阅读说明：本技术 一种异构十三醇的制备方法 (Preparation method of isomeric tridecanol ) 是由 黄少峰 袁帅 任亚鹏 许振成 黎源 于 2020-06-24 设计创作，主要内容包括：本发明涉及一种异构十三醇的制备方法,该方法以碳六烯烃为原料,催化二聚制备异构十二碳烯,异构十二碳烯经氢甲酰化和加氢制备异构十三醇产品。该方法使用碳六烯烃为原料制备异构十三醇,是一条创新的合成路线,为异构十三醇的生产提供了全新的方法。(The invention relates to a preparation method of isomeric tridecanol, which takes carbon hexaolefin as a raw material to prepare isomeric dodecene through catalytic dimerization, and the isomeric dodecene is subjected to hydroformylation and hydrogenation to prepare an isomeric tridecanol product. The method uses the carbon hexaolefin as the raw material to prepare the isomeric tridecanol, is an innovative synthetic route, and provides a brand new method for producing the isomeric tridecanol.)

1. A method for preparing isomeric tridecanol is characterized in that carbon hexaolefin is used as a raw material, dimerization is carried out under the action of a catalyst to prepare isomeric dodecene, the isomeric dodecene is subjected to hydroformylation reaction to prepare isomeric tridecanal, and the isomeric tridecanol is subjected to hydrogenation to prepare an isomeric tridecanol product.

2. The process of claim 1, wherein the carbon hexaolefin comprises a linear alpha olefin, a linear internal olefin, a branched alpha olefin, a branched internal olefin, preferably 1-hexene, 2-hexene, 3-hexene, 2-methyl-1-pentene, 3-methyl-2-pentene, 4-methyl-1-pentene, 4-methyl-2-pentene, 2, 3-dimethyl-1-butene, 2, 3-dimethyl-2-butene, 2-ethyl-1-butene, or 3, 3-dimethyl-1-butene.

3. The process according to claim 1 or 2, characterized in that the catalyst for the dimerization of the hexaolefins is a resin catalyst, preferably a metal-supported trifluoromethylpolystyrenesulfonic acid resin; more preferably, the metal is one or more of iron, cobalt, nickel, copper, zinc, scandium, titanium, vanadium, chromium, manganese, yttrium, zirconium, molybdenum, technetium, and/or the amount of catalyst is 0.1% to 10% by weight, preferably 2 to 5% by weight, based on the mass of the hexa-carbon olefin, and/or the reaction temperature is 50 to 150 ℃, preferably 80 to 120 ℃, the reaction pressure is 0 to 4MPaG, preferably 1 to 2MpaG, and the reaction time is 0.5 to 4 hours, preferably 1 to 2 hours.

4. The method according to claim 3, wherein the preparation method of the metal-supported trifluoromethyl polystyrene sulfonic acid resin comprises the following steps: (1) reacting polystyrene resin with methyl halide to generate methyl polystyrene resin, (2) reacting methyl polystyrene resin with sulfur dioxide to generate methyl polystyrene sulfonic acid resin, (3) reacting methyl polystyrene sulfonic acid resin with chlorine to generate trichloromethyl polystyrene sulfonic acid resin, (4) reacting trichloromethyl polystyrene sulfonic acid resin with fluorine-containing soluble salt, preferably potassium fluoride solution, to generate trifluoromethyl polystyrene sulfonic acid resin, (5) carrying out ion exchange on the trifluoromethyl polystyrene sulfonic acid resin and aqueous solution of metal compound, loading metal ions on the resin, filtering and drying to obtain the resin catalyst.

5. The method according to claim 4, wherein in the step (1), the catalyst for the reaction of the polystyrene resin and the halogenated methane is Lewis acid, preferably one or more of aluminum trichloride, boron trifluoride and titanium tetrachloride, and/or the amount of the catalyst is 2-10% of the mass of the polystyrene; and/or the feeding mass ratio of the polystyrene resin to the halogenated methane is 1:0.2-1:0.3, and/or the reaction temperature is 50-150 ℃, preferably 80-120 ℃, and/or the reaction time is 1-5h, preferably 2-3 h.

