KR20150126616A - Process for making linear long-chain alkanes from renewable feedstocks using catalysts comprising heteropolyacids - Google Patents

Abstract

A hydrodeoxygenation process for producing linear alkanes from feedstocks comprising a saturated or unsaturated C _10-18 oxygenate comprising an ester group, a carboxylic acid group, a carbonyl group and / or an alcohol group / RTI > The process comprises contacting the feedstock at a temperature of from about 150 DEG C to about 250 DEG C and at a hydrogen gas pressure of at least about 300 psig with (i) from about 0.1 wt% to about 10 wt% of a metal selected from the group IB, VIB, or VIII of the Periodic Table; By weight of catalyst and (ii) a heteropoly acid or heteropoly acid salt. By contacting the feedstock with the catalyst and the heteropoly acid or heteropoly acid salt under these temperature and pressure conditions, the C _10-18 oxygenate is hydrodeoxygenated to a linear alkane having the same carbon chain length as the C _10-18 oxygenate.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a process for preparing a linear long chain alkane from a renewable feedstock using a catalyst comprising a heteropoly acid,

This application claims the benefit of U.S. Provisional Patent Applications 61 / 782,172 and 61 / 782,198, filed March 14, 2013, both of which are incorporated herein by reference in their entirety.

The present invention is in the field of chemical processing. More specifically, the invention relates to a process for producing a linear long chain alkane from a feedstock comprising a C _10-18 oxygenate, such as a fatty acid and a triglyceride.

Long-chain alpha, omega-dicarboxylic acids (long-chain diacid, "LCDA"), i.e. those having a carbon chain length of 9 or more, are used in the synthesis of various chemical products and polymers (e.g. long chain polyamides) It is used as raw material. The types of chemical processes used to make long chain discrete have many limitations and disadvantages, the most important of which is that these processes are based on non-renewable petrochemical feedstocks. In addition, the multi-reaction conversion process used to produce long chain disac- tions generates undesirable by-products, heavy metal waste, and nitrogen oxides that need to be destroyed in a reduction furnace, leading to yield loss.

Considering the increased environmental footprint left by high-cost and fossil fuels and the world's limited oil reserves, a renewable source such as fats and oils obtained from plants, animals and microorganisms to produce chemicals and polymers , There is a growing interest in using long chain discrete, for example.

Long chain disaccharides may be prepared from long chain alkanes and long chain alkanes may be prepared by converting the fatty acids and triglycerides again via hydrodeoxygenation (HDO). The alkane product of this reaction can be used not only to produce long-chain disaccharides, but also as fuel by itself or as a mixture with diesel from petroleum feedstocks.

Conventional methods of deoxygenation to convert renewable feedstocks to long chain alkanes include catalytic hydrogenation, catalysis or thermal decarboxylation, catalytic decarbonylation and catalytic hydrogenolysis. Commercially available deoxygenation reactions are typically carried out under high pressure and high temperature in the presence of hydrogen gas, which makes the process costly. Some low-pressure deoxygenation processes have also been described; Such methods are problematic due to several disadvantages such as low activity, poor catalyst stability, and undesirable side reactions. Typically, these processes require high temperatures and result in high decarboxylation and decarbonylation, leading to shortening of the chain length of the long chain alkane product.

For example, U.S. Patent Application Publication No. 2012-0029250 discloses a process for the preparation of a compound of the formula (I) from decarboxylation to pentadecane (C15: 0) and heptadecane (C17: 0) from oleic acid 0). ≪ / RTI > This method also required a reaction temperature of 300 ° C or higher. In addition to bringing products with carbon losses, the deoxygenation process has also resulted in incompletely deoxygenated products such as stearic acid, unsaturated isomers of oleic acid, and branched products. Formation of the decarboxylated product as well as the branched product was also observed using the methods disclosed in U.S. Patent Nos. 8,193,400 and 7,999,142.

U.S. Patent No. 8,142,527 discloses a hydrogenated deoxygenation process that produces diesel fuel from vegetable and animal oils, which requires a reaction temperature of at least 300 ° C. The hydrogenated deoxygenation process disclosed by U.S. Patent No. 8,026,401 required a reaction temperature of 400 ° C or higher.

There is therefore a continuing need for a hydrogenated deoxygenation process that can be performed under conditions of low temperature and low pressure and reliably converts oil and fat fatty acids from renewable resources to long chain linear alkanes without substantial carbon loss.

In one embodiment, the present invention relates to a process for the preparation of a compound of _{formula I} from a feedstock comprising a saturated or unsaturated C _10-18 oxygenate comprising a moiety selected from the group consisting of an ester group, a carboxylic acid group, a carbonyl group and an alcohol group The present invention relates to a hydrogenated deoxygenation process for producing linear alkanes. The process comprises contacting the feedstock at a temperature of from about 150 DEG C to about 250 DEG C and at a hydrogen gas pressure of at least about 300 psig with (i) from about 0.1 wt% to about 10 wt% of a metal selected from the group IB, VIB, or VIII of the Periodic Table; By weight of catalyst and (ii) a heteropoly acid or heteropoly acid salt. By contacting the feedstock with the catalyst and the heteropoly acid or heteropoly acid salt under these temperature and pressure conditions, the C _10-18 oxygenate is hydrodeoxygenated to a linear alkane having the same carbon chain length as the C _10-18 oxygenate. Alternatively, the hydrogenated deoxygenation process further comprises recovering the linear alkane produced in the contacting step.

In a second embodiment, the _C10-18 oxygenate is a fatty acid or a triglyceride.

In a third embodiment, the feedstock comprises a vegetable oil or a fatty acid distillate thereof. The feedstock can be, for example, (i) a vegetable oil selected from the group consisting of soybean oil, palm oil and palm kernel oil; Or (ii) palm fatty acid distillates.

In a fourth embodiment, the catalyst comprises about 0.1 wt% to about 6 wt% platinum as metal. In a fifth embodiment, the catalyst comprises about 0.25 wt% to about 2 wt% platinum as metal.

In a sixth embodiment, the heteropoly acid or heteropoly acid salt comprises tungsten. In this embodiment, the heteropoly acid or heteropoly acid salt may further include, for example, phosphorus.

In the seventh embodiment, the heteropoly acid salt is a heteropoly acid cesium salt.

In an eighth embodiment, the catalyst further comprises a solid support.

In a ninth embodiment, the feedstock is contacted with a catalyst and a heteropoly acid salt, and the catalyst is bonded to a heteropoly acid salt.

In a tenth embodiment, the catalyst and the heteropoly acid or heteropoly acid salt are dry-mixed together before they are contacted with the feedstock. In an eleventh embodiment, the catalyst and the heteropoly acid are dry-mixed together before they are contacted with the feedstock.

In the twelfth embodiment, the temperature is about 200 DEG C and the pressure is about 400 psig.

In the thirteenth embodiment, the molar yield of the hydrogenated deoxygenation process is less than 10% for a reaction product having a carbon chain length that is shorter than the carbon chain length of the C _10-18 oxygenate by at least one carbon atom.

The disclosures of all patents and non-patent references cited herein are incorporated herein by reference in their entirety.

As used herein, the term " invention "or" disclosed invention "is not meant to be limiting and generally applies to any of the inventions defined in the claims or described herein. The terminology invention, the disclosed invention and the invention are used interchangeably herein.

The term " hydrodeoxygenation "(HDO)," hydrodeoxygenation process or reaction ","deoxygenation process or reaction" and "hydrotreating" are used interchangeably herein. As used herein, a hydrogenated deoxygenation refers to a chemical process in which hydrogen is used to reduce the oxygen content of oxygen-containing organic compounds such as esters, carboxylic acids, ketones, aldehydes, or alcohols. Complete hydrogenation deoxygenation of such a compound typically produces an alkane in which the carbon atom (s) previously bound to the oxygen atom is in a hydrogen-saturated state (i.e., the carbon atom is in the "hydrogenated deoxygenated state" . For example, the hydrogenated deoxygenation of a carboxylic acid group or an aldehyde group produces a methyl group (-CH ₃ ), whereas a hydrogenated deoxygenation of a ketone group produces an internal carbon moiety -CH ₂ -.

Hydrogenated deoxygenation processes as described herein also reduce alkene (C = C) and alkyne (C? C) groups to the C-C group. Thus, the hydrogenated deoxygenation process can also be referred to as a method of reducing the unsaturated moiety in an organic compound.

As used herein, hydrogenated deoxygenation does not refer to a method of reducing the oxygen content of a hydrocarbon through destroying a carbon-carbon bond, such as removal of a carboxylic acid group (i.e., decarboxylation ) Or removal of the carbonyl group (i. E., Decarbonylation). Hydrogenated deoxygenation herein does not refer to a method of incompletely reducing an oxygenated carbon moiety (i. E., Reduction of a carboxylic acid group to carbonyl or an alcohol group).

The terms "alkane", "paraffin", and "saturated hydrocarbon" are used interchangeably herein. As used herein, an alkane refers to a chemical compound consisting solely of hydrogen and carbon atoms, with the carbon atoms bound only by a single bond (i.e., they are saturated compounds). The alkane may be linear or branched and accordingly may have a methyl group at its end.

The terms "linear alkane", "straight chain alkane", " n -alkane", and " n -paraffin" are used interchangeably herein and refer to a straight- Quot; refers to an alkane bonded to two hydrogens and two carbons. The simplified formula for the linear alkane is C _n H _{2n + 2} . Linear alkanes differ from branched alkanes in that branched alkanes have at least three terminal methyl groups.

As used herein, the term "C _10-18 oxygenate" refers to a linear chain of 10 to 18 carbon atoms in which one or more carbon atoms is bonded to an oxygen atom (i.e., Oxygenated carbon). Such oxygen-bonded carbon atoms are included in the C _10-18 oxygenate in the form of one or more alcohols, carbonyls, carboxylic acids, esters, and / or ether moieties. As is understood in the art, the carboxylic acid, ester, and / or ether moiety, if present, will be located at one or both ends of the C _10-18 oxygenate.

The C _10-18 oxygenate can be a length of 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms but typically has 10, 12, 14, 16, or 18 carbon atoms Lt; / RTI > Examples of C _10-18 oxygenates as referred to herein include, but are not limited to, esters, carboxylic acids, ketones, aldehydes, and alcohols.

As used herein, the term "saturated C _10-18 oxygenates" refers to the configuration of carbon atoms of C _10-18 oxygenates (i. E., Double or triple bond, no) connected to each other by a single bond. An example of a saturated C _10-18 oxygenate is stearic acid (C 18: 0).

As used herein, the term "unsaturated C _10-18 oxygenates" is one or more double (alkenes), or triple (alkynes) C _10-18 oxygenates that bond is present at the carbon atom chains of C _10-18 oxygenates Quot; Examples of unsaturated C _10-18 oxygenates are oleic acid (C18: 1) and linoleic acid (C18: 2), which contain one and two double bonds, respectively.

As used herein, an "ester group" refers to an organic moiety having a carbonyl group (C = O) (defined below) that is adjacent to an ether bond. The general formula of the ester group is as follows:

R in the ester formula refers to a linear chain of 9 to 17 carbon atoms; In this way, the C = O carbon atom represents the 10th to 18th carbon atom of the C _10-18 oxygenate containing the ester group. The R 'group refers, for example, to an alkyl or aryl group. Examples of ester groups are found in mono-, di-, and triglycerides, each containing one, two, or three fatty acids esterified with glycerol. With respect to the above formula, the R 'group of the monoglyceride will refer to the glycerol moiety of the molecule. The linear alkanes produced from the esters by the disclosed hydrogenated deoxygenation process contain carbon atoms of the R group and the C = O group.

As used herein, "carboxylic acid group" or "organic acid group" refers to an organic moiety having a "carboxyl" or "carboxy" group (COOH). The general formula for the carboxylic acid group is:

R in the carboxylic acid formula refers to a linear chain of 9 to 17 carbon atoms; In this manner, the carboxyl group (COOH) carbon atom represents the 10th to 18th carbon atom of the C _10-18 oxygenate containing the carboxylic acid group. The linear alkanes produced by the disclosed hydrogenated deoxygenation process maintain the carboxyl group carbon atoms (i. _E. , The product is not decarboxylated with respect to the C _10-18 oxygenate substrate).

