Ketone production

Abstract

The present invention relates to a method of producing a ketone K1 of the Formula I: R1-C(=O)-R2, wherein a carboxylic acid R1-COOH and a carboxylic acid R2-COOH are reacted in the presence of a catalyst composition X to give K1 and CO2; and wherein R1 and R2 is independently a hydrocarbon group, preferably R1 and R2 is an organic radical selected from the group consisting of unsubstituted and mono- or polysubstituted, branched and straight-chain alkyl radicals, cycloalkyl radicals, alkenyl radicals having one or more double bonds, alkynyl radicals having one or more triple bonds, aryl radicals, alkylaryl radicals, arylalkyl radicals, arylalkenyl radicals, alkyloxyalkyl radicals, hydroxyalkyl radicals, aminoalkylradicals and alkylthioalkyl radicals; and wherein the catalyst composition X comprises: - at least one mixed oxide.

Description

[0001] 202400270 Foreign Filing 1

[0002] KETONE PRODUCTION

[0003] FIELD OF THE INVENTION

[0004] The present invention relates to a method of producing ketones from carboxylic acids. In particular, the method includes the use of a specific catalyst composition comprising at least one transition metal; and / or at least one mixed oxide comprising zirconium oxide and silicon dioxide.

[0005] BACKGROUND OF THE INVENTION

[0006] There are various well-known processes for the production of ketones from a variety of different raw materials. These processes for example include oxidation of secondary alcohols, Friedel-Crafts acylation, reaction of acid chlorides with organic cadmium compounds, acetoacetic ester synthesis and decarboxylation from acids, and also ketonisation of organic acids among others.

[0007] It is however, also well-known that there are several problems associated with these known processes to produce ketones. These include problems such as the unavailability and / or high cost of raw materials, the requirement of multi-stage processing, the low conversion of raw materials and / or the low selectivity of the desired ketones, the production of corrosive or hard-to-separate products amongst other problems of the known processes of ketone production.

[0008] In fact, the most used ketone manufacturing processes include the reaction of various different reactants at a specified temperature and pressure ranges in the presence of different catalysts. US4528400, US4874899, US4570021 , US4060555, US3966822, US3466334, and US3453331 are some examples of prior art that disclose a process of synthesizing ketones from a variety of starting products at a variety of temperature and pressure conditions.

[0009] A great deal of attention has been given to the selection of feed materials and the process parameters such as temperature and pressure in connection with the production of ketones. However, little, if any, attention has been given to evaluating the role of the catalyst in the ketone preparation process or to selecting or preparing the catalyst for the purpose of maximizing the conversion and selectivity of the feed material to the desired ketone product. US6369276 for example discloses a catalyst and catalyst structure for use in the production of organic compounds such as ketones, which has been formulated to optimize the conversion of feed reactants and selectivity to the desired ketone. However, the catalyst production is complicated.

[0010] Accordingly, there is a need in the art for a catalyst useful in the production of ketones from simple starting materials which not only allows the reaction to proceed, but which also optimizes the conversion and selectivity of the reaction to the desired ketone.202400270 Foreign Filing 2

[0011] DESCRIPTION OF THE INVENTION

[0012] The method according to any aspect of the present invention solves the problems above by using at least one specific ketonisation catalyst for the ketonisation of carboxylic acids to produce a corresponding ketone. In particular, the ketonisation catalyst is a special catalyst composition that comprises at least one transition metal; and / or at least one mixed oxide and the mixed oxide comprises zirconium dioxide and silicon dioxide and the mass ratio of zirconium dioxide to silicon dioxide in the mixed oxide is 86:14 to 99.9:0.1. It was found that, surprisingly, this specific ketonisation catalyst according to any aspect of the present invention catalyses ketone production from carboxylic acid. In particular, a high yield of ketone was obtained from a simple and cost efficient raw material - carboxylic acid. The ketone can be obtained in high yield and purity. Furthermore, it is possible to use smaller catalyst amounts compared to the related art and / or realize shorter reaction times. Moreover, the reactions are catalyzed at lower temperatures.

[0013] According to one aspect of the present invention, there is provided a method of producing a ketone K1 of the Formula I:

[0014] R1-C(=O)-R2 Formula I,

[0015] wherein a carboxylic acid R1-COOH and a carboxylic acid R2-COOH are reacted in the presence of a catalyst composition X to give K1 and CO2; and

[0016] wherein R1 and R2 is independently a hydrocarbon group, preferably R1 and R2 is an organic radical selected from the group consisting of unsubstituted and mono- or polysubstituted, branched and straightchain alkyl radicals, cycloalkyl radicals, alkenyl radicals having one or more double bonds, alkynyl radicals having one or more triple bonds, aryl radicals, alkylaryl radicals, arylalkyl radicals, arylalkenyl radicals, alkyloxyalkyl radicals, hydroxyalkyl radicals, aminoalkylradicals and alkylthioalkyl radicals; and wherein the catalyst composition X comprises:

[0017] at least one transition metal; and / or

[0018] at least one mixed oxide.

[0019] In particular, the carboxylic acid according to any aspect of the present invention has a formula R1-COOH or R2-COOH wherein R1 and R2 is independently a hydrocarbon group. In particular, suitable carboxylic acids are monofunctional or else difunctional or higher-functional carboxylic acids. Monocarboxylic acids contemplated include saturated and preferably unsaturated carboxylic acids such as benzoic acid, cyclohexanecarboxylic acid, 2-ethylhexanoic acid, caproic acid, caprylic acid, capric acid, lauric acid, natural and synthetic fatty acids, in particular acrylic acid, methacrylic acid, dimeric acrylic acid or crotonic acid. Suitable dicarboxylic acids are phthalic acid, isophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, maleic acid, fumaric acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, pimelic acid, suberic acid, sebacic acid, dodecanedioic acid, and hydrogenated dimeric fatty acids.202400270 Foreign Filing 3

[0020] More in particular, R1 or R2 is an organic radical, a hydrogen, an optionally unsaturated, optionally substituted, optionally one or more heteroatoms containing straight chain or branched alkyl group having upto 55 carbon atoms; an optionally unsaturated, optionally substituted, optionally one or more heteroatoms containing C5-8 cycloalkyl group; an optionally substituted aryl or heteroaryl group; or an optionally substituted benzyl group. In one example, the alkyl group is optionally interrupted by an oxygen atom or by an internal ester group. In one example, the alkyl group has 1 to 50 carbon atoms, particularly 10 to 50 carbon atoms, more particularly 4 to 12 carbon atoms.

