JP2011519344A - Method for producing short chain carboxylic acids and esters from biomass and products thereof - Google Patents

Abstract

A method of producing a mixture of short-chain carboxylic acids from biomass, adding biomass to a reaction vessel, heating and decomposing biomass, removing unnecessary unreacted substances and light ends from the decomposed biomass, Removing a mixture comprising a carboxylic acid having a carbon chain length of 2-16. A composition comprising a carboxyl group-containing compound derived from decomposing biomass having a carboxyl carbon chain length of 2 to 16 carbon atoms.
[Selection] Figure 1

Description

  The present invention relates to a method for producing short-chain carboxylic acids and esters from biomass and the products thereof.

One of the problems facing the modern industrialized society is the rapid depletion of crude oil, the primary resource for most transportation fuels and many organic chemicals. The petrochemical industry represents a substantial benefit to human society, and the invention and commercialization of alternative resources for petrochemical products is very important.
Two categories of organic chemicals that are frequently produced from petroleum are short-chain carboxylic acids and short-chain carboxylic esters. These chemicals are useful over a wide range including their use as monomers for a wide variety of polymer compounds, paints, coating materials and fragrance resources for perfumes and other necessities.
The use of short chain carboxylic acids as monomers is particularly important. In recent years, substantial efforts have been carried out to develop useful polymers from fatty acids linked within triacylglycerides. In steps such as the soy-based polyol (Soyol) process, triacylglyceride fatty acids are incorporated directly into the polymer compound. One disadvantage of these processes is that the resulting polymer compound has different properties, often inferior properties compared to existing polymer compounds made from petrochemical based monomers.
Surprisingly, very little work has been done to chemically modify triacylglycerides to produce fatty acid monomers and other mass-produced chemicals that are identical or nearly identical to existing monomers. Not done. Thus, there is a need to meet the demand for providing alternative sources of the chemicals as resource materials and crude oil decline.

  The invention described herein aims to provide a process for the production of commercial grade short chain carboxylic acids and short chain carboxylic acid esters from triacylglycerides, long chain fatty acids, long chain lipids or similar chemicals. .

One embodiment of the present invention is a method for producing a mixture of short chain carboxylic acids from biomass.
In the above method, biomass is charged into a reaction vessel, the biomass is heated and decomposed, unnecessary unreacted materials and light ends are removed from the decomposed biomass, and a carboxylic acid having a carbon chain length of 2 to 16 carbon atoms. Removing the containing mixture.

  Another embodiment of the present invention is a composition comprising a carboxyl group-containing compound derived by decomposing biomass and having a carboxyl carbon chain length of 2 to 16 carbon atoms.

  In the first form of the present invention, an oil comprising a main fatty acid obtained from a plant, represented by algae, derived from animal biomass or incorporated in a triacylglyceride derived from other sources is reacted. It is put into a container.

  In a second form of the invention, the oil is heated in a reaction vessel from a reduced pressure condition to a pressure of about 3000 psia to a temperature of about 100 ° C. to about 600 ° C. over a period of time sufficient to decompose the oil. During this process, unwanted material, unreacted oil and light ends are removed from the cracked oil. The purified material includes short chain carboxylic acids and compounds desirable for separation as fuel.

  In a third form of the invention, the short chain carboxylic acid compound is extracted from the fuel compound and purified. The short chain carboxylic acid generally contains a fatty acid having 2 to 12 carbon atoms (C2-C12). Desirable fuel components generally include alkanes, alkenes, aromatics, cycloparaffins and alcohols having 4 to 16 carbon atoms.

  In the fourth aspect of the present invention, preferential extraction of selected fatty acids is performed by liquid-liquid extraction using a basic aqueous solvent such as an amine such as trimethylamine. Regenerate the fatty acid-rich solvent to release the fatty acid from the solvent. Individual fatty acids having 2 to 12 carbon atoms are obtained in a purified form by physical and / or chemical separation.

