the dry weight of the fossil fuel or alternatively based on the weight of all dry solids in the feedstock composition, or based on the weight of the feedstock composition, respectively.
The caloric heat value of torrefied textile char is desirably similar to or better than that of coal. For example, the torrefied textile char can have a heat value of at least 13,000, or at least 13,500, or at least 14,000 BTU/lb., or in the range of 13,000 to 15,000 BTU/lb. (30 MJ/Kg-35 MJ/Kg), while bituminous coal can have a heat value in a range of 12,500 to 13,300 BTU/lb. (29-31 MJ/Kg). Further, any ash or non-organic material can be melted and vitrified into the ash or slag matrix that is produced from the inorganics in the coal.
The concentration of solids (e.g. fossil fuel and torrefied textile char) in the feedstock composition should not exceed the stability limits of a slurry or solids/solids mix, or the ability to pump or feed the feedstock at the target solids concentration to the gasifier. Desirably, the solids content of a slurry should be at least 50 wt. %, or at least 55 wt. %, or at least 60 wt. %, or at least 62 wt. %, or at least 65 wt. %, or at least 68 wt. %, or at least 69 wt. %, or at least 70 wt. %, or at least 75 wt. %, the remainder being a liquid phase that can include water and liquid additives. The upper limit is not particularly limited because it is dependent upon the gasifier design. However, given the practical pumpability limits of a solid fossil fuels feed and maintaining a homogeneous distribution of solids in the slurry, the solids content for a solid fossil slurry fed slagging gasifier desirably should not exceed 75 wt. %, or 73 wt. %, the remainder being a liquid phase that can include water and liquid additives (as noted above, gases are not included in the calculation of weight percentages). The solids concentration of a dry fed gasifier is desirably 95 wt. % or more, or 97 wt. % or more, or 98 wt. % or more, or 99 wt. % or more, or 100 wt. %, based on the weight of the gasifier feedstock composition (excluding the weight of the gas and moisture contained in the solids).
A slurry feedstock composition is desirably stable at 5 minutes, or even 10 minutes, or even 15 minutes, or even 20 minutes, or even ½ hour, or even 1 hour, or even two hours. A slurry feedstock is deemed stable if its initial viscosity is 100,000 cP or less. The initial viscosity can be obtained by the following method. A 500-600 g of a well-mixed sample is allowed to stand still in a 600 mL liter glass beaker at ambient conditions (e.g. 25° C. and about 1 atm). A Brookfield R/S Rheometer equipped with V80-40 vane operating at a shear rate of 1.83/s is submerged into the slurry to the bottom of the beaker after the slurry is well mixed (e.g. a homogeneous distribution of solids was formed). After a designated period of time, a viscosity reading is obtained at the start of rotation, which is the initial viscosity reading. The slurry is considered to be stable if the initial reading on starting a viscosity measurement is not more than 100,000 cP at the designated period of time. Alternatively, the same procedure can be used with a Brookfield viscometer with an LV-2 spindle rotating at a rate of 0.5 rpm. Since different viscosity value will be obtained using the different equipment, the type of equipment used should be reported. However, regardless of the differences, the slurry is considered stable under either method only if its viscosity is not more than 100,000 cP at the reported time.
The quantity of solids in the feedstock composition and their particle size are adjusted to maximize the solids content while maintaining a stable and pumpable slurry. A pumpable slurry is one which has a viscosity under 30,000 cP, or not more than 25,000 cP, or not more than 23,000 cP, and desirably not more than 20,000 cP, or not more than 18,000 cP, or not more than 15,000 cP, or not more than 13,000 cP, in each case at ambient conditions (e.g. 25° C. and 1 atm). At higher viscosities, the slurry becomes too thick to practically pump. The viscosity measurement to determine the pumpability of the slurry is taken by mixing a sample of the slurry until a homogeneous distribution of particles is obtained, thereafter immediately submerging a Brookfield viscometer with an LV-2 spindle rotating at a rate of 0.5 rpm into the well mixed slurry and taking a reading without delay. Alternatively, a Brookfield R/S rheometer with V80-40 vane spindle operating at a shear rate of 1.83/s can be used. The method of measurement is reported since the measured values between the two rheometers at their difference shear rates will generate different values. However, the cP values stated above apply to either of the rheometer devices and procedures.
In one embodiment or in combination with any of the mentioned embodiments, the slurry feedstock composition has a viscosity of 80,000 cP or less, or 70,000 cP or less, or 60,000 cP or less, 50,000 cP or less, or 40,000 cP or less, or 35,000 cP or less, or 25,000 cP or less, or 20,000 cP or less, or 15,000 cP or less, or 10,000 cP or less, in each case, at 5 minutes, or even 10 minutes, or even 15 minutes, or even 20 minutes, desirably at 5 minutes or at 20 minutes, or at 20 minutes and desirably at 60,000 cP or less or 40,000 cP or less.
In one embodiment or in combination with any of the mentioned embodiments, the fossil fuel is at least coal. The quality of the coal employed is not limited. Anthracite, bituminous, sub-bituminous, brown coal, and lignite coal can be sources of coal feedstock. To increase the thermal efficiency of the gasifier, the coal employed desirably has a carbon content that exceeds 35 wt. %, or at least 42 wt. %, based on the weight of the coal. Accordingly, bituminous or anthracite coal is desirable due to their higher energy content.
Sulfur is also typically present in solid fossil fuels. Desirably, the content of sulfur is less than 5 wt. %, not more than 4 wt. %, or not more than 3 wt. %, or not more than 2.5 wt. %, and also can contain a measure of sulfur, such as at least 0.25 wt. %, or at least 0.5 wt. %, or at least 0.75 wt. %, based on the weight of the solid fossil fuel.
It is also desirable to employ a solid fossil fuel with a low inherent moisture content to improve the thermal efficiency of the gasifier. Using coal having moisture contents less than 25 wt. % or less than 20 wt. % or less than 15 wt. % or not more than 10 wt. % or not more than 8 wt. % is desirable to improve the energy efficiency of the gasifier.
Desirably, the coal feedstock has a heat value of at least 11,000 BTU/lb., or at least 11,500 BTU/lb., or at least 12,500 BTU/lb., or at least 13,000 BTU/lb., or at least 13,500 BTU/lb., or at least 14,000 BTU/lb., or at least 14,250 BTU/lb., or at least 14,500 BTU/lb.
In a slurry fed gasifier, while it is possible that the feedstock composition may contain minor amounts of liquid hydrocarbon oils leached from torrefied textile char or coal, the feedstock composition desirably contains less than 5 wt. %, or not more than 3 wt. %, or not more than 1 wt. %, or not more than 0.1 wt. % liquid (at ambient conditions) non-oxygenated hydrocarbon petroleum oils introduced as such into the feedstock composition. Desirably, the feedstock composition contains less than 2 wt. %, or not more than 1 wt. %, or no added liquid fraction from refining crude oil or reforming any such fraction in a slurry feedstock stream or to a slurry fed gasifier.
In a slurry gasifier feedstock, the content of liquids, or the content of water, present in the feedstock composition is desirably not more than 50 wt. %, or not more than 35 wt. %, or not more than 32 wt. %, or not more than 31 wt. %, or not more than 30 wt. %, based on the weight of the feedstock composition. Desirably, in each case, the content of liquids or water in the feedstock composition for a slurry fed gasifier is desirably at least 10 wt. %, or at least 15 wt. %, or at least 20 wt. %, or at least 25 wt. %, or at least 27 wt. %, or at least 30 wt. %, based on the weight of the feedstock composition. The liquids present in the slurry gasifier feedstock desirably contain at least 95 wt. % water, or at least 96 wt. % water, or at least 97 wt. % water, or at least 98 wt. % water, or at least 99 wt. % water, based on the weight of all liquids fed to the gasifier. In another embodiment, other than chemical additives that are chemically synthesized and contain oxygen or sulfur or nitrogen atoms, the liquid content of the feedstock composition is at least 96 wt. % water, or at least 97 wt. % water, or at least 98 wt. % water, or at least 99 wt. % water, based on the weight of all liquids fed to the gasifier.
In one embodiment or in combination with any of the mentioned embodiments, at least a portion of the fuel feedstock to the gasifier is a liquid at 25° C. and 1 atmosphere, such as organic feedstocks, petroleum oils or fractions from refining or distilling crude oil, hydrocarbons, oxygenated hydrocarbons, or synthetic chemical compounds. These liquid feedstocks can be from any fraction from petroleum distillation or refining, or any chemical synthesized at a chemical manufacturing facility, provided they are liquid. These liquids are a carbon fuel source for gasifying into syngas. In one embodiment or in any of the mentioned embodiments, there is now also provided a combination of torrefied textile char and a hydrocarbon liquid fuel or oxygenated hydrocarbon liquid fuel that are liquid at 25° C. and 1 atmosphere. Depending on the nature of the liquid fuel feedstock, the torrefied textile char may be insoluble, partially soluble, or soluble in the liquid fuel feedstock.