As used herein, "carbonyl group" refers to a carbon atom (C = O) that is doubly-bonded to an oxygen atom. The carbonyl group may be located at one or both ends of the C _10-18 oxygenate; Such a molecule may be referred to as an aldehyde. Alternatively, one or more carbonyl groups may be located within the carbon atom chain of the C _10-18 oxygenate; Such a molecule may be referred to as a ketone.

As used herein, an "alcohol group" refers to a carbon atom that is attached to a hydroxyl (OH) group. One or more alcohol groups may be located on any carbon of the C _10-18 oxygenate (either or both ends, and / or one or more internal carbons of the C _10-18 oxygenated carbon chain).

The terms "feedstock" and "feedstock" are used interchangeably herein. The feedstock refers to a material comprising a saturated and / or unsaturated C _10-18 oxygenate. The feedstock may be a "renewable" or "bio-renewable" feedstock, which refers to a material obtained from a biological or biologically-derived source.

Examples of such feedstocks are materials containing monoglycerides, diglycerides, triglycerides, free fatty acids, and / or combinations thereof and include lipids such as fats and oils. These particular types of feedstock - which may also be referred to as "oleaginous feedstock" - include animal fats, animal fats, poultry fats, poultry oils, vegetable and vegetable fats, vegetable and vegetable oils, yeast oils, Rendered fat, refined oil, restaurant grease, brown grease, pulp industry frying oil, fish oil, fish fat, and combinations thereof. For feedstocks comprising fats or oils, it will be understood by those skilled in the art that all or most of the C _10-18 oxygenates are included in the feedstock in the form of esters (fatty acids esterified with glycerol). Hydrogenated deoxygenation of such _C.sub.10-18 oxygenates according to the disclosed method involves complete reduction of the ester group of the esterified fatty acid, which in part involves the destruction of the ester bond between the fatty acid and the glycerol molecule.

Alternatively, the feedstock may refer to a petroleum- or fossil fuel-derived material comprising a saturated or unsaturated C _10-18 oxygenate.

As used herein, the terms "fatty acid distillate" and "fatty acid distillate of an oil" refer to a composition comprising a fatty acid of a particular type of oil. For example, palm fatty acid distillates include fatty acids present in palm oil. Fatty acid distillates are generally a by-product of the vegetable oil purification process.

The terms "moiety", "chemical moiety", "functional moiety", and "functional group" are used interchangeably herein. As used herein, a moiety refers to a carbon group comprising a carbon atom bonded to an oxygen atom. As used herein, examples of moieties include esters, carboxylic acids, carbonyls and alcohol groups.

The terms "weight% "," weight percent (wt%) ", and "weight- weight percentage (% w / w)" are used interchangeably herein. Weight percent refers to the percentage by weight of the material when it is included in the composition or mixture. For example, weight percent refers to the percentage of metal based on the mass present in the catalyst, as described herein. Except as otherwise described, all percentages of the metals or other materials disclosed herein refer to the weight percent of metal or other materials in the catalyst.

As used herein, "psig" (pound-force per square inch gauge) refers to the unit of pressure for atmospheric pressure at sea level. For example, 30 psig represents an absolute pressure of 44.7 psi (i.e. 30 + psi 14.7 atmospheric pressure).

The terms "catalyst" and "metal catalyst" are used interchangeably herein. Catalysts include metals that themselves increase the rate of hydrogenated deoxygenation of C _10-18 oxygenates without being consumed or subject to chemical changes. The catalyst is generally present in minor amounts relative to the amount of reactant. In certain embodiments, the catalyst may also be characterized as a metal catalyst in the presence of a heteropoly acid or a heteropoly acid salt. Such can be accomplished by mixing the metal catalyst with a heteropoly acid or heteropoly acid salt (dry- or wet-mix), or by coupling the metal catalyst with a heteropoly acid or a heteropoly acid salt.

The terms "periodic table" and "element periodic table" are used interchangeably herein.

The terms "solid support", "support", and "catalyst support" are used interchangeably herein. Solid supports refer to materials in which the active metal is bonded or bonded. The catalysts described herein that contain a solid support are examples of "supported metal catalyst" or "supported catalyst ". In certain embodiments, the metal catalyst may be supported on the heteropoly acid salt.

As used herein, "heteropoly acid" refers to a compound having a central element and oxygen-bonded peripheral elements (e.g., H ₃ PW ₁₂ O ₄₀ , where P is the central element and W is the perimeter element) Quot; Several heteropoly acid structures have been described; For example, it is a Keggin structure, a Wells-Dawson structure, and an Anderson-Evans-Perloff structure. The central element in some embodiments may be Si, P, Ge, As, B, Ti, Ce, Co, Ni, Al, Ga, Bi, Cr, Sn, or Zr. Examples of surrounding elements may be metals such as W, Mo, V, or Nb. Heteropoly acid is soluble in water. As used herein, "heteropoly acid salt" is a heteropoly acid ionically bonded to a cation (eg, a cesium cation). The heteropoly acid salt may also be referred to as "cation-exchanged heteropoly acid ". The heteropoly acid salt referred to herein is insoluble in water.

The terms "specific surface area", "surface area", and "solid support surface area" are used interchangeably herein. The specific surface area of the solid support is expressed herein in grams per square gram of solid support (m ² / g). The specific surface area of the solid supports disclosed herein can be measured by, for example, the Brunauer, Emmett and Teller (BET) method (Brunauer et al., J. Am. Chem. Soc. 60: 309-319, incorporated herein by reference).

The terms "impregnation" and "loading" are used interchangeably herein. Impregnation refers to the process of making a metal salt into a finely divided form or layer on a solid support. Generally, the process involves drying a mixture containing a solid support and a metal salt solution and other water soluble compounds. The dried product may be referred to as a "pre-catalyst ". When the metal catalyst is supported on, for example, a heteropoly acid salt, the metal catalyst may be characterized as being impregnated or loaded onto the heteropoly acid salt.

As used herein, the terms "calcining" and "calcination" refer to thermal treatment of the pre-catalyst. This process can convert the dried metal salt of the pre-catalyst into, for example, a metal or oxide state. The heat treatment may be carried out in an inert or active atmosphere.

The terms "molar yield", "reaction yield", and "yield" are used interchangeably herein. The molar yield refers to the amount of product obtained from the chemical reaction as measured on a molar basis. This amount can be expressed as a percentage; That is, the% amount of a particular product in all reaction products.

The terms "reaction mix", "reaction mixture", and "reaction composition" are used interchangeably herein. The reaction mix may comprise, at a minimum, a feedstock (substrate), a metal catalyst, a heteropoly acid or heteropoly acid salt, and a solvent. The reaction mix may represent a mix as it exists before or during the application of the temperature and pressure conditions of the hydrogenated deoxygenation.

Hydrogenated deoxygenation processes that can be performed under low temperature and low pressure conditions and convert C _10-18 oxygenates in the feedstock into linear alkanes without substantial carbon loss are disclosed herein. Thus, the process produces less undesirable by-products and is more economical because it can proceed under lower temperature and lower pressure conditions.

Embodiments of the disclosed invention _relate to the production of linear alkanes from feedstocks comprising a saturated or unsaturated C _10-18 oxygenate comprising a moiety selected from the group consisting of an ester group, a carboxylic acid group, a carbonyl group and an alcohol group The present invention relates to a hydrogenated deoxygenating method for hydrogenation. The process comprises contacting the feedstock at a temperature of from about 150 DEG C to about 250 DEG C and at a hydrogen gas pressure of at least about 300 psig with (i) from about 0.1 wt% to about 10 wt% of a metal selected from the group IB, VIB, or VIII of the Periodic Table; By weight of catalyst and (ii) a heteropoly acid or heteropoly acid salt. By contacting the feedstock with the catalyst and the heteropoly acid or heteropoly acid salt under these temperature and pressure conditions, the C _10-18 oxygenate is hydrodeoxygenated to a linear alkane having the same carbon chain length as the C _10-18 oxygenate. Alternatively, the hydrogenated deoxygenation process further comprises recovering the linear alkane produced in the contacting step.

The feedstock used in certain embodiments of the disclosed invention can include materials comprising one or more of monoglycerides, diglycerides, triglycerides, free fatty acids, and / or combinations thereof, including fats and oils And the like. Examples of such feedstocks include fats and / or oils derived from animals, poultry, fish, plants, microorganisms, yeast, fungi, bacteria, algae, eugelanas and stramenopiles. Examples of vegetable oils include canola oil, corn oil, palm kernel oil, cherry seed oil, sesame oil, sorghum oil, soybean oil, Coconut oil, castor oil, peanut oil, palm oil, mustard oil, cottonseed oil, camellia oil, jatropha oil and cram oil. Other feedstocks include, for example, refined fat and oils, restaurant grease, yellow and brown grease, pulp industry frying oil, tallow, lard, train oil, milk fat, fish oil, Microbial oil, yeast biomass, microbial biomass, sewage sludge, and soap stock.

Derivatives of oils, such as fatty acid distillates, are another example of feedstocks that can be used in certain embodiments of the present invention. Vegetable oil distillates (for example, palm fatty acid distillates) are preferred examples of fatty acid distillates. Fatty acid distillates of any of the fats and oils disclosed herein may be used in certain embodiments of the present invention.

In a preferred embodiment of the present invention, the feedstock comprises vegetable oils and fatty acid distillates thereof. In another preferred embodiment, the feedstock comprises (i) a vegetable oil selected from the group consisting of soybean oil, palm oil and palm kernel oil; Or (ii) palm fatty acid distillates (e.g., those resulting from tablets of raw palm oil).

Palm oil is derived from the pulp of pulp of oil palm, while palm kernel oil is derived from the nucleus of oil palm. Fatty acids contained in palm oil typically include palmitic acid (about 44%), oleic acid (about 37%), linoleic acid (about 9%), stearic acid and myristic acid. The fatty acids contained in the palm kernel oil are typically lauric (about 48%), myristic acid (about 16%), palmitic acid (about 8%), oleic acid (about 15%), capric acid, caprylic acid , Stearic acid and linoleic acid. Soybean oil typically contains linoleic acid (about 55%), palmitic acid (about 11%), oleic acid (about 23%), linolenic acid and stearic acid.

Fossil fuel-derived and other types of feedstocks that can be used in certain embodiments of the disclosed invention include petroleum-based products, waste automotive oils and industrial lubricants, waste paraffin waxes, coal-derived liquids, polypropylene, high density polyethylene, and low density polyethylene A liquid derived from the depolymerization of plastics such as; And other synthetic oils generated as byproducts from petrochemical and chemical processes.

Examples of other feedstocks are described in U.S. Patent Application Publication No. 2011-0300594, which is incorporated herein by reference.

The C _10-18 oxygenate contained in the feedstock may be a fatty acid or a triglyceride. The feedstock may be in free form (i.e., non-esterified) or may comprise one or more fatty acids esterified. The esterified fatty acid may be contained, for example, in a glyceride molecule (i.e., in a fat or an oil) or a fatty acid alkyl ester (e.g., a fatty acid methyl ester or a fatty acid ethyl ester). The fatty acid (s) may be saturated or unsaturated. Examples of unsaturated fatty acids are monounsaturated fatty acids (MUFAs) when only one double bond is present in the fatty acid carbon chain, and when the fatty acid carbon chain has two or more double bonds, polyunsaturated fatty acid , PUFA). The carbon chain length of the fatty acid C _10-18 oxygenate in the feedstock may be 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms. Preferably, the carbon chain length is 10, 12, 14, 16, or 18 carbon atoms. Other preferred fatty acid lengths are 16 to 18 carbon atoms. Examples of fatty acids that may be present in the feedstock are provided in Table 1.