  In the fifth aspect of the present invention, the preferential extraction of the selected fatty acid is carried out by a sequential liquid-liquid extraction method using room temperature water in order to preferentially extract the fatty acid having 2 to 5 carbon atoms. Selectively extract fatty acids with 4 to 7 carbon atoms using high water or aqueous base, and preferentially extract fatty acids with 6 to 12 carbon atoms using pressurized hot water or other solvent. To do. After extraction, individual fatty acids having 2 to 12 carbon atoms are obtained in purified form by physical and / or chemical separation.

  In a sixth aspect of the invention, esterification of one or more individual short chain fatty acids having 2 to 12 carbon atoms or mixtures thereof is carried out using an alcohol or alcohol mixture. Esterified alcohols used for esterification include, but are not limited to, methanol, ethanol, normal propanol, isopropanol, normal butanol, isobutanol, allyl alcohol and other alcohols. After esterification, the esterified material is separated from unreacted material.

1 is a simplified block diagram illustrating one embodiment of a short chain carboxylic acid production process of the present invention. 1 is a simplified block diagram illustrating one embodiment of a short chain carboxylic acid extraction step of the present invention. 1 is a simplified block diagram illustrating one embodiment of a process for purifying a short chain carboxylic acid according to the present invention. It is the graph illustrated about the fatty acid extraction by the trimethylamine of this invention. 2 illustrates an ASPEN Plus simulation model of a series of distillation columns for separating and purifying the short chain carboxylic acid of the present invention.

For the purpose of accurately describing the present invention, the following terms are defined to have the following corresponding meanings:
“Biofuel” means any fuel derived from plant or animal biomass.
“Biomass” means all organic, non-fossil raw materials derived from mass materials of all biological organisms, excluding mass materials converted by geological processes in materials such as coal and petroleum .
“Biomass oil” means all oils derived from biomass resources.
A “carboxyl group” is a chemical molecule that contains a carbon atom double-bonded to an oxygen atom, where the same carbon atom is also connected to a hydroxyl group, and no other atoms are connected to the double-bonded oxygen atom by a chemical bond. Part. In certain aqueous solutions, the structure is acidic because the hydrogen atom on the hydroxyl group is immediately separated from the chemical molecule to form a cation (hydrogen atom) and an anion (the remainder of the chemical molecule).

“Catalyst” means a substance that promotes the rate or ease of a chemical reaction.
“Catalytic decomposition” means a decomposition step using a catalyst.
“Decomposition” means any process that alters the chemical composition of an organic chemistry or chemical mixture by breaking one or more carbon-carbon bonds in one or more molecules.
“Crop” means all plants.
“Diesel” means a fuel made commercially for diesel powered vehicles.
A “carboxylic acid ester” is a chemical substance formed by the reaction of a carboxylic acid and an alcohol, and the terminal hydrogen atom of the carboxyl group is replaced with a carbon chain (radical) from the alcohol.
“Fatty acid” means a carboxylic acid having a saturated or unsaturated aliphatic terminus.
"Hydroxyl group" means a part of a chemical molecule that contains an oxygen atom connected by a single bond to a hydrogen atom, is connected to the remaining chemical molecule by a single bond, and the hydrogen atom is not bonded to any other atom. To do.
“Light end” means a chemical that remains in the gas phase under temperature and pressure conditions where the middle distillate is in the liquid phase.

“Middle distillate” has the property of being symbiotic contained in gasoline, kerosene or diesel type fuel, or similar to the paraffin and / or olefin contained in gasoline, kerosene or diesel type fuel. It means a chemical substance with high volatility. The middle distillate also contains carboxylic acid.
“Plant” means all living organisms that are members of the plant kingdom or Chiorphyta (green algae).
“Vegetable oil” means a lipid derived from plant resources. Examples of vegetable oils include crop oil or oilseed oil and vegetable oil.
The “short chain carboxylic acid” means a compound having 12 or less carbon atoms containing a carboxyl group.
“Short-chain carboxylic acid ester” means a chemical substance derived from a short-chain carboxylic acid in which a carboxylic acid group is substituted with an ester group.

