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    • 专利摘要:
    PROCESS FOR THE DECARBOXYLATIVE KETONIZATION OF FATTY ACIDS, FATTY ACID DERIVATIVES OR MIXTURES THEREOF. IT IS A PROCESS FOR THE DECARBOXYLATIVE KETONIZATION OF FATTY ACIDS, FATTY ACID DERIVATIVES OR MIXTURES OF THEM IN THE LIQUID PHASE WITH METAL COMPOUNDS AS CATALYST IN WHICH FATTY ACIDS, FATTY ACID DERIVATIVES OR MIXTURES ARE ADDITIONAL MIXTURES.
    公开号:BR112017023522B1
    申请号:R112017023522-6
    申请日:2016-05-04
    公开日:2021-06-08
    发明作者:Olivier BACK；Rémy LEROY；Philippe Marion
    申请人:Rhodia Operations；
    IPC主号:
    专利说明:

    [01] This application claims priority from European Application No. 15305709.6 - filed May 7, 2015 - the contents of which are incorporated by reference in their entirety for any purpose.
    [02] The present invention relates to a process for the manufacture of long-chain internal ketones through decarboxylative ketonization of fatty acids or fatty acid derivatives.
    [03] The conversion of acids into respective ketones by decarboxylative ketonization is a well-known process that is also used commercially.
    [04] The process can be carried out in the gas phase at temperatures that typically exceed 350°C and typically more than 400°C for fatty acids in the presence of catalytic amounts of metal oxide compounds (eg, MgO, ZrO2, Al2O3, CeO2, MnO2, TiO2).
    [05] Carrying out the reaction in the gas phase with fatty acids with a high boiling point is difficult, since the evaporation of the reactants needs very high temperatures, which is detrimental to the process selectivity and leads to the formation of by-products unwanted.
    [06] Carrying out the process in the liquid phase offers certain advantages over the reaction in the gas phase, for example, typically higher productivities, reduced manufacturing costs and better selectivities for the subsequent preparation of the reaction mixture.
    [07] The German patent D.E. 295 657 refers to a process for the manufacture of ketones in which monocarboxylic acids that have a boiling point exceeding 300°C are heated in the liquid phase with small amounts of catalytically active metal compounds, silica gels or silicates at temperatures which do not substantially exceed 300°C. The organic acid is mixed with catalytically active species and is subsequently heated to the desired reaction temperature. The process was reported to yield the desired ketones in satisfactory yield and purity.
    [08] The process described in DE 295 657 does not produce the desired ketones in satisfactory yields, however, if the fatty acid starting material comprises fatty acids or fatty acid derivatives that have a boiling point of less than 300°C (which is the case for linear fatty acids that have 12 carbon atoms or less, such as: lauric acid, capric acid, caprylic acid...) in a more than negligible amount.
    [09] The German D.E. 259 191 refers to a process for making ketones by heating higher fatty acids with finely distributed metals and lowering the temperature before the ketone begins to decompose. In the example, the stearic acid is heated with cast iron powder to a temperature of 360°C and held at 360°C for about 4 h, then the product is cooled, and the ketone formed is isolated. The amount of cast iron is 10% by weight based on the amount of stearic acid which corresponds to stoichiometric amounts. Again, the process as described in this reference yields only small amounts of ketones if fatty acids having 12 carbon atoms or less are used as starting material or are present in the starting material in more than negligible amounts.
    [10] The document EP2468708 refers to the decarboxylative cross-ketonization of mixtures of aryl and alkyl carboxylic acids using iron catalysts such as magnetite nanopowders to obtain alkyl aryl ketones. According to the claimed process, a blend of an aromatic monocarboxylic acid, a second monocarboxylic acid selected from benzylic or aliphatic monocarboxylic acids and an iron containing catalyst are heated in a non-aqueous solvent to a temperature of at least 220°C for at least 10 h with continuous removal of water and carbon dioxide. After completion of the reaction, the mixture formed is distilled under reduced pressure, and the reaction product is obtained in the distillate. The use of a non-aqueous solvent is considered essential. However, reaction times of more than 10 hours are not suitable for synthesis on an industrial scale.
    [11] In Christoph Oppel's PhD thesis ("New methods of ketone synthesis, University of Kaiserslautern 2012), one of the inventors of document EP 2468708 above, experiments for the ketonization of lauric acid with metallic mediators are described. The reaction is carried out. at 340°C with various metal compounds including Fe and MgO and the 12-tricosanone ketone is obtained in satisfactory yields. The reaction is carried out in closed containers saturated with nitrogen. The water and carbon dioxide formed lead to an accumulation of pressure inside the closed system, and the reaction temperature of 340°C also contributes to the pressure build-up since the lauric acid at these temperatures is gaseous. The application of such a process on an industrial scale necessitates the use of autoclaves, which is expensive. The amount of metallic mediator in the examples in the table on page 88 of the PhD thesis is 50% mol based on the total amount of acid, which corresponds to the stoichiometric ratios, and the quanti. Totality of reagents is initially prepared and heated together.
    [12] Although the processes described in the prior art and referred to above yield ketones in satisfactory yields, some of them are not efficient during the initiation of fatty acids that contain 12 carbon atoms or less or a mixture of fatty acids that contain an amount of fatty acids that have carbon of 12 atoms or less. Furthermore, for some of the processes mentioned above, their use on an industrial scale is hampered by problems and necessitates expensive apparatus. Thus, there is still a need for a commercially applicable process for the manufacture of fatty acid ketones or their derivatives.
    [13] Thus, an objective of the present invention is to develop an easy and simple to use process for the synthesis of ketones by decarboxylative ketonization of fatty acids or fatty acid derivatives in the liquid phase in an open reaction system, especially starting from fatty acids having 12 carbon atoms or less or mixtures of fatty acids comprising at least 10 mol%, based on the total amount of carboxylic acids, fatty acids having 12 carbon atoms or less, or derivatives thereof.