[Table 1]

Although the oxygenates contained in the feedstock used in the disclosed invention have a length of 10 to 18 carbon atoms, other oxygenates whose carbon length is outside this range may also be present in the feedstock. For example, the glycerides and free fatty acids of fats and oils that may be used as feedstock may also contain carbon chains of about 8 to 24 carbon atoms in length. In other words, the feedstock need not contain only C _10-18 oxygenates.

The C _10-18 oxygens represented by lipid and free fatty acids include ester and carboxylic acid moieties, respectively. Other types of _C10-18 oxygenates may be included in the feedstock, for example, _C10-18 oxygenates containing one or more carbonyl and / or alcohol moieties. Another type of _C10-18 oxygenate may contain two or more of any of the moieties. Examples include two or more alcohol moieties (e.g., diols), carbonyl moieties (e.g., diketones or dialdehydes), carboxylic acid moieties (dicarboxylic acids), or ester moieties _Di -esters). &_{Lt; /} RTI > Alcohols and carboxylic acid moieties (e.g., hydroxycarboxylic acids), alcohols and ester moieties (e. G., Hydrocarbons such as hydrocarbons, C _10-18 oxygenates, including carbonyl and carboxylic acid moieties (e.g., keto acids), or carbonyl and ester moieties (e. G., Keto esters) Is another exemplary component of the feedstock that can be used in the form of a feedstock.

The feedstock may contain one or more C _10-18 oxygenates linked together by two or more esters and / or ether bonds. Such C _10-18 oxygenates are unbound from each other during the disclosed hydrogenated deoxygenation process; Removal of oxygen from such molecules destroys ester and / or ether bonds. Similarly, the fatty acid C _10-18 oxygenates as contained in the glyceride feedstock are unbound from the glycerol component of the glyceride during the disclosed hydrogenated deoxygenation process, because the fatty acid ester bond is destroyed by the removal of oxygen . Thus, even though the C _10-18 oxygenate is bound by ester and / or ether linkages, different types of linear alkanes can be produced from feedstocks containing two or more different C _10-18 oxygens. All these types of _C10-18 oxygenates can be a constituent of the feedstock.

The linear chain of the C _10-18 oxygenate is not bonded to any alkyl or aryl branch via a carbon-carbon bond from one of the carbon atoms of the linear chain. For example, in some embodiments, the palmitic acid is a C _10-18 oxygenate, but the palmitic acid (e.g., 15-methyl palmitoic acid) having an alkyl group substitution at one of its -CH ₂ -mutoes, Is not a type of C _10-18 oxygenate as described herein. The hydrogenated deoxygenation process of the present invention does not include an isomerization event including a step of removing and / or adding a carbon-carbon bond to the carbon of the C _10-18 oxygenate. Thus, branched alkane products such as isodecane, isododecane, isotetradecane, isohexadecane, and isooctadecane are not produced.

In certain embodiments of the disclosed invention, the C _10-18 oxygenate can constitute the feedstock itself. One example of such a feedstock is a pure or substantially pure preparation of a particular fatty acid. Alternatively, the feedstock may comprise a plurality of distinct C _10-18 oxygens (i. _E. , Discrete molecules not bonded to each other). A mixture of any of these feedstocks can be used as the co-feed component in the disclosed hydrogenated deoxygenation process.

The linear alkanes are formed from saturated or unsaturated C _10-18 oxygenates in the disclosed hydrogenated deoxygenation process. In certain embodiments, the resulting linear alkanes include decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, and octadecane, wherein the even number of carbon atoms Are generated in the preferred embodiment.

As discussed above, hexadecane is a linear alkane produced in certain embodiments of the disclosed hydrogenated deoxygenation process. Various C ₁₆ oxygenates can be used as the feedstock to produce hexadecane, including, for example, hexadecanol (e.g., cetyl alcohol), hexadecyl aldehyde, hexadecyl ketone, palmitic acid, Tylpalmitate, and / or any other C ₁₆ oxygenate wherein at least one carbon atom of the C ₁₆ chain is bonded to an oxygen atom. In certain embodiments, the feedstock may comprise any of these various C ₁₆ oxygenates. For example, the feedstock may be an oil or fat comprising palmitic acid (i.e. containing a palmitoyl group) or palmitoleic acid (i.e. containing a 9-hexadecenoyl group).

Octadecane is a linear alkane produced in certain embodiments of the disclosed hydrogenated deoxygenation process. Various C ₁₈ oxygenates can be used as the feedstock to produce octadecane, including, for example, octadecanol (e.g., stearyl alcohol), octadecyl aldehyde, octadecyl ketone, stearic acid, Aryl stearate, and / or any other C ₁₈ oxygenate wherein at least one carbon atom of the C ₁₈ chain is bonded to an oxygen atom. In certain embodiments, the feedstock may comprise any of these various < RTI ID = 0.0 > _C18 < / RTI > For example, the feedstock may be selected from the group consisting of stearic acid (i.e., containing a stearoyl group), oleic acid (i.e. containing a 9-octadecenoyl group), or linoleic acid (i.e. a 9,12-octadecadienoyl group ), ≪ / RTI >

In certain embodiments of the disclosed invention, the molar yield of linear alkanes is at least about 25%. In another embodiment, the molar yield of linear alkanes is about 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 19%, 20%, 21% , 24%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39% 54%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56% 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73% , 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90% , 92%, 93%, 94%, or 95% or more. For example, if lauric acid is a C _10-18 oxygenate contained in the feedstock for the process, the molar yield of dodecane is greater than about 25%.

The carbon chain length of the linear alkane product of the disclosed hydrogenated deoxygenation process is equal to the carbon chain length of the C _10-18 oxygenate. For example, when the C _10-18 oxygenate is palmitic acid, the resulting linear alkane is hexadecane; Both palmitic acid and hexadecane have a carbon chain length of 16 carbon atoms. Thus, the linear alkanes produced in the disclosed process represent fully hydrogen-saturated, reduced forms of the C _10-18 oxygenate in the feedstock. For example, the disclosed hydrogenated deoxygenation processes include decanes from capric acid; Dodecane from lauric acid; Tetradecane from myristic acid and myristoleic acid; Hexadecane from palmitic acid and palmitoleic acid; And octadecane from stearic acid, oleic acid and linoleic acid. These linear alkanes are produced in either the free or esterified state of the fatty acid. C _10-18 oxygenates linked to one or more other moieties via ester and / or ether linkages produce linear alkanes that exhibit a fully hydrogen-saturated, reduced form of the C _10-18 oxygenate during the disclosed process.

In certain embodiments of the disclosed invention, the molar yield for reaction products having a carbon chain length that is shorter than the carbon chain length of the C _10-18 oxygenate by at least one carbon atom is less than about 10%. For example, when lauric acid is a C _10-18 oxygenate contained in the feedstock for the process, the molar yield of undecane having a chain length of 11 carbon atoms is less than about 10%. In another embodiment, the molar yields for reaction products having carbon chain lengths that are shorter than the carbon chain length of the C _10-18 oxygenate by at least one carbon atom are about 1%, 2%, 3%, 4%, 5% , 6%, 7%, 8%, or 9%. The low level of such byproducts when using the disclosed invention reflects a low level of carbon loss from the C _10-18 oxygenates due to decarboxylation and / or decarbonylation events during the hydrogenated deoxygenation reaction. Thus, the disclosed method does not significantly destroy the carbon-carbon bond of the C _10-18 oxygenate.

In certain embodiments of the disclosed invention, the molar yields of other types of by-products are about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% 12%, 13%, 14%, or less than 15%. Such other byproducts may be incompletely incorporated into the C _10-18 oxygenate, which has at least one oxygenated carbon atom (e.g., an alcohol group, a carbonyl group, a carboxylic acid group, an ester group), and / Lt; RTI ID = 0.0 > reduced form. In certain embodiments of the hydrogenated deoxygenation process using lauric acid as the feedstock, examples of by-products include dodecanol and lauryl laurate.

The hydrogenated deoxygenation process of the present invention can be tested for its ability to convert dodecanol to dodecane. In other words, the method of hydrodeoxygenation for converting a C ₁₆ or C ₁₈ oxygenate to an alkane can be tested using lauric acid or dodecanol as feedstock; Such a method may have a molar yield of dodecane as listed above for a linear alkane when tested for lauric acid or dodecanol. Likewise, such methods can be used at concentrations of about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11% , 12%, 13%, 14%, or 15% by mole of the product.

The linear alkanes produced in the disclosed process can be isolated, for example, by close-cut distillation. If necessary, the linear alkanes can be further purified from more bulky reaction by-products using selective adsorption by molecular sieves. The molecular sieve may comprise a synthetic zeolite having a series of central cavities interconnected by pores. The pores are large enough to pass the linear alkane but not large enough to pass through the branched byproduct. Commercial isolation processes using molecular sieves include, for example, IsoSiv ™ (Dow Chemical Company), Molex ™ (UOP LLC) and Ensorve (Ensorb) < / RTI > (Exxon Mobil Corporation).

The disclosed invention comprises contacting a feedstock comprising a C _10-18 oxygenate with a catalyst and a heteropoly acid or heteropoly acid salt at a temperature of about 150 ° C to about 250 ° C and a hydrogen gas pressure of at least about 300 psig.

The step of contacting the feedstock with the catalyst and the heteropoly acid or heteropoly acid salt may be carried out in a reaction vessel or any other enclosure known in the art which enables the performance of the reaction under controlled temperature and pressure conditions . For example, the contacting step is carried out in a packed bed reactor, such as a plug flow reactor, a tubular reactor or other fixed bed reactor. It is to be understood that the packed bed reactor may be a single packed layer or it may comprise multiple layers in series and / or in parallel. Alternatively, the contacting step may be carried out in a slurry reactor including a batch reactor, a continuous stirred tank reactor, and / or a bubble column reactor. In the slurry reactor, the catalyst may be removed from the reaction mixture by filtration or centrifugation. The size / volume of the reaction vessel should be suitable for handling the feedstock and the selected amount of catalyst.

The contacting step may be performed in a continuous or batch processing system as is known in the art. The continuous process may be a multi-stage process using a series of two or more reactors in series. In this type of system, new hydrogen can be added at the inlet of each reactor. A recycle stream may also be used to help maintain the desired temperature in each reactor. The reactor temperature can also be controlled by controlling the new feedstock temperature and recycle rate.

In certain embodiments, the contacting step may comprise stirring the feedstock and the catalyst and the heteropoly acid or heteropoly acid salt before and / or during which the reaction components are subjected to the temperature and hydrogen gas pressure conditions. Stirring can be performed, for example, using a mechanical stirrer, or in a slurry reactor system.

The order in which the feedstock can be contacted with the catalyst and the heteropoly acid or heteropoly acid salt may vary. For example, the feedstock may be contacted with a preparation (a dry mix or a wet mix) that contains both a catalyst and a heteropoly acid or a heteropoly acid salt. Alternatively, for example, the feedstock may first be contacted with a catalyst in a reaction mix, and then a heteropoly acid or a heteropoly acid salt is added to the reaction mix. Alternatively, for example, the feedstock may first be contacted with a heteropoly acid or a heteropoly acid salt in the reaction mix, and then a catalyst is added to the reaction mix.

In certain embodiments, the contacting step can be performed in a solvent, such as an organic solvent or water. The solvent may be comprised of one type of solvent that is pure or substantially pure (e.g., greater than 99% or greater than 99.9% pure), or may comprise two or more different solvents mixed together. The solvent may be homogeneous (e.g., single-phase) or non-uniform (e.g., two or more phases). In a preferred embodiment, the feedstock, the catalyst and the heteropoly acid or heteropoly acid salt are contacted in an organic solvent. The organic solvent used in certain embodiments may be non-polar or polar. In another embodiment, the organic solvent comprises tetradecane, hexadecane, or dodecane. Alternatively, the organic solvent may be other alkanes, such as those having a chain length of 6 to 18 carbon atoms. The organic solvent can be selected based on its ability to dissolve hydrogen. For example, the solvent may have a relatively high solubility for hydrogen, such that substantially all of the hydrogen provided by the hydrogen gas pressure is present as a solution prior to and / or during the disclosed hydrogenated deoxygenation process. In certain embodiments, the heteropoly acid or heteropoly acid salt is insoluble in the organic solvent.