A “tar” is a very long chain chemical that is produced during a decomposition reaction.
“Pyrolysis” means a decomposition process that involves the addition of energy in the form of thermal energy measured by increasing the temperature of the material being decomposed.
“Triacylglyceride” or “TG” is the main component of unmodified vegetable oil and is an ester of glycerin and 3 fatty acids.
“Unreacted raw material” means a cracking reaction that does not coexist as a middle distillate mixture component, can be further adapted to cracking reactor conditions, and has a chemical component that can be converted into middle distillate and / or light end and / or tar It is a material in the container product stream. These compounds chemically contain starting raw materials, i.e., original triacylglycerides (triacylglycerides in the feedstock) or partially cracked paraffins, olefins or middle distillates with too many carbon atoms in the primary carbon chain. The length of the fatty acid chain on the carboxylic acid that cannot co-exist as a mixture component can be the same or the same as the similar fatty acid.

Prior inventions or publications that describe the use of thermal and catalytic cracking for the production of short chain carboxylic acids and / or esters are not certified. Thus, there is a need to develop a process that can convert crop oil, biologically produced lipids or animal fatty oil feedstocks into the above important and valuable chemicals. In previous inventions, thermal / catalysts were developed to develop animal fat-based chemicals capable of converting commercial chemicals produced from crop oils, biologically produced lipids or other feedstock resources. Utilizing separation science and technology linked with mechanical decomposition technology.
The present invention is directed to the production and purification of short chain carboxylic acids of 2 to 16 carbon atoms with the potential for continued conversion of vegetable oils, biologically produced lipids or animal fats to short chain carboxylic esters. Directly connected. Specifically, the feedstock is a triacylglyceride compound. The present invention provides a means to generate these valuable and necessary chemicals from new feedstocks that have not previously been utilized in their production. Chemical modification based on the use of cracking and separation techniques is designed to produce commercial quality short chain carboxylic acid chemical products that can directly replace the equivalent chemical products generated from other feedstock resources. .

  Exploration of thermal and catalytic degradation of triacylglycerides (individual triacylglycerides and vegetable oils) has occurred sporadically in the past decades. These achievements have proven that a set of organic reactions occur during the thermal / catalytic degradation of triacylglycerides. These reactions are shown in Table 1 below.

  The chemical composition of the degradation products produced and produced mainly from fresh or used vegetable oils has been reported in numerous studies. Known overall process paths are shown in Table 2 below.

Note) In Table 2, path 1 ^a is catalytic decomposition at low temperature: Alencar (1983);
Path 2 ^b is catalytic cracking at high temperature: Katikani (1995); temperature 450 ° C.
Pathway 3 ^c is a non-catalytic degradation at low temperature: Schwab (1988); temperature 300 ° C. to 360 ° C.
* Additional 9.7-10.1% is labeled "undissolved unsaturated compound".

  Surprisingly, conditions for producing commercially viable concentrations of short chain carboxylic acids have been discovered. During purification to remove light ends, heavy ends and unreacted material, the resulting middle distillate contains more than 5% short chain carboxylic acids, preferably more than 20% short chain carboxylic acids, more preferably Contains 30% or more short chain carboxylic acids, most preferably 60% or more short chain carboxylic acids. In the present invention, thermal or catalytic cracking techniques known in the art in connection with separation techniques such as distillation, filtration, solvent extraction and related science and technology for the special purpose of producing commercial quality short chain carboxylic acids from biomass. Is used. Conventionally, these same short chain carboxylic acids were produced from resources other than biomass.

  Furthermore, it has been discovered that further processing of some or all of the purified short chain carboxylic acid or mixtures thereof to produce short chain carboxylic acid esters has economic advantages. This embodiment utilizes an esterification reaction with one or more alcohols. These reactions are known in conjunction with separation techniques such as fractional distillation, filtration, solvent extraction and related technology for the special purpose of producing commercial quality short chain carboxylic acids derived from biomass. The length of the short-chain carboxylic acid ester that can be produced in this step is in the range of 2 to 16 carbon atoms.

