WO2019242038A1 - 一种二元羧酸的制备方法 - Google Patents

一种二元羧酸的制备方法 Download PDF

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WO2019242038A1
WO2019242038A1 PCT/CN2018/093445 CN2018093445W WO2019242038A1 WO 2019242038 A1 WO2019242038 A1 WO 2019242038A1 CN 2018093445 W CN2018093445 W CN 2018093445W WO 2019242038 A1 WO2019242038 A1 WO 2019242038A1
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reaction
acid
cyclohexene
catalyst
cyclohexyl acetate
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PCT/CN2018/093445
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French (fr)
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黄声骏
张大治
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中国科学院大连化学物理研究所
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Priority to JP2020565330A priority Critical patent/JP7132357B2/ja
Priority to US17/253,779 priority patent/US11999688B2/en
Publication of WO2019242038A1 publication Critical patent/WO2019242038A1/zh

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    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
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    • C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
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    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
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Definitions

  • the present application relates to a method for preparing a dicarboxylic acid, and belongs to the new technical field of chemical production and manufacturing.
  • Dicarboxylic acids are important chemical precursor materials in the polymer chemical industry and organic synthesis.
  • Adipic acid is a representative substance in dicarboxylic acids. At present, it is mainly produced by a cyclohexanol / cyclohexanone oxidation method. Representative routes are: 1) Cyclohexane is oxidized to cyclohexanol-cyclohexanone (KA oil), and KA oil is oxidized to produce adipic acid; 2) Cyclohexene is hydrated to produce cyclohexanol, and cyclohexanol is oxidized to produce hexane Diacid.
  • the one-way conversion of cyclohexane in the step of oxidizing cyclohexane to KA oil is low (usually, the conversion rate of cyclohexane is less than 6%), the operating conditions of the reaction process are not easy to control, and accidents are prone to occur.
  • the cyclohexene hydration route has significant advantages in terms of process operation safety, but still has the following problems: 1) High requirements for the purity of cyclohexene and water raw materials.
  • the solubility of cyclohexene and upstream materials such as cyclohexane in water are close, the content of cyclohexane impurities in the raw materials of cyclohexene must be reduced as much as possible to reduce the negative effect of the dissolution effect of the impurities in cyclohexane on the reaction rate; as raw materials
  • the oxygen content of the water has an effect on the hydration reaction and must be reduced as much as possible; 2)
  • the hydration reaction rate is slow. Due to the difference in polarity, the solubility of cyclohexene in water is very small; it causes the reaction concentration to limit the reaction rate; 3) the single-pass conversion is low.
  • Cyclohexene hydration is a thermodynamic equilibrium-restricted reaction. It is reported that even if the residence time of the cyclohexene feedstock in the slurry reactor is extended, the conversion rate of the cyclohexene in a single pass can still reach only about 12%. 4) The cost of reaction operation and subsequent separation and recycling is high. Because the reaction system is a three-phase complex system of "oil phase (cyclohexene)-water phase-solid phase (molecular sieve)".
  • adipic acid synthesis routes have also been reported.
  • US5166421 reports a method for preparing adipic acid using butadiene as a raw material through two hydroformylations. The total adipic acid yield of this route is not high, and the cost of the precious metal catalyst used is relatively high.
  • GB1402480 reports a method of first adding a cyclic monoolefin to a saturated fatty dibasic acid containing 4-12 carbon atoms to form a corresponding dibasic ester, and then oxidizing the resulting ester to obtain a dicarboxylic acid.
  • reaction raw material used in the addition reaction step is a solid-liquid two-phase, it can only perform batch operation, the reaction efficiency is not high, and the final product and the raw material are not easy to separate. Therefore, based on the current state of the technology, it is still necessary to develop new diacid production methods that have the characteristics of safe process operating conditions, fast reaction rates, high reaction conversion rates, and high atomic utilization.
  • a method for preparing a dicarboxylic acid includes the following steps:
  • the cyclic olefin contains five or more carbon atoms and contains one carbon-carbon double bond structure.
  • the cyclic olefin is at least one selected from the group consisting of a compound of the formula I, a compound of the formula II, a compound of the formula III, and a compound of the formula IV:
  • R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , and R 108 in Formula I are each independently selected from H, C 1 to C 3 hydrocarbon groups, halogen elements, or C 1 ⁇ C 3 halohydrocarbyl.