Certain embodiments of the invention include the use of solvents comprising tetradecane and hexadecane. Examples of such solvents include tetradecane-to-hexadecane ratios of about 15: 1, 16: 1, 17: 1, 18: 1, 19: 1, or 20: 1, For example, grams). In some embodiments, a ratio of about 17: 1 tetradecane to about-hexadecane is preferred. This relative amount of tetradecane and hexadecane-containing solvents can improve product yield in some of the hydrogenated deoxygenation reactions described herein.

The contacting step of the process of the present invention is carried out at a temperature of from about 150 DEG C to about 250 DEG C and at a hydrogen gas pressure of at least about 300 psig. In certain embodiments, the temperature may be about 150 ° C, 160 ° C, 170 ° C, 180 ° C, 190 ° C, 200 ° C, 210 ° C, 220 ° C, 230 ° C, 240 ° C, or 250 ° C. Alternatively, the temperature is from about 150 캜 to about 200 캜. In another embodiment, the temperature is about 200 DEG C and the pressure is about 400 psig. In certain embodiments, the hydrogen gas pressure may be from about 300 psig to about 1000 psig, from about 300 psig to about 500 psig, from about 350 psig to about 450 psig, or about 400 psig. Alternatively, in some embodiments, the hydrogen gas pressure is from about 300 psig to about 1000 psig.

In certain embodiments of the disclosed invention, the feedstock and the catalyst and the heteropoly acid or heteropoly acid salt are selected from the group consisting of about 2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17 , 18, 19, or 20 hours under said temperature and hydrogen pressure conditions. The feedstock and the catalyst may be subjected to such temperature and hydrogen pressure conditions, for example, for a continuous period of time.

In some embodiments, the feedstock is contacted with hydrogen in advance prior to contacting the feedstock with the catalyst and the heteropoly acid or heteropoly acid salt to form a feedstock / hydrogen mixture. In another embodiment, a solvent or diluent is added to the feedstock in advance before contacting the feedstock with hydrogen and / or catalyst and heteropoly acid or heteropoly acid salt. For example, after forming the feedstock / solvent mixture, it can then be contacted with hydrogen to form a feedstock / solvent / hydrogen mixture, which is then contacted with the catalyst and heteropoly acid or heteropoly acid salt.

A wide range of suitable catalyst concentrations can be used in the disclosed process, wherein the amount of catalyst per reactor is generally dependent on the type of reactor. For a fixed bed reactor, the volume of catalyst per reactor will be large while the volume in the slurry reactor will be smaller. Typically, the catalyst in the slurry reactor will comprise from 0.1 to about 30 weight percent of the reactor contents.

The disclosed invention relates to a process for _preparing a feedstock comprising contacting a feedstock comprising a _C10-18 oxygenate with (i) a catalyst comprising from about 0.1% to about 10% by weight of a metal selected from Groups IB, VIB, or VIII of the Periodic Table . Such metals include copper, silver, or gold, which is a Group IB metal; Chromium, molybdenum, or tungsten, a Group VIB metal; Or a Group VIII metal such as iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, or platinum. In certain preferred embodiments, the metal is platinum.

In a further embodiment, a second metal may be included in the catalyst, such as from about 0.5 wt% to about 15 wt% tungsten, rhenium, molybdenum, vanadium, manganese, zinc, chromium, germanium, tin, to be.

In certain embodiments, the catalyst comprises about 0.1 wt%, 0.25 wt%, 0.5 wt%, 0.75 wt%, 1.0 wt%, 1.5 wt% of one or more optional metals selected from Groups IB, VIB, or VIII of the Periodic Table 4.5 wt.%, 5.0 wt.%, 5.5 wt.%, 6.0 wt.%, 6.5 wt.%, 7.0 wt.%, 7.5 wt.%, 2.5 wt.%, 3.0 wt.%, 3.5 wt. 8.0 wt.%, 8.5 wt.%, 9.0 wt.%, 9.5 wt.% Or 10 wt.%. The second metal may be present in the catalyst in an amount of about 0.5 wt%, 1.0 wt%, 1.5 wt%, 2.0 wt%, 2.5 wt%, 3.0 wt%, 3.5 wt%, 4.0 wt%, 4.5 wt% , 5.5 wt%, 6.0 wt%, 6.5 wt%, 7.0 wt%, 7.5 wt%, 8.0 wt%, 8.5 wt%, 9.0 wt%, 9.5 wt%, 10.0 wt%, 10.5 wt%, 11.0 wt% 12.0 wt.%, 12.5 wt.%, 13.0 wt.%, 13.5 wt.%, 14.0 wt.%, 14.5 wt.%, Or 15.0 wt. In certain embodiments, the catalyst comprises one, two, or three or less different metals. In certain other embodiments, the catalyst comprises platinum as the only metal; A metal (e. G., Tungsten) present in the heteropoly acid or heteropoly acid salt can be used with such a catalyst.

In some embodiments of the present invention, the catalyst comprises platinum as the metal. In certain preferred embodiments, the catalyst comprises from about 0.1 wt% to about 6 wt% platinum as metal. In certain other preferred embodiments, the catalyst comprises from about 0.25 wt% to about 2 wt% platinum as metal. In another embodiment, the catalyst comprises from about 0.1 wt% to about 2 wt%, from about 0.25 wt% to about 2 wt%, from about 0.1 wt% to about 1 wt%, or from about 0.25 wt% to about 1 wt% Platinum.

In certain embodiments of the present invention, the catalyst further comprises a solid support. Various solid supports as known in the art can be included in the catalyst and include, for example, WO ₃ , Al ₂ O ₃ (alumina), TiO ₂ (titania), TiO ₂ -Al ₂ O ₃ , ZrO ₂ , Tungstated ZrO ₂ , SiO ₂ , SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , V ₂ O ₅ , MoO ₃ , or carbon (for example, activated carbon) . In certain preferred embodiments, the solid support comprises Al ₂ O ₃ or carbon. Thus, the solid support may comprise an inorganic oxide, a metal oxide or carbon. Other examples of solid supports that may be used include clays (e. G., Montmorillonite) and zeolites (e. G., HY zeolite). The support materials used in the catalyst, such as those described above, may be basic (pH 9.5 or higher), neutral, slightly acidic (pH 4.5 to 7.0), or acidic (lower than pH 4.5). Further examples of solid supports that can be used in certain embodiments of the disclosed invention are described in U.S. Patent 7,749,373, which is incorporated herein by reference.

The solid support used in certain embodiments of the disclosed invention may be porous, thereby increasing the surface area over which the metal catalyst is deposited. In certain preferred embodiments, the solid support comprises pores and has (i) a specific surface area of greater than or equal to 10 m ² / g and optionally less than or equal to 280 m ² / g, wherein the pores have a diameter greater than 500 angstroms The pore volume is at least 10 ml / 100 g; Or (ii) has a specific surface area of greater than or equal to 50 m ² / g and optionally less than or equal to 280 m ² / g, wherein the pores have a diameter greater than 70 angstroms and the pore volume of the support is greater than 30 ml / 100 g.

Thus, in certain embodiments, the specific surface area of the solid support is about or at least about 50, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, , 260, 270, 280, 290, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400 or 1500 m ² / g. The preparation of porous solid supports having specific specific surface areas can be carried out by adjusting the pore diameter and volume as is known in the art (see, for example, Trimm and Stanislaus, Applied Catalysis 21: 215-238; Kim et al., Mater. Res. Bull. 39: 2103-2112; Grant and Jaroniec, J. Mater. Chem. 22: 86-92).

In certain embodiments, the solid support has an average particle size and / or particle size distribution D50 of about 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, or 35 micrometers. The median value "D50" is the diameter (typically in micrometers) dividing the distribution of the support particles, where half of the support particles are above this diameter and half are below this diameter.

Solid supports for making catalysts used in certain embodiments of the disclosed invention are commercially available from, for example, Johnson Matthey, Inc. (West Deptford, NJ), BASF (USA), Evonik (Calvert City, Kentucky, USA) and Sigma-Aldrich (St. Louis, Missouri, USA). With respect to the support material from Johnson Matie (JM), the alumina particles referred to herein as # 32 (JM # 32) have an average particle size of 8 micrometers and a surface area of 300 m ² / g, (JM # 33) has an average particle size of 18 micrometers and a surface area of 180 m ² / g. Carbon particles, referred to herein as # 23 (JM # 23), have an average particle size of 30 microns meters and a surface area of 1500 m is ² / g, carbon particles, referred to as # 25 (JM # 25) in this specification an average particle size of 35 micrometers and a surface area of 900 m ² / g, # 26 herein ( JM # 26) has an average particle size of 30 micrometers and a surface area of 1500 m ² / g. With respect to the material from Ebonics, the designations F 101 XR, F 101 KYF, F 1181 XR and F 1181 KYF herein refer to carbon loaded with 1 wt% or 2 wt% platinum. In addition, with respect to the material from the ebonics, the carbon of F 101 XR in this specification is a powder with a particle size distribution D50 of 28 micrometers and a surface area of 1090 m ² / g, and the carbon of F 101 KYF herein is The particle size distribution D50 is 28 micrometers and the surface area is 1090 m ² / g, and the carbon of F 1181 XR in this specification is a powder having a particle size distribution D50 of 18 micrometers and a surface area of 1140 m ² / g, In this specification, the carbon of F 1181 KYF is a powder having a particle size distribution D50 of 18 micrometers and a surface area of 1140 m ² / g, and the carbon of "5% Pt + 5% Bi on ebonic carbon" The carbon having a particle size distribution D50 of 28 micrometers and a surface area of 1120 m ² / g, and the carbon of "1% Pt + 0.1% Cu on the ebonic carbon" in this specification is a particle size distribution D50 of 28 micrometers, Lt; ² > / g.

In certain embodiments, the supported metal catalyst may be in the form of particles, such as shaped particles. The catalyst particles can be shaped into cylinders, pellets, spheres, or any other shape. Cylindrical-shaped catalysts may have a hollow interior, with or without one or more reinforcing ribs. Other particle shapes that may be used include, for example, trilobe, cloverleaf, cross, "C" -shaped, rectangular- and triangular-shaped tubes. Alternatively, the supported metal catalyst may be in the form of powder or larger size cylinders or tablets.

The metal catalyst may be used with the heteropoly acid or heteropoly acid salt supported in certain embodiments. Heteropoly acid or heteropoly acid salt may be supported on any other support material such as those disclosed in the SiO _2, Al ₂ O _3, or the specification. In certain embodiments, the platinum may be loaded onto the supported heteropoly acid or heteropoly acid salt and thereby be supported thereby. For example, platinum can be loaded onto (i) SiO ₂ , Al ₂ O ₃ , or WPA supported on carbon, or (ii) Cs-WPA supported on SiO ₂ , Al ₂ O ₃ , .

Other examples of metal catalyst compositions that may be used in certain embodiments of the disclosed invention are described in U.S. Patent Application Publication Nos. 2011-0300594 and 2012-0029250, and U.S. Patent No. 8,084,655, all of which are incorporated herein by reference It is included as a reference.

The catalyst can be prepared using any of a variety of methods known in the art (see, for example, Pinna, 1998, Catalysis Today 41: 129-137; Catalyst Preparation: Science and Engineering , Ed. John JA Anderson and MF Garcia, London, UK: "Regalbuto, Boca Raton, FL: CRC Press, 2006]; Mul and Moulijn, Chapter 1 Preparation of supported metal catalysts, In: Supported Metals in Catalysis , Dowden and CC Kembell, London, UK: The Royal Society of Chemistry, 1981 (Eds.), Imperial College Press, 2011; Acres et al., The design and preparation of supported catalysts, In: Catalysis: A Specialist Periodical Report , Eds. , vol. 4, pp. 1-30]). The catalysts produced by the selected process are preferably active during the disclosed hydrogenated deoxygenation process, selective, recyclable, mechanically and thermochemically stable.