    [14] This objective was achieved with the process in accordance with claim 1, that is, a process for the decarboxylative ketonization of fatty acids, fatty acid derivatives or mixtures thereof in the liquid phase with metal compounds as the catalyst distinguished by fact that a) in a first step, an elemental metal or a compound of metal and the fatty acid, derived from fatty acid or mixture thereof comprising at least 10% by mol, based on the total amount of fatty acids or fatty acid derivatives, fatty acids that have 12 carbon atoms or less, or fatty acid derivatives that have 12 carbon atoms or less, are mixed in a molar ratio of 1:0.8 to 1:3.5 (metal of molar ratio: carboxyl group equivalent) and reacted for a Pi period of 5 min at 24 h at a temperature Ti of 100°C to 270°C in the substantial absence of additional solvents, and b) then the temperature is raised to a temperature T2 which is strictly above 270°C and up to 400°C, and additional fatty acids, fatty acid derivatives or a mixture thereof comprising at least 10% by mol, based on the total amount of fatty acids or fatty acid derivatives, of acids fatty acids having 12 carbon atoms or less or derived from such fatty acids are added in a P2 time period of 5 min to 24 h in the substantial absence of additional solvents until the molar ratio between fatty acid, fatty acid derivatives or mixtures thereof and metal are in the range of 6:1 to 99:1.
    [15] Certain preferred embodiments of the process in accordance with the present invention are set out in the dependent claims.
    [16] For example, a modality presented in claim 4 (hereinafter, modality E*) refers to a process for the decarboxylative ketonization of fatty acids, fatty acid derivatives or mixtures thereof in the liquid phase with metal compounds as a catalyst, distinguished by the fact that a) in a first step, an elemental metal or a metal compound and the fatty acid, fatty acid derivative or mixture thereof comprising at least 10% by mol, based on the total amount of fatty acids or fatty acid derivatives, fatty acids that have 12 carbon atoms or less, or fatty acid derivatives that have 12 carbon atoms or less, are mixed in a molar ratio of 1:0.8 and 1:3.5 ( metal of molar ratio: carboxyl group equivalent) and reacted for a period of 5 to 240 min at a temperature of 180 to 270°C in the substantial absence of additional solvents, and b) then the temperature is raised to 280 to 320°C , and the additional fatty acids, derived from fatty acid or a mixture thereof comprising at least 10 mol%, based on the total amount of fatty acids or fatty acid derivatives, of fatty acids having 12 carbon atoms or less or derivatives of such fatty acids, are added in a time period of 1 h to 24 h in the substantial absence of additional solvents until the molar ratio between fatty acid, fatty acid derivatives or mixtures thereof and metal is in the range of 6:1 to 99:1, [0021] Other modalities of the process according to the present invention are also presented in the detailed description hereinafter. Temperature T1
    [17] Temperature Ti is 100°C to 270°C.
    [18] Temperature Ti is preferably at least 180°C, more preferably at least 210°C and even more preferably at least 230°C.
    [19] Furthermore, the temperature Ti can be a maximum of 260°C.
    [20] The T1 temperature can be from 180°C to 270°C or from 210°C to 260°C.
    [21] Satisfactory results were obtained when T1 was in the range of 230°C to 270°C, in particular 240°C to 260°C. Temperature T2
    [22] The T2 temperature is strictly above 270°C and up to 400°C.
    [23] The T2 temperature can be strictly below 280°C. However, it is preferably at least 280°C, more preferably at least 290°C and even more preferably at least 300°C. It can be strictly above 320°C.
    [24] The T2 temperature can be strictly above 360°C. However, it is generally a maximum of 360°C and often a maximum of 340°C. It can be a maximum of 320°C.
    [25] The T2 temperature can be from 280°C to 320°C. The T2 temperature can also be strictly above 320°C and up to 360°C.
    [26] Satisfactory results were obtained when T2 was in the range of 280°C to 360°C, in particular, from 300°C to 340°C. Temperature difference T2 minus T1 (T2 -T1)
    [27] The temperature difference T2 minus T1 is advantageously at least 3°C. It is preferably at least 10°C, more preferably at least 30°C and even more preferably at least 45°C.
    [28] Furthermore, T2 -Ti is advantageously at most 100°C. It can be a maximum of 85°C, a maximum of 70°C or a maximum of 55°C.
    [29] Satisfactory results were obtained when T2 -Ti was in the range from 30°C to 100°C, in particular, from 45°C to 85°C. Certain combinations of temperature T1 and temperature T2
    [30] In a first embodiment, Ti is from 230°C to 270°C, whereas T2 is from 280°C to 400°C, preferably from 290°C to 360°C and more preferably from 300 °C to 340 °C.
    [31] In a second embodiment, T2 is strictly below 280°C, whereas Ti is 180°C to 270°C, preferably 230°C to 270°C and more preferably 240°C at 260°C.
    [32] In a third embodiment, T2 is from 280°C to 320°C, whereas Ti is from 180°C to 270°C, preferably from 230°C to 270°C and more preferably from 240 °C to 260 °C.
    [33] In a fourth embodiment, T2 is strictly above 320°C and up to 360°C, whereas Ti is from 180°C to 270°C, preferably from 230°C to 270°C and more preferably , from 240°C to 260°C.
    [34] In a fifth embodiment, T2 is strictly above 360°C, whereas Ti is from 180°C to 270°C, preferably from 230°C to 270°C and more preferably from 240°C at 260°C. Time period P1
    [35] The time period Pi can vary to some extent depending, notably, on the nature of the elemental metal or metal compound. In any case, the time period Pi is from 5 min to 24 h.
    [36] The time period Pi is preferably at least 10 min and more preferably at least 20 min.
    [37] Furthermore, the time period P1 is preferably at most 12 h, more preferably at most 8 h and even more preferably at most 5 h.
    [38] Satisfactory results were obtained with the P1 time period of 10 min to 8 h, in particular 20 min to 5 h.
    [39] Each specified lower limit, upper limit or range for time period P1 needs to be considered as explicitly described in combination with each specified lower limit, upper limit or range previously specified for temperature T1. Time period P2
    [40] The P2 time period can also vary to a large extent depending, notably, on the overall amount of acid or acid derivative used. In any case, the time period P2 is from 5 min to 24 h.