  • R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , and R 108 in the formula I are C 1 to C 3 alkyl groups.
  • R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 , R 209 , and R 210 in Formula II are independently selected from the group consisting of H, C 1 to C 3 hydrocarbon groups, and halogens. Element or C 1 to C 3 halogenated hydrocarbon group.
  • R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 , R 209 , and R 210 in the formula II are C 1 to C 3 alkyl groups.
  • R 301 , R 302 , R 303 , R 304 , R 305 , R 306 , R 307 , R 308 , R 309 , R 310 , R 311 , and R 312 in Formula III are each independently selected from H, C 1 to C A hydrocarbon group of 3 , a halogen element, or a halogenated hydrocarbon group of C 1 to C 3 .
  • R 301 , R 302 , R 303 , R 304 , R 305 , R 306 , R 307 , R 308 , R 309 , R 310 , R 311 , R 312 in the formula III are C 1 to C 3 alkyl groups. .
  • R 401 , R 402 , R 403 , R 404 , R 405 , R 406 , R 407 , R 408 , R 409 , R 410 , R 411 , R 412 , R 413 , R 414 in Formula IV are independently selected from H, a C 1 to C 3 hydrocarbon group, a halogen element, or a C 1 to C 3 halogenated hydrocarbon group.
  • R 401 , R 402 , R 403 , R 404 , R 405 , R 406 , R 407 , R 408 , R 409 , R 410 , R 411 , R 412 , R 413 , R 414 in Formula IV are C 1 to C 3 alkyl.
  • the lower monocarboxylic acid is selected from at least one compound having a chemical formula represented by Formula V:
  • R 501 is selected from H, a C 1 to C 3 hydrocarbon group, or a C 1 to C 3 halogenated hydrocarbon group.
  • R 501 is a C 1 to C 3 alkyl group or a vinyl group.
  • the lower monocarboxylic acid is selected from at least one of acetic acid, formic acid, and trifluoroacetic acid.
  • the product of the ring-opening oxidation reaction is represented by the following formulae X, XI, XII, and XIII.
  • lower monocarboxylic acids especially acetic acid
  • acetic acid have better mutual solubility with cyclic olefins.
  • the contact between the reactants is better, and the reactant ratio can have a wider adjustment range, so that it can have higher reactivity and selectivity.
  • the reaction mixture of acetic acid and cyclic olefin is a liquid phase, so the reaction in the present invention can be continuously operated using a fixed bed, and has higher efficiency.
  • the addition intermediate product obtained by using the saturated monocarboxylic acid of the present invention as a raw material is a liquid, such as cyclohexyl acetate.
  • the use of liquid cyclohexyl acetate is more conducive to subsequent oxidation operations.
  • the oxidation reaction step can be continuously operated, and the reaction speed is faster and the selectivity is higher.
  • the dicarboxylic acid product obtained after the oxidation reaction of the present invention is easier to separate from the saturated monocarboxylic acid.
  • the saturated monocarboxylic acids used in the present invention are cheaper.
  • the addition catalyst in step 1) contains at least one of a supported inorganic acid, a cation exchange resin, and a molecular sieve.
  • the acid catalyst is a solid acid catalyst.
  • the inorganic acid in the supported inorganic acid is selected from at least one of sodium hydrogen sulfate, sodium hydrogen phosphate, AlCl 3 and heteropoly acid
  • the carrier in the supported inorganic acid is selected from silica, At least one of diatomaceous earth and kaolin; the weight percentage content of the inorganic acid in the supported inorganic acid is 5-25%.
  • the cation exchange resin is a sulfonic acid type strongly acidic macroporous ion exchange resin, the Hammett index H 0 of the acid strength is ⁇ -10, and the ion exchange resin H + exchange capacity is above 1.0 mmol / L;
  • the molecular sieve is selected from at least one of HY, H ⁇ , and HZSM-5 molecular sieves whose topological structure is FAU, BEA, MFI; the weak acid center density of the molecular sieve is 0.005-0.35 mmol / g as measured by NH 3 chemisorption measurement.