In an embodiment, the water present in the feedstock stream is not wastewater, or in other words, the water fed to the solids to make the feedstock stream is not wastewater. Desirably, the water employed has not been industrially discharged from any process for synthesizing chemicals, or it not municipal wastewater. The water is desirably fresh water, or potable water.
In one embodiment or in combination with any mentioned embodiments, the feedstock stream comprises at least ground coal and torrefied textiles. Desirably, the feedstock stream also comprises water. The amount of water in the feedstock stream can range from 0 wt. % up to 50 wt. %, or from 10 wt. % to 40 wt. %, or from 20 wt. % to 35 wt. %. The feedstock stream is desirably a slurry containing water.
In addition to solid fossil fuel and torrefied textiles, other additives can be added to and contained in the feedstock composition, such as viscosity modifiers and pH modifiers. The total quantity of additives can range from 0.01 wt. % to 5 wt. %, or from 0.05 wt. % to 5 wt. %, or from 0.05 to 3 wt. %, or from 0.5 to 2.5 wt. %, based on the weight of the feedstock composition. The quantity of any individual additive can also be within these stated ranges.
The viscosity modifiers (which includes surfactants) can improve the solids concentration in a slurry gasifier feedstock. Examples of viscosity modifiers include:
More specific examples of alkyl-substituted aminobutyric acid surfactants include N-coco-beta-aminobutyric acid, N-tallow-beta-aminobutyric acid, N-lauryl-beta-aminobutyric acid, and N-oleyl-beta-aminobutyric acid. N-coco-beta-aminobutyric acid.
More specific examples of alkyl-substituted polyethoxylated amide surfactant include polyoxyethylene oleamide, polyoxyethylene tallowamide, polyoxyethylene laurylamide, and polyoxyethylene cocoamide, with 5-50 polyoxyethylene moieties being present.
More specific examples of the alkyl-substituted polyethoxylated quaternary ammonium salt surfactant include methylbis (2-hydroxyethyl) cocoammonium chloride, methylpolyoxyethylene cocoammonium chloride, methylbis (2-hydroxyethyl) oleylammonium chloride, methylpolyoxyethylene oleylammonium chloride, methylbis (2-hydroxyethyl) octadecylammonium chloride, and methylpolyoxyethylene octadecylammonium chloride.
More specific examples of sulfonates include sulfonated formaldehyde condensates, naphthalene sulfonate formaldehyde condensates, benzene sulfonate-phenol-formaldehyde condensates, and lingosulfonates.
More specific examples of phosphate salts include trisodium phosphate, potassium phosphate, ammonium phosphate, sodium tripolyphosphate or potassium tripolyphosphate.
Examples of polyoxyalkylene anionic or nonionic surfactants have 1 or more repeating units derived from ethylene oxide or propylene oxide, or 1-200 oxyalkylene units.
Desirably, the surfactant is an anionic surfactant, such as salts of an organic sulfonic acid. Examples are calcium, sodium and ammonium salts of organic sulfonic acids such as 2,6-dihydroxy naphthalene sulfonic acid, lignite sulfonic acid, and ammonium lignosulfonate.
Examples of pH modifiers include aqueous alkali metal and alkaline earth hydroxides such as sodium hydroxide, and ammonium compounds such as 20-50 wt. % aqueous ammonium hydroxide solutions. The aqueous ammonium hydroxide solution can be added directly to the feedstock composition prior to entry into the gasifier, such as in the coal grinding equipment or any downstream vessels containing the slurry.
In one embodiment or in combination with any of the mentioned embodiments, the atomic ratio of total oxygen to carbon entering the gasification zone can be a value in the range of 0.70 to less than 2, or from 0.9 to 1.9, or from 0.9 to 1.8, or from 0.9 to 1.5, or from 0.9 to 1.4, or from 0.9 to 1.2, or from 1 to 1.9, or from 1 to 1.8, or from 1 to 1.5, or from 1 to 1.2, or from 1.05 to 1.9, or from 1.05 to 1.8, or from 1.05 to 1.5, or from 1.05 to 1.2. The atomic ratio of free oxygen to carbon entering the gasification zone can also be within these same values. The weight ratio of both total oxygen and free oxygen to carbon in pounds entering the gasification zone can also each be within these stated values.
In one embodiment or in combination with any of the mentioned embodiments, the total carbon content in the feedstock composition is at least 40 wt. %, or at least 45 wt. %, or at least 50 wt. %, or at least 55 wt. %, or at least 60 wt. %, or at least 65 wt. %, and desirably at least 70 wt. %, or at least 75 wt. %, or at least 80 wt. %, or at least 85 wt. %, or at least 90 wt. %, each based on the total solids content.
In one embodiment or in combination with any of the mentioned embodiments, the gasifier feedstock composition is desirably injected along with an oxidizer into a refractory-lined combustion chamber (gasification zone) of the synthesis gas generating gasifier. The feedstock stream (desirably a slurry) and oxidizer are desirably sprayed through an injector into a gasification zone. The gasification zone can be under significant pressure, typically about 500 psig or more, or 600 psig or more, or 800 psig or more, or 1000 psig or more, or 1100 psig or more, or 1200 psig or more. For an entrained flow gasifier, the velocity or flow rate of the feedstock and oxidizer streams ejected from the injector nozzle into the gasification zone (or combustion chamber) will exceed the rate of flame propagation to avoid backflash.
In one embodiment or in combination with any of the mentioned embodiments, advantageously only one feedstock composition is charged to the gasifier or gasification zone, or in other words, all sources of carbon fuel are fed to the gasifier in only one stream.
In one embodiment or in combination with any of the mentioned embodiments, only one feedstock stream is necessary or employed to produce a torrefied textile derived syngas or product stream that is a raw material to synthesize a chemical compound.
In another embodiment, a chemical is made from a first torrefied textile derived syngas sourced from a first gasifier fed with a first feedstock composition containing a solid fossil fuel is not combined with a second syngas stream sourced from any other gasifier fed with second fossil fuel feedstock composition where the solid fossil fuel content between the first and second feedstock compositions differ by more than 20%, or more than 10%, or more than 5%, based on the weight of the all solids fed to the gasifiers. For example, a first torrefied textile derived syngas stream generated from a first feedstock composition containing 90 wt. % coal would not be combined with a torrefied textile derived syngas stream generated from a different gasifier fed with a feedstock composition containing 70 wt. % coal or no coal, but could be combined with one containing 72 wt. % coal or more.
In another embodiment, a first torrefied textile derived syngas sourced from a first gasifier fed with a first feedstock composition containing a first fixed carbon content is not combined with a second syngas stream sourced from any other gasifier fed with a second feedstock containing a second fixed carbon content, where the difference between the first and second fixed carbon contents is more than 20%, or more than 10%, or more than 5% of each other, based on the weight of the all solids fed to the gasifiers. For example, a first torrefied textile derived syngas stream generated from a first feedstock composition containing 70 wt. % fixed carbon based on the weight of the solids would not be combined with a torrefied textile derived syngas stream generated from a different gasifier fed with a feedstock composition containing 30 wt. % fixed carbon, but could be combined with one containing 56 wt. % fixed carbon if the limit of 20% is selected.
Prior to entry into the gasifier, the feedstock composition may be subjected to a variety of other optional processes. For example, a slurry can flow through a thickener in which excess water is eliminated from the slurry to obtain the final desired solids concentration of the slurry entering into the gasifier vessel. The feedstock composition may be pre-heated to prior to entry into the gasifier. In this embodiment, a slurry feedstock composition is heated to a temperature below the boiling point of water at the operating pressure existing in reaction zone. The preheater, when employed, reduces the heat load on the gasifier and improves the efficiency of utilization of both fuel and oxygen.
In one embodiment or in combination with any of the mentioned embodiments, at least 80 wt. % of all of the water required for the generation of synthesis gas in reaction zone is supplied in liquid phase. When petroleum coke is employed as fuel for the gas generator, part of the water, e.g., from 1 to about 90 percent by weight based on the weight of water, may be vaporized in the slurry feed preheater or combined with the oxidizing stream as vaporized water.