  The raw materials for this new process are triacylglycerides, free fatty acids or other carboxylic acids representing a group of chemicals found in plants or vegetable oils, or naturally synthesized biomass such as algae, animal fats or modified materials. Medium chain (10 to 14 carbon atoms) and long chain (greater than 16 carbon atoms) fatty acids found. Triacylglycerides in vegetable oils are generally long chain (over 16 carbon atoms) fatty acids (naturally synthesized carboxylic acids) connected via three medium chain fatty acids (10 to 14 carbon atoms) and / or glycerin groups. is there. These medium chain and / or long chain fatty acids can be purified, separated, chemically modified and used for food resources, chemical feedstocks, or potential transportation fuels. Plants and vegetable oils include flax, soy, safflower, sunflower, sesame, canola, rapeseed, jatropha, primrose, poppy, camelina, hamana, olives, coconut, coconut, cotton, corn, soy, jojoba, gumbana, tomatoes and nuts However, it is not limited to these. Some of the major commercial crop oil compositions are listed in Table 3.

  Representative fatty acids contained in crop oil include saturated as well as unsaturated fatty acids. Saturated fatty acids do not contain double bonds or other functional groups. Unsaturated fatty acids include two or more carbon atoms having a carbon-carbon double bond. Saturated acids include stearic acid (18 carbon atoms; 18: 0), palmitic acid (16 carbon atoms; 16: 0), myristic acid (14 carbon atoms; 14: 0) and lauric acid (12 carbon atoms). 12: 0). Unsaturated acids include linolenic acid (cis, cis, cis carbon atoms 18; 18: 3), linoleic acid (cis, cis carbon atoms 18; 18: 2), oleic acid (cis carbon atoms 18; 18 1), hexadecanoic acid (cis, cis carbon atoms 16; 16: 2)), palmitic acid (cis carbon atoms 16; 16: 1), myristoleic acid (cis carbon atoms 14; 14: 1), etc. Is included.

  Thermal or catalytic decomposition of medium chain (10 to 14 carbon atoms) and / or long chain (more than 16 carbon atoms) fatty acids (naturally synthesized carboxylic acids) is separated and combined with refining technology for fuel or fuel blending More specifically, it is well known that mixtures of chemicals suitable for use as components in diesel, kerosene, aviation turbine and automotive gasoline fuel can be produced. An example of a method for deriving fuel from biomass is described in US patent application Ser. No. 11 / 824,644 (Seames), which is hereby incorporated by reference. US patent application Ser. No. 11 / 824,644 describes a process for producing fuel from biomass having a cloud point of less than −10 ° C. The present invention describes processes that can produce short chain carboxylic acids and carboxylic acid esters as well as produce materials suitable for the fuel used or fuel blending feedstock. The combination of short chain carboxylic acid and acid ester production with fuel or fuel product provides the ability to produce two beneficial products instead of one using a set of cracking parameters.

  In the decomposition process, energy is used to break carbon-carbon bonds. Once destroyed, each carbon atom becomes a single electron and free radical. Free radical reactions lead to various products exemplified in Table 1. Large organic molecules can be broken down into smaller and more useful molecules by high pressure and / or temperature (pyrolysis) and optionally a catalyst (catalytic decomposition). Preliminary investigations are compatible with cracking processes that use either thermal or catalytic decomposition of medium chain fatty acids (10 to 14 carbon atoms) and long chain (more than 16 carbon atoms) fatty acids (natural synthetic carboxylic acids). It turned out to have sex. These techniques have been used in previous inventions and research to modify the chemical composition of crop oil or biodiesel. However, the above technique has not been utilized to produce commercial quality short chain carboxylic acids and / or esters.