  • the density of medium-strength acid centers is 0.01-0.5mmol / g, and the density of strong acid centers is 0.003-0.15mmol / g.
  • the molar ratio of the lower monocarboxylic acid to the cyclic olefin is 0.2-10.0, and the feed space velocity of the cyclic olefin is 0.6-3.0 g ⁇ g -1 ⁇ h -1 .
  • the molar ratio of acid to olefin may be any one of 0.2, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and any two of the above points. Any point value in the range.
  • the space velocity of the cyclic olefin can be 0.6 g ⁇ g -1 ⁇ h -1 , 1 g ⁇ g -1 ⁇ h -1 , 1.5 g ⁇ g -1 ⁇ h -1 , 2.0 g ⁇ g -1 ⁇ H -1 , 2.5 g ⁇ g -1 ⁇ h -1 , 3.0 g ⁇ g -1 ⁇ h -1 or any point value within a range consisting of any two points.
  • the addition reaction is performed in one or more reactors selected from at least one of a fixed bed reactor and a kettle reactor.
  • the conditions of the addition reaction are a pressure of 0.1-2.0 MPa and a reaction temperature of 50-150 ° C.
  • the pressure of the addition reaction may be any point value in the range of 0.1 MPa, 0.5 MPa, 1.0 MPa, 1.5 MPa, 2.0 MPa, or any two of the above point values.
  • the lower limit of the temperature of the addition reaction is selected from any point value or range from 50 to 60 ° C, and the upper limit of the temperature of the addition reaction is selected from any point value or range from 130 to 150 ° C.
  • the reaction conditions of the oxidation reaction in step 2) are: a reaction temperature of 40-120 ° C and a reaction pressure of 0.1-0.5 MPa.
  • the lower limit of the temperature of the oxidation reaction is selected from any point value or range from 40-50 ° C, and the upper limit of the temperature of the oxidation reaction is selected from any point value or range from 100-120 ° C.
  • the oxidant in step 2) is selected from at least one of HNO 3 , nitrite, and hydrogen peroxide.
  • the oxidation catalyst in step 2) is selected from the group consisting of NH 4 VO 3 , Cu (NO 3 ) 2 , Co (NO 3 ) 2 , Fe (NO 3 ) 3 , ammonium molybdate, ammonium tungstate, and heteropoly acid At least one of.
  • the molar ratio of the oxidant and the carboxylic acid cyclic ester in step 2) is
  • Oxidant, carboxylic acid cyclic ester and catalyst 3 to 15: 1;
  • the addition amount of the oxidation catalyst satisfies: after adding the oxidation catalyst, the mass concentration of each oxidation catalyst in the oxidation reaction system is 0.01-1.0%, respectively.
  • the oxidant may be one or more, and when determining the input amount, the mass concentration of each oxidant is calculated separately.
  • the intermediate product system containing a carboxylic acid cyclic ester is a mixed system after the addition reaction is completed or is only a carboxylic acid cyclic ester.
  • the preparation method further includes step 3):
  • step 3 After the ring-opening oxidation reaction is completed, the lower monocarboxylic acid in the separated product is recycled to the raw material of the addition reaction in step 1) for recycling.
  • the cyclic olefins and carboxylic acids are fed into a fixed-bed reactor, and the reactor is filled with a certain amount of solid catalyst.
  • Reaction operating pressure 0.1-2.0MPa
  • reaction temperature 50-150 ° C
  • cyclic olefin feed space velocity 0.6-3.0g ⁇ g -1 ⁇ h -1
  • acid-ene molar ratio 0.2-10.0
  • preferred operating conditions reaction The pressure is 0.1-1.1 MPa
  • the reaction temperature is 70-125 ° C
  • the cyclic olefin feed space velocity is 0.6-2.0 g ⁇ g -1 ⁇ h -1
  • the acid-olefin molar ratio 1-6 After the reaction is completed, the obtained product is separated by distillation to obtain a carboxylic acid cyclic ester product or a mixture of a carboxylic acid cyclic ester and a corresponding carboxylic acid with a purity greater than 99.5%.