    [41] The time period P2 is preferably at least 30 min, more preferably at least 1 h, and even more preferably at least 2 h.
    [42] Furthermore, the time period P2 is preferably at most 16 h and more preferably at most 8 h.
    [43] Satisfactory results were obtained with the P2 time period from 1 h to 16 h, in particular from 2 h to 8 h.
    [44] Each specified lower limit, upper limit or range for time period P2 needs to be considered as explicitly described in combination with each specified lower limit, upper limit or range considered for temperature T2. First step
    [45] In the first step of the process according to the present invention, the elemental metal (or a mixture of elemental metals) or a metal compound (or a mixture of metal compounds) and the fatty acid, derived from fatty acid or mixtures thereof comprising at least 10% by mol, based on the total amount of fatty acids or fatty acid derivatives, of fatty acids having 12 carbon atoms or less or derivatives of such fatty acids, are mixed in a molar ratio from 1:1.0 to 1:3.0 (mole ratio metal: carboxylate group equivalent) and reacted for a period of time P1 at a temperature T1 in the substantial absence of additional solvents, preferably, in the absence of solvent.
    [46] For example, in the E* mode, in the first step of the process, the elemental metal (or a mixture of elemental metals) or a metal compound (or a mixture of metal compounds) and the fatty acid, derived from acid fatty acids or mixtures thereof comprising at least 10% by mol, based on the total amount of fatty acids or fatty acid derivatives, of fatty acids having 12 carbon atoms or less or derivatives of such fatty acids, are mixed in one molar ratio of 1:1.0 to 1:3.0 (mole ratio metal: carboxylate group equivalent) and reacted for a time period of 5 to 240 min, preferably 10 to 180 min, and further preferably, 15 to 120 min, at a temperature of 180 to 270°C, preferably 190 to 260°C, and even more preferably 210 to 260°C in the substantial absence of additional solvents, preferably in the absence of solvent. In this E* modality, reaction times of 15 to 60 minutes at a reaction temperature of 220 to 260°C have sometimes been shown to be advantageous.
    [47] The number of carbon atoms always refers to the respective number in the free acid; if derivatives are used, the carbon number may be higher.
    [48] Suitable metals for use in the process in accordance with the present invention are selected from the group consisting of Mg, Ca, Al, Ga, In, Ge, Sn, Pb, As, Sb, Bi, Cd and the metals of transitions having an atomic number from 21 to 30. Suitable metal compounds are oxides of the above mentioned metals, naphthenate salts of the above mentioned metals or acetate salts of the above mentioned metals. Magnesium and iron and the oxides thereof, and in particular iron powder, are preferred.
    [49] The term fatty acids refers to carboxylic acids that contain at least 4 carbon atoms. The term derived from fatty acids refers to anhydrides produced from the condensation of 2 fatty acids or to esters produced by the condensation of fatty acids with alcohols.
    [50] Suitable fatty acid derivatives are fatty acid esters and anhydrides, however the use of these free fatty acids as such is used preferentially. Esters or anhydrides in the course of the reaction are converted to acids which then react with the metal or metal compound. However, especially in the case of esters, alcohols are formed as a by-product which then has to be removed at a later point in time, which requires additional labor and costs. However, if the esters are derived from alcohol derivatives, such as methanol, ethanol, propanol or butanol, the alcohols are progressively removed over the course of the reaction due to a reactive distillation.
    [51] Fatty acid or fatty acid derivatives can be used in the form of so-called fatty acid or fatty acid derivative cuts, which can be obtained by hydrolysis or alcoholysis of different natural fats and oils. Consequently, these cuts can contain various amounts of different linear fatty acids or linear fatty acid derivatives with different chain lengths. By way of example only, fatty acid cuts obtained from coconut oil which mainly comprise C12-C18 fatty acids can be mentioned in this document. Persons skilled in the art are fully aware of other fatty acid cuts obtainable from various sources and will select the best suitable starting materials based on the desired ketones.
    [52] Fatty acids having 12 carbon atoms or less, preferably 8 to 12 carbon atoms or derivatives of such acids (esters or anhydrides) constitute at least 10% by mol and preferably at least 15% by mol of the entire molar amount of the fatty acid mixture or mixture of fatty acid derivatives used as the starting material. These acids produce ketones that have a total carbon number of 23 or less that have proven advantageous in many applications. There is no specific upper limit to the amount of such fatty acids or fatty acid derivatives of acids having 12 carbon atoms or less, ie the starting material can also consist entirely of such fatty acids or fatty acid derivatives.
    [53] Subject to the above, preferred fatty acids for use in the process of the present invention are hexanoic acid, isostearic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, acid lignoceric acid, cerotic acid or mixtures thereof and preferred fatty acid derivatives are the esters and anhydrides of these acids.
    [54] It is understood that when one and only one fatty acid or fatty acid derivative is used as the starting material, it must have 12 carbon atoms or less.
    [55] Fatty acids can comprise one or more double bonds in the chain, such as oleic acid, linoleic acid, linolenic acid, erucic acid, palmitoleic acid or mixtures thereof.
    [56] During initiation of a single fatty acid, a symmetrical ketone is obtained as the reaction product; during initiation of a fatty acid cut, as described above, all ketones formed by combining the different alkyl groups of the starting acids are obtained, and the distribution of the different mixed ketones generally follows a statistical binomial law. The reaction equation can be summarized as follows:
    where Rn and Rm represent the alkyl groups of the fatty acids present in the cut. It will be evident that, for example, if three different acids are present, a total of six different ketones can be formed; three symmetric ketones where Rn and Rm are identical and three ketones mixed with different groups Rn and Rm.
    [57] According to a preferred embodiment, the metal is iron powder, or the metal compound is iron(ll) oxide or a mixed oxide of iron(ll) and iron(III), such as, for example, magnetite. Iron powder has economic advantages as it is inexpensive and abundantly available.
    [58] During the first step of the process, in accordance with the present invention, a metal carboxylate is formed as an intermediate species which in the subsequent step decomposes into the desired ketone and a metal oxide which is the active catalytic species for conversion of the acid or acid derivative added sequentially or continuously in the second step to the desired ketone containing the mixture.