The impregnation of the metal onto the solid support in the preparation of a given catalyst for use in the disclosed process can be achieved by mixing the solid support with a metal salt solution and heating the mixture at a suitable temperature (e.g., 100-120 < To obtain a dried product, and then calcining the dried product at a suitable temperature (e.g., 300 to 400 ° C) for a suitable time. The supported metal catalyst prepared by this procedure can then be impregnated with another metal if desired. Other ways of loading more than one metal into the support may be performed, if desired, by mixing the solid support with a metal salt solution, drying the mixture as above, drying the dried product with another metal salt solution Mixing, drying the mixture as above, and then calcining the dried product as above. If necessary, any of the above procedures can be adjusted accordingly to load the additional metal onto the solid support.

The present invention comprises contacting a feedstock comprising a _C10-18 oxygenate with a heteropoly acid or a heteropoly acid salt. Heteropoly acid as known in the art is a compound having a central element and a peripheral element to which oxygen is bonded. The central element may be, for example, Si, P, Ge, As, B, Ti, Ce, Co, Ni, Al, Ga, Bi, Cr, Sn, or Zr. Examples of surrounding elements may be metals such as W, Mo, V, or Nb. Several heteropoly acid structures have been described; For example, Keggin structure, Wells-Dowson structure, and Anderson-Evans-Perlope structure.

In certain embodiments, the heteropoly acid may have a chemical structure represented by one of the following formulas:

(I) H _k XM ₁₂ O ₄₀ or

(II) A _j H _k XM ₁₂ O ₄₀ , where

X (central element) is Si, P, Ge, As, B, Ti, Ce, Co, Ni, Al, Ga, Bi, Cr, Sn, or Zr;

M (peripheral element) is independently Mo, W, V, or Nb;

A (see Formula II) is an alkali metal element, an alkaline earth metal element, an organic amine cation, or a combination thereof;

k is 0 to 4;

j is 0 to 4;

At least one of j and k is greater than zero.

It will be understood in the art that formula (II) represents a heteropoly acid salt or a cation-exchanged heteropoly acid wherein A in formula (II) is a cation. Examples of A (cations) in formula II include metal ions such as lithium, sodium, potassium, cesium, magnesium, barium, copper, rubidium, thallium, gold or gallium ions; Accordingly, the heteropoly acid salt may be a heteropoly acid metal salt. Other examples of A in formula II include onium groups such as ammonium (NH ₄ ⁺ ) and organic amines. The cations in certain embodiments of formula II may be selected based on whether the cation-exchanged heteropoly acid is acidic and insoluble in water. Thus, in certain embodiments, the catalyst composition comprises a heteropoly acid salt that is acidic and insoluble in water. Such a heteropoly acid salt may be, for example, a cesium-exchanged heteropoly acid (heteropoly acid cesium salt). It will be understood in the art that the cesium ion in such a heteropoly acid salt represents an A group in formula (II). In certain other embodiments, group A may alternatively be potassium or ammonium. In some embodiments, j + k < = 4 in formula (II).

In certain embodiments of the disclosed invention, the heteropoly acid or heteropoly acid salt comprises tungsten (W). It will be understood in the art that tungsten in such heteropolyacids represents the surrounding element M in either formula I or formula II. In certain embodiments, the heteropoly acid or heteropoly acid salt comprises phosphorus (P). It will be understood in the art that phosphorus in such heteropoly acids represents a central element X in either formula I or formula II.

Examples of heteropolyacids that may be used includes the H ₃ PW ₁₂ O _{40 ·} (a tungstate, being abbreviated herein as "WPA"), and H ₄ SiW ₁₂ O _40, both of which comply with the general formula I. Examples of heteropoly acid salts include Cs _{2 . 5} H _{0 . 5} PW ₁₂ O ₄₀ (cesium tungstate cesium salt, abbreviated herein as "Cs-WPA") and Cs _{2 . 5} H _{0 . 5} SiW ₁₂ O ₄₀ , both of which are of formula (II).

In certain embodiments, the heteropoly acid may be in anhydrous or hydrated form. Hydrated heteropolyacid (i. E., Containing a determined number (crystallization water)), for example, _{H 3 PW 12 O 40 · (} H 2 O) x and _{H 4 SiW 12 O 40 · (} H 2 O) containing _x , Where x is one or more. However, in certain embodiments, the hydrated heteropoly acid is dehydrated prior to using the disclosed catalyst composition to make it.

When the feedstock is contacted with catalyst and heteropoly acid or heteropoly acid salt, various amounts of heteropoly acid or heteropoly acid salt may be used. For example, the weight percent of heteropoly acid or heteropoly acid salt in the reaction mix may be about 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 2.0, 2.1, , 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7% 4.5%, 4.0%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9% or 5.0% (% of the total weight of the reaction mix). The amount of heteropoly acid or heteropoly acid salt in the reaction mix may be mentioned differently, for example, referring to the amount of supported metal catalyst present in the reaction mix.

In certain embodiments, the amount of heteropoly acid or heteropoly acid salt in the reaction mix may be set as a percentage of the weight of the supported metal catalyst in the reaction mix. For example, if 0.10 g of supported metal catalyst is used, a "loading rate" of 50% of the heteropoly acid or heteropoly acid salt will mean that 0.05 g of heteropoly acid or heteropoly acid salt is used in this reaction. In some embodiments, a loading rate of about 10%, 20%, 30%, 40%, 50%, or 60% of the heteropoly acid or heteropoly acid salt can be used according to this measurement system.

In certain embodiments, the amount of heteropoly acid or heteropoly acid salt in the reaction mix may be set relative to the amount of tungsten (W) that can be introduced into the reaction using a particular heteropoly acid or salt thereof. For example, when tungstic acid (WPA) is used as the heteropoly acid in the reaction, the desired amount of W to be loaded into the supported metal catalyst will be equal to a predetermined percentage of the weight of the supported metal catalyst. As an example, if 0.1 g of the supported metal catalyst is used in the reaction mix and the desired "loading rate" of W is 2% using WPA, to provide 0.002 g of W, 2% Approximately 0.026 g of WPA will be used. The amount of WPA (0.026 g) to be used in this example is based on the presence of about 76.6 wt% W in one molecule of WPA. In some embodiments, about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% of W into the reaction mix by the use of heteropoly acid (e.g., WPA) A loading rate of 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 100% may be used according to this measurement system.

In certain embodiments, the feedstock is contacted with a catalyst and a heteropoly acid salt, and the catalyst is coupled to a heteropoly acid salt. This is an example where the heteropoly acid salt can effectively serve as a supporting material. In certain embodiments, in this role, the heteropoly acid salt may modify or enhance the activity of the metal catalyst and / or may itself contribute to the catalytic activity of the metal catalyst.

The preparation of the heteropoly acid salt as the metal catalyst support may be in accordance with any of the procedures known in the art or any of the procedures disclosed herein. The heteropoly acid salt in certain embodiments may be calcined (or not calcined) before it is used as a support. In certain embodiments, the loading of the heteropoly acid may be performed using wet-impregnation, for example, using a metal catalyst salt solution (e.g., ammonium platinate nitrate). For example, after the catalytic metal salt solution is applied to and removed from the heteropoly acid salt, the wet-impregnated heteropoly acid salt is dried at a suitable temperature (e.g., about 100 < 0 > C) Lt; RTI ID = 0.0 > 350 C) < / RTI >

In certain embodiments in which the metal catalyst is bonded to the heteropoly acid salt, the metal catalyst may be loaded at about 0.25 wt%, 0.5 wt%, 1.0 wt%, or 2.0 wt% of the finished catalyst composition. The metal catalyst may be, for example, platinum in any of these embodiments. In another example, the heteropoly acid salt may be a tungstate salt, such as cesium tungstate cesium salt. Any catalytically metal-bonded heteropoly acid salt as disclosed herein can be used in a hydrogenation deoxygenation reaction, for example, about 1 to 10 wt%, 1 to 5 wt% of the total weight of the reaction mix, , 2 to 5 wt%, 3 to 5 wt%, or 4 to 5 wt% (e.g., about 4.7 wt%).

The catalyst and the heteropoly acid or heteropoly acid salt are dry-mixed together before they are contacted with the feedstock in certain embodiments of the disclosed hydrogenated deoxygenation process. In another embodiment, the catalyst and heteropoly acid are dry-mixed together, before they are contacted with the feedstock.

In certain embodiments, the catalyst and the heteropoly acid or heteropoly acid salt may be prepared by mixing the catalyst with a heteropoly acid or a heteropoly acid salt under dry conditions. In other words, the mixing is carried out without the introduction of water or any solution. For example, a dry metal catalyst and a dry amount of heteropoly acid or heteropoly acid salt are combined and ground into a powder. The resulting powder contains fine particles of metal catalyst and heteropoly acid or heteropoly acid salt. This mixture can also be referred to as an intimate mixing. Thus, in certain embodiments, the catalyst composition comprises a dry mixture of a metal catalyst and a heteropoly acid or heteropoly acid salt. This mixture may also be referred to as a fine mixture, an intimate mixture, or a powder mixture.

In an alternative embodiment, the mixing may be carried out by mixing together the heteropoly acid or heteropoly acid salt, respectively, with a catalyst already in the powder form (i.e., mixing the metal catalyst powder with the heteropoly acid powder). Alternatively, one component that is not previously provided as a powder may be combined with another component already provided as a powder, and then the first component is ground (e.g., a metal catalyst powder and an uncompounded heteropoly acid salt Can be combined and subjected to grinding / pulverization).

Depending on the size of the operation, dry-mixing may be carried out using an industrial grinder as is known in the art or, on a smaller scale, dry-mixing may be carried out, for example using a mortar and pestle have. In some embodiments, dry-mixing may be performed so that a predetermined amount of pressure or force is applied to the particles to be mixed by the mixing device. For example, the mixing device may apply a force of about 100 to 500 pounds (e.g., about 300 pounds) to the admixed components. The force applied to the components to be mixed need not be evenly applied throughout the mixing process.

The mixing process may be performed for any suitable time. For example, the mixing of the metal catalyst component and the heteropoly acid component may be performed for about 1, 2, 3, 4, 5, 6, 7, 8, 9, or more than 10 minutes. Catalyst compositions made by dry-blending can be used in the hydrogenation deoxygenation reaction immediately after preparation (e.g., within about 15 or 30 minutes), or can be stored for later use, preferably in an inert atmosphere have.

Catalyst compositions prepared by dry-blending the metal catalyst component and the heteropoly acid or heteropoly acid component have an average mesh size (American Standard Scale) of, for example, about 140, 130, 120, 110, 100, 90, 80, 70, 60 , 50, or 40 (or about 140 to 40 mesh). In certain embodiments, the average particle size (e.g., the longest length dimension) is about 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, or 250 micrometers )to be. Thus, a dry mixture, a fine mixture, or an intimate mixture can refer to a mixture of metal catalyst particles and heteropoly acid / heteropoly acid particles having an average mesh size or particle size as listed above.

The term "dry mixture" refers to the state of the catalyst composition at the time of production. In this sense, in some embodiments, the catalyst composition may be one produced by dry-mixing. It will be appreciated that the use of a dry mixture in the disclosed hydrogenated deoxygenation process exposes it to a liquid, such as a solvent, a desired feedstock and / or a given product.

The heteropoly acid salt used in the various embodiments disclosed herein can be prepared by any means known in the art. Alternatively, it can be prepared by the following steps.

For example, a heteropoly acid aqueous solution can be prepared by first dehydrating the heteropoly acid (if hydrated) using heat (e.g., about 60 DEG C) and / or vacuum for a suitable period of time (e.g., about 2 hours) have. The dehydrated heteropoly acid is then dissolved in water to provide an aqueous solution. The heteropoly acid salt is precipitated from this solution to provide a heteropoly acid salt.

The salt used to precipitate the heteropoly acid ("heteropoly acid-precipitated salt") may be heated to a high temperature (e.g., about 420 < 0 > C) for a suitable period of time (e.g., about 2 hours) And / or dried under vacuum.