[0021] A particular substituent of the above defined groups is a hydroxyl group, especially an [alpha]-hydroxyl group.

[0022] In one example, the carboxylic acid is hexanoic acid, octanoic acid, stearic acid, oleic acid, linoleic acid, 27-stearoyloxy-heptacosanoic acid, 27-linoleoyloxy-heptacosanoic acid, [alpha]-hydroxy-stearic acid, lactic acid, retinoic acid, salicylic acid or ferulic acid. In particular, the carboxylic acid is an alkanoic acid comprising 1 to 22 carbon atoms, particularly a hexanoic acid.

[0023] The carboxylic acid used according to any aspect of the present invention may be produced using any method known in the art. In one example, the carboxylic acid may be produced using a biotechnological method. In particular, the carboxylic acid may be produced during a process offermentation in the presence of at least one microorganism. The microorganisms capable of producing the carboxylic acid may be cultivated with any culture media, substrates, conditions, and processes generally known in the art for culturing bacteria. Depending on the microorganism that is used for the carboxylic acid production, appropriate growth medium, pH, temperature, agitation rate, inoculum level, and / or aerobic, microaerobic, or anaerobic conditions are varied. A skilled person would understand the other conditions necessary to carry out the biotechnological method according to any aspect of the present invention. In particular, the conditions in the container (e.g. fermenter) may be varied depending on the microorganisms used. The varying of the conditions to be suitable for the optimal functioning of the microorganisms is within the knowledge of a skilled person. In one example, the method according to any aspect of the present invention may be carried out in an aqueous medium with a pH between 5 and 8, or 5.5 and 7. The pressure may be between 1 and 10 bar. The microorganisms may be cultured at a temperature ranging from about 20°C to about 80°C. In one example, the microorganism may be cultured at 37°C.

[0024] In some examples, for the growth of the microorganism and for its production of the carboxylic acid, the aqueous medium may comprise any nutrients, ingredients, and / or supplements suitable for growing the microorganism or for promoting the production of the carboxylic acid. In particular, the aqueous medium may comprise at least one of the following: carbon sources, nitrogen sources, such as an ammonium salt, yeast extract, or peptone; minerals; salts; cofactors; buffering agents; vitamins; and any other components and / or extracts that may promote the growth of the bacteria. The culture medium to be used must be suitable for the requirements of the particular strains.202400270 Foreign Filing 4

[0025] In another example, the microorganism according to any aspect of the present invention is at least one acetogenic bacteria or at least one microorganism for carbon chain elongation or a combination thereof.

[0026] In particular, the microorganisms (cells) are brought into contact with a carbon source which includes monosaccharides (such as glucose, galactose, fructose, xylose, arabinose, or xylulose), disaccharides (such as lactose or sucrose), oligosaccharides, and polysaccharides (such as starch or cellulose), one-carbon substrates and / or mixtures thereof. More in particular, the cells are brought into contact with a carbon source comprising CO and / or CO2 to produce the carboxylic acid. With respect to the source of substrates comprising carbon dioxide and / or carbon monoxide, a skilled person would understand that many possible sources for the provision of CO and / or CO2 as a carbon source exist. It can be seen that in practice, as the carbon source of the present invention, any gas or any gas mixture can be used which is able to supply the microorganisms with sufficient amounts of carbon, so that acetate and / or ethanol, may be formed from the source of CO and / or CO2. In particular, the microorganism may use synthesis gas, CO2, CO, combinations thereof or any other carbon source as a substrate for the organic product production.

[0027] The term "acetogenic bacteria" as used herein refers to a microorganism which is able to perform the Wood-Ljungdahl pathway and thus is able to convert CO, CO2 and / or hydrogen to acetate. These microorganisms include microorganisms which in their wild-type form do not have a Wood-Ljungdahl pathway, but have acquired this trait as a result of genetic modification. Such microorganisms include but are not limited to E. coli cells. These microorganisms may be also known as carboxydotrophic bacteria. Currently, almost 21 different genera of the acetogenic bacteria are known in the art, and these may also include some Clostridia. These bacteria are able to use carbon dioxide or carbon monoxide as a carbon source with hydrogen as an energy source. Further, alcohols, aldehydes, carboxylic acids as well as numerous hexoses may also be used as a carbon source. The reductive pathway that leads to the formation of acetate is referred to as acetyl-CoA or Wood-Ljungdahl pathway. In particular, the acetogenic bacteria may be selected from the group consisting of Acetoanaerobium notera (ATCC 35199), Acetonema longum (DSM 6540), Acetobacterium carbinolicum (DSM 2925), Acetobacterium malicum (DSM 4132), Acetobacterium species no. 446 (Morinaga et al., 1990, J. Biotechnol., Vol. 14, p.

[0028] 187-194), Acetobacterium wieringae (DSM 1911), Acetobacterium woodii (DSM 1030), Alkalibaculum bacchi (DSM 22112), Archaeoglobus fulgidus (DSM 4304), Blautia producta (DSM 2950, formerly Ruminococcus productus, formerly Peptostreptococcus productus), Butyribacterium methylotrophicum (DSM 3468), Clostridium aceticum (DSM 1496), Clostridium autoethanogenum (DSM 10061 , DSM 19630 and DSM 23693), Clostridium carboxidivorans (DSM 15243), Clostridium coskatii (ATCC no. PTA-10522), Clostridium drakei (ATCC BA-623), Clostridium formicoaceticum (DSM 92), Clostridium glycolicum (DSM 1288), Clostridium ljungdahlii (DSM 13528), Clostridium ljungdahlii C-01 (ATCC 55988), Clostridium ljungdahlii ERI-2 (ATCC 55380), Clostridium ljungdahlii 0-52 (ATCC 55989), Clostridium mayombei (DSM 6539), Clostridium methoxybenzovorans (DSM 12182), Clostridium ragsdalei (DSM 15248), Clostridium scatologenes (DSM 757), Clostridium species ATCC 29797 (Schmidt et al., 1986, Chem. Eng. Commun., Vol. 45, p. 61-73), Desulfotomaculum kuznetsovii (DSM 6115), Desulfotomaculum thermobezoicum subsp. thermosyntrophicum (DSM 14055), Eubacterium limosum (DSM 20543),202400270 Foreign Filing 5

[0029] Methanosarcina acetivorans C2A (DSM 2834), Moorella sp. HUC22-1 (Sakai et al., 2004, Biotechnol. Let., Vol. 29, p. 1607-1612), Moorella thermoacetica (DSM 521 , formerly Clostridium thermoaceticum), Moorella thermoautotrophica (DSM 1974), Oxobacter pfennig!! (DSM 322), Sporomusa aerivorans (DSM 13326), Sporomusa ovata (DSM 2662), Sporomusa silvacetica (DSM 10669), Sporomusa sphaeroides (DSM 2875), Sporomusa termitida (DSM 4440) and Thermoanaerobacter kivui (DSM 2030, formerly Acetogenium kivui).