6. The method according to claim 4 or 5, wherein in step (2), the mass ratio of the methyl polystyrene resin to the sulfur dioxide is 1:1-1:2, and/or the reaction temperature is 40-150 ℃, preferably 70-110 ℃, and/or the reaction time is 1-4h, preferably 2-3 h.

7. The method according to any one of claims 4 to 6, wherein in the step (3), the mass ratio of the methyl polystyrene sulfonic acid resin to the chlorine gas is 1:2-1:4, and/or the reaction temperature is 60-120 ℃, preferably 90-110 ℃, and/or the reaction time is 3-6h, preferably 4-5 h.

8. The method according to any one of claims 4 to 7, wherein in the step (4), the mass ratio of the trichloromethyl polystyrene sulfonic acid resin to the fluorine-containing soluble salt is 1:0.2-1:0.4, and/or the reaction temperature is 50-150 ℃, preferably 60-100 ℃, and/or the reaction time is 2-5h, preferably 3-4 h.

9. The method according to any one of claims 4 to 8, wherein in step (5), the metal to be loaded is one or more of iron, cobalt, nickel, copper, zinc, scandium, titanium, vanadium, chromium, manganese, yttrium, zirconium, molybdenum, technetium, and the metal compound is a water-soluble metal halide, oxide, sulfate or nitrate; and/or the total concentration of metal ions in the aqueous solution of the metal compound is 0.5-2.5mol/L, and/or the mass ratio of the trifluoromethyl polystyrene sulfonic acid resin to the aqueous solution of the metal compound is 1: 0.5-1: 10.

10. the process as claimed in any of claims 1 to 9, characterized in that the catalyst used for the hydroformylation comprises one or more of cobalt-based catalysts, rhodium-based catalysts and ruthenium-based catalysts, preferably comprises one or more of metallic cobalt, oxides of cobalt, cobalt carbonate, fatty acid salts of cobalt, metallic rhodium, oxides of rhodium, fatty acid salts of rhodium, complexes of rhodium, one or more of metallic ruthenium, oxides of ruthenium, fatty acid salts of ruthenium, complexes of ruthenium, and/or the amount of catalyst is from 0.01 to 10% by weight, preferably from 0.02 to 1% by weight, based on the mass of the isomeric dodecane olefin, and/or the reaction temperature is from 50 to 200 ℃, preferably from 100 ℃ to 120 ℃, and/or the reaction pressure is from 8 to 30MpaG, preferably from 10 to 30MpaG, and/or the reaction time is from 0.5 to 8h, preferably 3-5 h.

11. The process according to any one of claims 1 to 10, wherein the catalyst used for the hydrogenation of isomeric tridecanal comprises one or more of raney nickel, nickel alumina, palladium on carbon, palladium alumina, copper zinc alumina, preferably a nickel alumina catalyst; and/or the amount of the catalyst is 1-10 wt%, preferably 2-5 wt% of the mass of the isomeric tridecanal; and/or the reaction temperature is 50-200 ℃, preferably 120-150 ℃, and/or the reaction pressure is 1-20MpaG, preferably 10-15MPaG, and/or the reaction time is 0.5-5h, preferably 2-4 h.

Technical Field

The invention relates to a preparation method of isomeric tridecanol.

Technical Field

The isomeric tridecanol is saturated tridecanol with a certain branched chain structure, and the branched chain is a methyl or ethyl structure. Due to the branched carbon chain structure, the isomeric tridecanol has good wettability, permeability and emulsifying property, and is mainly used for producing the isomeric tridecanol polyoxyethylene ether nonionic surfactant. The long carbon chain of the isomeric tridecanol has higher branching degree, so that the isomeric tridecanol polyoxyethylene ether has stronger penetrability and wettability, good water solution stability, fast degradation speed and low toxicity because of no benzene ring and phenoxy. Octyl and nonyl phenol ethers have reproductive toxicity, are completely forbidden by the European Union, and isomeric tridecanol ethers are the best substitutes for octyl and nonyl phenol ethers.