In certain embodiments, the heteropolyacid-precipitated salt may contain an element or group represented by A in formula (II). For example, the salt may be one or more of carbonates, hydroxides, sulfates, or sulfides of any of the elements or groups represented by A in formula (II). Cs ₂ CO ₃ is an example of a carbonate that can be used as a heteropoly acid-precipitate salt.

In certain embodiments, the precipitated heteropoly acid salt is dried using heat (e. G., About 100 to 150 DEG C or 120 DEG C) and / or vacuum conditions for a suitable period of time can do. In certain embodiments, the dried product may be further calcined at a temperature of about 250-350 ° C. (eg, about 300 ° C.) for a suitable period of time (eg, about 1 hour).

The linear alkanes produced by the disclosed invention are suitable for use in producing long chain disaccharides by fermentation. For example, the linear alkanes can be used individually or in combination to provide 10 (decanedioic), 12 (dodecanedioic), 14 (tetradecanedioic), 16 (hexadecanedioic), or 18 ) ≪ / RTI > carbon dicarboxylic acid. Methods and microorganisms for fermenting linear alkanes with linear dicarboxylic acids are disclosed, for example, in U.S. Patent Nos. 5,254,466; 5,620,878; 5,648,247, and U.S. Patent Application Publication Nos. 2011-0300594, 2005-0181491, and 2004-0146999, all of which are incorporated herein by reference. Methods for recovering linear dicarboxylic acids from fermentation broth are also known and are described in some of the above references and also in U.S. Patent No. 6,288,275 and International Patent Application Publication No. WO 2000-020620 Same as.

Example

The present invention is further defined in the following Examples. It should be understood that these embodiments are indicative of preferred aspects of the present invention, but given as examples only. From the foregoing discussion and these examples, one skilled in the art can ascertain the essential characteristics of the present invention, and various modifications and variations of the present invention may be made without departing from the spirit and scope of the invention, .

Example 1

Catalyst synthesis: Al ₂ O ₃  2% tungsten / 5% platinum

This example describes the impregnation of tungsten (W) onto an alumina (Al ₂ O ₃ ) -supported platinum (Pt) catalyst. The resulting alumina-supported tungsten / platinum catalyst was used in the low temperature / low pressure hydrogenated deoxygenation process described in Example 2 and Example 3.

2 wt% tungsten was loaded onto a 5 wt% alumina-supported platinum catalyst (Pt / Al ₂ O ₃ ) using a wet impregnation process. To achieve tungsten impregnation on the support, 0.083 g of ammonium tungstate pentahydrate (Strem Chemicals, Newburyport, MA, lot number 19424200) was dissolved in 2 mL of deionized water. This solution was then treated with 2.92 g dry alumina-supported 5% platinum catalyst (Pt / Al ₂ O ₃ ) powder (# 33 from a heterogeneous catalyst screening kit from Johnson Matty, Inc., West Deptford, , Catalyst Designation No. B301099-5). The Pt / Al ₂ O ₃ powder has a 1% moisture content, uniform metal position, 180 m ² / g nitrobenzene activity of the specific surface area and 15 microns average particle size, and 200 mL H _2/15 min of the . The mixture-solution was vortexed for about 5 minutes. The samples were then dried in a vacuum oven at 110 캜 under a vacuum of 20 mm Hg for about 16 hours overnight. A small amount of nitrogen bleed was used to help remove water vapor during this drying process. The sample was then cooled to room temperature and then calcined at 350 DEG C for 3 hours.

Thus, a 2% tungsten / 5% platinum alumina-supported catalyst was obtained.

Example 2

Selective hydrogenation of lauric acid to dodecane in a 600 cc reactor Deoxygenation

This example describes selective hydrogenation dehydrogenation of lauric acid to dodecane using alumina-supported tungsten / platinum catalyst (2% W on 5% Pt / alumina) prepared in Example 1. [ This method was performed under conditions including a temperature of 200 DEG C and a pressure of 500 psig (pounds per square inch force gauge).

(Alfa Aesar, Ward Hill, Mass., USA; 99 +%), 30.5 g of lauric acid (Sigma Aldrich, St. Louis, Mo.; greater than 99%, lot number MKBG4553V), 253.0 g of tetradecane , Lot number E09Y007), 15.3 g of hexadecane (Sigma Aldrich, 99.9%, lot number 26396 JMV) and 3.19 g of the alumina-supported tungsten / platinum catalyst prepared in Example 1 in a 600 cc Hastelloy Parr (Hastelloy Parr) ^® was added to a pressure reactor. The mechanical stirrer was set at a rotational speed of 700 rpm. The reactor was purged 6 times with nitrogen gas by pressurizing the reactor to about 400 psig each time and then depressurizing it. The reactor was then purged with hydrogen gas six times by pressurizing the reactor to 200 psig and then depressurizing it.

After these purge cycles, the reactor was pressurized to about 100 psig of hydrogen and heated to 200 ° C. Once the reactor had equilibrated at 200 ° C, the reactor pressure was raised to an experimental setpoint of 500 psig. Samples of the input material (lard acid with tetradecane, hexadecane and W / Pt catalyst) were collected through the sample port immediately after reaching reaction conditions (200 ° C and 500 psig). Additional samples were collected hourly for the next 5 hours. After 6 hours at 200 ° C, the reactor was allowed to cool to 50 ° C and held overnight under these conditions.

The reactor was reheated again to 200 ° C. the next day and the hydrogen pressure was adjusted to 500 psig. Again, the samples were collected immediately after reaching the reaction conditions (200 < 0 > C and 500 psig) and then every hour for the next 6 hours thereafter. After 6 hours, the reactor was allowed to cool to room temperature, depressurized to ambient pressure, then disassembled and the reaction mixture was collected.

All of the collected samples were diluted with tetrahydrofuran and filtered through a standard 0.45 micrometer disposable filter. The filtered sample was then analyzed by GC / FID (gas chromatography / flame ionization detector) to identify its components and determine the concentrations of reactants and products. The individual components were identified by matching the residence time of these components with the residence time of certain calibration standards. The hexadecane contained in the reaction was used as an internal standard to determine the concentration of each of the individual components.

Concerning the final product of the reaction, the conversion of lauric acid was observed to be about 95%, while the molar yield of dodecane was about 65%. The molar yield was about 12% for dodecanol, about 11% for lauryl laurate and about 2% for undecane.

These results show that a feedstock comprising lauric acid, a C ₁₂ oxygenate, can be used to produce linear alkanes via a hydrogenated deoxygenation process using W / Pt / alumina catalysts under low and low pressure conditions . The hydrogenated deoxygenation process in most cases produced a completely deoxidized product (dodecane) with a small amount of certain byproducts.

Specifically, the low production of undecane (C ₁₁ ) demonstrates that only very low levels of carbon loss through lauric acid decarboxylation occurred during this process. The high level of dodecane produced with relatively small amounts of by-products dodecanol and lauryl laurate demonstrates that this method effectively deoxidizes the carboxylic acid moiety of the lauric acid feedstock.

In view of the results described in Examples 8 to 11, the inclusion of heteropoly acid or heteropoly acid salt would be applicable to the reaction procedures described in this Example.

Example 3

Selective hydrogenation of lauric acid to dodecane in a 20 cc multi-reactor system Deoxygenation

This example describes selective hydrogenation dehydrogenation of lauric acid to dodecane using alumina-supported tungsten / platinum catalyst (2% W on 5% Pt / alumina) prepared in Example 1. [ This method was performed under conditions including a temperature of 200 DEG C and a pressure of 400 psig.

A hydrogenated deoxygenation reaction was carried out in an Endeavor ^® reactor system containing eight stainless steel reaction vessels. Each vessel has a volume of about 25 mL and is equipped with mechanical agitation. A 20 mL glass vial is used as a liner for each reactor in this system.

(Sigma Aldrich, 99.9%, Sigma Aldrich, over 99%, lot No. MKBG4553V), 1.71 g of tetradecane (alpha emulsion, 99 +%, lot number E09Y007), 0.10 g of hexadecane 26396JMV lot number) and example 1 with 0.10 g of the alumina prepared in a support of the inde tungsten / platinum catalyst member ^® reaction was added to a 20 mL glass vial was used for one of the reaction vessels in the system. The system was sealed and connected to a high pressure gas manifold. The reactor was purged 4 times with nitrogen gas by pressurizing the reactor to 400 psig each time and then depressurizing it. The reactor was then purged with hydrogen gas three times by pressurizing the reactor to 400 psig and then depressurizing it.

After these purging cycles, the reactor was pressurized to 100 psig of hydrogen and heated to 200 ° C. Once the reactor temperature reached 200 캜, more hydrogen was added to the reactor to raise its pressure to an experimental setpoint of 400 psig. The reaction was carried out isothermally for 4 hours, the heat source was turned off and the reactor was cooled to below 50 < 0 > C. During the entire reaction period, the pressure was maintained at a set point of 400 psig by adding hydrogen whenever the pressure dropped below 399 psig.

After cooling the reactor, the glass vial used in the reaction was removed from the reactor and centrifuged at 2000 rpm for 5 minutes. The resulting sample was stripped off gently to separate the catalyst (solid sample) from the remainder of the reaction mixture (liquid sample). The liquid sample was further diluted with tetrahydrofuran and filtered through a standard 0.45 micrometer disposable filter. The filtered liquid sample was then analyzed by GC / FID to identify its constituents and determine the concentrations of reactants and products. The individual components were identified by matching the residence time of these components with the residence time of certain calibration standards. The hexadecane contained in the reaction was used as an internal standard to determine the concentration of each of the individual components.

Concerning the final product of the reaction, the conversion of lauric acid was observed to be about 99%, while the molar yield of dodecane was about 79% (Table 2, line 7). The molar yield was about 1% for dodecanol, about 2% for lauryl laurate and about 3% for undecane.

These results further demonstrate that the hydrogenated deoxygenation process using W / Pt / alumina catalyst under low temperature and low pressure conditions can be used to produce linear alkanes from the C ₁₂ oxygenate, lauric acid. The hydrogenated deoxygenation process yielded a fully deoxygenated full length product, dodecane, which in most cases had very small byproducts. The low level undecane produced indicates that there is little carbon loss during this process, while low levels of dodecanol and lauryl laurate indicate that the carboxylic acid moiety of lauric acid is efficiently deoxygenated.

In view of the results described in Examples 8 to 11, the inclusion of a heteropoly acid or a heteropoly acid salt would be applicable to the reaction procedures described in this Example.

Example 4

Selective hydrogenation of lauric acid to dodecane in a 20 cc multi-reactor system using various catalysts.

This example describes selective hydrogenation dehydrogenation of lauric acid to dodecane using various other catalysts other than 2% W on 5% Pt / alumina as described above. In the case of other catalysts containing platinum and tungsten, they differ in the amount of platinum and tungsten contained therein and / or in the manner in which platinum and tungsten are applied to the alumina support during catalyst preparation. Catalysts containing other metals such as nickel, copper, bismuth, molybdenum, palladium, manganese, chromium and vanadium were also tested.

Other catalysts were prepared and tested for their ability to catalyze the deoxygenation of lauric acid to dodecane according to the 20 cc reaction procedure described in Example 3. [ These other catalysts are listed in Table 2 and they were prepared in a manner similar to the protocol described in Example 1 to make 2% W on 5% Pt / alumina. Generally, catalysts containing tungsten and platinum were prepared by impregnating tungsten on alumina-supported platinum ("Pt / alumina") or impregnating tungsten and platinum on alumina. Alumina was impregnated with other metals (vanadium, palladium, manganese, chromium, molybdenum) in the preparation of other catalysts. Pt / alumina (referred to in Example 1) and alumina were both from Johnson Matthey, Inc.

[Table 2]

"0.4% W on 1% Pt / alumina", "0.8% W on 1% Pt / alumina", "2% W on 1% Pt / 2% W on 2% Pt / alumina, 5% W on 1% Pt / alumina, 7.5% W on 1% Pt / alumina, Catalysts listed in Table 2 as " 10% W on alumina / 5% W on 2% Pt / alumina ", "7.5% W on 2% Pt / Were prepared according to the procedure described in Example 1. However, different concentrations of ammonium tungstate pentahydrate were correspondingly used to load tungsten on Pt / alumina containing 1 wt.% Or 2 wt.% Platinum.