[0030] More in particular, the strain ATCC BAA-624 of Clostridium carboxidivorans may be used. Even more in particular, the bacterial strain labelled "P7" and "P11" of Clostridium carboxidivorans as described for example in U.S. 2007 / 0275447 and U.S. 2008 / 0057554 may be used. Another particularly suitable bacterium may be Clostridium ljungdahlii. In particular, strains selected from the group consisting of Clostridium ljungdahlii PETC, Clostridium ljungdahlii ERI2, Clostridium ljungdahlii COL and Clostridium ljungdahlii 0-52 may be used in the conversion of synthesis gas to the organic product. These strains for example are described in WO 98 / 00558, WO 00 / 68407, ATCC 49587, ATCC 55988 and ATCC 55989.

[0031] The chain elongating bacteria may be selected from the group consisting of Clostridium kluyveri (DSM 555), C.carboxidivorans (DSM 15243), Megasphaera cerevisiae (ATCC 43254; DSM 20462), Pseudoram ibacter alactolyticus (ATCC 23263; DSM 3980;), Eubacterium pyruvativorans (ATCC BAA-574), Acinetobacter sp. (DSM 586 and DSM 1845), Eubacterium limosum (ATCC 8486; DSM 20543), Megasphaera elsdenii (ATCC 25940; DSM 20460), Sporanaerobacter acetigenes (DSM 13106), Desulfosporosinus meridie (ATCC BAA-275; DSM 13257), Rhodobacteraceae DSM 15280, and Acetanaerobacterium sp. (DSM 102114) In particular the chain elongating bacteria may be selected from the group consisting of Clostridium kluyveri (DSM 555), and C.carboxidivorans (DSM 15243).

[0032] Mixtures of sources can be used as a carbon source.

[0033] According to any aspect of the present invention, a reducing agent, for example hydrogen may be supplied together with the carbon source. In particular, this hydrogen may be supplied when the CO and / or CO2 is supplied and / or used. In one example, the hydrogen gas is part of the synthesis gas present according to any aspect of the present invention. In another example, where the hydrogen gas in the synthesis gas is insufficient for the method of the present invention, additional hydrogen gas may be supplied. In one example, for the production of the organic product, a carbon source comprising CO and / or CO2 contacts the cells in a continuous gas flow. Even more in particular, the continuous gas flow comprises synthesis gas. These gases may be supplied for example using nozzles that open up into the aqueous medium, frits, membranes within the pipe supplying the gas into the aqueous medium and the like.

[0034] In particular, the carboxylic acid may be produced using any biotechnological method known in the art.

[0035] The catalyst composition X comprises at least one transition metal and / or at least one mixed oxide. In particular, the catalyst comprises at least one mixed oxide, where the mixed oxide comprises zirconium202400270 Foreign Filing 6

[0036] dioxide and silicon dioxide. In one example, the catalyst composition according to any aspect of the present invention comprises only a mixed oxide comprising zirconium dioxide and silicon dioxide. In particular, the mass ratio of zirconium dioxide to silicon dioxide in the mixed oxide is 50:50, 51:49, 52:48, 53:47, 54:46, 55:45, 56:44, 57:43, 58:42, 59:41, 60:40, 61:39, 62:38, 63:37, 64:36, 65:35, 66:34, 67:33, 68:32, 69:31, 70:30, 71:29, 72:28, 73:27, 74:26, 75:25, 76:24, 77:23, 78:22, 79:21, 80:20, 81:19, 82:18, 83:17, 84:16, 85:15, 86:14, 87:13, 88:12, 89:11, 90:10, 91:9, 92:8, 93:7, 94:6, 95:5, 96:4, 97:3, 98:2, or 99:1. More in particular, the mass ratio of zirconium dioxide to silicon dioxide in the mixed oxide is 50:50 to 99:1 , 55:45 to 99:1 , 60:40 to 99:1 , 70:30 to 99:1 , 80:20 to 99:1 , 90:10 to 99:1 , 50:50 to 95:5, 55:45 to 95:5, 60:40 to 95:5, 70:30 to 95:5, 80:20 to 95:5, 90:10 to 95:5. Even more in particular, the mass ratio of zirconium dioxide to silicon dioxide in the mixed oxide is 86:14 to 99.9:0.1 , particularly 90:10 to 97:3, more particularly 95:5. The stated mass ratio excludes, for example, silicon dioxide doped with zirconium dioxide. The mass ratio is calculated on the basis of the zirconium and silicon compounds used for the mixed oxide.

[0037] Catalyst compositions with mixed oxides outside of the specified mass ratio exhibit significantly lower activities. Moreover, the selectivity of the ketone formation decreases when the specified mass ratio is outside of that used according to any aspect of the present invention.

[0038] The term ‘mixed oxide’ is used interchangeably with the term “calcinated mixed oxide” and as used herein is understood as meaning a composition which comprises at least zirconium dioxide and silicon dioxide mixed together in a calcinated form. Zirconium dioxide and silicon dioxide are not present in the mixed oxide as concrete compounds, but serve merely as a base for calculating the mass ratios. The mixed oxide is obtained by calcination. The mixed oxide therefore does not constitute a physical mixture of zirconium dioxide and silicon dioxide, but a chemical mixture comprising at least silicon and zirconium cations with a unique crystal structure. In this regard, a physical mixture which comprises at least the two oxides and has not been calcined does not constitute a mixed oxide for the purposes of the invention. Nor is zirconium dioxide — doped or coated silicon dioxide included.