Currently, isomeric tridecanol is prepared by hydroformylation and hydrogenation of trimeric butene or tetrapropylene. Oligomerization of 1-butene or mixed C4 to form dimer and trimer, separation of trimer, hydroformylation and hydrogenation to prepare isomeric tridecanol. The oligomerization of 1-butene and mixed C4 has been reported in many patents, for example, EP0091232A2, US4225743, US5220088 and US5414160 use nickel salt and alkyl aluminum to homogeneously catalyze the oligomerization of 1-butene, the selectivity of product dimer is 80% -90%, the trimer selectivity is only 10% -20%, after the reaction is finished, acid quenching reaction is used, and the catalyst can not be regenerated. In US4737480, US4835331 and US4737479, aluminum oxide supported nickel oxide is used for catalyzing oligomerization of 1-butene after activation by alkyl aluminum, the selectivity of dimer is 80-90%, the selectivity of trimer is 10-20%, and the service life of the catalyst is not mentioned. NiO/A1 was used in CN1137420A, CN1137420A, CN1704388A and CN1721073A₂O₃The/aluminosilicate, the AMCM-56 molecular sieve, the M-ZSM-5 molecular sieve and the ZSM-5 molecular sieve catalyze butene oligomerization, the selectivity of tripolymer is less than 40 percent, the isomerization of products is serious, the branching degree of the dipolymer is high, carbon deposition is easy to generate in the molecular sieve catalyst, and the catalyst is quick to inactivate.

The propylene oligomerization product is separated into tetramer, and can be used for preparing isomeric tridecanol through hydroformylation and hydrogenation. CN1381432A, CN1398833A, CN1328876A, CN106732700A, CN201711126786 and the like adopt different types of catalysts to catalyze propylene oligomerization, and the tetramer selectivity is between 20% and 40%.

The tri-iso-butene or tetra-polypropylene hydroformylation reaction generally adopts cobalt or rhodium as a catalyst, and the cobalt or rhodium is converted into iso-tridecanal under the conditions of high temperature and high pressure, and the iso-tridecanol product is prepared after hydrogenation.

At present, propylene and butylene are used as raw materials for producing isomeric tridecanol, but propylene and butylene cannot be oligomerized in high selectivity to generate tetrapropylene and trimerized butylene, so that the yield of isododecene is insufficient, and further the productivity of isomeric tridecanol cannot meet the market requirement.

Disclosure of Invention

The invention aims to provide a method for preparing isomeric tridecanol, which is characterized in that isomeric tridecanol is produced by using carbon hexaolefin as a raw material through a brand-new process, so that the raw material source of isomeric tridecanol is enriched, and isomeric tridecanol can be prepared with high selectivity and high yield.

In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:

the preparation process of isomeric tridecanol includes dimerization of six carbon olefins in the presence of catalyst to prepare isomeric dodecene, hydroformylation of isomeric dodecene to prepare isomeric tridecanal, and hydrogenation of isomeric tridecanal to prepare isomeric tridecanol product.

The hexaolefins used include linear alpha olefins, linear internal olefins, branched alpha olefins, branched internal olefins including but not limited to 1-hexene, 2-hexene, 3-hexene, 2-methyl-1-pentene, 3-methyl-2-pentene, 4-methyl-1-pentene, 4-methyl-2-pentene, 2, 3-dimethyl-1-butene, 2, 3-dimethyl-2-butene, 2-ethyl-1-butene, 3, 3-dimethyl-1-butene.

The catalyst for the dimerization reaction of the hexa-carbon olefin is a resin catalyst, preferably metal-loaded trifluoromethyl polystyrene sulfonic acid resin; more preferably, the metal is one or more of iron, cobalt, nickel, copper, zinc, scandium, titanium, vanadium, chromium, manganese, yttrium, zirconium, molybdenum, technetium.