    [59] If a metal is used in the first step, said metal reacts with the fatty acid to a carboxylate of the metal with simultaneous formation of hydrogen gas. If a metal oxide is used in the first step, the formation of the carboxylate is accompanied by the simultaneous formation of water. The general equation for carboxylate formation in the first step (for a metal that has a valence of 2 as an example) can be represented as follows:
    I
    [60] The molar ratio of metal or metal compound to the total amount of carboxylic groups in the starting material in the first step is in the range of 1:0.8 to 1:3.5 and it is generally preferred to use a molar ratio which is sufficient to form the respective metal carboxylate and to convert all the present acid or acid derivative into the metal carboxylate, i.e. basically without leaving free carboxylic groups after carboxylate formation after the first step. Thus, for a divalent metal, the molar ratio of metal to carboxylic groups is preferably about 1:2 since two equivalents of acidic groups are needed to form the metal dicarboxylate of a divalent metal. If metal oxide compounds are used instead of elemental metal, the molar ratio given above is calculated with the amount of elemental metal in the oxide compound. The molar amount of carboxylic groups is calculated by considering the number of such groups in the fatty acid or fatty acid derivative that is used as a starting material. Thus, for example, an anhydride of an acid comprises two carboxylate functionalities and can provide two carboxylic groups for the formation of the metal carboxylate.
    [61] First-stage metal carboxylate formation can be conveniently monitored by IR IN SITU analysis. The carbonyl absorption band of the acid undergoes a bathochromic shift in the metal carboxylate, which allows monitoring of the reaction progress.
    [62] In accordance with a particularly preferred embodiment of the process in accordance with the present invention, iron powder is used as the metal as it is inexpensive and abundantly available. Second stage
    [63] In the second step of the process according to the present invention, the temperature is raised to a temperature T2, temperature at which the metal carboxylate advantageously decomposes into the desired ketone, metal oxide and carbon dioxide.
    [64] For example, in the E* mode, in the second stage of the process, the temperature is raised to 280 to 320°C, a temperature at which the metal carboxylate advantageously decomposes into the desired ketone, metal oxide and carbon dioxide. carbon.
    [65] Additional fatty acids, fatty acid derivatives or a mixture thereof comprising at least 10 mol%, based on the total amount of fatty acids or fatty acid derivatives, from fatty acids having 12 carbon atoms or less or derivatives of such fatty acids, are added in the second step, in the substantial absence of added solvent, preferably, in the absence of additional solvent. They can be added sequentially or continuously and are profitably added at a rate that prevents the accumulation of substantial amounts of free acid in the reaction system. Again, reaction progress and conversion of starting materials to carboxylates as intermediates, and ketones as end products can be conveniently monitored by appropriate methods such as IR analysis.
    [66] During the second step, additional fatty acids, fatty acid derivatives or a mixture thereof, are added in a P2 time period, which depends notably on the overall amount of acid or acid derivative used.
    [67] For example, in the E* mode, the time period P2 is in the range from 1 h to 24 h, preferably from 2 h to 12 h and particularly preferably from 2 to 8 hours.
    [68] The total amount of fatty acid material (fatty acid or fatty acid derivatives) added in the second step of the reaction is present such that the overall molar ratio between metal and the amount of carboxylic groups reached at the end of the second step is in the range of 1:6 to 1:99, i.e., the amount of metal compound is from about 1% by mol to about 14% by mol, and preferably from 2 to about 10% by mol of the total amount of fatty acids or fatty acid derivatives, ie the metal or metal compound actually works catalytically and is not consumed in the course of the reaction. For most of the processes described in the prior art in the liquid phase, the metal or metal compound was used in amounts greater than 50 mol% and, in many cases, even exceeding the molar amounts. Such high amounts of metal are not necessarily in the process according to the present invention, which is both a technical and economic advantage of the process according to the present invention over the prior art.
    [69] In accordance with the present invention, the temperature T2 is strictly above 270°C and up to 400°C. In accordance with embodiment E* of the present invention, the temperature in the second step reaction is within the range of 280 to 320°C and preferably within the range of 285 to 310°C.
    [70] The above for the composition of the fatty acid starting material in the first step of the process in accordance with the present invention also applies to the second step.
    [71] The process according to the present invention is carried out in a non-pressurized system, that is, without the application of superatmospheric pressure. Water and carbon dioxide by-products can be removed continuously during the course of the reaction. The proper equipment is known to persons skilled in the art and they will use the best equipment prepared for the specific situation. By way of example only, a so-called Dean-Stark trap can be used to remove the water formed during the reaction and such removal represents a preferred embodiment of the present invention.
    [72] The process according to the present invention is carried out in the substantial absence of the added solvent. The desired ketone formed during the reaction basically acts as a solvent for the reaction. Since the ketone generally formed at a higher boiling point than the fatty acids or fatty acid derivatives used as a starting material, this allows the reaction to be carried out in the liquid phase as desired without the addition of an external solvent that has that it must be removed at the end of the reaction and that it is costly and laborious and therefore undesirable. Time period P12
    [73] Additional fatty acids, fatty acid derivatives or mixtures thereof may be added in a period of time P2 under the conditions specified above immediately after the temperature has been raised to T2 (this particular modality corresponds to P12 as defined hereinafter , equal to 0).
    [74] Alternatively, after the temperature has been raised to T2 and before additional fatty acids, fatty acid derivatives or mixtures thereof are added in a period of time P2, said temperature can be maintained at temperature T2 for a period of time of time P12 (> 0).
    [75] The time period P12 is preferably at least 30 min and more preferably at least 1 h.
    [76] Furthermore, the time period P12 is preferably at most 5 h and more preferably at most 3 h.
    [77] Satisfactory results were obtained notably with P12 in the range of 30 min to 300 min, specifically 1 h to 3 h. Time period P23
    [78] Immediately after the additional fatty acids, fatty acid derivatives or mixtures thereof have been added over a period of time P2, the temperature may be lowered, possibly to a temperature T3 that is preferably in the range of about 5°C to about 50°C (this particular modality corresponds to P23, as hereinafter defined, equal to 0). The T3 temperature can be room temperature or a temperature slightly above room temperature.