[0039] In particular, the mixed oxide comprises zirconium dioxide and silicon dioxide or consists of these two oxides. The fraction of the sum of zirconium dioxide and silicon dioxide in the mixed oxide is particularly at least 20% by weight and more particularly at least 30% by weight, even more particularly 50% by weight and very particularly 95% by weight, in each case based on the total weight of the mixed oxide. The mixed oxide particularly consists of zirconium dioxide and silicon dioxide.

[0040] The catalyst compositions according to any aspect of the present invention comprises the mixed oxide. In one example of catalyst compositions according to any aspect of the present invention, the catalyst composition comprises transition metals. In particular, the transition metals are rare metals, or mixtures thereof. In this example, a support for the transition metal can be present which does not consist of the mixed oxide. Particularly, the support does not comprise the mixed oxide or consist of it. The mixed oxide as support, and also the inert support, can be present as powders or as mouldings, preference being202400270 Foreign Filing 7

[0041] given to these supports as mouldings. It is likewise preferred that the mixed oxide is present as moulding if the mixed oxide does not function as transition metal support.

[0042] Suitable mouldings are beads, extrudates, tablets, granules and pellets. The conversion of powders to mouldings is described for example in chapter 9 “Shaping of Solid Catalysts” in the book “Synthesis of Solid Catalysts”, ed K. P. de Jong, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Germany (2009).

[0043] The weight-based ratio of mixed oxide to transition metal, used according to any aspect of the present invention can be 99.9:0.1 to 50:50, particularly 99.5:0.5 to 80:20 and more particularly 99:1 to 90:10.

[0044] In one example, where the catalyst composition according to any aspect of the present invention comprises a transition metal and the transition metal is supported, the fraction of transition metal, based on the total weight of transition metal and support, can be 0.01 to 5% by weight, particularly 0.05 to 2.5% by weight and more particularly 0.3 to 2.0% by weight. The transition metal can be distributed on or within the support.

[0045] The transition metal of the catalyst composition according to any aspect of the present invention may be selected from the group consisting of Iron (Fe), Copper (Cu), Nickel (Ni), Titanium (Ti), Tungsten (W), Manganese (Mn), Cobalt (Co), Vanadium (V), Chromium (Cr), and mixtures thereof, with Manganese being preferred.. The transition metal can be present as powder (unsupported) or in supported form. The transition metals can be present as elemental metals or in the form of their oxides, preference being given to elemental metals.

[0046] A silicon dioxide as solid is understood as meaning a powder which does not form a stable dispersion in water. The silicon dioxide as solid particularly has a particle size d50 of less than 500 pm. In particular, the particle size is less than 500 pm, this upper limit being determined by means of sieve analysis (mesh of 500 pm; this upper limit, determined by means of sieve analysis, is consequently a maximum value and not an average value d50 ). Likewise, the solid particularly has a particle size d50 of greater than 100 nm. The particle size d50 is particularly greater than 500 nm and more particularly greater than 1 pm. The particle size d50 will be ascertained by laser diffraction in accordance with ISO 13320:2009. For the measurement operation, solid (according to manufacturer’s instructions) is placed into the Scirocco 2000 dispersing unit of a Malvern Mastersizer 2000. The pressure selected is 1 bar and the measurement is carried out.

[0047] Colloidal solutions of SiO2 such as Ludox (Grace Davison) and Kostrosol (CWK Bad Kostritz) are not preferred. These types of colloidal solutions generally comprise individual SiO2 particles with a size d50 between 5 and 30 nm. In order to ascertain the particle size of SiO2 in a colloidal solution, a Zetasizer of the nano line from Malvern is used. The measurement is carried out at room temperature.202400270 Foreign Filing 8

[0048] In particular, the silicon dioxide is produced by means of pyrogenic methods. The process is known to the person skilled in the art, e.g. from the series of papers “Fine Particles” No. 11 (7th Edition, 2003), company journal of Degussa AG.

[0049] The zirconium compound in the catalyst composition X according to any aspect of the present invention is selected from zirconium dioxide, zirconium hydroxide, zirconium acetate, zirconium nitrate, zirconium oxychloride, ammonium zirconium carbonate or mixtures thereof. In particular, the zirconium compound in the catalyst composition X according to any aspect of the present invention is zirconium dioxide, zirconium hydroxide or mixtures thereof.

[0050] Zirconium hydroxide is understood as meaning zirconium (IV) hydroxide.

[0051] It is likewise preferred to select the zirconium compound from a mixture comprising A and B. In this connection, A comprises zirconium dioxide, zirconium hydroxide and mixtures thereof. B is selected from zirconium acetate, zirconium nitrate, zirconium oxychloride, ammonium zirconium carbonate and mixtures thereof. The fraction of zirconium from A is particularly at least 85 mol %, particularly at least 90 mol %, based on the sum of zirconium from A and B.

[0052] As a result of the calcination, the zirconium compounds are reacted at least partially to give zirconium dioxide. In this regard, zirconium compounds, apart from zirconium dioxide itself, are referred to as precursors.

[0053] Preferably, the person skilled in the art selects time conditions through which at least 50 mol %, particularly at least 90 mol %, more particularly 95 mol % and even more particularly 100 mol %, of the zirconium compounds, in each case based on the sum of all zirconium compounds, have reacted to give zirconium dioxide.

[0054] The person skilled in the art can adjust the size of the BET surface area of the mixed oxide by known measures in order to obtain, for example, surface areas of less than 155 m2 / g. The higher the fraction of silicon dioxide in the mixed oxide, the higher the surface area will be. Consequently, at most 14% by weight of silicon dioxide, based on the total weight of the mixed oxide, are present. Furthermore, the calcination temperature influences the surface area: The lower the set temperature, the higher the surface area will be. Consequently, the calcination temperature is not below 300° C., preferably not below 400° C. Moreover, preferably no polymers for enlarging the surface area, as is described for example in EP-A-2108631 (US 2009 / 0255402), are present. By means of a few experiments, the person skilled in the art is able to undertake an adjustment of the surface area by virtue of the specified parameters.

