Patent Application
20150005551
The present technology relates generally to the processing of adulterated biorenewable feedstocks for manufacture of high quality hydroprocessed products. More particularly, and not by way of limitation, the present technology provides a method to produce a high quality hydroprocessed product with less adulterants than the feed stream.
Biomass is a renewable alternative to fossil raw materials in the production of fuels and chemicals. The increase of renewable products and biofuels production is part of the government's strategy of sustainability, improving energy security and reducing greenhouse gas emissions.
However, there is the potential for many sources of biomass to become contaminated with manufactured adulterants due to handling and processing. These adulterants can negatively impact both the processibility of the biomass feedstock and the performance of the finished products. Therefore, a great deal of time and expense has been invested in pretreatment of biomass to remove potential adulterants as well as native components that can negatively impact production (e.g. phosphorus, metals).
In one aspect, a method is provided involving contacting a feed stream comprising a biorenewable feedstock and adulterants with a catalyst in a fixed bed hydroprocessing reactor to produce a hydroprocessed product with less adulterants than the feed stream; wherein the fixed bed reactor is at a temperature less than about 750° F. (400° C.) and the fixed bed hydroprocessing reactor is at a pressure from about 200 psig (13.8 barg) to about 4,000 psig (275 barg).
In some embodiments, the hydroprocessed product comprises at least 80 wt % paraffins falling within the range of C11 to C24, where the paraffins comprise C16 and C18 paraffins; from about 0.1 wt % to about 7.0 wt % cycloparaffins; and from about 0.001 wt % to about 1.0 wt % aromatics. In some embodiments of such a hydroprocessed product, the hydroprocessed product is suitable for use as a diesel fuel.
In some embodiments, the adulterants include polymers, monomers of polymers, drugs, pesticides, polymer additives, food preservatives, or mixtures of any two or more thereof. In some embodiments, the adulterants comprise acrylonitrile butadiene styrene thermoplastic, polyacrylate rubber, ethylene-acrylate rubber, polyester urethane, bromo isobutylene isoprene rubber, polybutadiene rubber, chloro isobutylene isoprene rubber, polychloroprene, chlorosulphonated polyethylene, epichlorohydrin, ethylene propylene rubber, ethylene propylene diene monomer, polyether urethane, tetrafluoroethylene/propylene rubbers, perfluorocarbon elastomers, fluoroelastomer, fluoro silicone, fluorocarbon rubber, high density polyethylene, hydrogenated nitrile butadiene, polyisoprene, isobutylene isoprene rubber, low density polyethylene, polyethylene terephthalate, ethylene vinyl acetate, acrylonitrile butadiene, polyethylene, polyisobutene, polypropylene, polystyrene, poly vinyl choloride, polyvinylidene chloride, polyurethane, styrene butadiene, styrene ethylene butylene styrene copolymer, polysiloxane, vinyl methyl silicone, acrylonitrile butadiene carboxy monomer, styrene butadiene carboxy monomer, thermoplastic polyether-ester, styrene butadiene block copolymer, styrene butadiene carboxy block copolymer, polyesters, polyamides, polyacetals, or mixtures of any two or more thereof. In some embodiments, the adulterants include polyvinylidene chloride.
In some embodiments, the adulterants comprise a polymer additive. In some embodiments, the adulterants comprise acetamide, benzyl benzoate, benzyl butyl phthalate, bis(2-ethylhexyl)adipate, bis(2-ethylhexyl)phthalate, bisphenol A, bisphenol AF, 1,2-cyclohexane dicarboxylic acid diisononyl ester, dibutyl phthalate, dibutyl sebacate, diethylene glycol dinitrate, diisobutyl phthalate, diisodecyl phthalate, diisononyl phthalate, dimethyl methylphosphonate, 2,4-dinitrotoluene, dioctyl adipate, diisodecyl adipate, dioctyl terephthalate, dipropylene glycol, epoxidized soybean oil, ethyl butyrate, ethylene carbonate, furoin, neopentyl glycol, phthalate, polybutene, polycaprolactone, propylene carbonate, triacetin, tributyl phosphate, tricresyl phosphate, triethyl phosphate, triethylene glycol dinitrate, trimethylolethane trinitrate, asbestine, barium borate, brominated flame retardant, bromoform, calcium borate, chlorendic acid, decabromodiphenyl ether, 1,2-dibromoethane, dimethyl chlorendate, dimethyl methylphosphonate, heptazine, hexabromocyclododecane, octabromodiphenyl ether, pentabromodiphenyl ether, polybrominated biphenyl, polybrominated diphenyl ethers, polychlorinated biphenyl, tetrabromobisphenol A, tris(2,3-dibromopropyl) phosphate, tris(2-chloroethyl) phosphate, zinc borate, or mixtures of any two or more thereof.
In some embodiments, the adulterants include pesticides. In some embodiments, the adulterants include acephate, acetochlor, aldicarb, atrazine, bifenthrin, chloropicrin, chlorothalonil, chlorphyrifos, 2,4-dichlorophenoxyacetic acid, dichloropropene, dimethenamid, diuron, ethephon, fenoxycarb, glyphosate, 2-methyl-4-chlorophenoxyacetic acid, metham sodium, metham potassium, methyl bromide, metolachlor, paraquat, pendimethalin, propanil, simazine, trifluralin, or mixtures of any two or more thereof. In some embodiments, the adulterants include a polymer and a polymer additive.
In some embodiments, from about 100 to about 15,000 reactor volumes of biorenewable feedstock are processed prior to shutdown of the fixed bed hydroprocessing reactor. In some embodiments, the liquid hourly space velocity of the feed stream through the fixed bed hydroprocessing reactor is from about 0.2 hr−1 to about 10.0 hr−1. In some embodiments, the reactor comprises a hydrotreatment catalyst.
In some embodiments, the biorenewable feedstock comprises animal fats, animal oils, plant fats, plant oils, vegetable fats, vegetable oils, or greases. In some embodiments, the biorenewable feedstock comprises animal fats, poultry oil, soybean oil, canola oil, rapeseed oils, palm oil, palm kernel oil, jatropha oil, castor oil, camelina oil, algae oil, seaweed oil, halophile oils, rendered fats, restaurant greases, brown grease, yellow grease, waste industrial frying oils, fish oils, tall oil, or tall oil fatty acids. In some embodiments, the biorenewable feedstock comprises animal fats, restaurant greases, brown grease, yellow grease, or waste industrial frying oils. In some embodiments, the biorenewable feedstock comprises the fatty acid distillate from vegetable oil deodorization.
In some embodiments, the hydroprocessed product is suitable as a diesel fuel, a diesel fuel additive, a diesel fuel blendstock, a turbine fuel, a turbine fuel additive, a turbine fuel blendstock, an aviation fuel, an aviation fuel additive, or an aviation fuel blendstock. In some embodiments, the hydroprocessed product is fractionated to provide a middle distillate fraction. In some embodiments, the middle distillate fraction is suitable for use as a diesel fuel.
In some embodiments, the feed stream further comprises a diluent and the volume ratio of diluent to biorenewable feedstock falls within the range from about 0.5:1 to about 20:1.
Various embodiments are described hereinafter. It should be noted that the specific embodiments are not intended as an exhaustive description or as a limitation to the broader aspects discussed herein. One aspect described in conjunction with a particular embodiment is not necessarily limited to that embodiment and can be practiced with any other embodiment(s).
As used herein, “about” will mean up to plus or minus 10% of the particular term.
The use of the terms “a” and “an” and “the” and similar referents in the context of describing the elements (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the embodiments and does not pose a limitation on the scope of the claims unless otherwise stated. No language in the specification should be construed as indicating any non-claimed element as essential.
As used herein, “alkyl” groups include straight chain and branched alkyl groups having from 1 to about 22 carbon atoms. As employed herein, “alkyl groups” include cycloalkyl groups as defined below. Alkyl groups may be substituted or unsubstituted. Examples of straight chain alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples of branched alkyl groups include, but are not limited to, isopropyl, sec-butyl, t-butyl, neopentyl, and isopentyl groups.