    [79] Alternatively, after additional fatty acids, fatty acid derivatives or mixtures thereof have been added in a period of time P2, the temperature can be maintained at temperature T2 for a period of time P23 (> 0).
    [80] The time period P23 is preferably at least 30 min and more preferably at least 1 h.
    [81] Furthermore, the time period P23 is preferably at most 5 h and more preferably at most 3 h.
    [82] Satisfactory results were obtained notably when P23 was in a range of 30 min to 300 min, especially 1 h to 3 h. Fatty acid ketone recovery and metal compound recycling
    [83] Once the fatty acid derivative or the fatty acid added in the second step of the process according to the present invention has been converted, the desired ketone can easily be obtained, for example, by distillation under reduced pressure. Advantage can be taken of the ferromagnetic properties of metallic compounds formed during the reaction (such as iron oxides) to separate the metallic compounds from the ketone by applying a magnetic field. Another way to separate ketone from metal compound products is through simple filtration since metal compounds are not soluble in the ketones obtained as the reaction product. Persons skilled in the art are aware of representative techniques, therefore, it is not necessary to provide additional details in this document.
    [84] The entire process can advantageously be carried out under an inert gas atmosphere, and suitable inert gases are, for example, nitrogen or argon, to cite just two examples.
    [85] In accordance with another preferred embodiment of the present invention, after separation of the desired ketone, the remaining residue consisting mainly of metal compounds (eg, the bottom material after distillation) can be directly reused by a second acid addition cycle fatty acid or fatty acid derivative to be converted to the desired fatty acid ketones. In general, amounts as low as 1% mol of metal or metal compound, relative to the amount of carboxylic acid equivalents, are sufficient to obtain the desired ketones in satisfactory yield. It has been found that up to four cycles are possible without a significant loss of catalytic activity of the metal or metal compound (see Example 1).
    [86] Consequently, in another preferred embodiment of the process of the present invention, at the end of step b), the metal compounds are separated from the products using conventional techniques and then recycled for conversion to another batch of acids fatty acids or fatty acid derivatives or a mixture thereof comprising at least 10 mol%, based on the total amount of fatty acids or fatty acid derivatives, from fatty acids having 12 carbon atoms or less, or derived from such acids fatty.
    [87] The yield of the desired ketones after step two typically exceeds 60%, more preferably 70% and can be as high as more than 90%. Use of fatty acid ketone for the synthesis of secondary fatty alcohols
    [88] The fatty acid ketones obtained in accordance with the process of the present invention are advantageously used for the manufacture of respective secondary fatty alcohols. In order to obtain these alcohols, the fatty acid ketones obtained in the process according to the present invention are subjected to a hydrogenation reaction. The reaction is usually carried out using heterogeneous transition metal catalysts on a support in an autoclave with hydrogen gas as the hydrogenating agent.
    [89] By way of example only, palladium catalysts supported on carbon materials can be mentioned as catalysts. The hydrogenation reaction is normally carried out at a hydrogen pressure of 500 to 5,000 kPa and at a temperature in the range of 120 to 200°C without the use of an added solvent. Use of secondary fatty alcohols for the synthesis of internal olefins
    [90] The secondary alcohols obtained as described above can be further converted to internal olefins by a dehydration reaction.
    [91] Preferably, dehydration is carried out in the substantial absence of an added solvent, preferably in the absence of added solvent, with the use of aluminum oxide, preferably n-Al2O3 as a catalyst at a temperature in the range of 250 to 350° C and for a period of 30 min to 6 h.
    [92] Internal olefins obtained after dehydration as described above show a very low degree of double bond isomerization. The double bond is formed close to the alcohol group that is removed and so the olefins are internal olefins that have the double bond mainly in the middle of the chain. It is evident that the structure of the olefin obtained is mainly determined by the structure of the starting alcohols. The dehydration reaction is normally carried out in an inert atmosphere. Sulphonation of internal olefins
    [93] The internal olefins obtained after the dehydration described above can be sulfonated followed by an alkaline hydrolysis to obtain internal olefin sulfonates that are useful as surfactants.
    [94] According to a first alternative, sulfonation can be carried out using a falling film reactor, possibly a laboratory scale film reactor. This reactor can be equipped with a cooling jacket applied with cold water to prevent temperature rises in the reactor due to the high exothermicity of the reaction. By this reaction, the temperature of the cooling jacket is normally set at about 0 to 8°C.
    [95] A gas stream consisting of a mixture of sulfonating agent (eg anhydrous SO3) diluted with carefully dry inert gas (eg nitrogen or air) at a concentration typically in the range of 0.5 to 10, preferably 1 to 5% v/v (with particular preference about 2.5% v/v) is in contact with a falling film of liquid olefins. Gas streams and liquid phases are prepared in order to guarantee a residence period of 10 seconds to 10 min, preferably 1 min to 6 min (eg 3 minutes) in the reactor and a molar ratio SO3: internal olefin in the range from 0.7:1 to 1.5:1, preferably from 0.8:1 to 1.2:1 and most preferably from 0.9:1 to 1.1:1 (for example , with a maximum preferably of 1.05:1).
    [96] When using a mixture of internal olefins with different chain lengths (and thus different molecular weights), the total molar flux of internal olefins can be calculated using the average molecular weight of the olefin mixture.
    [97] Following the sulfonation reaction, the mixture leaving the reactor (composed mainly of β-sultones) can be allowed to age in order to allow transsulfonation to take place and the conversion of starting olefins to increase.
    [98] Then, the obtained mixture can be neutralized with the use of an aqueous solution of a base (eg NaOH) in a reactor which is preferably equipped with a mechanical stirring. Then, hydrolysis is carried out by heating the mixture under mechanical stirring. During this stage of the process, the β-sulfone is transformed into Internal Olefin Sulphonates through a ring opening reaction.