The oxidizer is desirably an oxidizing gas that can include air, and desirably is a gas enriched in oxygen at quantities greater than that found in air. The reaction of oxygen and solid fossil fuel is exothermic. Desirably, the oxidant gas contains at least 25 mole % oxygen, or at least 35 mole %, or at least 40 mole %, or at least 50 mol %, or at least 70 mole %, or at least 85 mole %, or at least 90 mole %, or at least 95 mole %, or at least 97 mole %, or at least 98 mole % oxygen, or at least 99 mole %, or at least 99.5 mole % based on all moles in the oxidant gas stream injected into the reaction (combustion) zone of the gasifier. In another embodiment, the combined concentration of oxygen in all gases supplied to the gasification zone is also in the above stated amount. The particular amount of oxygen as supplied to the reaction zone is desirably sufficient to obtain near or maximum yields of carbon monoxide and hydrogen obtained from the gasification reaction relative to the components in the feedstock composition, considering the amount relative to the feedstock composition, and the amount of feedstock charged, the process conditions, and the gasifier design.
In one embodiment or in combination with any of the mentioned embodiments, steam is not supplied to the gasification zone in a slurry fed gasifier. The amount of water in a slurry fed system is typically more than sufficient a co-reactant and heat sink to regulate the gasification temperature. The addition of steam in a slurry fed gasifier will generally unduly withdraw heat from the reaction zone and reduce its efficiency. In one embodiment or in combination with any of the mentioned embodiments, steam is fed to the gasification zone in any type of dry fed gasifier, such as an entrainment flow gasifier, a fluidized bed gasifier, or a fixed or moving bed gasifier. The addition of steam in dry fed gasifiers case is desirable to provide the raw material needed for the production of carbon monoxide.
Other reducible oxygen-containing gases may be supplied to the reaction zone, for example, carbon dioxide, or simply air. In one embodiment or in combination with any of the mentioned embodiments, no gas stream enriched in carbon dioxide or nitrogen (e.g. greater than the molar quantity found in air, or greater than 2 mole %, or greater than 5 mole %, or greater than 10 mole %, or greater than 40 mole %) is charged into a slurry fed gasifier. Many of these gases serve as carrier gases to propel a dry feed to a gasification zone. Therefore, in another embodiment, one or more of these gases are charged to the gasification zone as a carrier gas for the dry feed of solid fossil fuel and torrefied textiles. Due to the pressure within the gasification zone, these carrier gases are compressed to provide the motive force for introduction into the gasification zone. The expenditure of energy and equipment for compressing carrier gases to the feedstock composition is avoided is a slurry feed. Accordingly, in yet another embodiment, the feedstock composition containing at least torrefied textiles and solid fossil fuel flowing to the gasifier, or this feedstock composition as introduced to an injector or charge pipe, or this feedstock composition as introduced into the gasification zone, or a combination of all the above, does not contain gases compressed in equipment for gas compression. Alternatively, or in addition, other than the oxygen rich stream described above, no gas compressed in equipment for gas compression is fed to the gasification zone or even to the gasifier. It is noteworthy that high pressure charge pumps that process the slurry feed for introduction into the gasification zone are not considered gas compressing equipment.
In one embodiment or in combination with any of the mentioned embodiments, no gas stream containing more than 0.03 mole %, or more than 0.02 mole %, or more than 0.01 mole % carbon dioxide is charged to the gasifier or gasification zone. In another embodiment, no gas stream containing more than 77 mole %, or more than 70 mole %, or more than 50 mole %, or more than 30 mole %, or more than 10 mole %, or more than 5 mole %, or more than 3 mole % nitrogen is charged to the gasifier or gasification zone. In another embodiment, a gas stream containing more than 77 mole %, or more than 80 mole % nitrogen is charged to the gasifier or gasification zone. In another embodiment, steam is charged into the gasification zone or to the gasifier. In yet another embodiment, a gaseous hydrogen stream (e.g. one containing more than 0.1 mole % hydrogen, or more than 0.5 mole %, or more than 1 mole %, or more than 5 mole %) is not charged to the gasifier or to the gasification zone. In another embodiment, a stream of methane gas (e.g. one containing more than 0.1 mole % methane, or more than 0.5 mole %, or more than 1 mole %, or more than 5 mole % methane) is not charged to the gasifier or to the gasification zone. In another embodiment, the only gaseous stream introduced to the gasification zone is an oxygen rich gas stream as described above.
In one embodiment or in combination with any of the mentioned embodiments, the gasifier can be fed with two or more separate streams to the gasification zone. For example, one feedstock composition can contain natural gas (methane) in a concentration of at least 50 mole % and a second feedstock composition can contain torrefied textiles as a dry feed or as a slurry or dispersion in fuel liquids other than water or in liquids containing water or containing more than 50 wt. % water based on the weight of the water. In a natural gas fed gasifier, the amount of methane fed to the gasifier is at least 50 mole %, or at least 70 mole % or at least 80 mole % or at least 90 mole % based on the moles of all gases fed to the gasifier, or based on the moles of all feedstock fuel and reactants fed to the gasifier, or even based on the moles of all fuel fed to the gasifier. Suitable liquids as fuel include those mentioned above that are liquid at 25° C. and 1 atm.
The gasification process desirably employed is a partial oxidation gasification reaction. To enhance the production of hydrogen and carbon monoxide, the oxidation process involves partial, rather than complete, oxidization of the fossil fuel and torrefied textile char and therefore is desirably operated in an oxygen-lean environment, relative to the amount needed to completely oxidize 100% of the carbon and hydrogen bonds. This is in contrast to a combustion reaction which would employ a large stoichiometric excess of oxygen over that needed to make carbon monoxide, leading to the production primarily of carbon dioxide and water. In the particle oxidation gasification process, the total oxygen requirements for the gasifier is desirably at least 5%, or at least 10%, or at least 15%, or at least 20%, in excess of the amount theoretically required to convert the carbon content of the solid fuel and torrefied textile char to carbon monoxide. In general, satisfactory operation may be obtained with a total oxygen supply of 10 to 80 percent in excess of the theoretical requirements for carbon monoxide production. An example of a suitable amount of oxygen per pound of carbon is in the range of 0.4 to about 3.0-pound free oxygen per pound of carbon, or from 0.6 to 2.5, or from 0.9 to 2.5, or from 1 to 2.5, or from 1.1 to 2.5, or from 1.2 to 2.5 pounds of free oxygen per pound of carbon.
Mixing of the feedstock composition and the oxidant is desirably accomplished entirely within the reaction zone by introducing the separate streams of feedstock and oxidant so that they impinge upon each other within the reaction zone. Desirably, the oxidant stream is introduced into the reaction zone of the gasifier at high velocity both exceed the rate of flame propagation and to improve mixing with the feedstock composition. The oxidant is desirably injected into the gasification zone in the range of 25 to 500 feet per second, or 50 to 400 ft/s, or 100 to 400 ft/s. These values would be the velocity of the gaseous oxidizing stream at the injector-gasification zone interface, or the injector tip velocity.
The feedstock composition and the oxidant can optionally be preheated to a temperature above about 200° C., or at least 300° C., or at least 400° C. Advantageously the gasification process does not require preheating the feedstock composition to efficiently gasify the fuel, and a pre-heat treatment step would result in lowering the energy efficiency of the process. Desirably, the feedstock composition, and optionally the oxidant, are not preheated prior to their introduction into the gasifier. A preheat treatment step would be contacting the feedstock composition or oxidant with equipment that raises the temperature of the feedstock composition sufficiently such that the temperature of the feedstock composition or oxidant stream is above 200° C., or above 190° C., or above 170° C., or above 150° C., or above 130° C., or above 110° C., or above 100° C., or above 98° C., or above 90° C., or above 80° C., or above 70° C., or above 60° C., immediately prior to introduction into a injector on the gasifier. For example, while coal can be dried with hot air above 200° C., this step would not be considered a preheat of the feedstock composition if the feedstock composition is below 200° C. upon its introduction into the injector.
In another embodiment, no thermal energy (other than incidental heat from processing equipment such as mills, grinders or pumps) is applied to the feedstock composition containing both torrefied textile char and the solid fossil fuel, or to the oxidant stream, at any point prior to its introduction into the injector, or gasifier, or gasification zone (other than the temperature increase experienced in a injector) that would increase the temperature of the stream by more than 180° C., or more than 170° C., or more than 160° C., or more than 150° C., or more than 140° C., or more than 130° C., or more than 120° C., or more than 110° C., or more than 100° C., or more than 90° C., or more than 80° C., or more than 70° C., or more than 60° C., or more than 50° C., or more than 40° C., or more than 30° C.