Cycloalkyl groups are cyclic alkyl groups such as, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. In some embodiments, the cycloalkyl group has 3 to 8 ring members, whereas in other embodiments the number of ring carbon atoms range from 3 to 5, 6, or 7. Cycloalkyl groups further include polycyclic cycloalkyl groups such as, but not limited to, norbornyl, adamantyl, bornyl, camphenyl, isocamphenyl, and carenyl groups, and fused rings such as, but not limited to, decalinyl, and the like. Cycloalkyl groups also include rings that are substituted with straight or branched chain alkyl groups as defined above.
The term “aromatics” as used herein is synonymous with “aromates” and means both cyclic aromatic hydrocarbons that do not contain heteroatoms as well as heterocyclic aromatic compounds. The term includes monocyclic, bicyclic and polycyclic ring systems. The term also includes aromatic species with alkyl groups and cycloalkyl groups. Thus, aromatics include, but are not limited to, benzene, azulene, heptalene, phenylbenzene, indacene, fluorene, phenanthrene, triphenylene, pyrene, naphthacene, chrysene, anthracene, indene, indane, pentalene, and naphthalene, as well as alkyl and cycloalkyl substituted variants of these compounds. In some embodiments, aromatic species contains 6-14 carbons, and in others from 6 to 12 or even 6-10 carbon atoms in the ring portions of the groups. The phrase includes groups containing fused rings, such as fused aromatic-aliphatic ring systems (e.g., indane, tetrahydronaphthene, and the like).
“Oxygenates” as used herein means carbon-containing compounds containing at least one covalent bond to oxygen. Examples of functional groups encompasses by the term include, but are not limited to, carboxylic acids, carboxylates, acid anhydrides, aldehydes, esters, ethers, ketones, and alcohols, as well as heteroatom esters and anhydrides such as phosphate esters and phosphate anhydrides. Oxygenates may also be oxygen containing variants of aromatics, cycloparaffins, and paraffins as described herein.
The term “paraffins” as used herein means non-cyclic, branched or unbranched alkanes. An unbranched paraffin is an n-paraffin; a branched paraffin is an iso-paraffin. “Cycloparaffins” are cyclic, branched or unbranched alkanes.
The term “paraffinic” as used herein means both paraffins as defined above as well as predominantly hydrocarbon chains possessing regions that are alkane, either branched or unbranched, with mono- or di-unsaturation (i.e. one or two double bonds), halogenation from about 30 wt % to about 70 wt %, or where the hydrocarbon is both unsaturated and halogenated. However, the term does not describe a halogen on a carbon involved in a double bond. The term also encompasses alkyl alcohols, alkyl carboxylic acids, alkyl aldehydes, alkyl ketones, alkyl esters, and alkyl ethers.
Adulterants as used herein refer to human synthesized compounds and substances that may become associated with a biorenewable feedstock. Examples of adulterants include, but are not limited to, polymers, oligomers, additives associated with polymers and oligomers, (e.g. plasticizers; inorganic additives incorporated into a polymer), residual monomers or plasticizers incorporated into the polymers and oligomers, pesticides (also known as biocides, and including but not limited to insecticides, fumigants, fungicides, herbicides, and plant growth regulators), preservatives, drugs, man-made halogenated organics, and man-made organometallic complexes.
Hydroprocessing as used herein describes the various types of catalytic reactions that occur in the presence of hydrogen without limitation. Examples of the most common hydroprocessing reactions include, but are not limited to, hydrogenation, hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrotreating (HT), hydrocracking (HC), aromatic saturation or hydrodearomatization (HDA), hydrodeoxygenation (HDO), decarboxylation (DCO), hydroisomerization (HI), hydrodewaxing (HD), hydrodemetallization (HDM), decarbonylation, methanation, and reforming. Depending upon the type of catalyst, reactor configuration, reactor conditions, and feedstock composition, multiple reactions can take place that range from purely thermal (i.e. do not require catalyst) to catalytic. In the case of describing the main function of a particular hydroprocessing unit, for example an HDO reaction system, it is understood that the HDO reaction is merely one of the predominant reactions that are taking place and that other reactions may also take place.
Decarboxylation (DCO) is understood to mean hydroprocessing of an organic molecule such that a carboxyl group is removed from the organic molecule to produce CO2, as well as decarbonylation which results in the formation of CO.
Pyrolysis is understood to mean thermochemical decomposition of carbonaceous material with little to no diatomic oxygen or diatomic hydrogen present during the thermochemical reaction. The optional use of a catalyst in pyrolysis is typically referred to as catalytic cracking, which is encompassed by the term as pyrolysis, and is not be confused with hydrocracking
Hydrotreating (HT) involves the removal of elements from groups 3, 5, 6, and/or 7 of the Periodic Table from organic compounds. Hydrotreating may also include hydrodemetallization (HDM) reactions. Hydrotreating thus involves removal of heteroatoms such as oxygen, nitrogen, sulfur, and combinations of any two more thereof through hydroprocessing. For example, hydrodeoxygenation (HDO) is understood to mean removal of oxygen by a catalytic hydroprocessing reaction to produce water as a by-product; similarly, hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) describe the respective removal of the indicated elements through hydroprocessing.
Hydrogenation involves the addition of hydrogen to an organic molecule without breaking the molecule into subunits. Addition of hydrogen to a carbon-carbon or carbon-oxygen double bond to produce single bonds are two nonlimiting examples of hydrogenation. Partial hydrogenation and selective hydrogenation are terms used to refer to hydrogenation reactions that result in partial saturation of an unsaturated feedstock. For example, vegetable oils with a high percentage of polyunsaturated fatty acids (e.g. linoleic acid) may undergo partial hydrogenation to provide a hydroprocessed product wherein the polyunsaturated fatty acids are converted to mono-unsaturated fatty acids (e.g. oleic acid) without increasing the percentage of undesired saturated fatty acids (e.g. stearic acid). While hydrogenation is distinct from hydrotreatment, hydroisomerization, and hydrocracking, hydrogenation may occur amidst these other reactions.
Hydrocracking (HC) is understood to mean the breaking of a molecule's carbon-carbon bond to form at least two molecules in the presence of hydrogen. Such reactions typically undergo subsequent hydrogenation of the resulting double bond.
Hydroisomerization (HI) is defined as the skeletal rearrangement of carbon-carbon bonds in the presence of hydrogen to form an isomer. Hydrocracking is a competing reaction for most HI catalytic reactions and it is understood that the HC reaction pathway, as a minor reaction, is included in the use of the term HI. Hydrodewaxing (HDW) is a specific form of hydrocracking and hydroisomerization designed to improve the low temperature characteristics of a hydrocarbon fluid.
Hydrocarbonaceous is defined as being primarily composed of organic molecules containing carbon and hydrogen (i.e. hydrocarbon), but also include constituents of other organic molecules such as those comprised of atoms selected from groups 3 through group 7 of the Periodic Table (e.g. boron, nitrogen, oxygen, phosphorus, sulfur, and/or halogens).
“Aviation fuel” as used herein includes both jet fuel and aviation gasoline. Jet fuel also goes by the term aviation turbine fuel.
“Turbine fuel” as used herein includes, but is not limited to, a fuel combusted with compressed air to drive an electric generator, or to power ships and tanks. Turbine fuels are typically diesel or kerosene boiling range fuels.
The present technology provides methods and systems for the hydroprocessing of feed streams that include adulterants, such that the hydroprocessed product produced has less adulterants. Accordingly, the present technology also provides compositions with a reduced level of adulterants. Contrary to the requirements for purified biorenewable feedstocks, the present technology allows for the processing of contaminated, and therefore cheaper, biorenewable feedstocks.
