Patent Application
20240327720
The field is processes for producing product streams from renewable feed streams. Specifically, the field is processes for producing detergent streams and fuel streams from renewable feed streams.
Sustainable chemicals are gaining significant attention by the market due to a reduced carbon footprint. One example is green linear alkylbenzenes that are organic compounds produced from sustainable feedstocks. Palm Kernel oil (PKO) and Coconut Kernel oil are examples of sustainable feeds that have significant (>40%) carbon content in the desirable range of C10-C13. However, land usage concerns of PKO and limited availability of coconut oil call for alternate feedstocks. Using conventional process technologies such as hydrocracking, hydro-isomerization, the C16-C22 range n paraffins can be readjusted to desirable range of C10-C13, but with poor linearity due to branching/isomerization. Producing green n-paraffins with high linearity and yields which are suitable for Green LAB production is therefore desirable. While the alkyl carbon number, “n” can have any practical value, detergent manufacturers desire that alkylbenzenes have alkyl carbon number in the range of 9 to 16 and preferably in the range of 10 to 13. These specific ranges are often required when the alkylbenzenes are used as intermediates in the production of surfactants for detergents. The alkyl carbon number in the range of 10 to 13 falls in line with the specifications of the detergents industry.
Because the surfactants created from alkylbenzenes are biodegradable, the production of alkylbenzenes has grown rapidly since their initial uses in detergent production in the 1960s. The linearity of the paraffin chain in the alkylbenzenes is key to the material's biodegradability and effectiveness as a detergent. A major factor in the final linearity of the alkylbenzenes is the linearity of the paraffin component.
While detergents made utilizing alkylbenzene-based surfactants are biodegradable, previous processes for creating alkylbenzenes are not based on renewable sources. Specifically, alkylbenzenes are currently produced from kerosene refined from crude extracted from the earth. Due to the growing environmental prejudice against fossil fuel extraction and economic concerns over exhausting fossil fuel deposits, there may be support for using an alternate source for biodegradable surfactants in detergents and in other industries.
Accordingly, it is desirable to provide linear alkylbenzenes with a high degree of linearity that are made from biorenewable sources instead of being extracted from the earth. Further, it is desirable to provide renewable linear alkylbenzenes from easily processed triglycerides and fatty acids from vegetable, animal, nut, and/or seed oils. Palm kernel oil, coconut oil and babassu oil have a composition that is high in the desirable range of C10-C13 n-paraffins that aligns with the alkyl carbon number range desired of the detergent industry. Most other renewable triglyceride sources have a high amount of nC16 to nC18 content and it is desirable to be able to convert those feeds to nC10 to nC13 feeds with a high per-pass yield. In addition to the use of biorenewable sources discussed above, a feed or a portion of a feed may be obtained from Fischer Tropsch liquids. Other renewable sources of hydrocarbons such as those obtained from carbon dioxide to hydrocarbon processes are another area for obtaining the hydrocarbons to be used in the process. These nC10 to nC13 intermediate products are useful in eventually making linear alkylbenzene types of detergents through additional process steps. It is further desirable that the resulting nC10 to nC13 paraffins are linear products with a minimum of branched isomer products.
Biofuels may be co-produced with linear alkylbenzenes. Other desirable features and characteristics of the present invention will become apparent from the subsequent detailed description of the invention and the appended claims, when taken in conjunction with the accompanying drawing and this background.
We have discovered that feeds containing longer normal paraffins with 14-22 carbon atoms, derived from biorenewable feeds such as fats oils and greases with high content of triglycerides, can be converted to paraffin compositions containing normal paraffins with 10-13 carbon atoms favored in detergent alkylation, by use of a preferred catalyst such as a group VI or VIII metal catalyst or a mixture of group VI and VIII metal catalysts on a neutral support. Some suitable catalysts include Ru—ZrO2 or Pt—Al2O3 or Ni—ZrO2 or a Mo-based catalyst such as Mo on alumina or a tungsten catalyst. The per-pass nC10 to nC13 yield from the new catalyst and process can be significantly higher (˜30%) than what one can obtain from the prior art process. It was found that depending upon the catalyst that is used that the yield of the desired C10-C13 may vary, the linearity of the C10-C13 with normal hydrocarbons preferred and the amount of methane produced as a byproduct.