  FIG. 1 is a simplified block process flow diagram of one embodiment of a short-chain carboxylic acid production process. Biomass 10 (including crop oil, lipids and animal fat feedstock) is produced in a process that is currently available or can be discovered in the future. Biomass 10 may be preheated or fed directly to the cracking reactor for pyrolysis step 12. By varying the time, temperature and pressure at which a particular feedstock remains under cracking conditions, the desired degree of cracking (conversion) can be controlled. Temperature and time (residence time) are more important process variables with pressure playing a secondary role. The product of the cracking process depends on the cracking conditions, the original composition of biomass 10 and the gaseous environment present in the cracking reactor. In general, biomass 10 is heated in a cracking reactor to a temperature of 100 ° C. to 600 ° C. for a residence time of 1 minute to 180 minutes under reduced pressure conditions to 3000 psia. The temperature range is preferably 300 ° C to 500 ° C, most preferably 390 ° C to 440 ° C. The cracking conditions are varied based on detailed chemical analysis to produce an optimal mixture of short chain carboxylic acid and fuel components.

The catalyst can be used to improve the yield of the desired product, reduce the formation of unwanted products, or increase the cracking reaction efficiency due to low pressure, temperature or residence time requirements. Catalysts include, but are not limited to, rare metals such as zeolite, carbon and palladium, niobium, molybdenum, platinum, titanium, aluminum, cobalt, gold, and mixtures thereof.
The cracked product is processed in various processing and purification steps 14 depending on the product material. The output from the cracking reactor depends on the specific cracking reactor design used. The following are examples of reactor types known to those skilled in the art: batch, continuous flow system, packed bed flow, and fluidized bed. The materials produced in the cracking reactor are generally defined as light end 16, unreacted raw material 18 (recyclable), residual material or residue (tar) 20, and middle distillate 22.

  The light end 16 is an unreacted gas phase material added to the reactor to manipulate the cracking reaction, such as hydrogen, nitrogen or water vapor in addition to small molecular weight organic chemicals and hydrocarbons generated in the cracking reactor. . Small molecular weight organic chemicals and hydrocarbons (eg methane, methanol, ethane, ethanol, n-pentane, i-pentane, pentene, pentanol n-butane, i-butane, butanol, butane, methyl ester, ethyl ester, etc.) Have undesirable (eg, excessively volatile) chemical and physical properties when present in substantial concentrations of short chain carboxylic acid extract or middle distillate fuel components. The light end is separated from other materials exiting the reactor in the purification step 14 by gas-liquid phase separation, fractional distillation, concentration or other processes.

  The unreacted raw material 18 is a chemical substance entering the decomposition reactor, but is not converted into a chemical substance having a carbon chain shorter than 16 carbon atoms. These materials have several chemical and physical properties that are undesirable in fuel products. Unreacted raw material is separated from middle distillate components in the purification step 14 by distillation or other separation techniques. Unreacted or undecomposed raw material 18 is then returned to the cracking reactor, fed to a second cracking reactor, or available for some other purpose.

Residual material or residual tar 20 is a chemical that is produced during the cracking reaction and has a higher molecular weight, lower volatility and / or lower heat than desired in middle distillate 22. Some of the residual components 20 can be separated from the middle distillate 22 with unreacted raw materials 18 and can be processed by these unreacted raw materials 18. The other residual components 20 which are generally of higher molecular weight are in the form of solid components (at room temperature) after the decomposition reaction. These compounds are typically known as “tars”. Tar 20 contains valuable chemicals, such as boiler fuel or other by-products that can be extracted from residual material 20 by various processing methods including solvent extraction, fractional distillation, etc., or is converted to valuable chemicals by chemical reaction Can contain chemicals that can. Depending on the design of the cracking reactor, tar 20 may not be accepted for further processing.
This type of tar 20 can be oxidized, burned, or removed from the cracking reactor or cracking catalyst by methods known in the art.

Middle distillate component 22 is a short chain carboxylic acid portion of the residual material that is a short chain carboxylic acid compound produced in the cracking reactor and contributes to the desired chemical and physical properties of the fuel or fuel blended feed product. is there.
Short chain carboxylic acid 28 is removed from middle distillate 22 using one or more processing methods (step 24) including solvent extraction, distillation, and the like. One embodiment of this type of process is illustrated in FIG. Middle distillate 22 enters the short chain fatty acid (SCFA) extraction column at step 30. A solvent such as a 40% aqueous solution of trimethylamine, warm water or aqueous sodium hydroxide is transferred to the extraction tower. As the solvent passes through the column, it absorbs short chain fatty acids and produces an SCFA-rich solvent, while other components (eg, biofuel component 26) remain in the separation liquid phase and are separated and removed from the column. The mixed short chain fatty acid 28 is separated from the solvent. The solvent is then regenerated (step 32) and returned to the extraction column.