Thus, in an aspect, a method is provided that involves contacting a feed stream, where the feed stream includes a biorenewable feedstock and adulterants, with a catalyst in a fixed bed hydroprocessing reactor to produce a hydroprocessed product with less adulterants than the feed stream. The fixed bed hydroprocessing reactor is at a temperature less than about 750° F. (400° C.), and is at a pressure from about 200 psig (13.8 barg) to about 4,000 psig (275 barg). The hydroprocessed product possesses less adulterants than the feed stream in its undistilled form, although in some embodiments the hydroprocessed product may be further distilled. In some embodiments, the fixed bed hydroprocessing reactor is a continuous fixed bed hydroprocessing reactor. In some embodiments, the hydroprocessed product is suitable as a diesel fuel, a diesel fuel additive, a diesel fuel blendstock, a turbine fuel, a turbine fuel additive, a turbine fuel blendstock, an aviation fuel, an aviation fuel additive, an aviation fuel blendstock, or a combination of any two or more thereof.
In some embodiments, the process converts at least a portion of the adulterants into hydroprocessed product. In some such embodiments, the method converts at least about 0.01 wt % of the adulterants into hydroprocessed product. The weight percent of the adulterants converted into hydroprocessed product may be about 0.05 wt %, about 0.1 wt %, about 0.5 wt %, about 1 wt %, about 5 wt %, about 10 wt %, about 15 wt %, about 20 wt %, about 25 wt %, about 30 wt %, about 35 wt %, about 40 wt %, about 45 wt %, about 50 wt %, about 55 wt %, about 60 wt %, about 65 wt %, about 70 wt %, about 75 wt %, about 80 wt %, about 85 wt %, about 90 wt %, about 95 wt %, about 98 wt %, about 99 wt %, or any ranges including and in between any two of these values or above any one of these values.
The amount of adulterants in the feed stream may be about 0.01 wppm based on the biorenewable feedstock. The amount of adulterants as based on the biorenewable feedstock may be about 0.05 wppm, about 0.1 wppm, about 0.5 wppm, about 0.1 wppm, about 5 wppm, about 10 wppm, about 15 wppm, about 20 wppm, about 25 wppm, about 30 wppm, about 35 wppm, about 40 wppm, about 45 wppm, about 50 wppm, about 55 wppm, about 60 wppm, about 65 wppm, about 70 wppm, about 75 wppm, about 80 wppm, about 85 wppm, about 90 wppm, about 95 wppm, about 100 wppm, about 105 wppm, about 110 wppm, about 115 wppm, about 120 wppm, about 125 wppm, about 130 wppm, about 135 wppm, about 140 wppm, about 145 wppm, about 150 wppm, about 155 wppm, about 160 wppm, about 165 wppm, about 170 wppm, about 175 wppm, about 180 wppm, about 185 wppm, about 190 wppm, about 195 wppm, about 200 wppm, about 225 wppm, about 250 wppm, about 275 wppm, about 300 wppm, about 325 wppm, about 350 wppm, about 375 wppm, about 400 wppm, about 425 wppm, about 450 wppm, about 475 wppm, about 500 wppm, about 550 wppm, about 600 wppm, about 650 wppm, about 700 wppm, about 750 wppm, about 800 wppm, about 850 wppm, about 900 wppm, about 1000 wppm, and ranges including and between any two of these values and above any one of these values.
The amount of adulterants in the feed stream may be reduced by about 0.01%. The amount of adulterants may be reduced by about 0.05%, about 0.1%, about 0.5%, about 1%, about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, about 98%, about 99%, about 100%, or ranges including and between any two of these values and above any one of these values. The reduction in the amount of adulterants may be measured by directly determining the adulterants in the hydroprocessed product and comparing with the amount of adulterants in the feed stream. Alternatively, the reduction in the amount of adulterants may be measured by concentrating the adulterant such as through distillation, reaction, extraction, or combinations which are well known to those skilled in analytical chemistry. Such techniques can improve the resolution of the adulterant concentration in the respective composition tested.
Adulterants of the present technology are typically associated with the biorenewable feedstock employed. In some embodiments, the adulterants include polymers, monomers of polymers, pesticides, additives, halogenated organic compounds, or mixtures of any two or more thereof. In some embodiments, the adulterants include dissolved adulterants, solubilized adulterants, particulate adulterants, or mixtures of any two or more thereof. In some embodiments, the particulate adulterants are less than about 1 mm in diameter. In some embodiments, the particulate adulterants are less than about 100 μm in diameter. In some embodiments, the particulate adulterants are less than about 80 μm in diameter. In some embodiments, the particulate adulterants are less than about 50 μm in diameter. In some embodiments, the particulate adulterants are less than about 10 μm in diameter. In some embodiments, the particulate adulterants are less than about 1 μm in diameter. In some embodiments, the particulate adulterants are less than about 0.1 μm in diameter.
Association of the adulterants may occur through a variety of routes and sources. For example, in meat processing plants and the rendering of tallow, animal carcasses and packaged goods may be wrapped in plastic films, some of which may end up in the rendered fats. Two common plastic films are polyethylene (PE) and polyvinylidene chloride (PVDC). In facilities where packaged meats are recycled (e.g. when product is past its shelf life, pieces of packaging material, plastic liners, and even used latex gloves may become mixed in with the rendered fat. Some of the polymeric materials and the associated additives may be incorporated into the fat as particulate material, solubilized material, or a mixture of both. Similarly, in recovering waste vegetable oils and restaurant greases, contamination by packages from the fried foods, plasticware, transfer hoses, and a multitude of other sources of contamination may occur. While various pretreatment steps may reduce particulate matter and even solubilized material to some degree, the solubilized polymeric adulterant may still persist in the material. Some adulterants may be monomers incorporated within the polymer or provided by decomposition of the polymer.
Pesticides, wood preservatives, and drugs are other adulterants that may be associated with the biorenewable feedstock. Many drugs and pesticides are fat soluble and may enter the food chain through consumption of plants, grain, seeds, as well as runoff into the water system in the case of fish (e.g. fish oil). These adulterants may end up in animal fat as well as plant oils and algal oils. Drugs are typically more common in animal fats than in other sources of fatty acids, where the primary source may be in the application of veterinary medicine. Wood preservatives are expected to be less prevalent in fats and oils than pesticides, but may enter the food supply in a similar fashion to pesticides.
Food preservatives, including anti-oxidants, are other type of adulterant that may be present in oils and fats from packaged food operations. Preservatives are added to packaged foods to increase the shelf life of the food.
A partial list of polymers is provided in Table 1.
In some embodiments, the adulterants include acrylonitrile butadiene styrene thermoplastic, polyacrylate rubber, ethylene-acrylate rubber, polyester urethane, bromo isobutylene isoprene rubber, polybutadiene rubber, chloro isobutylene isoprene rubber, polychloroprene, chlorosulphonated polyethylene, epichlorohydrin, ethylene propylene rubber, ethylene propylene diene monomer, polyether urethane, tetrafluoroethylene/propylene rubbers, perfluorocarbon elastomers, fluoroelastomer, fluoro silicone, fluorocarbon rubber, high density polyethylene, hydrogenated nitrile butadiene, polyisoprene, isobutylene isoprene rubber, low density polyethylene, polyethylene terephthalate, ethylene vinyl acetate, acrylonitrile butadiene, polyethylene, polyisobutene, polypropylene, polystyrene, poly vinyl choloride, polyvinylidene chloride, polyurethane, styrene butadiene, styrene ethylene butylene styrene copolymer, polysiloxane, vinyl methyl silicone, acrylonitrile butadiene carboxy monomer, styrene butadiene carboxy monomer, thermoplastic polyether-ester, styrene butadiene block copolymer, styrene butadiene carboxy block copolymer, polyesters, polyamides, polyacetals, or mixtures of any two or more thereof.
In some embodiments, the adulterants include a polymer additive. A partial list of polymer additives is provided in Table 2.