Additional details and embodiments of the disclosure will become apparent from the following detailed description of the disclosure.
The present disclosure endeavors to produce alkylbenzenes for detergent production and jet fuel and/or diesel from renewable sources. The raw materials for the generation of linear alkyl benzenes are normal C10 to C13 olefins, which can be generated by dehydrogenation of normal C10-C13 paraffins. Normal paraffins with 10 to 13 carbons are the desired number of carbons that detergent producers desire for the addition of the alkyl group on the alkylbenzenes used in detergents. While current processes generally use fossil sources of normal paraffins such as kerosene, there is a need for bio-renewable sources of normal paraffins. The most available source of bio-renewable n-paraffins is to subject a stream containing triglycerides or fatty acids to a deoxygenation process such as hydrodeoxygenation to generate an intermediate stream of normal paraffins. However, most triglyceride and fatty acid containing feedstocks produce normal paraffins with 16 to 18 carbons, and in some cases 22 carbons, when deoxygenated. These normal paraffins are of longer chain length than desired by detergent producers. Some renewable sources such as palm kernel oil (PKO), coconut oil and babassu oil have fatty acids that produce normal paraffins with 10 to 13 carbons when deoxygenated, so one path to generate C10 to C13 normal paraffins is to use one of these triglyceride containing feeds. In a broad description, it has been found desirable to be able to take an intermediate stream containing broad range of C16-C22 normal paraffins that was generated from readily available fats, oils and greases (FOGS) to produce a desired product stream of normal C10-C13 by a hydrocracking-like process. The intermediate feed stream is treated as necessary to remove sulfur which deactivates the catalyst. A difference between the catalysts typically used for hydrotreating and for instant the hydrocracking-like step is that the hydrocracking catalysts have been reduced rather than sulfided.
The hydrocarbons that are subjected to linear cracking reactions may be Fischer Tropsch liquids that are the product of a pretreated biomass that is subjected to gasification to produce a bio-syngas that is subjected to a Fischer Tropsch reaction. The Fischer-Tropsch process is a collection of chemical reactions that converts a mixture of carbon monoxide and hydrogen, known as syngas, into liquid hydrocarbons. These reactions occur in the presence of metal catalysts, typically at temperatures of 150-300° C. (302-572° F.) and pressures of one to several tens of atmospheres.
In its usual implementation, carbon monoxide and hydrogen, the feedstocks for Fischer Tropsch, are produced from coal, natural gas, or biomass in a process known as gasification. In the present embodiment a plant or animal source is used. The process then converts these gases into synthetic lubrication oil and synthetic fuel.
We have found that the selection of particular metal catalysts can produce a much higher yield of normal paraffins with 10-13 carbons from a stream containing normal paraffins of 14 to 22 carbons than in previous processes. Compared to the traditional LAB process where the feed is from petroleum, the feed for this process starts with nC10-nC57 hydrocarbons that are from renewable sources such as soybean oil, corn oil and other fats, oils, and greases from biological sources. This renewable n-paraffin feed is generally obtained by hydrodeoxygenation of triglycerides in a process such as Ecofining by UOP LLC, Des Plaines, IL. With the catalyst that is used herein, it has been found that the nC16-C18 intermediate stream is able to generate linear cracking products with low amounts of branched isomer production.
The catalysts are chosen from Group VI metals, Group VIII metals or mixtures of two or more Group VI and/or Group VIII metals. The preferred metals include molybdenum, tungsten, aluminum and nickel/aluminum. This catalyst metal is on a neutral support. Neutral support is meant to be a support material that is acidicly neutral, Of the preferred catalysts, the Ru catalyst exhibits much higher activity and per-pass nC10 to nC13 yield than the other catalysts. Under the optimized reaction conditions, it also produces very small amounts of methane and isomerized product. This has been found to be the best catalyst for such chemical transformation process. The Pt—Al2O3 catalyst can produce even lower methane yield than the Ru based catalyst with slightly less linear product yield. However, it was found that the Mo containing catalysts produced high yield of the desired nC10-nC13 with a high degree of linearity and low amounts of methane.