  Once the short chain carboxylic acids (fatty acids) 28 are sequestered from the middle distillate 22, they are processed and further purified. The additional purification step produces a product stream containing the main single component or characteristic group of the short chain carboxylic acid 28. One embodiment of a typical purification mechanism is illustrated in FIG. Light fatty acids (5 or less carbon atoms) and heavy fatty acids (6 to 16 carbon atoms) are separated from the mixed short-chain fatty acid 28 by the mixed short-chain fatty acid separator 34. The separated fatty acid is further separated using a distillation column, and a fatty acid having a specific carbon chain length is extracted. For example, light short chain fatty acids are transferred to a series of distillation columns. Acetic acid is isolated in acetic acid tower 36, propanoic acid is isolated in propanoic acid tower 38, butyric acid is isolated in butyric acid tower 40, and valeric acid is isolated in valeric acid tower 42. Low volatile (heavy) short chain fatty acids are similarly sequestered using the hexanoic acid tower 44, the heptanoic acid tower 46 and the heavy short chain fatty acid separator 48 (for fatty acids having 8 or more carbon atoms on the carbon chain). Is done. The purification step selected will depend on the technique used to separate the short chain carboxylic acid 28 from the middle distillate 22 fuel component.

  The individual or mixture of short chain carboxylic acids 28 produced in this step can be further processed to form short chain carboxylic esters by reacting the short chain carboxylic acid with one or more alcohols. Unreacted and / or by-product materials are then removed from the product short chain carboxylic acid ester to obtain a commercial quality short chain carboxylic acid ester.

  In one embodiment of the present invention, a triacylglyceride crop oil, biologically produced lipid, animal fatty oil or these oils (biomass 10) in a cracking reactor in a pressure range from reduced pressure to 3000 psia. The ester-converted derivative is heated to a temperature in the range of 300 ° C. to 500 ° C., and in the presence of a gaseous environment that can include an inert gas such as nitrogen, water vapor, hydrogen, gas phase organic chemicals, or other gaseous mixtures. A residence time in the range of 1 minute to 180 minutes affects the decomposition reaction which changes the chemical composition of the contents of the decomposition reactor. Steam (cracked product) leaving the cracking reactor is a secondary chemical by cooling, partial enrichment, steam / liquid separation, solvent extraction to produce an acceptable transportation fuel such as aviation turbine fuel or diesel fuel Or downstream processing including other chemical / physical property manipulation, in situ reaction, fractional distillation or flash separation. Liquids and solids (residues) leaving the cracking reactor are cooled or heated to produce acceptable fuel by-products or by-products, liquid / solid separation, vapor / liquid separation, vapor / solid separation, solvent extraction Undergoes downstream processing including extraction of secondary chemicals by or other chemical / physical property manipulation. Unreacted material and partially reacted material 22 separated from either the cracked product or the residue are returned to the cracking reactor, routed to the addition cracking reactor, or used in other processes.

Example 1: Short chain fatty acid production from soybean oil A 2 liter per hour continuous cracking reactor system was used as the cracking reactor. Thermal decomposition under reduced pressure was applied to soybean oil. The output from the cracking reactor (cracker) was analyzed and then further processed. Light weight hydrocarbons were removed in the inclusion distillation column, and the heaviest hydrocarbons were removed using the second inclusion distillation column. This produced a middle distillate containing a high percentage of short chain carboxylic acids. The middle distillate was then mixed with an equal amount of room temperature, purified water, and the oil and water phases were separated. In this step, most fatty acids having 2 to 4 carbon atoms were removed. The oil from this extraction was then mixed with an equal volume of 1M sodium hydroxide in purified water and the oil and water phases separated. Table 4 summarizes the results of short chain fatty acid extraction using water and sodium hydroxide. The amount of short chain fatty acid (SCFA) extracted is represented by% (w / w) of middle distillate 18.