In some embodiments, the adulterants include acetamide, benzyl benzoate, benzyl butyl phthalate, bis(2-ethylhexyl) adipate, bis(2-ethylhexyl) phthalate, bisphenol A, bisphenol AF, 1,2-cyclohexane dicarboxylic acid diisononyl ester, dibutyl phthalate, dibutyl sebacate, diethylene glycol dinitrate, diisobutyl phthalate, diisodecyl phthalate, diisononyl phthalate, dimethyl methylphosphonate, 2,4-dinitrotoluene, dioctyl adipate, diisodecyl adipate, dipropylene glycol, epoxidized soybean oil, ethyl butyrate, ethylene carbonate, furoin, neopentyl glycol, phthalate, polybutene, polycaprolactone, propylene carbonate, triacetin, tributyl phosphate, tricresyl phosphate, triethyl phosphate, triethylene glycol dinitrate, trimethylolethane trinitrate, asbestine, barium borate, brominated flame retardant, bromoform, calcium borate, chlorendic acid, decabromodiphenyl ether, 1,2-dibromoethane, dimethyl chlorendate, dimethyl methylphosphonate, heptazine, hexabromocyclododecane, octabromodiphenyl ether, pentabromodiphenyl ether, polybrominated biphenyl, polybrominated diphenyl ethers, polychlorinated biphenyl, tetrabromobisphenol A, tris(2,3-dibromopropyl)phosphate, tris(2-chloroethyl)phosphate, zinc borate, or mixtures of any two or more thereof. In some embodiments, the adulterants include both a polymer and a polymer additive.
In some embodiments, the adulterants comprise hindered phenol, hydroquinone, phosphite, or thioester anti-oxidants. In some embodiments, the adulterants include styrenated phenol, alkylated hindered phenols, 2-tert-butyl-4-methylphenol, 2- and 3-tert-butyl-4-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, 2,6-distyrenated p-cresol, 2,6-di-tert-butyl-4-nonylphenol, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3′,5′-di-tert-butylanilino)-1,3,5-triazine, 2,5-di-tert-amylhydroquinone, mono-tert-butylhydroquinone, hydroquinone monomethyl ether, 2,5-di-t-butyl hydroquinone, tris(p-nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, distearyl pentaerythritol diphosphite, dilauryl-3,3′-thio-dipropionate, distearyl-3,3′-thio-diproprionate, ditridecyl-thio-dipropionate, thiodipropionic acid, or mixtures of any two or more thereof.
In some embodiments, the adulterants include pesticides, such as insecticides, fumigants, fungicides, herbicides, and plant growth regulators. In some embodiments, the adulterants include 1-bromo-3-chloro-5,5-dimethylhydantoin, ethyl (R)-2-[4-(6-chloro-1,3-benzoxazol-2-yloxy)phenoxy]propionate, 2-methyl-4-chlorophenoxyacetic acid, methyl 2-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)methylamino]carbonyl]amino]sulfonyl]benzoate, abamectin, acephate, acetamiprid, acetochlor (2-Chloro-N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)acetamide), aldicarb (2-methyl-2-(methylthio)propanal O—(N-methylcarbamoyl)oxime), amitraz, 3-amino-1,2,4-triazole, ancymidol, anilazine, atrazine, azinphos-methyl, azinphos-ethyl, azoxystrobin, bentazon, bifenthrin, bendiocarb, bensulide, boscalid, brodifacoum, bromadiolone, bromethalin, bromoxynil, (3aR,7aS)-2-[(trichloromethyl)sulfanyl]-3a,4,7,7a-tetrahydro-1H-isoindole-1,3(2H)-dione, carbaryl, carbathiin, carbofuran, chloroneb, chlorophacinone, chloropicrin, chlorothalonil, chlorphropham, chlorphyrifos, chlormequat chloride, clethodim, clodinafop-propargyl, clofentezine, clopyralid, clothianidin, cyfluthrin ([(R)-cyano-[4-fluoro-3-(phenoxy)phenyl]methyl] (1R,3R)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropane-1-carboxylate), cyhalothrin, cymoxanil, cypermethrin, cyprodinil, cyromazine, daminozide, dazomet, (Z,E)-tetradeca-9,12-dienyl acetate, deltamethrin, desmedipham, diazinon (O,O-diethyl O-[4-methyl-6-(propan-2-yl)pyrimidin-2-yl]phosphorothioate), dicamba, dichlobenil, diclofop-methyl, dicloran, 2,4-dichlorophenoxyacetic acid (“2,4-D”), dichloropropene, dichlorvos, dicofol, didecyl dimethyl ammonium chloride, difenoconazole, difenzoquat, dimethenamid, dimethoate, dimethomorph, dinocap, diphacinone, diquat, diuron (3-(3,4-dichlorophenyl)-1,1-dimethylurea), dodemorph acetate, dodine, endosulfan, S-ethyl N,N-dipropylcarbamothioate, ethalfluralin, ethametsulfuron-methyl, ethephon, etridiazole, fenbuconazole, fenbutatin-oxide, fenhexamid, fenoxaprop-p-ethyl, fenoxycarb, ferbam, florasulam, fluazifop-p-butyl, fludioxonil, fluoroxypyr, flusilazole, folpet, glufosinate, glyphosate, hexazinone, imazamethabenz, imazamox, imazethapyr, imidacloprid, iprodione, isoxaben, kinoprene, kresoxim-methyl, linuron, malathion, mancozeb, maneb (manganese ethylene-1,2-bisdithiocarbamate, polymer), 2-methyl-4-chlorophenoxyacetic acid (MCPA), 4-(4-chloro-2-methylphenoxy)butanoic acid (MCPB), mecoprop, mefenoxam, metalaxyl, metham sodium, metham potassium, methamidophos, methomyl, methoxyfenozide, methoprene, methyl bromide, metiram, metolachlor ((S)-2-chloro-N-(2-ethyl-6-methyl-phenyl)-N-(1-methoxypropan-2-yl)acetamide), metribuzin, metsulfuron methyl, myclobutanil, naled (1,2-dibromo-2,2-dichloroethyl dimethyl phosphate), napropamide, naptalam, nicosulfuron, nonanoic acid, oxadiazon, oxamyl, oxycarboxin, oxyfluorfen, paclobutrazol, paraquat (1,1′-dimethyl-4,4′-bipyridinium dichloride), pendimethalin, permethrin, phenmediphan, phosalone, phosmet, pirimicarb, prohexadione calcium, prometryne, propanil, propiconazole, propyzamide, pyraclostrobin, pyrethrin I, pyrethrin II, pyridaben, quinclorac, quintozene, rimsulfuron, sethoxydim, simazine (6-chloro-N,N′-diethyl-1,3,5-triazine-2,4-diamine), spinosyn A, spinosyn D, tebuconazole, tebufenozide, tefluthrin, terbacil, terbufos, tetrachlorvinphos, thiabendazole, thiamethoxam, thifensulfuron methyl, thiophanate methyl, thiram (dimethylcarbamothioylsulfanyl N,N-dimethylcarbamodithioate), tralkoxydim, triadimenol, triallate, tribenuron methyl, trichlorfon, trifluralin, triforine, trinexapac, trinexapac-ethyl, triticonazole, uniconazole, vinclozolin, warfarin, or mixtures of any two or more thereof. In some embodiments, the adulterants include carbamates, organophospates, and phenoxy components. In some embodiments, the adulterants include acephate, acetochlor (2-chloro-N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)acetamide), aldicarb (2-methyl-2-(methylthio)propanal O—(N-methylcarbamoyl)oxime), atrazine, bifenthrin, chloropicrin, chlorothalonil, chlorphyrifos, 2,4-dichlorophenoxyacetic acid (“2,4-D”), dichloropropene, dimethenamid, diuron (3-(3,4-dichlorophenyl)-1,1-dimethylurea), ethephon, fenoxycarb, glyphosate, 2-methyl-4-chlorophenoxyacetic acid (MCPA), metham sodium, metham potassium, methyl bromide, metolachlor ((S)-2-chloro-N-(2-ethyl-6-methyl-phenyl)-N-(1-methoxypropan-2-yl)acetamide), paraquat (1,1′-dimethyl-4,4′-bipyridinium dichloride), pendimethalin, propanil, simazine, trifluralin, or mixtures of any two or more thereof.