The process of the invention employs a gasification process, which is distinct from a combustion process that generates primarily carbon dioxide and water, or a pyrolysis process which is a thermal process that degrades a fuel source in the absence of air or oxygen and generates primarily a liquid, or plasma processes in that gasification does not employ a plasma arc.
In one embodiment, the type of gasification technology employed is a partial oxidation entrained flow gasifier that generates torrefied textile derived syngas. This technology is distinct from fixed bed (alternatively called moving bed) gasifiers and from fluidized bed gasifiers. In fixed bed (or moving bed gasifiers), the feedstock stream moves in a countercurrent flow with the oxidant gas, and the oxidant gas typically employed is air. The feedstock stream falls into the gasification chamber, accumulates, and forms a bed of feedstock. Air (or alternatively oxygen) flows from the bottom of the gasifier up through the bed of feedstock material continuously while fresh feedstock continuously falls down from the top by gravity to refresh the bed as it is being combusted. The combustion temperatures are typically below the fusion temperature of the ash and are non-slagging. Whether the fixed bed operated in countercurrent flow or in some instances in co-current flow, the fixed bed reaction process generates high amount of tars, oils, and methane produced by pyrolysis of the feedstock in the bed, thereby both contaminating the torrefied textile derived syngas produced and the gasifier. The contaminated torrefied textile derived syngas requires significant effort and cost to remove tarry residues that would condense once the torrefied textile derived syngas is cooled, and because of this, such torrefied textile derived syngas streams are generally not used to make chemicals and are instead used in direct heating applications, or as liquid fuels. Downdraft fixed or moving bed gasifiers produce less or no tar. Fixed or moving bed gasifiers already equipped or built to be equipped with tar removal processes are suitable to accept a feed of the torrefied textiles.
In one embodiment or in any of the mentioned embodiments, the torrefied textile char is fed to a fixed or moving bed gasifier. For fixed bed, moving bed or other solid feed gasifier technologies that can accept larger feedstocks (up to 4″), the torrefied textile char can be fed neat (without having to form a slurry) to the gasifier as 100% of the feed or mixed with other gasifier fuel. For example, the torrefied textile char can be a base feed material that makes it possible to gasify other difficult to gasify materials, such as bio-sludge or other low energy feeds or plastics that might tend to melt and clump if fed by themselves. These types of gasifiers are usually lower pressure (atmospheric to 300 psig) since sealing feed mechanisms with large feedstocks is very difficult.
In one embodiment or in any of the mentioned embodiments, the torrefied textile char is a carrier material for another gasifier fuel. For example, plastics can be melted and commingled with the torrefied textile char during a densification process to produce densified torrefied textile char containing thermoplastic polymer. Alternatively, a liquid substance such as biosludge can infused or partially absorbed into the structure of the torrefied textile char to form a sludge infused torrefied textile char that is fed to a gasifier.
In a fluidized bed, the feedstock material in the gasification zone is fluidized by action of the oxidant flowing through the bed at a high enough velocity to fluidize the particles in the bed. In a fluidized bed, the homogeneous reaction temperatures and low reaction temperatures in the gasification zone also promotes the production of high amounts of unreacted feedstock material and low carbon conversion, and operating temperatures in the fluidized bed are typically between 800-1000° C. Further, in a fluidized bed, it is important to operate below slagging conditions to maintain the fluidization of the feedstock particles which would otherwise stick to the slag and agglomerate. By employing an entrained flow gasification, these deficiencies present with fixed (or moving bed) and fluidized bed gasifiers that are typically used to process waste materials is overcome.
In one embodiment or in combination with any of the mentioned embodiments, the feedstock stream is introduced at the top ⅛ section of the gasifier, desirably at the top 1/12 of the gasifier height defined by the gasifier shell (not including the injector height protruding from the top of the shell or pipes protruding from the bottom of the shell). The feedstock composition is desirably not introduced into a side wall of the gasifier. In another embodiment, the feedstock composition is not a tangential feed injector.
In another embodiment, oxidant is introduced at the top ⅛ section of the gasifier, desirably at the top 1/12 of the gasifier height defined by the gasifier shell. The oxidant is desirably not introduced into the side wall of the gasifier or bottom of the flow gasifier. In another embodiment, both the feedstock composition and oxidant are introduced at the top ⅛ section of the gasifier, desirably at the top 1/12 of the gasifier height defined by the gasifier shell. Desirably, the oxidant and feedstock composition are fed co-currently to ensure good mixing. In this regard, a co-current feed means that the axis of the feedstock and oxidant streams are substantially parallel (e.g. not more than a 25° deviation, or not more than a 20°, or not more than a 15°, or not more than a 10°, or not more than a 8°, or not more than a 6°, or not more than a 4°, or not more than a 2°, or not more than a 1° deviation from each other) and in the same direction.
The feedstock and oxidant streams are desirably introduced into the gasification zone through one or more injector nozzles. Desirably, the gasifier is equipped with at least one of the injector nozzles in which through that injector nozzle both a feedstock stream and an oxidant stream are introduced into the gasification zone.
While the feedstock stream can be a dry feed or a slurry feed, the feedstock stream is desirably a slurry.
The syngas produced in the gasification process is desirably used at least in part for making chemicals. Many synthetic processes for making chemicals are at high pressure, and to avoid energy input into pressurizing the torrefied textile derived syngas stream, desirably the gasifier is also run at high pressure, particularly when the torrefied textile derived syngas stream is directly or indirectly in gaseous communication with a vessel in which a chemical is synthesized. Dry feeds to a gasifier operating at high pressure are specially treated to ensure that the feed can be effectively blown and injected into the high-pressure gasification zone. Some techniques include entraining a flow of nitrogen at high pressure and velocity, which tends to dilute the syngas stream and reduce the concentration of desirably components such as carbon monoxide and hydrogen. Other carrier or motive gases include carbon monoxide, but like nitrogen, these gases are compressed before feeding into or compressed with the solid fossil fuels, adding to the energy requirements and capital cost of feed lock hoppers and/or compressing equipment. To deal with these issues, many dry feed gasifiers will operate at lower pressures, which for the mere production of electricity is sufficient, but is undesirable for gasifiers producing a syngas stream for making chemicals. With a slurry feed, a motive gas is not necessary and can readily be fed to a high-pressure gasifier that produces syngas as high pressure, which is desirable for making chemicals. In one embodiment or in combination with any of the mentioned embodiments, the feedstock stream is not processed through a lock hopper prior to entering an injector or entering the gasification zone. In another embodiment, the feedstock composition containing size reduced textiles and solid fossil fuel is not pressurized in a lock hopper prior to feeding to the injector or gasification zone.
Desirably, the gasifier is non-catalytic, meaning that gasifier does not contain a catalyst bed, and desirably the gasification process is non-catalytic, meaning that a catalyst is not introduced into the gasification zone as a discrete unbound catalyst (as opposed to captive metals in the torrefied textile char or solid fossil fuel that can incidentally have catalytic activity). The gasification process in the reaction zone is desirably conducted in the absence of added catalysts and contains no catalyst bed. The gasification process is also desirably a slagging gasification process; that is, operated under slagging conditions (well above the fusion temperature of ash) such that a molten slag is formed in the gasification zone and runs along and down the refractory walls.
In another embodiment, the gasifier is not designed to contain a pyrolysis zone. Desirably, the gasifier is not designed to contain a combustion zone. Most preferably, the gasifier is designed to not contain, or does not contain, either a combustion zone or a pyrolysis zone. The pyrolysis zone incompletely consumes the fuel source leading to potentially high amounts of ash, char, and tarry products. A combustion zone, while absent in tars, produces high amounts of CO2 and lower amounts of the more desirably carbon monoxide and hydrogen. Desirably, the gasifier is a single stage reactor, meaning that there is only one zone for conversion of the carbon in the feedstock to torrefied textile derived syngas within the gasifier shell.
The gasification zone is void or empty space defined by walls in which oxidation reactions occur and allow gases to form within the space. Desirably, gasification zone does not have a bath of molten material or molten material that accumulates at the bottom of the gasification zone to form a bath. The gasification zone is desirably not enclosed on the bottom but rather is in gaseous communication with other zones below the gasification zone. Slag, while molten, does not accumulate at the bottom of the gasification zone but rather runs down the sides of the refractory and into a zone below the gasification zone, such as a quench zone to solidify the slag.
The flow of hot raw torrefied textile derived syngas in the gasifier is desirably vertically downward, or a down-flow gasifier. Desirably, the flow of torrefied textile derived syngas generated in the gasifier is downward from the highest point of injecting the feedstock composition, desirably from the point of all feedstock stream locations. In another embodiment, the location for withdrawing the torrefied textile derived syngas stream from the gasifier is lower that at least one location for introducing the feedstock stream, desirably lower than all locations for introducing a feedstock stream.