To limit catalyst deactivation and poisoning, the feed is treated to remove sulfur contamination for the supported catalysts. The feed has less than 1 wt ppm sulfur content but for the purposes of this disclosure, a feed with less than 100 wt, ppm is considered to be sulfur free. Without this treatment, sulfur accumulates on the catalyst and leads to deactivation. A high temperature hydrogen treatment is shown to recover some of the lost activity.
The bio-renewable triglyceride containing feed is subjected to hydrodeoxygenation to generate the intermediate normal paraffin feed. The hydrodeoxygenation reactor reacts the bio-renewable triglyceride containing feed with hydrogen and converts triglycerides and free fatty acids to propane, water, n-paraffins and small amounts of ammonia, carbon monoxide and carbon dioxide. Generally, the n-paraffins are separated from the water and gaseous products in a separator to generate the intermediate normal paraffin stream. Hydrodeoxygenation should be complete or nearly complete such that the intermediate feed stream contains less than about 1000 ppm of oxygen, preferably less than 10 ppm of oxygen. The hydrodeoxygenation reactor temperatures are kept low, less than 343° C. (650° F.) for typical biorenewable feedstocks and less than 304° C. (580° F.) for feedstocks with higher free fatty acid (FFA) concentration to avoid polymerization of olefins found in FFA. Generally, hydrodeoxygenation reactor pressure of about 700 kPa (100 psig) to about 21 MPa (3000 psig) are suitable.
As used herein, the term “separator” means a vessel which has an inlet and at least an overhead vapor outlet and a bottoms liquid outlet and may also have an aqueous stream outlet from a boot. A flash drum is a type of separator which may be in downstream communication with a separator which may be operated at higher pressure. The term “communication” means that fluid flow is operatively permitted between enumerated components, which may be characterized as “fluid communication”. The term “downstream communication” means that at least a portion of fluid flowing to the subject in downstream communication may operatively flow from the object with which it fluidly communicates.
The term “column” means a distillation column or columns for separating one or more components of different volatilities. Unless otherwise indicated, each column includes a condenser on an overhead of the column to condense and reflux a portion of an overhead stream back to the top of the column and a reboiler at a bottom of the column to vaporize and send a portion of a bottoms stream back to the bottom of the column. Feeds to the columns may be preheated. The top pressure is the pressure of the overhead vapor at the vapor outlet of the column. The bottom temperature is the liquid bottom outlet temperature. Unless indicated otherwise, overhead lines and bottoms lines refer to the net lines from the column downstream of any reflux or reboil take-off to the column. Stripper columns may omit a reboiler at a bottom of the column and instead provide heating requirements and separation impetus from a fluidized inert media such as steam.
As used herein, the term “linearity” is the mole percentage of hydrocarbons calculated by dividing the moles of normal hydrocarbons divided by the total moles of hydrocarbons.
The catalysts that are used in the hydrocracking reactions are selected from Group VIB and Group VIII metals with a neutral support. Unlike the catalyst supports in some other reactions, there is no acid functionality in these catalyst supports including no zeolites and no amorphous AI/Si in the support. Some more preferred catalysts include Ru on ZrO2 catalyst, a Pt on Al2O3 catalyst, a Ni on alumina catalyst, Ni on ZrO2 catalyst, NiO/clay catalyst, a Ni—Mo on alumina catalyst and a Mo catalyst that may be on alumina. The catalyst may be Ru—ZrO2 (0.1 wt %)
Preferred cracking reaction conditions for the hydrocracking-like process include a temperature from about 230° C. (446° F.) to about 455° C. (850° F.), suitably 316° C. (600° F.) to about 427° C. (800° F.) and preferably 343° C. (650° F.) to about 399° C. (750° F.). For the Ru—ZrO2 catalyst, being the most active, suitable temperatures are lower than for the other catalysts; generally, about 230° C. (446° F.) to about 300° C. (572° F.). Suitable reaction pressure is from about 2.8 MPa (gauge) (400 psig) to about 17.5 MPa (gauge) (2500 psig), a liquid hourly space velocity of the fresh hydrocarbonaceous intermediate feed stream from about 0.1 hr−1, suitably 0.5 hr−1, to about 5 hr−1, preferably from about 1.5 to about 4 hr−1, and a hydrogen rate of about 84 Nm3/m3 (500 scf/bbl), to about 1,011 Nm3/m3 oil (6,000 scf/bbl), preferably about 168 Nm3/m3 oil (1,000 scf/bbl) to about 2,016 Nm3/m3 oil (12,000 scf/bbl). The cracking reactor is generally downstream of a reactor containing hydrotreating catalyst or a combination of hydrotreating catalysts.