Any of the previously described adulterants may also be included in the feed stream as mixtures of any two or more thereof of the adulterants. Combinations of any two or more members of the above recited groupings of adulterants as well as combinations of any two or more of the above recited adulterants are within the scope of the present technology and presently described method. In some embodiments, the adulterants include polyvinylidene chloride and a polymer additive. In some embodiments, the adulterants include polyvinylidene chloride and a pesticide.
The fixed bed reactor is at a temperature less than about 750° F. (400° C.). In some embodiments, the temperature is from about 70° F. (20° C.) to about 750° F. (400° C.). In some embodiments, the temperature is from about 140° F. (60° C.) to about 750° F. (400° C.). In some embodiments, the fixed bed reactor is at a temperature falling in the range from about 480° F. (250° C.) to about 750° F. (400° C.). The fixed bed reactor may operate at a temperature of about 80° F. (25° C.), about 100° F. (38° C.), about 150° F. (65° C.), about 200° F. (95° C.), about 250° F. (120° C.), about 300° F. (150° C.), about 350° F. (175° C.), about 400° F. (205° C.), about 450° F. (230° C.), about 500° F. (260° C.), about 540° F. (280° C.), about 570° F. (300° C.), about 610° F. (320° C.), about 645° F. (340° C.), about 680° F. (360° C.), about 720° F. (380° C.), and ranges including and in between any two of these values. The weighted average bed temperature (WABT) is commonly used in fixed bed, adiabatic hydroprocessing reactors to express the “average” temperature of the reactor which accounts for the nonlinear temperature profile between the inlet and outlet of the reactor.
In the equation above, Tiin and Tiout refer to the temperature at the inlet and outlet, respectively, of catalyst bed i. As shown, the WABT of a reactor system with N different catalyst beds may be calculated using the WABT of each bed (WABTi) and the weight of catalyst in each bed (Wci).
The feed stream is combined with a hydrogen-rich treat gas. The ratio of hydrogen-rich treat gas to biorenewable feedstock is in the range of about 2,000 to about 10,000 SCF/bbl (in units of normal liter of gas per liter of liquid (Nl/l), about 355 Nl/l to about 1780 Nl/l). The ratio of hydrogen-rich treat gas to biorenewable feedstock may be about 2,500 SCF/bbl (about 445 Nl/l), about 3,000 SCF/bbl (about 535 Nl/l), about 3,500 SCF/bbl (about 625 Nl/l), about 4,000 SCF/bbl (about 710 Nl/l), about 4,500 SCF/bbl (about 800 Nl/l), about 5,000 SCF/bbl (about 890 Nl/l), about 5,500 SCF/bbl (about 980 Nl/l), about 6,000 SCF/bbl (about 1070 Nl/l), about 6,500 SCF/bbl (about 1160 Nl/l), about 7,000 SCF/bbl (about 1250 Nl/l), about 7,500 SCF/bbl (about 1335 Nl/l), about 8,000 SCF/bbl (about 1425 Nl/l), about 8,500 SCF/bbl (about 1515 Nl/l), about 9,000 SCF/bbl (about 1600 Nl/l), about 9,500 SCF/bbl (about 1690 Nl/l), and ranges including and in between any two of these values. The hydrogen-rich treat gas contains contain from about 70 mol % to about 100 mol % hydrogen. In terms of mass ratio, the ratio of the feed stream to hydrogen-rich treat gas is from about 5:1 to 25:1. The ratio of the feed stream to hydrogen-rich treat gas may be about 6:1, about 7:1, about 8:1, about 9:1, about 10:1, about 11:1, about 12:1, about 13:1, about 14:1, about 15:1, about 16:1, about 17:1, about 18:1, about 19:1, about 20:1, about 22:1, about 23:1, about 24:1, and ranges including and in between any two of these values or greater than any one of these values.
In some embodiments, the fixed bed reactor includes a hydrogenation catalyst. The hydrogenation catalyst may include Co, Mo, Ni, Pt, Pd, Ru, W, NiMo, NiW, CoMo, or combinations of any two or more thereof. In some embodiments, the hydrogenation catalyst includes NiMo, NiW, CoMo, and combinations of any two or more thereof. Supports for the hydrogenation catalyst include alumina and alumina with silicon oxides and/or phosphorus oxides. It should be noted that one of ordinary skill in the art can select an appropriate hydrogenation catalyst to provide a particular result and still be in accordance with the present technology.
In some embodiments, the fixed bed reactor includes a hydrotreatment catalyst. The hydrotreatment catalyst may include Co, Mo, Ni, Pt, Pd, Ru, W, NiMo, NiW, CoMo, or combinations of any two or more thereof. In some embodiments, the hydrotreatment catalyst includes NiMo, NiW, CoMo, and combinations of any two or more thereof. Supports for the hydrotreatment catalyst include alumina and alumina with silicon oxides and/or phosphorus oxides. It should be noted that one of ordinary skill in the art can select an appropriate hydrotreatment catalyst to provide a particular result and still be in accordance with the present technology.
In some embodiments, the fixed bed reactor includes a hydroisomerization catalyst. The hydroisomerization catalyst may be a bifunctional catalyst. Bifunctional catalysts are those having a hydrogenation-dehydrogenation activity from a Group VIB and/or Group VIII metal, and acidic activity from an amorphous or crystalline support such as amorphous silica-alumina (ASA), silicon-aluminum-phosphate (SAPO) molecular sieve, mesoporous material (MCM), zirconia and/or anion-modified zirconia, or aluminum silicate zeolite (ZSM). In some embodiments the metal includes platinum, palladium, or tungsten. In some embodiments, the support includes HF-treated alumina, silica alumina, zirconia, zirconium sulfate, SAPO-11, SAPO-31, SAPO-41, MCM-41, Zeolite Y, mordenite, ZSM-22, and ZSM-48. In some embodiments, the hydroisomerization catalyst includes Pt/Pd-on-ASA or Pt-on-SAPO-11. However, it should be noted that one of ordinary skill in the art can select an appropriate hydroisomerization catalyst to provide a particular result and still be in accordance with the present technology.
To maintain the active metal sulfide functionality of the hydrotreatment and/or hydroisomerization catalyst despite the negligible presence of organic sulfur in most biorenewable feedstocks, the feed stream may be supplemented with a sulfur compound that decomposes to hydrogen sulfide when heated and/or contacted with a catalyst. In some embodiments, the sulfur compound includes methyl mercaptan, ethyl mercaptan, n-butyl mercaptan, dimethyl sulfide (DMS), dimethyl disulfide (DMDS), dimethylsulfoxide (DMSO), diethyl sulfide, di-tert-butyl polysulfide (TBPS), di-octyl polysulfide, di-tert-nonyl polysulfude (TNPS), carbon disulfide, thiophene, or mixtures of any two or more thereof. The concentration of the sulfur compound in the feed stream may be from about 50 ppm to about 2,000 ppm by weight sulfur. The feed stream may include a fossil-fuel fraction wherein the fossil-fuel fraction provides the sulfur, either in combination with or in the absence of the above mentioned sulfur compounds.
The fixed bed reactor is at a pressure falling in the range from about 200 psig (about 13.8 barg) to about 4,000 psig (about 275 barg). The pressure may be about 300 psig (21 barg), about 400 psig (28 barg), about 500 psig (34 barg), about 600 psig (41 barg), about 700 psig (48 barg), about 800 psig (55 barg), about 900 psig (62 barg), about 1,000 psig (69 barg), about 1,100 psig (76 barg), about 1,200 psig (83 barg), about 1,300 psig (90 barg), about 1,400 psig (97 barg), about 1,500 psig (103 barg), about 1,600 psig (110 barg), about 1,700 psig (117 barg), about 1,800 psig (124 barg), about 1,900 psig (131 barg), about 2,000 psig (138 barg), about 2,200 psig (152 barg), about 2,400 psig (165 barg), about 2,600 psig (179 barg), about 2,800 psig (193 barg), about 3,000 psig (207 barg), about 3,200 psig (221 barg), about 3,400 psig (234 barg), about 3,600 psig (248 barg), about 3,800 psig (262 barg), about 3,900 psig (269 barg), and any ranges including and in between any two of these values. In some embodiments, the pressure is from about 1,000 psig (69 barg) to about 2,000 psig (138 barg).