The gasifier can contain refractory lining in the gasification zone. While a steam generating membrane or jacket between the gasifier wall and the surfaces facing the gasification zone can be employed, desirably the gasifier does not contain a membrane wall, or a steam generating membrane, or a steam jacket in the gasification zone or between inner surfaces facing the gasification zone and the gasifier shell walls as this removes heat from the gasification zone. Desirably, the gasification zone is lined with refractory, and optionally there is no air or steam or water jacket between the refractory lining the gasification zone (or optionally in any reaction zone such as combustion or pyrolysis) and the outer shell of the gasifier.
The gasification process is desirably a continuous process meaning that the gasifier operates in a continuous mode. The inclusion of torrefied textiles into the feedstock composition can be intermittent or continuous provided that a continuous feed of fossil fuel is fed to the gasifier since the gasification process in the gasifier is in a continuous mode. By a continuous mode for gasifier operation is meant that the gasification process is continuous for at least 1 month, or at least 6 months, or at least 1 year. Desirably, the inclusion of torrefied textiles in the feedstock composition is continuous for at least 1 day, or at least 3 days, or at least 14 days, or at least 1 month, or at least 6 months, or at least 1 year. A process is deemed continuous despite shut-downs due to maintenance or repair.
The feedstock can be fed into the gasification zone through one or more injectors. In one embodiment or in combination with any of the mentioned embodiments, the gasifier contains only one injector. In another embodiment, the gasifier contains only one location for introducing feedstock. Typically, the injector nozzle serving the gasification chamber is configured to have the feedstock stream concentrically surround the oxidizer gas stream along the axial core of the nozzle. Optionally, the oxidizer gas stream can also surround the feedstock stream annulus as a larger, substantially concentric annulus. Radially surrounding an outer wall of the outer oxidizer gas channel can be an annular cooling water jacket terminated with a substantially flat end-face heat sink aligned in a plane substantially perpendicular to the nozzle discharge axis. Cool water is conducted from outside the combustion chamber into direct contact with the backside of the heat sink end-face for conductive heat extraction.
The reaction between the hydrocarbon and oxygen should take place entirely outside the injector proper to prevent localized concentration of combustible mixtures at or near the surfaces of the injector elements.
In one embodiment or in combination with any of the mentioned embodiments, the gasification zone, and optionally all reaction zones in the gasifier are operated at a temperature in the range of at least 1000° C., or at least 1100° C., or at least 1200° C., or at least 1250° C., or at least 1300° C., and up to about 2500° C., or up to 2000° C., or up to 1800° C., or up to 1600° C., each of which are well above the fusion temperature of ash, and are desirably operated to form a molten flow of slag in the reaction zone. In one embodiment or in combination with any of the mentioned embodiments, the reaction temperature is desirably autogenous. Advantageously, the gasifier operating in steady state mode is at an autogenous temperature and does not require application of external energy sources to heat the gasification zone. In a fixed bed, moving bed, or fluidized bed gasifier, the gasification zone is generally below 1000° C., or not above 950° C., or not higher than 800° C.
In one embodiment or in combination with any of the mentioned embodiments, the gasifier does not contain a zone within the gasifier shell to dry feedstock such as the coal, pet-coke, or torrefied textiles prior to gasification. The increase in temperature within the injector is not considered a zone for drying.
Desirably, the gasification zone is not under negative pressure during operations, but rather is under positive pressure during operation. The gasification zone is desirably not equipped with any aspirator or other device to create a negative pressure under steady state operation.
The gasifier can be operated at a pressure within the gasification zone (or combustion chamber) of at least 200 psig (1.38 MPa), or at least 300 psig (2.06 MPa), or at least 350 psig (2.41 MPa), and desirably at least 400 psig (2.76 MPa), or at least 420 psig (2.89 MPa), or at least 450 psig (3.10 MPa), or at least 475 psig (3.27 MPa), or at least 500 psig (3.44 MPa), or at least 550 psig (3.79 MPa), or at least 600 psig (4.13 MPa), or at least 650 psig (4.48 MPa), or at least 700 psig (4.82 MPa), or at least 750 psig (5.17 MPa), or at least 800 psig (5.51 MPa), or at least 900 psig (6.2 MPa), or at least 1000 psig (6.89 MPa), or at least 1100 psig (7.58 MPa), or at least 1200 psig (8.2 MPa). The particular operating pressure on the high end is regulated with a variety of considerations, including operating efficiency, the operating pressures needed in chemical synthesis gasifiers particularly with integrated plants, and process chemistry. Suitable operating pressures in the gasification zone on the high end need not exceed 1300 psig (8.96 MPa), or need not exceed 1250 psig (8.61 MPa), or need not exceed 1200 psig (8.27 MPa), or need not exceed 1150 psig (7.92 MPa), or need not exceed 1100 psig (7.58 MPa), or need not exceed 1050 psig (7.23 MPa), or need not exceed 1000 psig (6.89 MPa), or need not exceed 900 psig (6.2 MPa), or need not exceed 800 psig (5.51 MPa), or need not exceed 750 psig (5.17 MPa). Examples of suitable desirably ranges include 400 to 1000, or 425 to 900, or 450 to 900, or 475 to 900, or 500 to 900, or 550 to 900, or 600 to 900, or 650 to 900, or 400 to 800, or 425 to 800, or 450 to 800, or 475 to 800, or 500 to 800, or 550 to 800, or 600 to 800, or 650 to 800, or 400 to 750, or 425 to 750, or 450 to 750, or 475 to 750, or 500 to 750, or 550 to 750, each in psig.
Desirably, the average residence time of gases in the gasifier reactor are very short to increase throughput. Since the gasifier is operated at high temperature and pressure, substantially complete conversion of the feedstock to gases can occur in a very short time frame. The average residence time of the gases in the gasifier can be as short as less than 30 seconds, or not more than 25 seconds, or not more than 20 seconds, or not more than 15 seconds, or not more than 10 seconds, or not more than 7 seconds. Desirably, the average residence time of gases in all zones designed for conversion of feedstock material to gases is also quite short, e.g. less than 25 seconds, or not more than 15 seconds, or not more than 10 seconds, or not more than 7 seconds, or not more than 4 seconds. In these time frames, at least 85 wt. %, or at least or more than 90 wt. %, or at least 92 wt. %, or at least 94 wt. % of the solids in the feedstock can be converted to gases (substances which remain as a gas if the gas stream were cooled to 25° C. and 1 atm) and liquid (substances which are in liquid state if the gas stream is cooled to 25° C. and 1 atm such as water), or more than 93 wt. %, or more than 95 wt. %, or more than 96 wt. %, or more than 97 wt. %, or more than 98 wt. %, or more than 99 wt. %, or more than 99.5 wt. %.
A portion of ash and/or char in the gasifier can be entrained in the hot raw torrefied textile derived syngas stream leaving the gasification reaction zone. Ash particles in the raw torrefied textile derived syngas stream within the gasifier are particles which have not reached the melting temperature of the mineral matter in the solid fuel. Slag is substantially molten ash or molten ash which has solidified into glassy particles and remains within the gasifier. Slag is molten until quenched and then form beads of fused mineral matter. Char are porous particles that are devolatilized and partially combusted (incompletely converted) fuel particles. The particulate matter gathered in the bottom part of the gasifier, or the quench zone, are predominately slag (e.g. above 80 wt. % slag) and the remainder is char and ash. Desirably, only trace amounts of tar or no tar is present in the gasifier, or in the quench zone, or in the gasification zone, or present in the hot raw torrefied textile derived syngas within the gasifier, or present in the raw torrefied textile derived syngas discharged from the gasifier (which can be determined by the amount of tar condensing from the torrefied textile derived syngas stream when cooled to a temperature below 50° C.). Trace amounts are less than 0.1 wt. % (or less than 0.05 wt. % or less than 0.01 wt. %) of solids present in the gasifier, or less than 0.05 volume %, or not more than 0.01 vol %, or not more than 0.005 vol %, or not more than 0.001 volume %, or not more than 0.0005 vol %, or not more than 0.0001 vol % in the raw torrefied textile derived syngas stream discharged from the gasifier.
In another embodiment, the process does not increase the amount of tar to a substantial extent relative to the same process except replacing the torrefied textiles with the same amount and type of solid fossil fuel used in the feedstock composition containing the torrefied textiles.