As " 2% W on phase 2% Pt on alumina ", and "2% W on phase 2% Pt on alumina 2% The catalysts listed in 2 were prepared by sequentially impregnating platinum and tungsten on alumina. The 2% Pt catalyst on 2% W on alumina and the 2% Pt on W on alumina catalyst was first loaded onto the alumina-supported tungsten (after forming alumina-supported tungsten) loading tungsten on alumina . Conversely, 2% W on 2% Pt on alumina and 5% W on 2% Pt on alumina were prepared by first dissolving (after alumina-supported platinum forming) platinum loaded onto platinum on alumina-supported platinum Lt; / RTI > Each metal was loaded on a support in a manner similar to that described in Example 1. Briefly, a tungsten salt (ammonium tungstate pentahydrate) or a platinum salt (platinous amines nitrate) was dissolved in deionized water and then mixed with alumina. The mixture was dried at 110 DEG C under a vacuum of 20 mmHg for about 16 hours, cooled, and then calcined at 350 DEG C for 3 hours to obtain alumina-supported tungsten or platinum. Subsequently, the impregnation of the following metal (tungsten or platinum) was carried out using the same procedure, but alumina-supported tungsten or platinum produced from the first step was used as the loading target. Thus, the production of these specific catalysts involved two calcination steps. 2% W on Pd on alumina ", 2% Cr on 2% Pd on alumina ", and " The catalysts listed in Table 2 were prepared as "2% Mn on 2% Pd on alumina" and "2% V on 2% Pd on alumina.

The catalysts listed in Table 2 as "2% W and 2% Pt on alumina" and "5% W and 2% Pt on alumina" were prepared using one calcination step as follows. The platinum nitrate solution was mixed with alumina and then dried at 110 < 0 > C under vacuum of 20 mm Hg for about 16 hours. The dried product was then mixed with the ammonium tungstate pentahydrate solution and then dried as described above. The dried product containing both platinum and tungsten together with alumina was then calcined at 350 DEG C for 3 hours. Using the appropriate metal salts and carbon as supports, similar methods were used correspondingly to prepare the catalysts listed in Table 2 as "1% Pt and 0.1% Cu on carbon " and" 5% Pt and 5% Respectively.

The results listed in Table 2 indicate that some catalysts in addition to 2% W on 5% Pt / alumina can catalyze the hydrogenated deoxygenation of dodecane of lauric acid at 200 [deg.] C and 400 psig. For example, the product of the reaction using 2% W on 2% Pt / alumina (Table 2, row 6) and 5% W on 2% Pt on alumina (Table 2, row 11) catalyst, The yield was two times higher than the respective molar yield of undecane. In addition, the reaction using some of the catalysts in Table 2 had a molar yield of dodecane of more than 25%. For example, the reaction using three separate preparations of a 5% W catalyst on 2% Pt / alumina resulted in a dodecane yield of over 56%, with undecane yield being below 3%.

In view of the results described in Examples 8 to 11, the inclusion of a heteropoly acid or a heteropoly acid salt would be applicable to the reaction procedures described in this Example.

Example 5

Selective hydrogenation of lauric acid to dodecane in a 20 cc multi-reactor system using a catalyst containing alumina at various pH levels

This example describes selective hydrogenation dehydrogenation of lauric acid to dodecane using a catalyst containing 5% W and 2% Pt supported on an acidic, weakly acidic, neutral, or basic alumina solid support.

The catalysts in this example were prepared using a specific type (acidic, weakly acidic, neutral or basic) alumina according to the method described in Example 4 for the catalyst designated as "5% W on 2% Pt on alumina & . These catalysts were then used in the hydrogenation dehydrogenation reaction of lauric acid under the conditions described in Example 3. The results of these reactions are listed in Table 3.

[Table 3]

The results listed in Table 3 demonstrate that catalysts containing 5% W and 2% Pt supported on acidic, slightly acidic, neutral, or basic alumina are both hydrogenated at 200 [deg.] C and 400 psig to dodecane of lauric acid Indicating that it was possible to catalyze deoxygenation. All reactions gave 22% to 32% of dodecane while less than 3% of undecane were obtained. These results suggest that catalysts containing various amounts of tungsten and platinum supported on alumina at various pH levels can catalyze C _{10-18 oxyhydrogenated} deoxygenation.

In view of the results described in Examples 8 to 11, the inclusion of a heteropoly acid or a heteropoly acid salt would be applicable to the reaction procedures described in this Example.

Example 6

Selective hydrogenation of lauric acid to dodecane in a 20 cc multi-reactor system using a 6 hour reaction period.

This example demonstrates that selective hydrogenation of lauric acid to dodecane using various catalysts according to the reaction procedure described in Example 3, except that the conditions of 200 < 0 > C and 400 psig were maintained for 6 hours instead of 4 hours, Describe additive deoxygenation.

A catalyst in this example containing tungsten and Pt / alumina (alumina-supported platinum) was prepared according to the procedure described in Example 4. [ 5% Mo on a 2% Pt / alumina catalyst was prepared according to a similar procedure. These catalysts were then used in the hydrogenation dehydrogenation reaction of lauric acid under the conditions described in Example 3 except that the reaction conditions of 200 ° C and 400 psig were maintained for 6 hours instead of 4 hours. The results of these reactions are listed in Table 4.

[Table 4]

The results listed in Table 4 demonstrate that the reaction conditions described in Example 3, except that a 6 hour period at 200 < 0 > C and 400 psig was used, resulted in hydrogenated deoxygenation of lauric acid to dodecane, . Specifically, a catalyst having 2% platinum and 2%, 5%, 7.5%, or 10% tungsten was able to obtain 40% to 82% of dodecane with an undecane yield of 4% or less.

Table 4 also shows that catalysts containing 5% molybdenum and 2% platinum supported on alumina were effective in catalyzing hydrogenation dehydrogenation of lauric acid to dodecane with very little undecane. This observation suggests that catalysts comprising platinum and molybdenum are useful for performing certain C _{10-18 oxyhydrogenated} deoxygenation processes as described herein.

In view of the results described in Examples 8 to 11, the inclusion of a heteropoly acid or a heteropoly acid salt would be applicable to the reaction procedures described in this Example.

Example 7

Selective hydrogenation of lauric acid to dodecane in a 20 cc multi-reactor system using various solvent conditions.

This example illustrates the selective reaction of lauric acid with dodecane using a catalyst containing tungsten and platinum according to the reaction procedure described in Example 3 with the exception that different solvents and different amounts of lauric acid substrate were used. Hydrogenated deoxygenation is described.

The catalysts used in this example, containing 2% tungsten and 5% platinum, were prepared according to the procedures described in Examples 1 and 4. This catalyst was then used in the hydrogenolysis dehydrogenation reaction of lauric acid under the conditions described in Example 3, with the following exceptions. The reaction was carried out using 1 or 2 g of lauric acid base instead of 0.20 g of lauric acid. Also, hexadecane (1 g) alone, water (1 g), or no solvent was used as opposed to about 17: 1 mixture of tetradecane and hexadecane as the solvent. The results of these reactions are listed in Table 5.

[Table 5]

The results listed in Table 5 indicate that the catalyst comprising tungsten and platinum performs well in a hydrogenated deoxygenation reaction using an organic solvent such as hexadecane. However, the reaction without solvent is effective: a 2% W catalyst on 5% Pt / alumina in the absence of solvent was able to catalyze the reaction and this reaction was only 15% with a 1% yield of undecane / RTI >

Based on this example and Example 3 where a 2% W catalyst on 5% Pt / alumina was used in a solvent containing tetradecane and hexadecane, these organic solvents and similar organic solvents were added _{Lt; RTI ID = 0.0} > _C10-18 < / RTI > _{oxyhydrogenated} deoxygenation process.

In view of the results described in Examples 8 to 11, the inclusion of a heteropoly acid or a heteropoly acid salt would be applicable to the reaction procedures described in this Example.

Example 8

Selective hydrogenation of lauric acid to dodecane in the presence of heteropoly acid in a 40 cc reactor Deoxygenation

This example describes selective hydrogenation dehydrogenation of lauric acid to dodecane using a carbon-supported platinum catalyst prepared in a reaction containing tungstic acid, heteropoly acid (abbreviated herein as WPA). This method was performed under conditions including a temperature of 200 DEG C and a pressure of 1000 psig.

6.0 g of lauric acid (Sigma Aldrich, greater than 99%, lot number MKBG4553V, St. Louis, Mo.), 5.4 g of tetradecane (AlphaEdson, Ward Hill, Mass .; 99+%, lot number E09Y007 ) (Dry weight of 0.6 g) (solvent for this reaction), 0.6 g of hexadecane (Sigma Aldrich, 99.9%, lot number 26396 JMV), Johnson Matthey, Inc., West Deptford, ) Of carbon-supported 1% platinum catalyst (JM # 25 carbon support) and 0.174 g of WPA (Sigma Aldrich Inc.) (where WPA is about 1.3 wt% of the reaction mix) are ground in a mortar and pestle, It was then added to a 40 cc Hastelloy ^® pressure reactor equipped with a magnetic stirrer. The reactor was purged three times with nitrogen gas by pressurizing the reactor to about 150 psig each time and then depressurizing it. The reactor was then purged 3 times with hydrogen gas by pressurizing the reactor to 150 psig and then depressurizing it.

After these purge cycles, the reactor was pressurized to about 250 psig of hydrogen and heated to 200 ° C. Once the reactor had equilibrated at 200 ° C, the reactor pressure was raised to an experimental setpoint of 1000 psig. After 6 hours at 200 ° C, the reactor was allowed to cool to 50 ° C and held overnight under these conditions.

The next day, the reactor was opened and samples were taken for GC analysis and resealed. The reactor was purged in a manner similar to the previous day with three nitrogen purges each and three hydrogen purges each to achieve 250 psig hydrogen in the reactor. The reactor was then reheated to 200 ° C and once the set point temperature had been reached, the hydrogen pressure was increased to 1000 psig. After 6 hours, the reactor was allowed to cool to room temperature and stayed overnight.

The third run was followed the day before, which included precise sample recovery and reactor preparation. Samples were run for an additional 6 hours to give a total run time of 18 hours over the course of 3 days. After the third run, samples were collected, transferred on GC and passed through GC, as shown below.

All of the collected samples were diluted with tetrahydrofuran and filtered through a standard 0.2 micrometer disposable filter. The filtered sample was then analyzed by GC / FID (gas chromatography / flame ionization detector) to identify its components and determine the concentrations of reactants and products. The individual components were identified by matching the residence time of these components with the residence time of certain calibration standards. The hexadecane contained in the reaction was used as an internal standard to determine the concentration of each of the individual components.

Concerning the final product of the reaction, the conversion of lauric acid was observed to be about 99%, while the molar yield of dodecane was about 73%. The molar yield was about 0% for dodecanol and lauryl laurate and about 1% for undecane, where the mass balance is close to about 76% of the mass considered.

These results show that feedstocks comprising lauric acid, a C ₁₂ oxygenate, can be used to produce linear alkanes via hydrogenated deoxygenation processes using carbon-supported platinum catalysts in the presence of heteropoly acids under low temperature conditions . The hydrogenated deoxygenation process in most cases produced a completely deoxidized product (dodecane) with a small amount of certain byproducts.

Specifically, the low production of undecane (C ₁₁ ) demonstrates that only very low levels of carbon loss through lauric acid decarboxylation occurred during this process. The high level of dodecane produced with relatively small amounts of by-products dodecanol and lauryl laurate demonstrates that this method efficiently deoxidizes the carboxylic acid moiety of the lauric acid feedstock.

Thus, the mixing of the supported metal catalyst with the heteropoly acid provided a catalyst that efficiently catalyzed the conversion of oxygenated carbon chains to linear alkanes, while minimizing the chain length reduction in the hydrogenated deoxygenation process.