In some embodiments, the feed stream further comprises a diluent. The diluent may include a recycled hydroprocessed product, a distilled fraction of the hydroprocessed product, a petroleum hydrocarbon fluid, a synthetic hydrocarbon product stream from a Fischer-Tropsch process, a hydrocarbon product stream produced by fermentation of sugars (e.g. farnesene), natural hydrocarbons such as limonene and terpene, natural gas liquids, or mixtures of any two or more thereof. In some embodiments, the hydrocarbonaceous diluent includes a recycled hydroprocessed product, a distilled fraction of the hydroprocessed product, a petroleum hydrocarbon fluid, or mixtures of two or more thereof. The ratio of hydrocarbonaceous diluent to biorenewable feedstock falls within the range from about 0.5:1 to about 20:1. The ratio of hydrocarbonaceous diluent to biorenewable feedstock may be about 1:1, about 2:1, about 3:1, about 4:1, about 5:1, about 6:1, about 7:1, about 8:1, about 9:1, about 10:1, about 11:1, about 12:1, about 13:1, about 14:1, about 15:1, about 16:1, about 17:1, about 18:1, about 19:1, and ranges including and between any two of these values.
In some embodiments, the hydroprocessed product includes a hydrogenated product. In some embodiments, the hydrogenated product includes a hydrogenated free fatty acid, a hydrogenated fatty acid ester, or mixtures thereof. In some embodiments, the hydrogenated fatty acid ester includes a hydrogenated triglyceride. In some embodiments, the hydrogenated product includes a partially hydrogenated product. In some embodiments, the hydrogenated product includes a fully hydrogenated product. For example, in some embodiments, the hydrogenated product includes a partially hydrogenated free fatty acid, a partially hydrogenated fatty acid ester, or mixtures thereof. In some embodiments, the hydrogenated product includes a partially hydrogenated triglyceride. In some embodiments, the hydrogenated product includes a fully hydrogenated free fatty acid, a fully hydrogenated fatty acid ester, or mixtures thereof. In some embodiments, the hydrogenated product includes a fully hydrogenated triglyceride.
In some embodiments, the hydroprocessed product includes at least 80 wt % paraffins falling within the range of C11 to C24, where the paraffins include C16 and C18 paraffins; from about 0.1 wt % to about 7.0 wt % cylcoparaffins; and from about 0.001 wt % to about 1.0 wt % aromatics. In some embodiments of such a hydroprocessed product, the hydroprocessed product is suitable as a diesel fuel, a diesel fuel additive, a diesel fuel blendstock, a turbine fuel, a turbine fuel additive, a turbine fuel blendstock, an aviation fuel, an aviation fuel additive, or an aviation fuel blendstock. In some embodiments of such a hydroprocessed product, the hydroprocessed product is suitable as a diesel fuel.
In some embodiments, the hydroprocessed product may contain paraffins in the amount of about 82 wt %, about 84 wt %, about 86 wt %, about 88 wt %, about 90 wt %, about 92 wt %, about 94 wt %, about 96 wt %, about 98 wt %, about 99 wt %, and any range in between any two of these values or above any one of these values. In some embodiments, the paraffins include at least about 50% wt % C16 and C18 paraffins. In some embodiments, the paraffins include at least about 55% wt % C16 and C18 paraffins. In some embodiments, the paraffins include at least about 60 wt % C16 and C18 paraffins. In some embodiments, the paraffins include C12, C16, and C18 paraffins. In some embodiments, the paraffins include C14, C16, and C18 paraffins. In some embodiments, the paraffins include C12, C14, C16, and C18 paraffins. In some embodiments, the paraffins include iso-paraffins and n-paraffins. In some embodiments where the paraffins include iso-paraffins and n-paraffins, the ratio of iso-paraffins to n-paraffins is at least about 4:1. The ratio of iso-paraffins to n-paraffins may be about 4.5:1, about 5:1, about 5.5:1, about 6:1, about 6.5:1, about 7:1, about 8:1, about 9:1, about 10:1, about 11:1, about 12:1, about 13:1, about 14:1, about 15:1, about 16:1, about 17:1, about 18:1, about 19:1, about 20:1, about 21:1, about 22:1, about 23:1, about 24:1, about 25:1, about 26:1, about 27:1, about 28:1, about 29:1, about 30:1, and ranges including and between any two of these values or above any one of these values. In some embodiments, the ratio of iso-paraffins to n-paraffins is greater than about 5:1. In some embodiments, the ratio of iso-paraffins to n-paraffins is between about 5:1 and about 10:1.
In some embodiments, at least 70 wt % of the iso-paraffins are mono-methyl branched paraffins. The mono-methyl branched paraffins may be about 72 wt %, about 74 wt %, about 76 wt %, about 78 wt %, about 80 wt %, about 82 wt %, about 84 wt %, about 86 wt %, about 88 wt %, about 90 wt %, about 92 wt %, about 94 wt %, about 96 wt %, about 98 wt %, about 99 wt %, and ranges including and between any two of these values or above any one of these values. Examples of the mono-methyl branched paraffins include, but are not limited to, 4-methyl heptadecane, 3-methyl hexadecane, and 2-methyl pentadecane. The conversion of the n-paraffins to iso-paraffins may produce different amounts of mono-methyl terminal branched products (i.e. 2-methyl branched). Thus, in some embodiments of the mono-methyl branched iso-paraffins, less than about 30 wt % are terminal branched. In some embodiments, less than about 20 wt % of the mono-methyl branched iso-paraffins are terminal branched. In some embodiments, less than about 15 wt % of the mono-methyl branched iso-paraffins are terminal branched. In some embodiments, less than about 10 wt % of the mono-methyl branched iso-paraffins are terminal branched. In some embodiments, less than about 5 wt % of the mono-methyl branched iso-paraffins are terminal branched. However, in some embodiments, greater than about 30 wt % of the mono-methyl branched paraffins are terminal branched.
In some embodiments, the hydroprocessed product contains about 0.1 wt % to about 7.0 wt % cycloparaffins. The hydroprocessed product may have cycloparaffins in the amount of about 6 wt %, about 5 wt %, about 4 wt %, about 3 wt %, about 2 wt %, about 1 wt %, about 0.9 wt %, about 0.8 wt %, about 0.7 wt %, about 0.6 wt %, about 0.5 wt %, about 0.4 wt %, about 0.3 wt %, about 0.2 wt %, about 0.1 wt %, and any range including and in between any two of these values or below any one of these values.
In some embodiments, the hydroprocessed product contains from about 1.0 wt % to about 0.001 wt % aromatics. The hydroprocessed product may contain aromatics in the amount of about 0.9 wt %, about 0.8 wt %, about 0.7 wt %, about 0.6 wt %, about 0.5 wt %, about 0.4 wt %, about 0.3 wt %, about 0.2 wt %, about 0.1 wt %, about 0.09 wt %, about 0.08 wt %, about 0.07 wt %, about 0.06 wt %, about 0.05 wt %, about 0.04 wt %, about 0.03 wt %, about 0.02 wt %, about 0.01 wt %, about 0.009 wt %, about 0.008 wt %, about 0.007 wt %, about 0.006 wt %, about 0.005 wt %, about 0.004 wt %, about 0.003 wt %, about 0.002 wt %, about 0.001 wt %, and ranges including and between any two of these values or below any one of these values. In some embodiments, the hydroprocessed product contains less than about 0.5 wt % total aromatics. In some embodiments, the hydroprocessed product has less than about 0.01 wt % benzene. The hydroprocessed product may contain benzene in the amount of about 0.008 wt %, about 0.006 wt %, about 0.004 wt %, about 0.002 wt %, about 0.001 wt %, about 0.0008 wt %, about 0.0006 wt %, about 0.0004 wt %, about 0.0002 wt %, about 0.0001 wt %, about 0.00008 wt %, about 0.00006 wt %, about 0.00004 wt %, about 0.00002 wt %, about 0.00001 wt % and ranges including and between any two of these values or less than any one of these values. Such low values of benzene may be determined through appropriate analytical techniques, including but not limited to two dimensional gas chromatography of the composition. In some embodiments, the hydroprocessed product has less than about 0.00001 wt % of benzene.