Example 2: Production of short-chain fatty acids from soybean oil using an aqueous amine solution In the same manner as in Example 1, soybean oil was produced from middle distillate 18 containing a high percentage of short-chain carboxylic acid. Middle distillate 18 was then mixed with 25% (w / w) aqueous trimethylamine solution at room temperature in a separatory funnel. The addition amount of the aqueous amine solution was 0.002 mol of trimethylamine per gram of middle distillate 18. Next, the aqueous phase and the organic phase were separated, and the acid value of the middle distillate 18 was measured according to ASTM method D3242. FIG. 4 illustrates the results of short chain fatty acid extraction using an aqueous amine solution. As shown in the figure, the acid value of the middle distillate 18 after extraction decreased to almost zero, indicating that all of the fatty acids were extracted and actually became an aqueous phase.

  Data from these experiments was collected to form an ASPEN Plus simulation model, in which a short chain carboxylic acid was separated and purified based on volatility in a series of distillation columns. The simulation result is shown in FIG. The mixture of fatty acids (carboxylic acids) is transferred to the distillation column T100 via the heat exchanger HX by the pump P100. Fatty acids having 2 to 5 carbon atoms in the carbon chain are separated from the mixture and sent to the distillation column T200. Fatty acids having 2 or 3 carbon atoms are separated and sent to the distillation column T300. The distillation column T300 separates fatty acid having 2 carbon atoms (acetic acid) from fatty acid having 3 carbon atoms (propanoic acid). Similarly, the fatty acid having 4 or 5 carbon atoms is sent from the distillation column T200 to the distillation column T500. The distillation column T500 separates fatty acids having 4 carbon atoms (butyric acid) from fatty acids having 5 carbon atoms (valeric acid). Similarly, the distillation column T800 separates fatty acids having 6 or 7 carbon atoms from fatty acids having 8 or more carbon atoms. The fatty acid having 6 or 7 carbon atoms is sent to the distillation column T900, where the fatty acid having 6 carbon atoms (hexanoic acid) is separated from the fatty acid having 7 carbon atoms (heptanoic acid). The estimated yield for the simulated purification is listed in FIG.

The methods for producing short chain carboxylic acids and acidic esters described herein provide a useful means of creating valuable chemicals from biomass rather than petroleum precursors. This method also enables the simultaneous production of chemicals useful for fuel utilization using the same decomposition parameters. Efficiency gains are also realized because two useful sets of chemicals can be generated utilizing steps sharing some of the same processing conditions.
Although the presently preferred embodiments of the invention have been described above, it will be appreciated that various changes can be made and equivalents can be substituted for the components without departing from the scope of the invention. This is a matter of course for those skilled in the art. It should also be noted that various modifications and the like can be made to adapt to the teachings of the present invention and to suit a particular situation or material without departing from the essential scope of the present invention. Accordingly, the invention is not limited to the specific embodiments disclosed, but the invention is intended to include all embodiments encompassed within the scope of the appended claims.

Claims (22)