  • the oxidation reaction step is as follows: a certain amount of oxidant is added to the kettle reactor, a certain amount of catalyst is added, and the solution is stirred and dissolved at a certain speed (100-300 rmp / min). The mass concentration of each catalyst in the solution ranges from 0.01 to 1.0%.
  • the reactor temperature was raised to the reaction temperature, and then a carboxylic acid cyclic ester, or a carboxylic acid cyclic ester and a corresponding carboxylic acid mixture was added.
  • the reaction temperature range is 40-120 ° C, and the molar ratio of nitric acid to carboxylic acid cyclic ester is 3-15. After 10-60 minutes of reaction, the reaction was stopped. The material is cooled, separated by crystallization, washed and purified to obtain the corresponding diacid product.
  • the addition reaction uses a cyclic olefin and a lower monocarboxylic acid as raw materials.
  • the reactants used can be mutually soluble, so it can conveniently increase the acid-olefin ratio in the reactants, increase the conversion of cyclic olefins (the cyclic olefin conversion can reach more than 95%), and make the reactant molecules Can better contact between them and increase the reaction rate.
  • the lower monobasic acid used in the addition reaction of the present application is more acidic, and the reaction rate and conversion rate of the addition reaction are significantly improved compared to the weakly acidic high carbon number carboxylic acid.
  • the solid acid catalyst preferred in the present application has suitable acid strength and acid center number distribution, has an excellent pore system and a large specific surface area. Therefore, it shows high one-way conversion and selectivity of target products in the addition reaction. The catalyst and product are easily separated and less corrosive to the equipment.
  • the addition reaction of this application can adopt a fixed bed reaction process, the addition reaction can be continuously operated, the reaction efficiency is improved, and the space-time yield of the reaction can reach more than 2.0 kg ⁇ kg -1 ⁇ h -1 .
  • the addition-oxidation synthesis route provided by this application has a high yield of dibasic acid. Based on cyclic olefins, the yield of the corresponding dibasic acid can reach more than 95%
  • FIG. 1 shows the change of cyclohexene conversion and cyclohexyl acetate selectivity with time in Example 32.
  • the addition reaction product was rectified to obtain cyclohexyl acetate with a purity of greater than 99.5%.
  • the cyclohexyl acetate is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 145.5 g of 65% nitric acid is added to a 250 ml reaction kettle, and 5.5 g of copper nitrate trihydrate and 0.17 g of ammonium metavanadate are added.
  • the reactor temperature was raised to 70 ° C.
  • the catalyst was dissolved by vigorous stirring. 17.8 g of cyclohexyl acetate obtained in the addition reaction was added to the reaction solution.
  • the reaction was stirred for 40 minutes. Then, the temperature of the reaction kettle was lowered to room temperature, and the reaction was stopped.
  • the reaction product was analyzed by liquid chromatography for product composition.
  • the conversion rate of cyclohexyl acetate was 100%, the yield of adipic acid was 96.9%, the yield of glutaric acid was 2.8%, and the yield of succinic acid was 0.1%.
  • the addition reaction product was rectified to obtain cyclohexyl acetate with a purity of greater than 99.5%.
  • the cyclohexyl acetate is further oxidized.
  • the specific reaction steps are as follows: 121.2 g of 65% nitric acid is added to a 250 ml reaction kettle, and 3.7 g of copper nitrate trihydrate and 0.11 g of ammonium metavanadate are added.
  • the reactor temperature was raised to 70 ° C.
  • the catalyst was dissolved by vigorous stirring. 17.8 g of cyclohexyl acetate obtained in the addition reaction was added to the reaction solution.
  • the reaction was stirred for 40 minutes. Then, the temperature of the reaction kettle was lowered to room temperature, and the reaction was stopped.
  • the reaction product was analyzed by liquid chromatography for product composition.
  • the conversion of cyclohexyl acetate was 100%, the yield of adipic acid was 96.6%, the yield of glutaric acid was 3.1%, and the yield of succinic acid was 0.1%.
  • the addition reaction product was rectified to obtain cyclohexyl acetate with a purity of greater than 99.5%.
  • the cyclohexyl acetate is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 105.0 g of 60% nitric acid is added to a 250 ml reaction kettle, and 2.2 g of copper nitrate trihydrate and 0.07 g of ammonium metavanadate are added.