As used herein, the term “a component-rich stream” or “a component stream” means that the stream coming out of a vessel has a greater concentration of the component than the feed to the vessel. As used herein, the term “a component-lean stream” means that the lean stream coming out of a vessel has a smaller concentration of the component than the feed to the vessel.
A basic process design showing a hydrotreating reactor and hydrocracking-like cracking reactor with the hydrocracking-like process in back-stage configuration is shown in
The following are several examples of the use of different catalysts to crack a paraffin into the desired C10-C13 paraffins.
A normal pentadecane (n-C15) feed was contacted with a 0.75% wt Pt on γ-alumina catalyst, with 0.75% wt Cl at conditions of 350° C., 500 psig, 1 h−1 WHSV, 10 H2/HC, 1 g catalyst. The reaction generated 40% n-C15 conversion. On carbon basis, selectivities were as follows: 0.79% methane, 39.50% C2-C8 normal paraffins, 38.08% C9-C12 normal paraffins, 10.91% C13 and C14 normal paraffins and 10.74% isomerized pentadecanes. The advantages seen were a low degree of methane production but there was low activity and high feed isomerization levels that may limit recycling.
A n-C15 feed was contacted with a catalyst consisting of 0.5% wt Ru on ZrO2 at 245° C., 200 psig, 2 h−1 WHSV, 25 H2/HC (by moles), 0.5 g catalyst. The reaction generated 75% n-C15 conversion. The selectivities on a carbon basis were C1 8.36%, C2 to C8 normal paraffins 34.65%, C9 to C12 normal paraffins 34.60%, C13 and C14 normal paraffins 21.94% and iC15 0.44%. The advantages found were high activity and low level of isomerization but there was higher production of methane than with the Pt-based catalyst.
A n-C15 feed was contacted with a catalyst consisting of 0.1% wt Ru on ZrO2 at 285° C., 500 psig, 1 hr−1 WHSV, 25 H2/HC (by moles), 1 g catalyst. The reaction generated 98% n-C15 conversion. The selectivities on a carbon basis were C1 3.08%, C2-C8 normal paraffins 58%, C9-C12 normal paraffins 34.57%, C13-C14 normal paraffins 4.33% and no detectable isomerized C15 or heavier products.
The Ru-based catalyst is sensitive to sulfur in the feed. In the examples, all clean parts were used in the testing. Previous testing with sulfur contaminated reactor yielded very low activity. Therefore, use of Ru based catalyst requires very low levels of sulfur ˜<0.1 ppm, preferably <0.03 ppm S in feed to maintain activity.
Table 1 shows the experimental results from a feed containing 10 wt % n-C16 and 90 wt % nC18 contacted with a number of different catalysts including catalysts containing Pt on alumina, Ni on alumina, NiO on clay, Ni on alumina dispersed on an inert core, Ni—Mo on alumina and Mo on alumina. Each individual catalyst testing was carried out in a 0.46″ ID once through plant having a Gas, Liquid Feed, Rx, Stripper and Product collection section. Reactor was loaded with the catalyst/SiC ratio 3. A sulfur adsorbent was placed in the pre-heat zone of the reactor to ensure the feed that enters the reactor has no sulfur in it. All catalysts were in-situ reduced in hydrogen at temperatures ˜400° C. followed by inducting the catalyst with 90/10 nC18/nC16 blend. Using the same feed, under conditions outlined in Table 1 catalyst activity measurements were taken. In general, it preferred to maximize yield of normal C10-C13, maximize linearity and minimize methane byproduct level.
While the following is described in conjunction with specific embodiments, it will be understood that this description is intended to illustrate and not limit the scope of the preceding description and the appended claims.
Without further elaboration, it is believed that using the preceding description that one skilled in the art can utilize the present disclosure to its fullest extent and easily ascertain the essential characteristics of this disclosure, without departing from the spirit and scope thereof, to make various changes and modifications of the disclosure and to adapt it to various usages and conditions. The preceding preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limiting the remainder of the disclosure in any way whatsoever, and that it is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.