The preparation method of the resin catalyst for dimerization of the hexa-carbon olefin comprises the following steps: (1) reacting macroporous polystyrene resin with methyl halide (preferably methyl chloride/methyl bromide/methyl iodide) to generate methyl polystyrene resin, (2) reacting methyl polystyrene resin with sulfur dioxide to generate methyl polystyrene sulfonic acid resin, (3) reacting methyl polystyrene sulfonic acid resin with chlorine to generate trichloromethyl polystyrene sulfonic acid resin, (4) reacting trichloromethyl polystyrene sulfonic acid resin with fluorine-containing soluble salt, preferably potassium fluoride solution, to generate trifluoromethyl polystyrene sulfonic acid resin, (5) exchanging trifluoromethyl polystyrene sulfonic acid resin with aqueous solution of metal compound, loading metal ions on the resin, filtering, and drying to obtain a resin catalyst for dimerization.

Wherein, in the step (1), the reaction catalyst of the polystyrene resin and the chloromethane/bromomethane/iodomethane is Lewis acid, which comprises aluminum trichloride, boron trifluoride, titanium tetrachloride and the like, the mass ratio of the polystyrene resin to the halogenated methane is 1:0.2-1:0.3, the reaction temperature is 50-150 ℃, preferably 80-120 ℃, and the reaction time is 1-5h, preferably 2-3 h. The amount of the catalyst is 2-10% of the mass of the polystyrene. After the reaction is finished, filtering to obtain the methyl polystyrene resin, and drying at the temperature of 100 ℃ and 120 ℃ for 24-48 h.

In the step (2), the mass ratio of methyl polystyrene resin to sulfur dioxide is 1:1-1:2, the reaction temperature is 40-150 ℃, preferably 70-110 ℃, and the reaction time is 1-4h, preferably 2-3 h. And (4) discharging unreacted sulfur dioxide after the reaction is finished, and replacing nitrogen for three times to obtain the methyl polystyrene sulfonic acid resin.

In the step (3), the mass ratio of methyl polystyrene sulfonic acid resin to chlorine gas is 1:2-1:4, the reaction temperature is 60-120 ℃, preferably 90-110 ℃, and the reaction time is 3-6h, preferably 4-5 h. And discharging unreacted chlorine after the reaction is finished, and replacing nitrogen for three times to obtain the trichloromethyl polystyrene sulfonic acid resin.

In the step (4), trichloromethyl polystyrene sulfonic acid resin and fluorine-containing soluble salt, preferably potassium fluoride aqueous solution react without a catalyst, the mass ratio of chloromethyl polystyrene sulfonic acid resin to potassium fluoride is 1:0.2-1:0.4, the reaction temperature is 50-150 ℃, preferably 60-100 ℃, and the reaction time is 2-5h, preferably 3-4 h. And (3) after the reaction is finished, washing with deionized water, and drying at the temperature of 100-120 ℃ for 24-48h to obtain the trifluoromethyl polystyrene sulfonic acid resin.

In the step (5), the loaded metal is one or more of iron, cobalt, nickel, copper, zinc, scandium, titanium, vanadium, chromium, manganese, yttrium, zirconium, molybdenum and technetium, and the metal compound used in the loading process is water-soluble metal halide, oxide, sulfate, nitrate and the like. The loading process is actually that hydrogen ions in the sulfonic acid and metal ions are subjected to proton exchange, the hydrogen ions are replaced, and the metal ions are combined with the sulfonate. The total concentration of metal ions in the aqueous solution of the metal compound is 0.5-2.5mol/L, and the mass ratio of the trifluoromethyl polystyrene sulfonic acid resin to the aqueous solution of the metal compound is 1: 0.5-1: 10, filtering after the loading is finished, washing with deionized water, and drying at the temperature of 120 ℃ for 24-48h to obtain the final catalyst.

The reaction process for the preparation of the resin catalyst is shown in the following formula:

wherein X represents chlorine, bromine and iodine, M represents iron, cobalt, nickel, copper, zinc, scandium, titanium, vanadium, chromium, manganese, yttrium, zirconium, molybdenum, technetium, polystyrene polymerization degree n is 100-10000, a, b, c, p and q are integers between 1 and 5, and represent-CH₃，-SO₃H，-CCl₃，-CF₃，-SO₃The number of M.