[0055] A method of producing the catalyst composition X according to any aspect of the present invention, is described in EP3002058A1. Based on the methods disclosed in EP3002058A1, a skilled person would be able to produce the catalyst composition X that will be suitable for production of at least one ketone K1 from carboxylic acids according to any aspect of the present invention.202400270 Foreign Filing 9

[0056] Any ketone may be produced according to any aspect of the present invention depending on the starting carboxylic acids. In particular, the ketone K1 has a structure R1-C(=O)-R2, where R1 and R2 can be a variety of carbon-containing substituents. Ketones contain a carbonyl group -C(=O)- (which contains a carbon-oxygen double bond C=O). In particular, the ketone may comprise at least three carbon atoms. More in particular, the ketone in the method according to any aspect of the present invention may be a C3 to C31 ketone. In one example, the ketone is at least one 6-undecanone which is a dialkyl ketone with formula (CH3(CH2)4)2CO and / or the carboxylic acid is a hexanoic acid.

[0057] In particular, the catalyst composition K1 according to any aspect of the present invention is specifically suited for producing ketones from a carboxylic acids. The catalyst composition K1 comprises at least a mixed oxide of zirconium dioxide and silicon dioxide. In particular, the catalyst composition according to any aspect of the present invention comprises only a mixed oxide of zirconium dioxide and silicon dioxide with a mass ratio of 50:50 to 99:1 , particularly with a mass ratio of 86:14 to 99.9:0.1 , more particularly 90:1 O to 97:3, even more particularly 95:5.

[0058] It would be within the knowledge of a skilled person to determine the suitable conditions for the use of the different ketonization catalysts in the method according to any aspect of the present invention. In particular, the temperature has to be at least 300°C for the carboxylic acids to be converted to the corresponding ketone. More in particular, the temperature may be maintained at about 300, 325, 350, 355, 360, 365, 370, 375, 380, 385, 390, 395, or 400°C during the method according to any aspect of the present invention. Even more in particular, the reaction temperature may be 350-420, 350-415, 350-410, 350-405, 350-400, 350-395, 350-390, 350-385, 350-380, 350-375, 350-370, 350-365, 350-360, 355-420, 355-415, 355-410, 355-405, 355-400, 355-395, 355-390, 355-385, 355-380, 355-375, 355-370, 355-365, 355-360, 360-420, 360-415, 360-410, 360-405, 360-400, 360-395, 360-390, 360-385, 360-380, 360-375, 360-370, 360-365, 365-420, 365-415, 365-410, 365-405, 365-400, 365-395, 365-390, 365-385, 365-380, 365-375, 365-370, 370-420, 370-415, 370-410, 370-405, 370-400, 370-395, 370-390, 370-385, 370-380, 370-375, 375-420, 375-415, 375-410, 375-405, 375-400, 375-395, 375-390, 375-385, 375-380, 380-420, 380-415, 380-410, 380-405, 380-400, 380-395, 380-390, 380-385, 385-420, 385-415, 385-410, 385-405, 385-400, 385-395, 385-390, 390-420, 390-415, 390-410, 390-405, 390-400, 390-395, 395-420, 395-415, 395-410, 395-405, 395-400, 400-420, 400-415, 400-410, or 400-405 °C. More in particular, the method according to any aspect of the present invention is carried out at a temperature between 350°C and 390°C.

[0059] The method according to any aspect of the present invention may comprise a further step of extracting the ketone produced. Any method known in the art may be used to extract the ketone. In particular, distillation or basic washing may be used to extract the ketone.

[0060] The term “contacting”, as used herein, means bringing about direct contact between the carboxylic acid with at least one catalyst composition according to any aspect of the present invention in the medium in step (a). For example, the carboxylic acid, and the catalyst composition may be in202400270 Foreign Filing 10

[0061] different compartments and brought together to produce the ketone K1 according to any aspect of the present invention.

[0062] Under suitable conditions, the ketone K1 is converted to the corresponding alkane A1 in the presence of at least the catalyst composition X. A skilled person would understand what suitable conditions are required to produce the corresponding alkane A1 from the K1 produced according to any aspect of the present invention. In particular, contact with the catalyst composition X has to be maintained longer that the ketone K1 converts to the corresponding alkene.

[0063] A skilled person would understand the suitable conditions for alkane production from a ketone. In particular, a suitable higher pressure and temperature would be necessary for the reaction to take place.

[0064] In particular, when the ketone K1 comes in contact with the catalyst composition X, catalytic hydrogenation of the ketone K1 takes place and the corresponding linear alkanol is produced, particularly a molecule of hydrogen is added across the carbon-oxygen double bond to ultimately furnish the alkanol, particularly 6-undecanol when the K1 is undecanone. The corresponding linear alkanol produced according to any aspect of the present invention may then be dehydrated to form the corresponding alkene at the suitable temperature and pressure. Increasing the temperature and pressure would result in the dehydration of the ketone to the corresponding alkene. It would be within the knowledge of a skilled person to determine the suitable conditions for the use of the different ketonization catalysts in the method according to any aspect of the present invention. In particular, the ketonization catalyst may be a zirconia catalyst and may be used in the conversion of a ketone to the corresponding alkene. In particular, the temperature has to be at least 350°C for the ketone to be converted to the corresponding alkene. More in particular, the temperature may be maintained at about 350, 355, 360, 365, 370, 375, 380, 385, 390, 395, or 400°C during the method according to any aspect of the present invention. Even more in particular, the reaction temperature may be 350-420, 350-415, 350-410, 350-405, 350-400, 350-395, 350-390, 350-385, 350-380, 350-375, 350-370, 350-365, 350-360, 355-420, 355-415, 355-410, 355- 405, 355-400, 355-395, 355-390, 355-385, 355-380, 355-375, 355-370, 355-365, 355-360, 360-420, 360- 415, 360-410, 360-405, 360-400, 360-395, 360-390, 360-385, 360-380, 360-375, 360-370, 360-365, 365- 420, 365-415, 365-410, 365-405, 365-400, 365-395, 365-390, 365-385, 365-380, 365-375, 365-370, 370- 420, 370-415, 370-410, 370-405, 370-400, 370-395, 370-390, 370-385, 370-380, 370-375, 375-420, 375- 415, 375-410, 375-405, 375-400, 375-395, 375-390, 375-385, 375-380, 380-420, 380-415, 380-410, 380- 405, 380-400, 380-395, 380-390, 380-385, 385-420, 385-415, 385-410, 385-405, 385-400, 385-395, 385- 390, 390-420, 390-415, 390-410, 390-405, 390-400, 390-395, 395-420, 395-415, 395-410, 395-405, 395- 400, 400-420, 400-415, 400-410, or 400-405 °C. More in particular, the method according to any aspect of the present invention is carried out at a temperature between 350°C and 390°C. Even more in particular, alkenes are produced from ketones using the catalyst composition X at reaction temperatures of 350°C -390 °C.