The quantity of tar generated in the process with the feedstock containing the torrefied textiles is less than 10% higher, or less than 5% higher, or less than 3% higher, or less than 2% higher, or not higher at all, than the amount of tar generated with the same feedstock replacing the torrefied textiles with the same solid fossil fuel under the same conditions.
To avoid fouling downstream equipment from the gasifier (scrubbers, CO/H2 shift reactors, acid gas removal, chemical synthesis), and the piping in-between, the torrefied textile derived syngas stream should have low or no tar content. The torrefied textile derived syngas stream as discharged from the gasifier desirably contains no or less than 4 wt. %, or less than 3 wt. %, or not more than 2 wt. %, or not more than 1 wt. %, or not more than 0.5 wt. %, or not more than 0.2 wt. %, or not more than 0.1 wt. %, or not more than 0.08 wt. %, or not more than 0.05 wt. %, or not more than 0.02 wt. %, or not more than 0.01 wt. %, or nor more than 0.005 wt. % tar, based on the weight of all condensable solids in the torrefied textile derived syngas stream. For purposes of measurement, condensable solids are those compounds and elements that condense at a temperature of 15° C./1 atm.
In another embodiment, the tar present, if at all, in the torrefied textile derived syngas stream discharged from the gasifier is less than 10 g/m3 of the torrefied textile derived syngas discharged, or not more than 9 g/m3, or not more than 8 g/m3, or not more than 7 g/m3, or not more than 6 g/m3, or not more than 5 g/m3, or not more than 4 g/m3, or not more than 3 g/m3, or not more than 2 g/m3, and desirably not more than 1 g/m3, or not more than 0.8 g/m3, or not more than 0.75 g/m3, or not more than 0.7 g/m3, or not more than 0.6 g/m3, or not more than 0.55 g/m3, or not more than 0.45 g/m3, or not more than 0.4 g/m3, or not more than 0.3 g/m3, or not more than 0.2 g/m3, or not more than 0.1 g/m3, or not more than 0.05 g/m3, or not more than 0.01 g/m3, or not more than 0.005 g/m3, or not more than 0.001 g/m3, or not more than 0.0005 g/m3, in each case Normal (15° C./1 atm). For purposes of measurement, the tars are those tars that would condense at a temperature of 15° C./1 atm, and includes primary, secondary and tertiary tars, and are aromatic organic compounds and other than ash, char, soot, or dust. Examples of tar products include naphthalenes, cresols, xylenols, anthracenes, phenanthrenes, phenols, benzene, toluene, pyridine, catechols, biphenyls, benzofurans, benzaldehydes, acenaphthylenes, fluorenes, naphthofurans, benzanthracenes, pyrenes, acephenanthrylenes, benzopyrenes, and other high molecular weight aromatic polynuclear compounds. The tar content can be determined by GC-MSD.
In another embodiment, the tar yield of the gasifier (combination of tar in torrefied textile derived syngas and tar in reactor bottoms and in or on the ash, char, and slag) is not more than 4 wt. %, or not more than 3 wt. %, or not more than 2.5 wt. %, or not more than 2.0 wt. %, or not more than 1.8 wt. %, or not more than 1.5 wt. %, or not more than 1.25 wt. %, or not more than 1 wt. %, or not more than 0.9 wt. %, or not more than 0.8 wt. %, or not more than 0.7 wt. %, or not more than 0.5 wt. %, or not more than 0.3 wt. %, or not more than 0.2 wt. %, or not more than 0.1 wt. %, or not more than 0.05 wt. %, or not more than 0.01 wt. %, or not more than 0.005 wt. %, or not more than 0.001 wt. %, or not more than 0.0005 wt. %, or not more than 0.0001 wt. %, based on the weight of solids in the feedstock composition fed to the gasification zone.
The amount of gasifier char (or incompletely converted carbon in the feedstock left over after gasification is complete) generated by conversion of the carbon sources in the feedstock composition is not more than 15 wt. %, or not more than 12 wt. %, or not more than 10 wt. %, or not more than 8 wt. %, or not more than 5 wt. %, or not more than 4.5 wt. %, or not more than 4 wt. %, or not more than 3.5 wt. %, or not more than 3 wt. %, or not more than 2.8 wt. %, or not more than 2.5 wt. %, or not more than 2.3 wt. %, or not more than 4.5 wt. %, or not more than 4.5 wt. %, or not more than 4.5 wt. %.
In the process, char can be recycled back to the feedstock composition to the gasifier containing the torrefied textiles. In another embodiment, the efficiencies and features can be obtained without recycling char back to the gasification zone.
The total amount of gasifier char (or incompletely converted carbon in the feedstock after gasification is completed) and slag (if any) generated in the gasifier or by the process is desirably not more than 20 wt. %, or not more than 17 wt. %, or not more than 15 wt. %, or not more than 13 wt. %, or not more than 10 wt. %, or not more than 9 wt. %, or not more than 8.9 wt. %, or not more than 8.5 wt. %, or not more than 8.3 wt. %, or not more than 8 wt. %, or not more than 7.9 wt. %, or not more than 7.5 wt. %, or not more than 7.3 wt. %, or not more than 7 wt. %, or not more than 6.9 wt. %, or not more than 6.5 wt. %, or not more than 6.3 wt. %, or not more than 6 wt. %, or not more than 5.9 wt. %, or not more than 5.5 wt. %, in each case based on the weight of the solids in the feedstock composition. In another embodiment, the same values apply with respect to the total amount of ash, slag, and char generated in the gasifier or by the process, based on the weight of the solids in the feedstock composition. In another embodiment, the same values apply with respect to the total amount of ash, slag, and char generated in the gasifier or by the process, based on the weight of the solids in the feedstock composition. In another embodiment, the same values apply with respect to the total amount of ash, slag, char and tar generated in the gasifier or by the process, based on the weight of the solids in the feedstock composition.
The raw syngas stream flows from the gasification zone to a quench zone at the bottom of the gasifier where the slag and raw syngas stream are cooled, generally to a temperature below 550° C., or below 500° C., or below 450° C. The quench zone contains water in a liquid state. The hot syngas from the gasification zone may be cooled by directly contacting the syngas stream with liquid water. The syngas stream can be bubbled through the pool of liquid water, or merely contact the surface of the water pool. In addition, the hot syngas stream may be cooled in a water jacketed chamber having a height that above the top surface of the water pool to allow the hot syngas to both contact the water pool and be cooled in the water jacketed chamber. Molten slag is solidified by the quench water and most of the ash, slag and char are transferred to the water in the quench tank. The partially cooled gas stream, having passed through the water in the quench zone, may be then discharged from the gasifier as a raw syngas stream and passed through a water scrubbing operation to remove any remaining entrained particulate matter.
The pressure in the quench zone is substantially the same as the pressure in the gasification zone located above the water level in the gasifier, and a portion of the quench water and solids at the bottom of the quench tank is removed by way of a lock hopper system. A stream of quench water carrying fine particles exits the gasifier quench zone in response to a liquid level controller and can be directed to a settler. The solids and water from the lock hopper may then flow into a water sump or settler where optionally the coarse particulate solids may be removed by screens or filter thereby producing a dispersion of fine particulate solids.
The raw gas stream discharged from the gasification vessel includes such gasses as hydrogen, carbon monoxide, carbon dioxide and can include other gases such as methane, hydrogen sulfide and nitrogen depending on the fuel source and reaction conditions. Carbon dioxide in the raw torrefied textile derived syngas stream discharged from the gasification vessel is desirably present in an amount of less than 20 mole %, or less than 18 mole %, or less than 15 mole %, or less than 13 mole %, or not more than 11 mole %, based on all moles of gases in the stream. Some nitrogen and argon can be present in the raw torrefied textile derived syngas stream depending upon the purity of the fuel and oxygen supplied to the process.
In one embodiment or in combination with any of the mentioned embodiments, the raw torrefied textile derived syngas stream (the stream discharged from the gasifier and before any further treatment by way of scrubbing, shift, or acid gas removal) can have the following composition in mole % on a dry basis and based on the moles of all gases (elements or compounds in gaseous state at 25° C. and 1 atm) in the raw torrefied textile derived syngas stream:
The gas components can be determined by FID-GC and TCD-GC or any other method recognized for analyzing the components of a gas stream.
The molar hydrogen/carbon monoxide ratio is desirably at least 0.65, or at least 0.68, or at least 0.7, or at least 0.73, or at least 0.75, or at least 0.78, or at least 0.8, or at least 0.85, or at least 0.88, or at least 0.9, or at least 0.93, or at least 0.95, or at least 0.98, or at least 1.