The dimerization reaction principle of the hexa-carbon olefin is an acid-catalyzed carbonium ion mechanism, firstly, the hexa-carbon olefin is protonated under the action of acid, and cations of the hexa-carbon olefin generated continue to react with one molecule of the hexa-carbon olefin to generate isomeric decadiene. The resin catalyst used for dimerization introduces trifluoromethyl on a polystyrene structure, the strong electron-withdrawing effect of the trifluoromethyl greatly enhances the acidity of a sulfonic group, and simultaneously, the supported metal and C6 olefin form a coordination effect, so that the metal center selectively catalyzes C6 olefin to be dimerized with high selectivity, and the occurrence of other side reactions such as trimerization and the like is reduced. The dosage of the dimerization catalyst is 0.1-10 wt%, preferably 2-5 wt% of the mass of C6 olefin, the reaction temperature is 50-150 ℃, preferably 80-120 ℃, the reaction pressure is 0-4MPaG, preferably 1-2MpaG, the reaction time is 0.5-4h, preferably 1-2h, and after the reaction is finished, the reaction liquid is rectified to separate an isomeric dodecene product for hydroformylation.

The isomeric decadiene, carbon monoxide and hydrogen are subjected to hydroformylation reaction to generate isomeric tridecanal. The catalyst used for the hydroformylation reaction comprises one or more of cobalt catalyst, rhodium catalyst and ruthenium catalyst, specifically comprises metal cobalt, cobalt oxide, cobalt carbonate, cobalt fatty acid salt, metal rhodium, rhodium oxide, rhodium fatty acid salt, rhodium complex, metal ruthenium, ruthenium oxide, ruthenium fatty acid salt, ruthenium complex and the like, preferably rhodium catalyst, the amount of the catalyst is 0.01-10 wt% of the mass of isomeric dodecene, preferably 0.02-1 wt%, the reaction temperature is 50-200 ℃, preferably 100-. In the hydroformylation process, synthetic gas is used as one of reaction raw materials, and the mol feed ratio of the synthetic gas to dodecene is more than 1.

The reactor used for hydroformylation is a stirred tank or a bubble column, preferably a tank reactor.

The isomeric tridecylaldehyde generated by the hydroformylation reaction needs to be converted into isomeric tridecanol through a hydrogenation reaction, the catalyst used for hydrogenation of the isomeric tridecylaldehyde comprises raney nickel, nickel aluminum oxide, palladium carbon, palladium aluminum oxide, copper aluminum oxide and copper zinc aluminum oxide, preferably a nickel aluminum oxide catalyst, the dosage of the catalyst is 1-10 wt%, preferably 2-5 wt% of the mass of the isomeric tridecylaldehyde, the reaction temperature is 50-200 ℃, preferably 120-150 ℃, the reaction pressure is 1-20MpaG, preferably 10-15MPaG, and the reaction time is 0.5-5h, preferably 2-4 h. In the hydrogenation process, hydrogen is used as one of reaction raw materials, and the molar charge ratio of the hydrogen to the isomeric tridecanal is more than 1. The reactor used for the dimerization and hydrogenation reaction is a stirred tank or a fixed bed, preferably a fixed bed reactor, and the space velocity of the fixed bed is preferably 0.5-1h^-1。

Compared with the prior art, the invention has the following advantages:

(1) a brand new preparation method of isomeric tridecanol changes the traditional route of using tetrapropylene or trimeric butylene as raw materials, innovatively uses the hexaolefin as the raw material, and makes the production raw materials of isomeric tridecanol more abundant.

(2) The method can prepare the isomeric tridecanol with high selectivity and high yield, and effectively solves the problem of insufficient yield caused by insufficient source of tetrapropylene or tributylene which is the raw material for producing the isomeric tridecanol at present.

The specific implementation mode is as follows:

the present invention is further illustrated by the following examples, which include, but are not limited to, the scope of the present invention.