In some embodiments, the hydroprocessed product has a sulfur content less than about 5 wppm. The hydroprocessed product may have a sulfur content of about 4 wppm, about 3 wppm, about 2 wppm, about 1 wppm, about 0.9 wppm, about 0.8 wppm, about 0.7 wppm, about 0.6 wppm, about 0.5 wppm, about 0.4 wppm, about 0.3 wppm, about 0.2 wppm, about 0.1 wppm, and ranges including and between any two of these values or less than any one of these values. In some embodiments, the hydroprocessed product has a sulfur content less than about 2 wppm.
In some embodiments, the hydroprocessed product has less than about 0.1 wt % oxygenates. The hydroprocessed product may have oxygenates in the amount of about 0.09 wt %, about 0.08 wt %, about 0.07 wt %, about 0.05 wt %, about 0.04 wt %, about 0.03 wt %, about 0.02 wt %, about 0.01 wt %, and ranges including and between any two of these values or below any one of these values. Such low values of oxygenates can be detected through appropriate analytical techniques, including but not limited to Instrumental Neutron Activation Analysis.
In some embodiments, the biorenewable feedstock may be pretreated. Such pretreatments include, but are not limited to, degumming, neutralization, bleaching, deodorizing, or a combination of any two or more thereof. One type of degumming is acid degumming, which involves contacting the fat/oil with concentrated aqueous acids. Exemplary acids are phosphoric, citric, and maleic acids. This pretreatment step removes metals such as calcium and magnesium in addition to phosphorus. Neutralization is typically performed by adding a caustic (referring to any base, such as aqueous NaOH) to the acid-degummed fat/oil. The process equipment used for acid degumming and/or neutralization may include high shear mixers and disk stack centrifuges. Bleaching typically involves contacting the degummed fat/oil with adsorbent clay and filtering the spent clay through a pressure leaf filter. Use of synthetic silica instead of clay is reported to provide improved adsorption. The bleaching step removes chlorophyll and much of the residual metals and phosphorus. Any soaps that may have been formed during the caustic neutralization step (i.e. by reaction with free fatty acids) are also removed during the bleaching step. The aforementioned treatment processes are known in the art and described in the patent literature, including but not limited to U.S. Pat. Nos. 4,049,686, 4,698,185, 4,734,226, and 5,239,096.
Bleaching as used herein is a filtration process common to the processing of glyceride oils. Many types of processing configurations and filtration media such as diatomaceous earth, perlite, silica hydrogels, cellulosic media, clays, bleaching earths, carbons, bauxite, silica aluminates, natural fibers and flakes, synthetic fibers and mixtures thereof are known to those skilled in the art. Bleaching can also be referred to by other names such as clay treating which is a common industrial process for petroleum, synthetic and biological feeds and products.
Additional types of filtration may be performed to remove suspended solids from the biorenewable feedstock before and/or after and/or in lieu of degumming and/or bleaching. In some embodiments, rotoscreen filtration is used to remove solids larger than about 1 mm from the biorenewable feedstock. Rotoscreen filtration is a mechanically vibrating wire mesh screen with openings of about 1 mm or larger that continuously removes bulk solids. Other wire mesh filters of about 1 mm or larger housed in different types of filter may be also be employed, including self-cleaning and backwash filters, so long as they provide for bulk separation of solids larger than 1 mm, such as from about 1 mm to about 20 mm. In embodiments where bleaching through clay-coated pressure leaf filter is not used, cartridge or bag filters with micron ratings from about 0.1 to about 100 may be employed to ensure that only the solubilized and or finely suspended (e.g. colloidal phase) adulterants are present in the feed stream. Filtration is typically performed at temperatures high enough to ensure the feed stream is a liquid of about 0.1 to 100 cP viscosity. This generally translates into a temperature range of 20° C. to 90° C. (about 70° F. to about 195° F. For example,
In some embodiments, from about 100 to about 15,000 reactor volumes of biorenewable feedstock are processed prior to shutdown of the fixed bed hydroprocessing reactor. The reactor volumes of biorenewable feedstock processed may be about 200, about 300, about 400, about 500, about 600, about 700, about 800, about 900, about 1,000, about 1,100, about 1,500, about 2,000, about 2,500, about 3,000, about 3,500, about 4,000, about 4,500, about 5,000, about 5,500, about 6,000, about 6,500, about 7,000, about 7,500, about 8,000, about 8,500, about 9,000, about 9,500, about 10,000, about 10,500, about 11,000, about 11,500, about 12,000, about 12,500, about 13,000, about 13,500, about 14,000, about 14,500, or any range including and between any two of these values or greater than any one of these values.
In some embodiments, the liquid hourly space velocity (LHSV) of the biorenewable feedstock through the fixed bed hydroprocessing reactor is from about 0.2 h−1 to about 10.0 h−1. The LHSV may be about 0.3 h−1, about 0.4 h−1, about 0.5 h−1, about 0.6 h−1, about 0.7 h−1, about 0.8 h−1, about 0.9 h−1, about 1.0 h−1, about 1.2 h−1, about 1.4 h−1, about 1.6 h−1, about 1.8 h−1, about 2.0 h−1, about 2.2 h−1, about 2.4 h−1, about 2.6 h−1, about 2.8 h−1, about 3.0 h−1, about 3.2 h−1, about 3.4 h−1, about 3.6 h−1, about 3.8 h−1, about 4.0 h−1, about 4.2 h−1, about 4.4 h−1, about 4.6 h−1, about 4.8 h−1, about 5.0 h−1, about 5.2 h−1, about 5.4 h−1, about 5.6 h−1, about 5.8 h−1, about 6.0 h−1, about 6.2 h−1, about 6.4 h−1, about 6.6 h−1, about 6.8 h−1, about 7.0 h−1, about 7.2 h−1, about 7.4 h−1, about 7.6 h−1, about 7.8 h−1, about 8.0 h−1, about 8.2 h−1, about 8.4 h−1, about 8.6 h−1, about 8.8 h−1, about 9.0 h−1, about 9.2 h−1, about 9.4 h−1, about 9.6 h−1, about 9.8 h−1, and ranges including and between any two of these values or above any one of these values.
In some embodiments, the biorenewable feedstock includes free fatty acids, fatty acid esters (including mono-, di-, and trigylcerides), or combinations thereof. In some embodiments, the biorenewable feedstock includes animal fats, animal oils, plant fats, plant oils, vegetable fats, vegetable oils, greases, or mixtures of any two or more thereof. In some embodiments, the fatty acid esters include fatty acid methyl ester, a fatty acid ethyl ester, a fatty acid propyl ester, a fatty acid butyl ester, or mixtures of any two or more thereof. In some embodiments, the biorenewable feedstock comprises the fatty acid distillate from vegetable oil deodorization. Depending on level of pretreatment, fats, oils, and greases, may contain between about 1 wppm and about 1,000 wppm phosphorus, and between about 1 wppm and about 500 wppm total metals (mainly sodium, potassium, magnesium, calcium, iron, and copper). Plant and/or vegetable oils include, but are not limited to, soybean oil, canola oil, rapeseed oil, tall oil, tall oil fatty acid, palm oil, palm oil fatty acid distillate, palm kernel oil, jatropha oil, sunflower oil, castor oil, camelina oil, algae oil, seaweed oil, oils from halophiles, and mixtures of any two or more thereof. These may be classified as crude, degummed, and RBD (refined, bleached, and deodorized) grade, depending on level of pretreatment and residual phosphorus and metals content. However, any of these grades may be used in the present technology. Animal fats and/or oils as used above includes, but is not limited to, inedible tallow, edible tallow, technical tallow, floatation tallow, lard, poultry fat, poultry oils, fish fat, fish oils, and mixtures of any two or more thereof. Greases may include, but are not limited to, yellow grease, brown grease, waste vegetable oils, restaurant greases, trap grease from municipalities such as water treatment facilities, and spent oils from industrial packaged food operations, and mixtures of any two or more thereof.