  • the reactor temperature was raised to 70 ° C.
  • the catalyst was dissolved by vigorous stirring. 17.8 g of cyclohexyl acetate obtained in the addition reaction was added to the reaction solution.
  • the reaction was stirred for 40 minutes. Then, the temperature of the reaction kettle was lowered to room temperature, and the reaction was stopped.
  • the reaction product was analyzed by liquid chromatography for product composition.
  • the conversion rate of cyclohexyl acetate was 100%
  • the yield of adipic acid was 96.1%
  • the yield of glutaric acid was 3.5%
  • the yield of succinic acid was 0.1%.
  • the addition reaction product was rectified to obtain cyclohexyl acetate with a purity of greater than 99.5%.
  • the cyclohexyl acetate is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 78.8 g of 60% nitric acid is added to a 250 ml reaction kettle, and 0.6 g of copper nitrate trihydrate and 0.02 g of ammonium metavanadate are added.
  • the reactor temperature was raised to 70 ° C.
  • the catalyst was dissolved by vigorous stirring. 17.8 g of cyclohexyl acetate obtained in the addition reaction was added to the reaction solution. The reaction was stirred for 40 minutes.
  • the addition reaction product was rectified to obtain cyclohexyl acetate with a purity of greater than 99.5%.
  • the cyclohexyl acetate is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 63.1 g of 50% nitric acid is added to a 250 ml reaction kettle, and 1.0 g of copper nitrate trihydrate and 0.04 g of ammonium metavanadate are added.
  • the reactor temperature was raised to 70 ° C.
  • the catalyst was dissolved by vigorous stirring. 17.8 g of cyclohexyl acetate obtained in the addition reaction was added to the reaction solution.
  • the reaction was stirred for 40 minutes. Then, the temperature of the reaction kettle was lowered to room temperature, and the reaction was stopped.
  • the reaction product was analyzed by liquid chromatography for product composition.
  • the conversion rate of cyclohexyl acetate was 100%, the yield of adipic acid was 93.1%, the yield of glutaric acid was 6.0%, and the yield of succinic acid was 0.4%.
  • the addition reaction product was rectified to obtain cyclohexyl acetate with a purity of greater than 99.5%.
  • the cyclohexyl acetate is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 87.5 g of 45% nitric acid is added to a 250 ml reaction kettle, and 1.7 g of copper nitrate trihydrate and 0.04 g of ammonium metavanadate are added.
  • the reactor temperature was raised to 70 ° C.
  • the catalyst was dissolved by vigorous stirring. 17.8 g of cyclohexyl acetate obtained in the addition reaction was added to the reaction solution.
  • the reaction was stirred for 60 minutes. Then, the temperature of the reaction kettle was lowered to room temperature, and the reaction was stopped.
  • the reaction product was analyzed by liquid chromatography for product composition.
  • the conversion rate of cyclohexyl acetate was 100%, the yield of adipic acid was 95.1%, the yield of glutaric acid was 4.5%, and the yield of succinic acid was 0.3%.
  • the addition reaction product was rectified to obtain cyclohexyl acetate with a purity of greater than 99.5%.
  • the cyclohexyl acetate is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 110.3 g of 50% nitric acid is added to a 250 ml reaction kettle, and 1.7 g of copper nitrate trihydrate and 0.08 g of ammonium metavanadate are added. The temperature of the reaction kettle was raised to 50 ° C. The catalyst was dissolved by vigorous stirring. 17.8 g of cyclohexyl acetate obtained in the addition reaction was added to the reaction solution. The reaction was stirred for 60 minutes.
  • the addition reaction product was rectified to obtain cyclohexyl acetate with a purity of greater than 99.5%.
  • the cyclohexyl acetate is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 110.3 g of 50% nitric acid is added to a 250 ml reaction kettle, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate are added. The temperature of the reaction kettle was raised to 40 ° C. The catalyst was dissolved by vigorous stirring. 17.8 g of cyclohexyl acetate obtained in the addition reaction was added to the reaction solution. The reaction was stirred for 60 minutes.
  • the addition reaction product was rectified to obtain cyclohexyl acetate with a purity of greater than 99.5%.