    [99] Sulphonation, digestion, and hydrolysis reactions can be followed using NMR analysis. At the end of the process, the amount of water in the medium can be adjusted in order to reach an aqueous solution of Internal Olefin Sulphonates with a desired concentration of active matter.
    [100] According to a 2nd modality, sulfonation can be carried out in a reactor (batch) equipped with mechanical stirring in the liquid phase using an IN-SITU prepared sulfonation reagent, eg "SO3-dioxane". This modality is now described by way of an example.
    [101] In a round bottom flask, anhydrous dioxane and anhydrous trichloromethane (1:2 and 1:5 mixing ratio in v/v) are mixed and cooled to a temperature in the range of -5 to 10°C, preferably at about 0°C. Then, liquid SO3 (2 molar equivalents) is added slowly under stirring for 10 minutes to generate the SO3-dioxane complex which precipitates out of the mixture with white crystals.
    [102] Then, the internal olefins (1 equivalent) are slowly added under stirring at a temperature of -5 to 10°C, preferably about 0°C, to the reaction medium over a period of 0.3 to 3 h, preferably, for approximately 1 hour, and the mixture is allowed to warm to room temperature. During this period, the color of the mixture changes from light yellow to dark brown, and NMR analysis indicates that almost all internal olefin completion has occurred (about 94% conversion of olefin to sultones). Then all volatiles (CHCl3 and dioxane) are removed under vacuum.
    [103] Then 2.4 equivalents of an aqueous solution of NaOH (10% by weight) are added to the residue, and the resulting mixture is stirred at room temperature for approximately 1 hour to ensure complete neutralization.
    [104] Next, hydrolysis is carried out by stirring the reaction mixture at 95°C overnight. NMR analysis indicates complete conversion of sultones to internal olefin sulfonates.
    [105] At the end of the process, the amount of water is adjusted in order to achieve an aqueous solution of Internal Olefin Sulphonates with an adequate concentration of active matter, eg 30% by weight.
    [106] The process of the present invention thus provides easy access to internal ketones which are versatile starting materials for a variety of products as outlined above.
    [107] The process yields the desired ketones in high yield only in smaller amounts (or no amount) of unwanted by-products that are obtained and that can be easily separated from the reaction mixture.
    [108] Ketones can be separated from the reaction mixture by convenient and economical processes, and the catalytic material can be used for several catalytic cycles without significant deterioration of catalytic activity.
    [109] The following examples show the effectiveness of the process and further explain the process of the present invention. Example 1 - Synthesis of 12-tricosanone (lauric acid diketone)
    [110] The reaction was carried out under argon in a round bottom flask equipped with mechanical stirring, Dean-Stark apparatus and an addition funnel. In the reactor, 700 mg of iron powder was dispensed and 20g of lauric acid was introduced into the addition funnel.
    [111] The first partial amount of 5g of acid was added to the reactor, and the temperature was adjusted to 250°C. The mixture was stirred at this temperature for 30 minutes during which the color of the media changed to black, and H2 gas was released.
    [112] Then the temperature was raised to 300°C, the mixture was stirred for 1 h 30 min, and the remaining amount of lauric acid (15 grams) was slowly added to the reactor over 4 h 30 min at a rate of flow, which allowed to keep the concentration of lauric acid in the reaction media very low (no accumulation of free acid in the solution).
    [113] At the end of the reaction, the addition funnel was repeated by a distillation apparatus, and the products were distilled off at 290°C to 340°C under a pressure of 5 kPa.
    [114] Then, the distillation apparatus was replaced by the addition funnel which contains a new batch of 20g of fatty acids, and the operations described above were repeated for another cycle. No additional amount of iron was needed. The residue in the flask remaining after distillation was effective in converting the next batch of acids.
    [115] Overall, 4 cycles were performed without any loss of performance, thereby reducing the iron concentration to less than 1% by weight relative to the amount of converted fatty acids.
    [116] Conversion, selectivity, and yield (measured by gas chromatography (GC) and isolates) are given in Table 1 below. Table 1 (all values in % in theory)

    [117] The data show the superior selectivity and yield of the desired ketone. Example 2 - Cutting coconut fatty acids as starting material
    [118] Conversion of 400g coconut fatty acids having the following weight distribution: C12: 55%, C14: 21%, C16: 13%, C18: 12%.
    [119] The transformation was carried out using 6.4 g of iron powder (1.6% by weight) and through 2 cycles involving a total of 200 g of fatty acids per cycle.
    [120] The reaction was carried out under argon in a 1 L round bottom flask equipped with mechanical stirring, Dean-Stark apparatus and an addition funnel.
    [121] In the 250 mL addition funnel, 200 g of coconut fatty acids were introduced and kept in molten form by an external heater.
    [122] 6.4 g of iron powder were dispensed into the reactor, and a first portion of fatty acids (approximately 58 mL) was added to the reactor. The mixture was stirred (500 rpm) at 250°C for 30 minutes in order to convert iron to iron salts. During this period, the mixture color changed to black, and hydrogen was released. Then, the temperature was raised to 300°C to 320°C to carry out the transformation into fatty ketones. The mixture was stirred at this temperature for 1 h 30 min, and the remaining part of fatty acids was slowly added to the reactor over 5 hours in a flow that allowed to maintain a low concentration of fatty acids in the solution (no accumulation of free acids in the solution ). At the end of the reaction, the addition funnel was replaced by a distillation apparatus, and the fatty ketones were recovered by distillation (290°C to 340°C, 5 kPa).
    [123] A first crop of 141 g of fatty ketone was recovered as a white wax.
    [124] The residue left in the reactor vessel and consisting mainly of iron salts was used to convert the remaining 200 g of fatty acids in a second cycle. In order to achieve this, the distillation apparatus was replaced by the addition funnel containing 200 g of molten fatty acids, and the operational steps described above were repeated.
    [125] The total reaction yield after these 2 cycles was: 79% isolated as a white wax. Example 3 - Conversion of internal ketones to secondary alcohols
    [126] This example describes the hydrogenation of the ketones obtained in accordance with the present invention to obtain the corresponding secondary fatty acid alcohols. The reaction was carried out without any solvent using heterogeneous Pd/C (3%) as a catalyst and in an autoclave equipped with a Rushton turbine.