[0065] In particular, at least for the alkene production from the ketone K1 , the method is carried on in a reactor and the gases in the reactor are moving at gas hourly space velocity (GHSV) of 1 to 1000 m3 / (m x h). More in particular, reactor may be a heated continuous flow-bed reactor. The GHSV refers to the speed202400270 Foreign Filing 11

[0066] of gases moving in the reactor per hour, particularly to the speed of gases moving over the catalyst. In particular, the gases in the reactor are at least ketone and / or the hydrogen releasing agent. More in particular, the gases in the reactor are at least ketone and hydrogen. The GHSV is 2 to 1000, 3 to 1000, 4 to 1000, 5 to 1000, 10 to 1000, 15 to 1000, 20 to 1000, 25 to 1000, 30 to 1000, 35 to 1000, 40 to 1000, 45 to 1000, 50 to 1000, 55 to 1000, 60 to 1000, 65 to 1000, 70 to 1000, 75 to 1000, 80 to 1000, 85 to 1000, 90 to 1000, 95 to 1000, 100 to 1000, 5 to 900, 10 to 900, 15 to 900, 20 to 900, 25 to 900, 30 to 900, 35 to 900, 40 to 900, 45 to 900, 50 to 900, 55 to 900, 60 to 900, 65 to 900, 70 to 900, 75 to 900, 80 to 900, 85 to 900, 90 to 900, 95 to 900, 100 to 900, 5 to 800, 10 to 800, 15 to 800, 20 to 800, 25 to 800, 30 to 800, 35 to 800, 40 to 800, 45 to 800, 50 to 800, 55 to 800, 60 to 800, 65 to 800, 70 to 800, 75 to 800, 80 to 800, 85 to 800, 90 to 800, 95 to 800, 100 to 800, 5 to 700, 10 to 700, 15 to 700, 20 to 700, 25 to 700, 30 to 700, 35 to 700, 40 to 700, 45 to 700, 50 to 700, 55 to 700, 60 to 700, 65 to 700, 70 to 700, 75 to 700, 80 to 700, 85 to 700, 90 to 700, 95 to 700, 100 to 700, 5 to 600, 10 to 600, 15 to 600, 20 to 600, 25 to 600, 30 to 600, 35 to 600, 40 to 600, 45 to 600, 50 to 600, 55 to 600, 60 to 600, 65 to 600, 70 to 600, 75 to 600, 80 to 600, 85 to 600, 90 to 600, 95 to 600, 100 to 600, 5 to 500, 10 to 500, 15 to 500, 20 to 500, 25 to 500, 30 to 500, 35 to 500, 40 to 500, 45 to 500, 50 to 500, 55 to 500, 60 to 500, 65 to 500, 70 to 500, 75 to 500, 80 to 500, 85 to 500, 90 to 500, 95 to 500, or 100 to 500 m3 / (m x h). In particular, the GHSV is 5 to 500, 5 to 400, 10 to 400, 15 to 400, 20 to 400, 25 to 400, 30 to 400, 35 to 400, 40 to 400, 45 to 400, 50 to 400, 55 to 400, 60 to 400, 65 to 400, 70 to 400, 75 to 400, 80 to 400, 85 to 400, 90 to 400, 95 to 400, or 100 to 400, 5 to 300, 10 to 300, 15 to 300, 20 to 300, 25 to 300, 30 to 300, 35 to 300, 40 to 300, 45 to 300, 50 to 300, 55 to 300, 60 to 300, 65 to 300, 70 to 300, 75 to 300, 80 to 300, 85 to 300, 90 to 300, 95 to 300, or 100 to 300, 5 to 200, 10 to 200, 15 to 200, 20 to 200, 25 to 200, 30 to 200, 35 to 200, 40 to 200, 45 to 200, 50 to 200, 55 to 200, 60 to 200, 65 to 200, 70 to 200, 75 to 200, 80 to 200, 85 to 200, 90 to 200, 95 to 200, or 100 to 200, 5 to 150, 10 to 150, 15 to 150, 20 to 150, 25 to 150, 30 to 150, 35 to 150, 40 to 150, 45 to 150, 50 to 150, 55 to 150, 60 to 150, 65 to 150, 70 to 150, 75 to 150, 80 to 150, 85 to 150, 90 to 150, 95 to 150, or 100 to 150 m3 / (m x h). In particular, the GHSV is 5 to 500 m3 / ( m3 / (m x h). More in particular, the GHSV is 10 to 150 m3 / (m3x h). It is especially advantageous when the gases in the reactor are moving at this speed as then the ketone has sufficient time to be in contact with the catalyst and be converted into the alkene. The GHSV of the gaseous ketone may be measured using any means known in the art. In particular, the GHSV may be measured using a flow indicator. Namely, an indicator that can be used to measure the gas volume or the mass of the gases in the reactor where the method according to any aspect of the present invention is carried out.

[0067] A hydrogen releasing agent or hydrogen may be present at least during the alkene production from the ketone K1. The hydrogen releasing agent may be any compound that donates a H atom to the ketone to produce the corresponding alcohol and from there the alkene. In particular, the hydrogen releasing agent may be hydrogen or at least one carboxy acid or organic acid. More in particular, the hydrogen releasing agent is at least one alkanoic acid comprising 1 to 22 carbon atoms. The hydrogen releasing agent may therefore be at least one alkanoic acid comprising 1 to 22 carbon atoms or hydrogen. In particular the alkanoic acid is selected from straight chain alkanoic acids comprising 4 to 18, preferably 5 to 12, carbon atoms. More in particular, the alkanoic acid is hexanoic acid.202400270 Foreign Filing 12

[0068] The hydrogen releasing agent may be supplied during the process of ketone K1 production.