In some embodiments, the biorenewable feedstock comprises animal fats, poultry oil, soybean oil, canola oil, rapeseed oils, palm oil, palm kernel oil, jatropha oil, castor oil, camelina oil, algae oil, seaweed oil, halophile oils, rendered fats, restaurant greases, brown grease, yellow grease, waste industrial frying oils, fish oils, tall oil, tall oil fatty acids, or mixtures of any two or more thereof. In some embodiments, the biorenewable feedstock includes animal fats, restaurant greases, brown grease, yellow grease, waste industrial frying oils, or mixtures of any two or more thereof.
In some embodiments, the hydroprocessed product is fractionated to provide a middle distillate fraction. In some embodiments, the middle distillate fraction is suitable as a diesel fuel. In some embodiments, the fractionation is conducted in a distillation column equipped with a reboiler or stripping steam in the bottom of the column, and a condenser at the top. The reboiler or stripping steam provide the thermal energy to vaporize the heavier fraction of the hydrocarbons while the condenser cools the lighter hydrocarbon vapors to return hydrocarbon liquid back into the top of the column. The distillation column is equipped with a plurality of plates or beds of packing material wherein the rising vapor and falling liquid come into counter-current contact. The column's temperature profile from bottom to top is dictated by the composition of the hydrocarbon feed and the column pressure. In some embodiments, column pressures range from about 200 psig (about 13.8 barg) to about −14.5 psig (about −1 barg). The column is equipped with one or a plurality of feed nozzles. A portion of the condenser liquid (typically 10 to 90 vol %) is drawn off as overhead distillate product while the rest is allowed to refluxed back to the column. In some embodiments, the column separates the product into a light and a heavy hydrocarbon fraction. In some embodiments, a broad boiling hydrocarbon feed may be separated into three or more fractions (e.g. a C5-C8 naphtha overhead fraction, a C9-C14 jet fuel side draw, and a C15-C18+ diesel bottoms fraction). While some embodiments employ a plurality of draw-off nozzles to fractionate the feed into multiple cuts in the same column, other embodiments achieve the same separation using a plurality of columns in series, each separating the feed into an overhead fraction and a bottom fraction.
In some embodiments and in lieu of hydroisomerizing, the paraffinic product from the HDO reaction, or a portion thereof, can be hydrocracked, dehydrogenated, oligomerized, and/or reformed to produce other products or chemical feedstocks.
The present technology, thus generally described, will be understood more readily by reference to the following examples, which are provided by way of illustration and are not intended to be limiting of the present technology.
A fixed-bed hydroprocessing reactor containing two catalyst beds was loaded with two types of hydrotreating catalyst. The bottom bed was filled with a high activity NiMo catalyst and the top bed with a lower activity Mo catalyst. Both catalysts were in the oxide form when loaded and were sulfided during reactor startup.
The feedstock processed was a mixture of commercially traded animal fats, vegetable oils (including used cooking oil), and greases (a “FOG” feed). The FOG feeds contained between 52% and 88% unsaturated fatty acids, indicating that they would undergo exothermic hydrodeoxygenation, as well as adulterants. PE is used herein as an illustrative example of an adulterant associated with the feedstock.
The reactor was pressurized with hydrogen and controlled at about 1,800 psig pressure (124 barg). The feedstock was pumped to the reactor at a rate equivalent to 0.72 to 1.1 LHSV (vol/h FOG feed per vol NiMo catalyst). The feedstock was combined with heated hydrocarbon diluent to achieve a reactor inlet temperature within the 510° F. (266° C.) to 540° F. (282° C.) range. The hydrocarbon diluent was the product of the reaction and which was combined with feed at a 2:1 ratio (vol diluent:vol feed). Hydrogen was introduced to the reactor at a rate of 5,000 SCF/bbl (890 Nl/l) along with the feed and diluent. Additional hydrogen was introduced to the reactor as quench gas between the top and bottom beds to control the outlet temperature to a value between 680° F. (360 C) to 710° F. (377° C.). The WABT of the reactor was thus between about 620° F. (327° C.) and 653° F. (345° C.). The hydrodeoxygenated (HDO) product was further processed via hydroisomerization and distillation to provide a hydrocarbon product meeting diesel fuel specifications (“FOG diesel”). A portion of the HDO product was recycled and used as diluent for the feed as described herein.
Notably, as shown in Table 3, the hydroprocessing of feedstocks consistently yielded high quality FOG diesel despite the variable adulterant concentration of the feed.
Based upon the feedstocks processed during Year 1 and Year 2, the estimated annual average PE in the feedstock was 54 ppm and 20 ppm, respectively. During the same period of time (e.g. over 100 samples tested), the annual averages of finished diesel carbon residue (per ASTM D524) were 0.036 wt %. Converting to a whole diesel basis, this is equivalent to 36 ppm for both Year 1 and Year 2 and indicates the robustness of the present technology in successful long-term processing of adulterated feedstocks into a finished fuel. In addition, there were no engine performance related problems associated with the renewable fuel, both in blended and neat forms, ranging from the use of the fuel in conventional on and off-road diesel applications to high performance race engines and large locomotive engines.
A portion of the renewable diesel product of Example 1 was distilled to produce a biorenewable jet fuel fraction (“FOG kerosene”). The distillation was performed to achieve a 270° C. cut-point (target final boiling point) for the jet fuel, consistent with final boiling point specification of 300° C. max.
Table 4 provides a summary of the specification test results for the biorenewable jet fuel according to the present technology in comparison to the industry minimum standard for synthetic jet fuel (D7566), a synthetic jet fuel produce by the Fischer-Tropsch Gas-to-Liquid (GTL) process, and a petroleum jet fuel (JP-8). The GTL jet fuel fraction (“GTL synthetic kerosene” in Table 4) was produced from conversion of natural gas to syngas, followed by Fischer-Tropsch synthesis. The GTL synthetic kerosene provides a baseline for an “adulterant free” fuel. As observed in Table 4, the thermal stability and existent gum values (indicators of residual adulterants) for the biorenewable jet fuel produced by the present method was the same as the “adulterant free” GTL synthetic kerosene. Specifically, the thermal stability test at 325° C. produced no tube pressure drop (0 mm Hg) or discoloration (rating 1). This is in contrast to a 2 mm Hg observed pressure drop for the JP-8 fuel at the less severe test condition of 260° C.
While certain embodiments have been illustrated and described, it should be understood that changes and modifications can be made therein in accordance with ordinary skill in the art without departing from the technology in its broader aspects as defined in the following claims.
The embodiments, illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein. Thus, for example, the terms “comprising,” “including,” “containing,” etc. shall be read expansively and without limitation. Additionally, the terms and expressions employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the claimed technology. Additionally, the phrase “consisting essentially of” will be understood to include those elements specifically recited and those additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase “consisting of” excludes any element not specified.
The present disclosure is not to be limited in terms of the particular embodiments described in this application. Many modifications and variations can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Functionally equivalent methods and compositions within the scope of the disclosure, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that this disclosure is not limited to particular methods, reagents, compounds compositions or biological systems, which can of course vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.
In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.
As will be understood by one skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilled in the art all language such as “up to,” “at least,” “greater than,” “less than,” and the like, include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member.
All publications, patent applications, issued patents, and other documents referred to in this specification are herein incorporated by reference as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated by reference in its entirety. Definitions that are contained in text incorporated by reference are excluded to the extent that they contradict definitions in this disclosure.
Other embodiments are set forth in the following claims.