    [127] The hydrogenation was carried out on a cut of internal fatty ketones obtained by condensation reaction carried out on a cut of C12-C18 coconut fatty acids following the procedure described in Example 2.
    [128] The reaction was carried out in a 750 mL autoclave equipped with a Rushton turbine. 28 g of Pd/C (3%) of 280 g of fatty ketones were introduced into the reactor which was sealed. Then, the temperature was adjusted to 80°C, and the mixture was stirred at 1000 rpm. The reactor atmosphere was purified 3 times with 4 MPa nitrogen, then 3 times with 3 MPa hydrogen. Then, the temperature was raised to 150°C, and the mixture was stirred at that temperature maintaining 3 MPa of hydrogen until completion of the reaction (monitored by GC analysis). At the end of the reaction, the mixture was allowed to cool to 80°C, and the reactor was purged with nitrogen. The 1st crop of product (180 g) was obtained by filtration, and the remaining part was extracted using 400 ml of hot toluene. After evaporation of the solvent, a total amount of 247g of white solid was obtained corresponding to an isolated yield of 88%. Example 4 - Dehydration of secondary alcohols to internal olefins
    [129] In this example, the secondary fatty alcohols obtained in Example 3 were dehydrated with limited isomerization of the C=C bond. The reaction was carried out without solvent and with the use of AbCh-n as a catalyst. The water generated during the reaction was trapped with a Dean-Stark apparatus.
    [130] The olefins obtained were long straight chain internal olefins with a C=C double bond located approximately in the middle of the chain. The structure of the olefin was mainly determined by the structure of the starting alcohols obtained in the 2nd step. During initiation with a not very large fatty acid cut (eg C12-C18 cut), the ketone obtained and the alcohols obtained by hydrogenation are almost symmetrical with -OH located approximately in the middle of the chain. Therefore, after dehydration, the C=C double bond is located near the middle of the chain.
    [131] The reaction was carried out under argon.
    [132] 47 g of an internal alcohol cutoff obtained in accordance with Example 3, followed by 4.7 g of AhOs-n were added to a round bottom flask equipped with a Dean-Stark apparatus and magnetic stirring. Then, the mixture was stirred at 300°C for 2 hours. After completion of the reaction, the product was extracted using 150 mL of hot toluene. After evaporation of the solvent, the product was obtained as a pale yellow liquid (39 g) corresponding to an isolated yield of 87%.
    [133] The product consisted of a cut of internal fatty olefins with a C=C bond located near the middle of the chain. During initiation of a cut of C12-C18 coconut fatty acids with an even number of carbon atoms, the olefins obtained have an odd number of carbon atoms. The weight distribution of the olefins which depend on the weight distribution of the starting fatty acids followed approximately a binomial distribution. Example 5 - Comparative example
    [134] Lauric acid was mixed with 12.5% mol of iron powder and heated to 298°C (lauric acid boiling point) and held at this temperature for 5 hours. Then the composition of the reaction product was determined. The yield of 12-tricosanone was only 18%, and a significant amount of undecane was formed (8%). In addition, substantial amounts of unreacted lauric acid were still present (total lauric acid conversion is 46%). This comparative example shows that adding the total amount of acid in one step rather than sequentially does not yield the desired ketones in a satisfactory yield and, in addition, a large amount of unwanted by-products are formed. Example 6 - Synthesis of nonadecan-10-one (C10 diketone capric acid)
    [135] The reaction was carried out under argon in a 250 mL round bottom flask equipped with mechanical stirring, with a Dean-Stark apparatus and an addition funnel. In the reactor, 2.0 g (35.8 mmols) of iron powder was dispensed, and 50 g (290.4 mmols) of capric acid was introduced into the addition funnel.
    [136] A first partial amount of 12.5 g of capric acid was added to the reactor, and the temperature was adjusted to 250°C. The mixture was stirred at this temperature for 1 h 45. During this period, the color of the media changed to black and H2 gas was released. FTIR analysis of the crude mixture showed completed formation of iron carboxylate intermediate.
    [137] Then, the temperature was raised to 315°C, and the mixture was stirred for 1 h 30 min in order to transform the iron carboxylate complex into ketone, CO 2 and into iron oxide.
    [138] Then, the remaining amount of capric acid (37.5 g) was slowly added to the reactor over 5 h at a flow rate, which allowed to keep the concentration of capric acid in the reaction media very low (no accumulation of low acid in the solution). In practice, this can be done by successive slow additions of 12.5 g of capric acid every 1.5 h.
    [139] After the addition of capric acid was completed, the mixture was allowed to stir at 315°C until the intermediate iron complex was no longer detected by FTIR.
    [140] When the reaction was complete, the mixture was allowed to cool to room temperature, and 200 mL of CHCl3 was added to the crude media. The mixture was stirred at 40°C to solubilize the product (nonadecan-10-one). The suspension obtained was filtered through a silica plug and eluted using 1.5 L of chloroform. Evaporation of the solvent provided 39.7 g (140.5 mmols) of the nonadecan-10-one product as an analytically pure yellow powder. (97% isolated yield). Example 7 - Synthesis of a cut of C15 - C35 ketones with initiation of a cut of C8-C18 coconut saturated fatty acids
    [141] The reaction was carried out under argon in a 750 mL reactor equipped with mechanical stirring, with a Dean-Stark apparatus and with an addition funnel. In the reactor, 6.8 g (0.12 mol) of iron powder were dispensed and 200 g (0.97 mol) of coconut saturated fatty acid cut (with the following distribution: C8: 7% by weight, C10: 8% by weight, C12: 48% by weight, C14: 17% by weight, C16: 10% by weight, C18: 10% by weight) were introduced into the addition funnel.
    [142] The first 50 g partial amount of fatty acids was added to the reactor, and the temperature was adjusted to 250°C. The mixture was stirred at this temperature for 4 h. During this time, the color of the media changed to black, and H2 gas was released. FTIR analysis of the crude mixture showed full formation of intermediate iron carboxylate complexes.