[0069] In one example, where the ketone K1 undecanone, the corresponding alkanol is 6-undecanol and the corresponding alkene is 5-undecene.

[0070] The corresponding alkene is then converted to the respective alkane A1 , in the presence of at least one hydrogenation metal catalyst for catalytic hydrogenation of the alkene to a corresponding alkane A1. Any hydrogenation metal catalyst may be used to carry out this step of alkane A1 production.

[0071] In particular, the hydrogenation metal catalyst may be a homogeneous or heterogeneous catalyst.

[0072] Homogeneous metal catalysts may be metal complexes that are known in the art. In particular, the hydrogenation metal catalyst may be a heterogeneous catalyst. Some advantages of using multiphase catalytic reactions using solid catalysts include easy separation of catalysts and products, easy recovery, and catalyst recycling, and relatively mild operating conditions. There are also clear economic and environmental incentives in using heterogeneous catalysts. In particular, the hydrogenation metal catalyst may be selected from the group consisting of ruthenium (Ru) catalyst, rhenium (Re) catalyst, nickel (Ni) catalyst, iron (Fe), cobalt (Co), palladium (Pd) catalyst and platinum (Pt) catalyst. More in particular, the catalyst may be selected from the group consisting of Ni, Pd and Pt catalyst. In one example, the hydrogenation metal catalyst used according to any aspect of the present invention may be nickel nanoparticles as described in Alonso, F. Tetrahedron, 2008, 64: 1847-52. In another example, Iron(ll) PNP Pincer Complexes may be used as the hydrogenation metal catalyst for hydrogenation of the alkene to alkane, as disclosed in Gorgas, N., Organometallics, 2014, 33 (23): 6905-6914. In yet another example, magnetite nanoparticles of ruthenium (Ru) catalyst, rhenium (Re) catalyst, nickel (Ni) catalyst, iron (Fe), cobalt (Co), palladium (Pd) catalyst or platinum (Pt) catalyst as described in Tariq Shah M., et al., ACS Applied Materials & Interfaces, 2015: 7(12), 6480-9 may be used as the heterogenous hydrogenation metal catalyst according to any aspect of the present invention.

[0073] In yet another example, a copper-phosphine complex is used as a homogeneous hydrogenation metal catalyst according to any aspect of the present invention as disclosed in Chen, J-X., Tetrahedron, 2000, 56: 2153-2166. In a further example, a heterogenous Pt catalyst, in particular a Pt / AI2O3 catalyst, as disclosed in Journal of Molecular Catalysis A: 30 Chemical, 2014, 388-389: 116-122 may be used in hydrogenation of the alkene in to alkane. ChemSusChem, 2017: 10(11), 2527-2533 also discloses a variety of heterogenous catalysts such as Pt / C, Ru / C, and Pd / C that may be used in combination with or without an acid catalyst for the hydrogenation of alkene to alkane. Based on the above, a skilled person may determine a suitable hydrogenation catalyst to be used according to any aspect of the present invention to yield alkane A1 from the alkene.

[0074] The hydrogenation metal catalyst used in the step of alkane A1 production from alkene is preferably selected from the group consisting of ruthenium (Ru) catalyst, rhenium (Re) catalyst, nickel (Ni) catalyst, iron (Fe), cobalt (Co) and platinum (Pt) catalyst.202400270 Foreign Filing 13

[0075] The final product from the method according to any aspect of the present invention in the presence of the catalyst composition X and a hydrogenation catalyst is therefore an alkane A1 .

[0076] Some advantages of using multiphase catalytic reactions using the solid catalyst of the catalyst composition X include easy separation of catalysts and products, easy recovery, and catalyst recycling, and relatively mild operating conditions. There are also clear economic and environmental incentives in using the catalyst composition X.

[0077] A skilled person would easily be able to determine and vary the conditions, particularly temperature, pressure and reaction time accordingly to efficiently produce a ketone K1 and / or alkane A1 starting from carbonic acid according to any aspect of the present invention.

[0078] According to a further aspect of the present invention, there is provided a ketone K1 of formula I produced from the method according to any aspect of the present invention.

[0079] R1-C(=O)-R2 Formula I,

[0080] wherein R1 and R2 is independently a hydrocarbon, preferably R is an organic radical selected from the group comprising unsubstituted and mono- or polysubstituted, branched and straight-chain alkyl radicals, cycloalkyl radicals, alkenyl radicals having one or more double bonds, alkynyl radicals having one or more triple bonds, aryl radicals, alkylaryl radicals, arylalkyl radicals, arylalkenyl radicals, alkyloxyalkyl radicals, hydroxyalkyl radicals and alkylthioalkyl radicals.

[0081] According to yet another aspect of the present invention, there is provided an alkane A1 produced from the method according to any aspect of the present invention. Catalytic hydrogenation in the presence of the catalyst composition X results in the alkene being converted to form the corresponding linear alkane. The catalyst composition X is thus capable of providing dehydrating and / or hydrogenating properties in any reaction.

[0082] According to a further aspect of the present invention, there is provided a use of a catalyst composition X to produce a ketone K1 of the Formula I:

[0083] R1-C(=O)-R2 Formula I,

[0084] wherein a first carboxylic acid R1-COOH and a second carboxylic acid R2-COOH are reacted in the presence of a catalyst composition X to give K1 and CO2; and

[0085] wherein R1 and R2 is independently a hydrocarbon group, preferably R1 and R2 is an organic radical selected from the group consisting of unsubstituted and mono- or polysubstituted, branched and straightchain alkyl radicals, cycloalkyl radicals, alkenyl radicals having one or more double bonds, alkynyl radicals having one or more triple bonds, aryl radicals, alkylaryl radicals, arylalkyl radicals, arylalkenyl radicals, alkyloxyalkyl radicals, hydroxyalkyl radicals, aminoalkylradicals and alkylthioalkyl radicals; and wherein the catalyst composition X comprises:202400270 Foreign Filing 14

[0086] at least one transition metal; and / or

[0087] at least one mixed oxide.

[0088] According to a further aspect of the present invention, there is provided a use the catalyst composition X to produce an alkane A1.

[0089] In one example, the ketone K1 is undecanone, the carboxylic acid is hexanoic acid and the alkane A1 is undecane.

[0090] Unless stated otherwise, all percentages (%) given are percentages by mass.