Example 9

Selective Hydrogenation of Lauric Acid to Dodecane Using Supported Platinum Catalysts Prepared in the Presence of Heteropolyacids

This example describes selective hydrogenation dehydrogenation of lauric acid to dodecane using various supported platinum catalysts prepared in the presence of tungstic acid (WPA), a heteropoly acid. This method was performed in a 20 cc multi-reactor system under conditions including a temperature of 200 < 0 > C and a pressure of 400 psig.

In the Endeavor ^® reactor system that contains eight stainless steel reactor vessel it was performed hydrogenation deoxygenation reaction. Each vessel has a volume of about 25 mL and is equipped for mechanical agitation. A 20 mL glass vial is used as a liner in each reactor in this system.

0.10 g of the dry weight of the carbon-or alumina-supported platinum catalyst and 0.05 g of the WPA a mortar and blended with pestle and grinding, followed by Endeavor ^® reaction a 20 mL glass vial was used for one of the reaction vessels in the system Lt; / RTI > This formulation represents a catalyst with 50% by weight of WPA used (listed as "WPA with 50% catalyst loading rate " in Table 6), based on the weight of supported platinum catalyst. Other amounts of WPA were also used, e.g., 30% based on the weight of supported platinum catalyst (i.e., 0.03 g WPA and 0.10 g supported platinum catalyst).

Table 6 lists other amounts of WPA in the catalyst, such as "W of 2% loading rate using WPA. &Quot; This was calculated as follows: Calculating the tungsten (W) content of WPA and using the amount of WPA, this would provide the total mass of W, and the total mass of W was 2% based on the weight of the supported platinum catalyst . For example, when 0.10 g of supported platinum catalyst is used, about 0.002 g of W is required for "W" of 2% loading with the use of WPA. Based on the presence of about 76.6 wt% of W in one molecule of WPA, about 0.026 g of WPA is mixed with the catalyst to load 0.002 g of W. "5% loading rate W", "10% loading rate W" using WPA, "W" 30% loading rate using WPA, "WPA using 50% The same type of calculation was used to produce W "% of loading rate, and" W "catalyst of 100% loading using WPA.

After preparing the catalyst dry-mix, 0.20 g of lauric acid (Sigma Aldrich, more than 99%, lot number MKBG4553V), 1.71 g of tetradecane (alpha emulsion, 99 +%, lot number E09Y007) , And 0.10 g of hexadecane (Sigma Aldrich, 99.9%, lot # 26396JMV) were added to the vial containing the catalyst. The system was sealed and connected to a high pressure gas manifold. The reactor was purged 4 times with nitrogen gas by pressurizing the reactor to 400 psig each time and then depressurizing it. The reactor was then purged with hydrogen gas three times by pressurizing the reactor to 400 psig and then depressurizing it.

After these purging cycles, the reactor was pressurized to 100 psig of hydrogen and heated to 200 ° C. Once the reactor temperature reached 200 캜, more hydrogen was added to the reactor to raise its pressure to an experimental setpoint of 400 psig. The reaction was carried out isothermally for 4 hours, the heat source was turned off and the reactor was cooled to below 50 < 0 > C. During the entire reaction period, the pressure was maintained at a set point of 400 psig by adding hydrogen whenever the pressure dropped below 399 psig.

After cooling the reactor, the glass vial used in the reaction was removed from the reactor and centrifuged at 2000 rpm for 5 minutes. The resulting sample was stripped off gently to separate the catalyst (solid sample) from the remainder of the reaction mixture (liquid sample). The liquid sample was further diluted with tetrahydrofuran and filtered through a standard 0.45 micrometer disposable filter. The filtered liquid sample was then analyzed by GC / FID to identify its constituents and determine the concentrations of reactants and products. The individual components were identified by matching the residence time of these components with the residence time of certain calibration standards. The hexadecane contained in the reaction was used as an internal standard to determine the concentration of each of the individual components. The results of these implementations-each of which uses a particular catalyst / WPA formulation-are provided in Table 6.

Thus, the bonding of the metal catalyst to the heteropoly acid salt provides a catalyst that efficiently catalyzes the conversion of the oxygenated carbon chain to the linear alkane while minimizing the chain length reduction in the hydrogenated deoxygenation process. This mixing procedure should also be applicable when using heteropoly acid salts.

[Table 6]

The results in Table 6 show that a hydrogenated deoxygenation process using a supported platinum catalyst prepared in the presence of heteropoly acid can be used to produce linear alkanes from the C ₁₂ oxygenate lauric acid under low and low pressure conditions . The hydrogenated deoxygenation process yielded a fully deoxygenated full length product, dodecane, which in most cases had very small byproducts. The low level undecane produced indicates that there is little carbon loss during this process, while low levels of dodecanol and lauryl laurate indicate that the carboxylic acid moiety of lauric acid is efficiently deoxygenated.

Thus, the dry-mixing of the supported metal catalyst and heteropoly acid provides a catalyst that can be used in a hydrogenated deoxygenation process to convert the oxygenated carbon chain to a linear alkane. Such a dry-mixing procedure would also be applicable when using heteropoly acid salts.

Example 10

Preparation of Heteropoly Cesium Salt

This example describes a general procedure for preparing partially Cs-exchanged heteropoly acids Cs _2.5 H _0.5 PW ₁₂ O ₄₀ and Cs _2.5 H _0.5 SiW ₁₂ O ₄₀ . These heteropoly acid cesium salts were used in Example 11 to prepare various catalyst compositions containing heteropoly acid salts and platinum loaded thereon. The resulting catalyst composition can be used in a hydrogenated deoxygenation reaction procedure.

A cesium salt of tungsten heteropoly acid was prepared using an aqueous solution of Cs ₂ CO _{3 and} an aqueous solution of H ₃ PW ₁₂ O ₄₀ or H ₄ SiW ₁₂ O ₄₀ . The heteropoly acid H ₃ PW ₁₂ O ₄₀ or H ₄ SiW ₁₂ O ₄₀ was first prepared for use as an aqueous solution by dehydrating it at 60 ° C under vacuum for 2 hours. The aqueous solution was dehydrated Cs ₂ CO ₃ eseo 420 ℃ for 2 hours under vacuum prior to using it to prepare.

An aqueous solution of H ₃ PW ₁₂ O ₄₀ (0.08 mol dm ^-3 ) or H ₄ SiW ₁₂ O ₄₀ (0.08 mol dm ^-3 ) was added to a solution of Cs ₂ CO ₃ (0.25 mol / L) at a rate of 1 mL / Lt; RTI ID = 0.0 > Cs-exchanged < / RTI > heteropoly acid. The resulting white colloidal suspension (precipitated heteropoly acid salt) was evaporated at 50 < 0 > C under vacuum to a solid. The solids were then placed in a 120 [deg.] C vacuum oven for 2 hours to remove water. Optionally, the dried solids were calcined in air at 300 < 0 > C for 1 hour.

In this way, partially Cs-exchanged heteropoly acids Cs _2.5 H _0.5 PW ₁₂ O ₄₀ and Cs _2.5 H _0.5 SiW ₁₂ O ₄₀ were prepared. In the present specification, Cs _2.5 H _0.5 PW ₁₂ O ₄₀ is also referred to as cobalt tungstate cesium salt (Cs-WPA). The following Example 11 describes the use of Cs-WPA in the preparation of certain catalyst compositions for performing a selective hydrodeoxygenation reaction.

Example 11

Selective Hydrogenation of Lauric Acid to Dodecane Using a Catalyst Containing a Platinum-Bonded Tungstate Cesium Salt

This example describes selective hydrogenation dehydrogenation of lauric acid to dodecane using a catalyst prepared by loading platinum onto cesium tungstate cesium salt (Cs-WPA). This method was performed in a 20 cc multi-reactor system under conditions including a temperature of 200 < 0 > C and a pressure of 400 psig.

Platinum was loaded by wet-impregnation onto Cs-WPA as prepared in Example 10, using an aqueous solution of ammonium nitrate. Using a suitable amount of ammonium nitrate solution, 0.25 wt%, 0.5 wt%, 1.0 wt%, or 2.0 wt% Pt was loaded on the Cs-WPA catalyst component. Wet-impregnation was performed on the calcined or non-calcined Cs-WPA (see Example 10). The wet-impregnated sample was dried at 100 < 0 > C under mild vacuum and then calcined in a calcining furnace at 350 < 0 > C for 3 hours.

0.10 g inde The calcined catalyst preparation reaction member ^® reaction was added to individual 20 mL glass vial used in the container in the system. Next, 0.20 g of lauric acid (Sigma Aldrich, over 99%, lot number MKBG4553V), 1.71 g of tetradecane (alpha emulsion, 99 +%, lot number E09Y007) g of hexadecane (Sigma Aldrich, 99.9%, lot # 26396JMV) was added to the vial containing the catalyst. Inde samples carried out at 20 cc member ^® reactor system and analyzed in the same manner as that described in Example 9. The results are summarized in Table 7.

[Table 7]

The results in Table 7 show that a hydrogenated deoxygenation process using a platinum catalyst loaded on a heteropoly acid salt can be used to produce linear alkanes from a C ₁₂ oxygenated lauric acid under low and low pressure conditions Proves. The hydrogenated deoxygenation process yielded a fully deoxygenated full length product, dodecane, which in most cases had very small byproducts. The low level undecane produced indicates that there is little carbon loss during this process, while low levels of dodecanol and lauryl laurate indicate that the carboxylic acid moiety of lauric acid is efficiently deoxygenated.

Thus, the bonding of the metal catalyst to the heteropoly acid salt provides a catalyst that efficiently catalyzes the conversion of the oxygenated carbon chain to the linear alkane while minimizing the chain length reduction in the hydrogenated deoxygenation process.

Claims (15)

From a feedstock comprising a saturated or unsaturated C _10-18 oxygenate comprising a moiety selected from the group consisting of an ester group, a carboxylic acid group, a carbonyl group, and an alcohol group, A hydrogenated deoxygenation process for producing an alkane,
a) contacting the feedstock at a temperature of from about 150 ° C to about 250 ° C and at a hydrogen gas pressure of at least about 300 psig with (i) from about 0.1% to about 10% by weight of a metal selected from Groups IB, VIB, or VIII of the Periodic Table; (Ii) contacting a heteropolyacid or heteropoly acid salt, wherein the C _10-18 oxygenate is hydrodeoxygenated to a linear alkane, and the linear alkane is a carbon that is the same as the C _10-18 oxygenate Have chain length -; And
b) optionally, recovering the linear alkane produced in step (a). The method of claim 1, wherein the C _10-18 oxygenate is a fatty acid or triglyceride. The method according to claim 1, wherein the feedstock comprises a vegetable oil or a fatty acid distillate thereof. 4. The process according to claim 3, wherein the feedstock comprises
(i) vegetable oils selected from the group consisting of soybean oil, palm oil and palm kernel oil; or
(ii) a palm fatty acid distillate. The process of claim 1, wherein the catalyst comprises from about 0.1 wt% to about 6 wt% platinum as metal. 6. The method of claim 5, wherein the catalyst comprises from about 0.25 weight percent to about 2 weight percent platinum as metal. The method of claim 1, wherein the heteropoly acid or heteropoly acid salt comprises tungsten. 8. The process according to claim 7, wherein the heteropoly acid or heteropoly acid salt further comprises phosphorus. The method according to claim 1, wherein the heteropoly acid salt is a heteropoly acid cesium salt. The process according to claim 1, wherein the catalyst further comprises a solid support. 2. The process according to claim 1, wherein the feedstock is contacted with a catalyst and a heteropoly acid salt, and the catalyst is bonded to a heteropoly acid salt. The process according to claim 1, wherein the catalyst and the heteropoly acid or heteropoly acid salt are dry-mixed together before they are contacted with the feedstock. 13. The process according to claim 12, wherein the catalyst and the heteropoly acid are dry-mixed together before they are contacted with the feedstock. 2. The method of claim 1, wherein the temperature is about 200 < 0 > C and the pressure is about 400 psig. The process according to any one of the preceding claims, wherein the molar yield is less than 10% for a reaction product having a carbon chain length shorter than the carbon chain length of the _C10-18 oxygenate by at least one carbon atom.