    [143] The temperature was then raised to 330°C, and the mixture was stirred at that temperature for 2 h. During this time, the intermediate iron carboxylate complexes were decomposed into fatty ketones, iron oxide and CO2.
    [144] The remaining fatty acids (150 g) were slowly introduced into the reactor at a flow rate so that the temperature of the reaction medium did not drop below 320°C, which allowed to maintain the fatty acid concentration in the medium of very low reaction. An average addition flow rate of about 25 g fatty acids/hour has been proven to be satisfactory. In practice, this has been achieved by successive slow additions (1 hour per addition) of 3 50 g portions of molten fatty acids per 1 hour of stirring at 330°C between each addition.
    [145] At the end of the third and last additions, the crude medium was stirred at 330°C for 2 h, and the reaction progress was monitored by FTIR. When the reaction was complete (there was no more iron complex detected by FTIR), the mixture was allowed to cool to room temperature, and 400 mL of CHCl3 was added to the crude media. The mixture was stirred at 40°C to solubilize the product (C15-C35 ketones). The suspension obtained was filtered through a silica plug (400 g) and eluted using 3 L of chloroform. Evaporation of solvent provided 161 g (0.46 mol) of the product C15-C35 ketones as an analytically pure white wax (95% isolated yield).
    [146] If the description of any patents, patent applications and publications that are incorporated herein by reference conflict with the description of this application to the extent that this would render a term incomprehensible, the present description shall take precedence.
    权利要求:
    Claims (15)
    [0001]
    1. Process for the decarboxylative ketonization of fatty acids, fatty acid esters produced by the condensation of fatty acids with methanol, ethanol, propanol or butanol, or mixtures thereof in the liquid phase with metal compounds as catalysts, characterized by the fact that a) in a first step, an elemental metal or a compound of metal and the fatty acid, the fatty acid ester or mixture thereof comprising at least 10 mol%, based on the total amount of fatty acids or fatty acid esters , from fatty acids that have 12 carbon atoms or less, or fatty acid esters that have 12 carbon atoms or less, are mixed in a molar ratio of 1:0.8 to 1:3.5 (mole ratio metal : equivalent of carboxyl group) and react for a period Pi of 5 min to 24 h at a temperature Ti of 100°C to 270°C in the absence of additional solvents, and b) then the temperature is raised to a temperature T2 which is strictly above 270°C and up to 400°C, and the additional fatty acids, fatty acid esters or a mixture thereof comprising at least 10 mol%, based on the total amount of fatty acids or fatty acid esters, of fatty acids having i2 carbon atoms or less or of esters of such fatty acids are added for a period of time P2 from 5 min to 24 h in the absence of additional solvents until the molar ratio between fatty acid, fatty acid esters or mixtures thereof and metal is in the range of 6: ia 99:i.
    [0002]
    2. Process according to claim 1, characterized in that the temperature Ti is from 230°C to 270°C.
    [0003]
    3. Process according to claim 1 or 2, characterized in that the temperature T2 is 280°C to 320°C.
    [0004]
    4. Process according to claim 3, characterized in that - the temperature Ti is from 180°C to 270°C, preferably from 210°C to 260°C - the time period Pi is from 5 min to 240 min, and - the time period P2 is ih to 24 h.
    [0005]
    5. Process according to claim 1 or 2, characterized in that the temperature T2 is strictly above 320°C and up to 360°C.
    [0006]
    6. Process according to any one of claims 1 to 5, characterized in that a metal selected from the group consisting of Mg, Ca, Al, Ga, In, Ge, Sn, Pb, As, Sb, Bi, Cd e in transition metals that have an atomic number from 2i to 30 or a mixture thereof or an oxide of these metals or a mixture thereof is used.
    [0007]
    7. Process according to any one of claims 1 to 6, characterized in that the water formed during the reaction is continuously removed from the reaction mixture.
    [0008]
    8. Process according to claim 4, 6 or 7, characterized in that step a) is carried out at a temperature Ti of 190°C to 260°C for a duration of 15 min to 120 min, and the acid fatty acid, fatty acid ester or mixture thereof, in step b), is added for a P2 period of 2 to 12 hours.
    [0009]
    9. Process according to any one of claims 1 to 8, characterized in that a fatty acid ester produced by the condensation of fatty acids with methanol, ethanol, propanol or butanol is used as the starting material.
    [0010]
    10. Process according to any one of claims 1 to 8, characterized in that one and only one fatty acid, such as capric acid or lauric acid, is used as the starting material.
    [0011]
    11. Process according to any one of claims 1 to 8, characterized in that a fatty acid cut is used as starting material.
    [0012]
    12. Process according to claim 11, characterized in that the acid cut is a fatty acid cut from coconut oil.
    [0013]
    13. Process according to any one of claims 1 to 12, characterized in that, after the temperature has been raised to T2 and before the additional fatty acids, fatty acid esters or mixtures thereof are added in a period of time P2, said temperature is maintained at temperature T2 for a period of time P12 of 30 min to 300 min.
    [0014]
    14. Process according to any one of claims 1 to 13, characterized in that after the additional fatty acids, fatty acid esters or mixtures thereof have been added for a period of time P2, the temperature is maintained at temperature T2 for a P23 time period of 30 min to 300 min.
    [0015]
    15. Process according to any one of claims 1 to 14, characterized by the fact that at the end of step b) the metallic compounds are separated from the products using conventional techniques and then are recycled for the conversion of another batch of acids fatty acids or fatty acid esters or a mixture thereof comprising at least 10% by mol, based on the total amount of fatty acids or fatty acid esters, of fatty acids having 12 carbon atoms or less, or esters of such fatty acids.
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    JP6930920B2|2021-09-01|
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    法律状态:
    2020-03-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-11-10| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2021-04-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-06-08| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 04/05/2016, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP15305709.6|2015-05-07|
    EP15305709|2015-05-07|
    PCT/EP2016/060106|WO2016177842A1|2015-05-07|2016-05-04|Process for the decarboxylative ketonization of fatty acids or fatty acid derivatives|
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