In the foregoing, all temperatures are set forth in degrees Celsius and, all parts and percentages are by weight, unless otherwise indicated. A first embodiment of the disclosure is a process for converting a renewable feedstream to a C10 normal to C13 normal paraffin stream by first treating the renewable feedstream to remove heteroatoms such as sulfur, oxygen and nitrogen to produce a heteroatom-free feedstream and contacting said heteroatom-free feedstream in a cracking reactor with a catalyst selected from Group VIB or Group VIII metals or mixtures of two or more Group VIB and Group VIII metals and a neutral support. An embodiment of the disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the catalyst comprises a Ru—ZrO2, Pt—Al2O3, Ni—ZrO2, tungsten-containing catalyst or a Mo-containing catalyst or mixtures thereof. An embodiment of the disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the catalyst comprises Ru—ZrO2 (0.1-10 wt %). An embodiment of the disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the catalyst comprises about 5-30 wt % Mo on alumina. An embodiment of the disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the Mo containing catalyst further comprises about 0.05-5.0 wt % Ni. An embodiment of the disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein said biorenewable feedstream comprises carbon chains comprising C10 to C57 carbons. An embodiment of the disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph process of claim 1 wherein said biorenewable feedstream comprises carbon chains comprising C10 to C18 carbons An embodiment of the disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the biorenewable feedstream is selected from triglycerides, fats, oils or greases. An embodiment of the disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the biorenewable feedstream undergoes an additional conversion process to an intermediate stream comprising normal paraffins and where at least a port of the intermediate stream comprising normal paraffins is converted to the C10 normal to C13 normal paraffin stream. An embodiment of the disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the C10 to C13 normal paraffin stream has over 90% linearity. An embodiment of the disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the C10 to C13 normal paraffin stream has over 95% linearity. An embodiment of the disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the normal paraffin stream has over 98% linearity An embodiment of the disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising treating the C10 normal to C13 normal paraffin stream to remove isomerized C10 to C13 hydrocarbons. An embodiment of the disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the sulfur is removed from the biorenewable feed stream by sending the biorenewable feedstream through an adsorption bed before being sent to be contacted with said catalyst. An embodiment of the disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the process produces less than 25 wt % methane. An embodiment of the disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein said process produces less than 5% methane. An embodiment of the disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the feedstream is first sent to a hydrotreating reactor and then sent to a reactor and then the C10-C13 stream is sent to be converted to a linear alkyl benzene. An embodiment of the disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein said catalyst in said hydrocracking reactor is partially reduced. An embodiment of the disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the cracking reactor is a combination of a hydrotreating and hydrocracking reactor.
A second embodiment of the disclosure is a process for converting a feedstream to nC10 to nC13 linear hydrocarbons comprising sending a Fischer Tropsch liquid feedstream to a hydrocracking reactor to remove heteroatoms to produce an effluent stream, separating said effluent stream in a separation column into a C9− stream, a C10-C13 product stream and a C14+ stream, sending said C14=stream to a linear cracking reactor to produce a second C10-C13 stream and other hydrocarbons and sending said second C10-C13 stream and other hydrocarbons through said separation column.
A third embodiment of the disclosure is a process for converting a feedstream to nC10 to nC13 linear hydrocarbons comprising sending a hydrocarbon liquid feedstream to a hydrotreating reactor to remove heteroatoms to produce an effluent stream, separating said effluent stream in a separation column into a C9− stream, a C10-C13 product stream and a C14+ stream, sending said C14+ stream to a linear cracking reactor to produce a second C10-C13 stream and other hydrocarbons and sending said second C10-C13 stream and other hydrocarbons to said separation column. An embodiment of the disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the feedstream comprises palm kernel oil, coconut oil or babassu oil. An embodiment of the disclosure is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein gas is separated from the effluent upstream of the separation column.
This application is a continuation-in-part of U.S. application Ser. No. 18/394,840, filed on Dec. 22, 2023 which claims priority to provisional application 63/436,508, filed Dec. 31, 2022.
| Number | Date | Country | |
|---|---|---|---|
| 63436508 | Dec 2022 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 18394840 | Dec 2023 | US |
| Child | 18742761 | US |