The total amount of hydrogen and carbon monoxide relative to the total amount of torrefied textile derived syngas discharged from the gasifier on a dry basis is high, on the order of greater than 70 mole %, or at least 73 mole %, or at least 75 mole %, or at least 77 mole %, or at least 79 mole %, or at least 80 mole %, based on the syngas discharged.
In another embodiment, the dry torrefied textile derived syngas production expressed as gas volume discharged from the gasifier per kg of solid fuel (e.g. torrefied textile char and coal) charged to all locations on the gasifier is at least 1.7, or at least 1.75, or at least 1.8, or at least 1.85, or at least 1.87, or at least 1.9, or at least 1.95, or at least 1.97, or at least 2.0, in each case as N m3 gas/kg solids fed.
The carbon conversion efficiency in one pass is good and can be calculated according to the following formula:
The carbon conversion efficiency in the process in one pass can be at least 70%, or at least 73%, or at least 75%, or at least 77%, or at least 80%, or at least 82%, or at least 85%, or at least 88%, or at least 90%, or at least 93%.
In another embodiment, the raw torrefied textile derived syngas stream contains particulate solids in an amount of greater than 0 wt. % up to 30 wt. %, or greater than 0 wt. % up to 10 wt. %, or greater than 0 wt. % up to 5 wt. %, or greater than 0 wt. % up to 1 wt. %, or greater than 0 wt. % up to 0.5 wt. %, or greater than 0 wt. % up to 0.3 wt. %, or greater than 0 wt. % up to 0.2 wt. %, or greater than 0 wt. % up to 0.1 wt. %, or greater than 0 wt. % up to 0.05 wt. %, each based on the weight of solids in the feedstock composition. The amount of particulate solids in this case is determined by cooling the torrefied textile derived syngas stream to a temperature of below 200° C., such as would occur in a scrubbing operation.
The cold gas efficiency of the process using the torrefied textiles/solid fossil fuel as a percent can be calculated as:
The cold gas efficiency is at least 60%, or at least 65%, or at least 66%, or at least 67%, or at least 68%, or at least 69%, or desirably at least 70%, or at least 71%, or at least 72%, or at least 73%, or at least 74%, or at least 75%, or at least 76%, or at least 77%, or at least 78%, or at least 79%.
In one embodiment or in combination with any of the mentioned embodiments, hydrogen and carbon monoxide from the raw torrefied textile derived syngas stream discharged from the gasifier or from a scrubbed or purified torrefied textile derived syngas stream are not recycled or recirculated back to a gasification zone in a gasifier. Desirably, carbon dioxide from the raw torrefied textile derived syngas stream discharged from the gasifier or from a scrubbed or purified torrefied textile derived syngas stream is not recycled or recirculated back to a gasification zone in a gasifier. Desirably, no portion of the torrefied textile derived syngas stream discharged from the gasifier or from a scrubbed or purified torrefied textile derived syngas stream is recycled or recirculated back to a gasification zone in a gasifier. In another embodiment, no portion of the torrefied textile derived syngas discharged from the gasifier is used to heat the gasifier. Desirably, no portion of the torrefied textile derived syngas made in the gasifier is burned to dry the solid fossil fuel.
The feedstock stream is gasified with the oxidizer such as oxygen desirably in an entrained flow reaction zone under conditions sufficient to generate a molten slag and ash. The molten slag and ash are separated from the syngas and quench cooled and solidified. In a partial oxidation reactor, the coal/size reduced textiles/water mixture is injected with oxygen and the coal/rubber will react with oxygen to generate a variety of gases, including carbon monoxide and hydrogen (syngas). The molten slag and unreacted carbon/size reduced textiles accumulate into a pool of water in the quench zone at the bottom part of the gasifier to cool and solidify these residues.
In one embodiment or in combination with any of the mentioned embodiments, the gasification process is under slagging conditions, and the slag is discharged from the gasifier as a solid. Slag is cooled and solidified within the gasifier in a quench zone within the shell of the gasifier, and is discharged from the gasifier shell as a solid. The same applies to ash and char. These solids discharged from the gasifier are accumulated into a lock hopper which can then be emptied. The lock hopper is generally isolated from the gasifier and the quench zone within the gasifier.
The process can be practiced on an industrial scale and on a scale sufficient to provide torrefied textile derived syngas as a raw material to make chemicals on an industrial scale. At least 300 tons/day, or at least 500 t/d, or at least 750 t/d, or at least 850 t/d, or at least 1000 t/d, or at least 1250 t/d, and desirably at least 1500 t/d, or at least 1750 t/d, or even at least 2000 t/d of solids can be fed to the gasifier. The gasifier is desirably not designed to be mobile and is fixed to and above the ground, and desirably stationary during operations.
The torrefied textile derived syngas compositional variability produced by gasifying the feedstock containing the solid fossil fuel and torrefied textiles is quite low over time. In one embodiment or in combination with any of the mentioned embodiments, the compositional variability of the torrefied textile derived syngas stream is low during a time period when the feedstock composition contains the solid fossil fuel and the torrefied textiles. The compositional variability of the torrefied textile derived syngas stream can be determined by taking at least 6 measurements of the concentration of the relevant gaseous compound in moles in equal time sub-periods across the entire time that the feedstock solids content is consistent and contain torrefied textiles, such entire time not to exceed 12 days. The mean concentration of the gaseous compound is determined over the 6 measurements. The absolute value of the difference between the number farthest away from the mean and the mean number is determined and divided into the mean number×100 to obtain a percent compositional variability.
The compositional variability of any one of:
In another embodiment, variability of the torrefied textile derived syngas stream generated by all feedstock sources containing fuel (liquid, gas, or solid) at least one of which contains torrefied textiles (“textile case”) is compared to a benchmark variability of the torrefied textile derived syngas stream generated from the same feedstocks without the torrefied textiles and the torrefied textiles amount is replaced by a corresponding amount of the same fuel (“base case”) and processed under the same conditions to obtain a % switching variability, or in other words, the torrefied textile derived syngas variability generated by switching between the two feedstock compositions. The torrefied textile derived syngas variation of the textile case can be less than, or no different than, or if higher can be similar to the torrefied textile derived syngas variation of the base case. The time periods to determine variations is set by the shorter of a 12-day period or the time that torrefied textiles are present in the feedstock composition, and that time period is the same time period used for taking measurements in the solid fossil fuels only case. The measurements for the base case are taken within 1 month before feeding a feedstock containing torrefied textiles to the gasifier or after the expiration of feeding a feedstock containing torrefied textiles to the gasifier. The variations in torrefied textile derived syngas composition made by each of the streams is measured according to the procedures states above. The torrefied textile derived syngas variability from the textile case is less than, or the same as, or not more than 15%, or not more than 10%, or not more than 5%, or not more than 4%, or not more than 3%, or not more than 2%, or not more than 1%, or not more than 0.5%, or not more than 0.25% of the torrefied textile derived syngas variability of the base case. This can be calculated as:
where % SV is percent torrefied textile derived syngas switching variability on one or more measured ingredients in the torrefied textile derived syngas composition; and
Vt is the torrefied textile derived syngas compositional variability using feedstock(s) containing torrefied textiles and a second source of fuel together in one stream or in separate feedstock streams; and
Vb is the torrefied textile derived syngas compositional variability using the base case streams (same type and amount of fuel feedstock without the torrefied textiles), where the solids concentration is the same in both cases, the fuel is the same in both cases other than the presence of absence of the torrefied textiles, and the feedstocks are gasified under the same conditions, other than temperature fluctuations which may autogeneously differ as a result of having torrefied textiles in the feedstock, and the variabilities are with respect to any one or more of the torrefied textile derived syngas compounds identified above. In the event that the % SV is negative, then the torrefied textile derived syngas textile case variability is less than the torrefied textile derived syngas base case.
In another embodiment, the ratio of carbon monoxide/hydrogen generated from one or more streams that contain torrefied textiles and other fuel sources (textile case) is similar to the carbon monoxide/hydrogen ratio generated from the same stream(s) replacing the torrefied textiles content with the same fuel (base case). The carbon monoxide/hydrogen ratio between the textile case and the base case can be within 10%, or within 8%, or within 6%, or within 5%, or within 4%, or within 3%, or within 2%, or within 1.5%, or within 1%, or within 0.5% of each other. The percentage similarity can be calculated by taking the absolute value of the differences in CO/H2 ratios between the textile case and the base case and dividing that number into the CO/H2 ratio of the base case×100.