[0091] The examples adduced hereinafter describe the present invention by way of example, without any intention that the invention, the scope of application of which is apparent from the entirety of the description and the claims, be restricted to the embodiments specified in the examples.

[0092] EXAMPLES

[0093] Example 1

[0094] The reaction was conducted in a heated continuous flow-bed reactor. Gaseous hexanoic acid (1 .2 m3 / h) was continuously fed to a reactor charged with zirconium oxide on silica (95 wt.%, 10.15 kg) at 343°C. The gaseous out stream was collected and analyzed by gas chromatography (GC) for its composition. In total, 3 kg of hexanoic acid was fed to the reactor, leading to a 2.2 kg mixture consisting of 99% 6-undecanone and <1% hexanoic acid, alongside 0,6 kg of carbon dioxide and 0,2 kg water.

[0095] Example 2

[0096] The reaction was conducted in a heated continuous flow-bed reactor. Gaseous hexanoic acid (1 .2 m3 / h) was continuously fed to a reactor charged with zirconium oxide on silica (95 wt.%, 10.2 kg) at 365°C. The gaseous out stream was collected and analyzed by nuclear magnetic resonance spectroscopy (NMR) for its composition. In total, 3 kg of hexanoic acid was fed to the reactor, leading to a 2.3 kg mixture consisting of 15% undecene and 75% 6-undecanone and 10% of byproducts, alongside 0,5 kg of carbon dioxide and 0,2 kg water. The residual amount of hexanoic acid was lower than the detection limit.

[0097] Example 3The reaction was conducted in a heated continuous flow-bed reactor. Gaseous hexanoic acid (1.2 m3 / h) was continuously fed to a reactor charged with manganese oxide on silica (28 wt.%, 8 kg) at 370°C. The gaseous out stream was collected and analyzed by nuclear magnetic resonance spectroscopy (NMR) for its composition. Under steady-state conditions 3 kg of hexanoic acid was fed to the reactor, leading to a 2.3 kg mixture consisting of 65% 6-undecanone, 32% hexanoic acid and <3% of byproducts, alongside 0.4 kg of carbon dioxide and 0.3 kg water.

Claims

202400270 Foreign Filing 15CLAIMS1. A method of producing a ketone K1 of the Formula I:R1-C(=O)-R2 Formula I,wherein a carboxylic acid R1-COOH and a carboxylic acid R2-COOH are reacted in the presence of a catalyst composition X to give K1 and CO2; andwherein R1 and R2 is independently a hydrocarbon group, preferably R1 and R2 is an organic radical selected from the group consisting of unsubstituted and mono- or polysubstituted, branched and straight-chain alkyl radicals, cycloalkyl radicals, alkenyl radicals having one or more double bonds, alkynyl radicals having one or more triple bonds, aryl radicals, alkylaryl radicals, arylalkyl radicals, arylalkenyl radicals, alkyloxyalkyl radicals, hydroxyalkyl radicals, aminoalkylradicals and alkylthioalkyl radicals; andwherein the catalyst composition X comprises:at least one mixed oxide; andwherein the mixed oxide is of zirconium dioxide and silicon dioxide; andwherein a mass ratio of zirconium dioxide to silicon dioxide in the mixed oxide is 86:14 to 99.9:0.1.

2. The method according to any one of the preceding claims, wherein the carboxylic acids are reacted in the presence of the catalyst composition X at a temperature of at least 300°C.

3. The method according to any one of the preceding claims, wherein the carboxylic acid is an alkanoic acid comprising 1 to 22 carbon atoms, preferably a hexanoic acid.

4. The method according to any one of the preceding claims, wherein the ketone K1 is undecanone and the carboxylic acid is hexanoic acid.

5. The method according to any one of the preceding claims, wherein the support in the catalyst composition X does not comprise the mixed oxide.

6. The method according to any one of the preceding claims, wherein under suitable conditions, the ketone K1 is converted to the corresponding alkane A1 in the presence of the catalyst composition X and a hydrogenation catalyst.

7. A ketone K1 of formula I produced from the method according to any one of the claims 1 to 5:R1-C(=O)-R2 Formula I,202400270 Foreign Filing 16wherein R1 and R2 is independently a hydrocarbon, preferably R is an organic radical selected from the group comprising unsubstituted and mono- or polysubstituted, branched and straightchain alkyl radicals, cycloalkyl radicals, alkenyl radicals having one or more double bonds, alkynyl radicals having one or more triple bonds, aryl radicals, alkylaryl radicals, arylalkyl radicals, arylalkenyl radicals, alkyloxyalkyl radicals, hydroxyalkyl radicals and alkylthioalkyl radicals.

8. An alkane A1 produced from the method according to claim 7.

9. Use of a catalyst composition X to produce a ketone K1 of the Formula I:R1-C(=O)-R2 Formula I,wherein a first carboxylic acid R1-COOH and a second carboxylic acid R2-COOH are reacted in the presence of a catalyst composition X to give K1 and CO2; andwherein R1 and R2 is independently a hydrocarbon group, preferably R1 and R2 is an organic radical selected from the group consisting of unsubstituted and mono- or polysubstituted, branched and straight-chain alkyl radicals, cycloalkyl radicals, alkenyl radicals having one or more double bonds, alkynyl radicals having one or more triple bonds, aryl radicals, alkylaryl radicals, arylalkyl radicals, arylalkenyl radicals, alkyloxyalkyl radicals, hydroxyalkyl radicals, aminoalkylradicals and alkylthioalkyl radicals; andwherein the catalyst composition X comprises:at least one mixed oxide; andwherein the mixed oxide comprises zirconium dioxide and silicon dioxide; andwherein a mass ratio of zirconium dioxide to silicon dioxide in the mixed oxide is 86:14 to 99.9:0.1.

10. Use of a catalyst composition X and a hydrogenation catalyst to produce an alkane A1 wherein the catalyst composition X comprises:at least one mixed oxide;wherein the mixed oxide comprises zirconium dioxide and silicon dioxide; and wherein a mass ratio of zirconium dioxide to silicon dioxide in the mixed oxide is 86:14 to 99.9:0.1; and.

11. Use according to any one of the preceding claims 9 to 10, wherein the ketone K1 is undecanone, the carboxylic acid is hexanoic acid and the alkane A1 is undecane.