  A method of producing a mixture of short chain carboxylic acids from biomass, wherein the biomass is charged into a reaction vessel and allowed to spend sufficient time to decompose the biomass from a reduced pressure condition to a pressure of about 3000 psia, about 100 ° C. to about 100 ° C. The biomass is heated in a reaction vessel at a temperature of 600 ° C. to remove unwanted materials, unreacted materials and light ends from the decomposed biomass, and at least about 5% carbon chain lengths of 2 to 16 carbon atoms are obtained. Removing the mixture containing the carboxylic acid.   The method of claim 1, wherein the removal mixture comprises 20% or more carboxylic acid.   The method of claim 2, wherein the removal mixture comprises 30% or more carboxylic acid.   4. The method of claim 3, wherein the removal mixture comprises 60% or more carboxylic acid.   The method of claim 1, further comprising purifying the mixture to one or more carboxylic acids having a carbon chain length of 2 to 16 carbon atoms.   6. The method of claim 5, wherein the purification is selected from the group consisting of solvent extraction, fractional distillation, and combinations thereof.   6. The method of claim 5, wherein the purified mixture is reacted with an alcohol to produce one or more carboxylic acid esters having a carbon chain length of 2 to 16 carbon atoms.   8. The method of claim 7, wherein the alcohol is selected from the group consisting of methanol, ethanol, normal propanol, isopropanol, normal butanol, isobutanol, allyl alcohol, and combinations thereof.   The biomass is soybean oil, canola oil, palm oil, sunflower oil, corn oil, amanine oil, jatropha oil, cottonseed oil, safflower oil, hamana oil, primrose oil, sesame oil, rapeseed oil, olive oil, coconut oil, camelina, jojoba, gumbai 2. The method of claim 1, wherein the method is selected from the group consisting of nazuna, tomatoes and combinations thereof.   The method according to claim 1, wherein the temperature of the reaction vessel is 300C to 500C.   The process of claim 1, wherein the oil is heated in the reaction vessel over a period of time ranging from 1 minute to 180 minutes.   The method of claim 1, wherein heating of the reaction vessel occurs in a gaseous environment, the gaseous environment comprising at least one of an inert gas, nitrogen, water vapor, hydrogen, or a mixture of gas phase organic chemicals.   The method of claim 1, further comprising adding a catalyst to the reaction vessel.   The method of claim 1, wherein the reaction vessel is of a type selected from the group consisting of batch, continuous flow system, packed bed currency flow, and fluidized bed.   2. The mixture of claim 1, wherein the mixture comprises an alkane, alkene, aromatic compound, cycloparaffin or alcohol having a carbon chain length of 4 to 12 carbon atoms, and a fatty acid having a carbon chain length of 2 to 16 carbon atoms. the method of.   16. The mixture of claim 15, wherein the mixture comprises alkanes, alkenes, aromatics, cycloparaffins or alcohols having a carbon chain length of 4 to 8 carbon atoms, and fatty acids having a carbon chain length of 2 to 10 carbon atoms. the method of.   Solvent extraction is performed by contacting water with a mixture having a solvent selected from the group consisting of a basic aqueous solution or an aqueous amine solution, removing one or more carboxylic acids and solvents from the mixture, and removing the one or more carboxylic acids from the solvent. 7. The method of claim 6, comprising separating from.   17. The method of claim 16, wherein the carboxylic acid is recovered from water and a basic aqueous solution or other solvent by fractional distillation, evaporation, vaporization, pH adjustment or other physical or chemical separation principles.   A carboxyl group-containing compound produced by the method according to claim 1, wherein the compound has a carbon chain length of 2 to 16 carbon atoms.   The carboxyl group-containing compound according to claim 19, wherein the compound is a carboxylic acid.   20. The compound of claim 19, wherein the compound is a carboxylic acid ester, wherein the carboxylic acid ester is formed by reacting a carboxylic acid produced by the method of claim 1 with an alcohol.   A method of producing a fuel composition having a short chain carboxylic acid and a low cloud point from biomass, wherein the biomass is charged into a reaction vessel and allowed to spend sufficient time to decompose the biomass from about reduced pressure conditions to about 3000 psia. Under pressure, the biomass is heated in a reaction vessel at a temperature of about 100 ° C. to about 600 ° C. to remove unwanted materials, unreacted materials and light ends from the decomposed biomass, and alkanes having at least 4 to 16 carbon atoms; A cracked biomass fraction containing an alkene, an aromatic compound, cycloparaffin or alcohol, a fatty acid having 2 to 16 carbon atoms, or a fatty acid methyl ester having 2 to 16 carbon atoms is recovered, and has 2 to 16 carbon atoms A mixture containing a carboxylic acid having a carbon chain length is removed, and the recovered cracked biomass fraction is combined to give a cloud point of -1. The method comprising producing a fuel composition below ° C..

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