In another embodiment, the amount of CO2 generated from a textile case is similar to the amount of carbon dioxide generated from a base case. The process can be conducted such that the amount of CO2 generated from textile case is no more than 25%, or no more than 20%, or no more than 15%, or no more than 13%, or no more than 10%, or no more than 8%, or no more than 7%, or no more than 6%, or no more than 5%, or no more than 4%, or no more than 3%, or no more than 2%, or no more than 1%, or no more than 0.75%, or no more than 0.5%, or nor more than 0.25%, or no more than 0.15%, or no more than 0.1% greater than the amount of carbon dioxide generated from a base case. The percentage similarity can be calculated by subtracting the amount of CO2 generated in a torrefied textile derived syngas stream using the textile case from the amount of CO2 generated in a torrefied textile derived syngas stream using the base case, and dividing that number by the CO2 generated in a torrefied textile derived syngas stream using the base case.
In another embodiment, there is provided a continuous process for feeding a gasifier with a continuous feedstock composition containing solid fossil fuel and intermittently feeding a feedstock composition containing torrefied textiles and solid fossil fuel, while maintaining a negative, zero, or minimal torrefied textile derived syngas compositional switching variability over time frames that includes feedstocks with and without the torrefied textiles using torrefied textile derived syngas produced using feedstocks without the torrefied textiles as the benchmark. For example, switching frequency between feedstocks without the torrefied textiles (base case) and the identical feedstocks except replacing a portion of the fuel with the torrefied textiles (textile case) can be at least 52×/yr, or at least 48×/yr, or at least 36×/yr, or at least 24×/yr, or at least 12×/yr, or at least 6×/yr, or at least 4×/yr, or at least 2×/yr, or at least 1×/yr, or at least 1×/2 yr, and up to 3×/2 yr, without incurring a torrefied textile derived syngas switching variability beyond the percentages express above. One switch is counted as the number of times in a period that the textile case is used.
To illustrate an example of a slurry fed slagging entrained flow process, reference made to
The grinder can also be equipped with a classifier to remove particles above the target maximum particle size. An example of a classifier is a vibrating sieve or a weir spiral classifier.
The coal grinder zone (which includes at least the grinding equipment, feed mechanisms to the grinder, and any classifiers) is a convenient location for combining torrefied textiles particles through line 4 to the coal. The desired amount of coal and torrefied textiles can be combined onto a weigh belt or separately fed though their dedicated weigh belts that feed the grinding apparatus. The water slurry of ground coal and torrefied textiles is discharged through line 5 and pumped into a storage/charge tank 6 that is desirably agitated to retain a uniform slurry suspension. Alternatively, or in addition to the grinder 2 location, torrefied textiles can be added into the charge/storage tank 6 through line 7, particularly when this tank is agitated.
The feedstock composition is discharged from tank 6 directly or indirectly to the gasifier 9 through line 8 into the injector 10 in which the coal/rubber/water slurry is co-injected with an oxygen-rich gas from line 11 into the gasification reaction zone 12 where gasification takes place. The injector 10 may optionally be cooled with a water line 13 feeding a jacket on the injector and discharged through line 14. After start-up and in a steady state, the reaction in the reaction zone 12 takes place spontaneously at an autogenous temperature in the ranges noted above, e.g. 1200° C. to 1600° C. and at a pressure in the ranges note above, e.g. 10-100 atmospheres. The gaseous reaction products of the partial oxidation reaction include carbon monoxide, hydrogen, with lesser amounts of carbon dioxide and hydrogen sulfide. Molten ash, unconverted coal or rubber, and slag may also be present in the reaction zone 12.
The gasifier 9 is illustrated in more detail in
Turning back to
The temperature of the raw torrefied textile derived syngas stream exiting the gasification vessel through line 16 can be within a range of 150° C. to 700° C., or from 175° C. to 500° C. Desirably, the temperature of the raw torrefied textile derived syngas discharged from the gasifier is not more than 500° C., or less than 400° C., or not more than 390° C., or not more than 375° C., or not more than 350° C., or not more than 325° C., or not more than 310° C., or not more than 300° C., or not more than 295° C., or not more than 280° C., or not more than 270° C. The temperature of the raw torrefied textile derived syngas exiting the gasification vessel is substantially reduced from the temperature of the reaction product gases within the reaction zone. The temperature reduction between the gasification zone gas temperature (or alternatively all reaction zones if more than one stage is used) and the raw torrefied textile derived syngas temperature discharged from the gasifier vessel can be at least 300° C., or at least 400° C., or at least 450° C., or at least 500° C., or at least 550° C., or at least 600° C., or at least 650° C., or at least 700° C., or at least 800° C., or at least 900° C., or at least 1000° C., or at least 1050° C., or at least 1100° C.
As shown in
As shown in
Solids, including unconverted particulate coal, settle by gravity from the water in settling tank 24 and are drawn off through line 27 as a concentrated slurry of ash, unconverted coal and soot in water. This slurry may be optionally be recycled to grinding zone 2 via line 28. If desired, a portion of the slurry from line 27 may be diverted through line 29 into mix tank 6 to adjust the concentration of solids in the water-coal-rubber slurry feed stream charged to the gasifier. Also, as shown in
As shown in
Alternatively, or in addition, the quench water through line 33 feeding the quench water zone can supplied from a torrefied textile derived syngas scrubber downstream from the gasifier as shown in
If desired, high temperature surfactants can be added to the quench water directly into the quench zone/chamber. Examples of such surfactants include any one of the surfactants mentioned above to stabilize the feedstock composition, such as ammonium lignosulfonate or an equivalent surfactant which is thermally stable at temperatures of about 300° F. to about 600° F. Other surfactants include organic phosphates, sulfonates and amine surfactants. The surfactants are used to establish a stable suspension of soot in the water at the bottom of the quench chamber, where the soot concentration can be at least 1 wt. %, or in the range of about 3.0 weight % to about 15.0 weight %, each based on the weight of the water in the quench chamber. The concentration of active surfactants in the bottom of the quench zone can vary from about 0.01 weight % to about 0.30 weight %.
Also, as illustrated in
As shown in
In an alternative embodiment as shown in
In an alternate embodiment, as shown in
An example of the operation of the gasifier and scrubber is illustrated in
The resulting mixture of gas and water formed in contactor 55 is directed into scrubber 59 through a dip leg 60 which extends downwardly into the lower portion of scrubber 59. The gas stream from contactor 55 also carries entrained solid particles of unconsumed fuel or ash. A body of water is maintained in the scrubber 59, the level of which may be controlled in any suitable manner, for example by means of a liquid level controller 61, shown diagrammatically. The dip leg 60 discharges the mixture of water and gas below the level of water contained in the scrubber 59. By discharging the mixture of gas and water through the open end of dip leg 60 into intimate contact with water, solid particles from the gas stream are trapped in the water.
Scrubber 59 is suitably in the form of a tower having an optionally packed section 62 above the point of entry of the gas stream from contactor 55. Water from line 63 is introduced into scrubber 59 above the level of the packing material 62. In packed section 62, the gas stream is intimately contacted with water in the presence of suitable packing material, such as ceramic shapes, effecting substantially complete removal of solid particles from the gas stream. Product gas, comprising carbon monoxide and hydrogen and containing water vapor, atmospheric gases, and carbon dioxide, is discharged from the upper end of scrubber 59 through line 64 at a temperature corresponding to the equilibrium vaporization temperature of water at the pressure existing in scrubber 59. Clean torrefied textile derived syngas from line 64 may be further processed, for example, for the production of higher concentrations of hydrogen by water-gas shift reaction and suitable downstream purification to remove sulfur.
Water from the lower portion of scrubber 59 is passed by pump 65 through line 56 to injectors 56 and 57. Clarified water from settler 66 also may be supplied to line 56 by pump 67 through line 68. Water is withdrawn from scrubber 59 by pump 69 and passed through valve 70 responsive to liquid level control 61 on the scrubber and passed into quench zone 71 via line 72 to control the liquid level in scrubber 59.
Any heavy solid particles removed from the gas stream in the dip leg 60 settling into water slurry are collected the water bath at the bottom of the scrubber 59 and discharged at the bottom leg 73 at periodic intervals through line 74 as controlled by valve 75.
Any suitable scrubber design can be used in the process. Other scrubber designs include a tray type contacting tower wherein the gases are counter currently contacted with water. Water is introduced into the scrubber at a point near the top of the tower.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2020/029457 | 4/23/2020 | WO | 00 |
| Number | Date | Country | |
|---|---|---|---|
| 62838964 | Apr 2019 | US | |
| 62838962 | Apr 2019 | US | |
| 62838965 | Apr 2019 | US | |
| 62838963 | Apr 2019 | US |