  • the cyclohexyl acetate is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 110.3 g of 50% nitric acid is added to a 250 ml reaction kettle, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate are added. The temperature of the reaction kettle was raised to 60 ° C. The catalyst was dissolved by vigorous stirring. 17.8 g of cyclohexyl acetate obtained in the addition reaction was added to the reaction solution. The reaction was stirred for 40 minutes.
  • the addition reaction product was rectified to obtain cyclohexyl acetate with a purity of greater than 99.5%.
  • the cyclohexyl acetate is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 110.3 g of 50% nitric acid is added to a 250 ml reaction kettle, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate are added.
  • the reactor temperature was raised to 80 ° C.
  • the catalyst was dissolved by vigorous stirring. 17.8 g of cyclohexyl acetate obtained in the addition reaction was added to the reaction solution.
  • the reaction was stirred for 30 minutes. Then, the temperature of the reaction kettle was lowered to room temperature, and the reaction was stopped.
  • the reaction product was analyzed by liquid chromatography for product composition.
  • the conversion rate of cyclohexyl acetate was 100%, the yield of adipic acid was 95.1%, the yield of glutaric acid was 3.6%, and the yield of succinic acid was 0.4%.
  • the addition reaction product was rectified to obtain cyclohexyl acetate with a purity of greater than 99.5%.
  • the cyclohexyl acetate is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 110.3 g of 50% nitric acid is added to a 250 ml reaction kettle, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate are added. The temperature of the reaction kettle was raised to 90 ° C. The catalyst was dissolved by vigorous stirring. 17.8 g of cyclohexyl acetate obtained in the addition reaction was added to the reaction solution. The reaction was stirred for 30 minutes.
  • a supported phosphomolybdic acid catalyst HPM / SiO 2 was charged into the middle of a stainless steel tubular fixed bed reactor, and the upper and lower sides of the catalyst were respectively filled with quartz sand.
  • the reactor temperature was raised to 100 ° C and the reaction pressure was 2.0 MPa.
  • the reactants cyclohexene and acetic acid were respectively fed into the reactor, and the molar ratio of acetic acid to cyclohexene was 4: 1.
  • the feed space velocity of cyclohexene was 1.0 g ⁇ g -1 ⁇ h -1 .
  • the reaction was run continuously for 250 hours. After the reaction products were collected, the composition of the products was analyzed by gas chromatography.
  • the cyclohexene conversion was 81.2%, and the selectivity to cyclohexyl acetate was 97.6%.
  • the addition reaction product was rectified to obtain cyclohexyl acetate with a purity of greater than 99.5%.
  • the cyclohexyl acetate is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 110.3 g of 50% nitric acid is added to a 250 ml reaction kettle, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate are added. The temperature of the reaction kettle was raised to 100 ° C. The catalyst was dissolved by vigorous stirring. 17.8 g of cyclohexyl acetate obtained in the addition reaction was added to the reaction solution. The reaction was stirred for 30 minutes.
  • a supported silicotungstic acid catalyst HSW / SiO 2 was charged into the middle of a stainless steel tubular fixed-bed reactor, and the upper and lower sides of the catalyst were respectively filled with quartz sand.
  • the reactor temperature was raised to 120 ° C and the reaction pressure was 2.0 MPa.
  • the reactants cyclohexene and acetic acid were respectively fed into the reactor, and the molar ratio of acetic acid to cyclohexene was 4: 1.
  • the feed space velocity of cyclohexene was 1.0 g ⁇ g -1 ⁇ h -1 .
  • the reaction was run continuously for 250 hours. After the reaction products were collected, the composition of the products was analyzed by gas chromatography.
  • the conversion of cyclohexene was 84.9%, and the selectivity to cyclohexyl acetate was 97.1%.
  • the addition reaction product was rectified to obtain cyclohexyl acetate with a purity of greater than 99.5%.
  • the cyclohexyl acetate is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 110.3 g of 50% nitric acid is added to a 250 ml reaction kettle, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate are added. The temperature of the reaction kettle was raised to 120 ° C. The catalyst was dissolved by vigorous stirring. 17.8 g of cyclohexyl acetate obtained in the addition reaction was added to the reaction solution. The reaction was stirred for 20 minutes.
  • a supported silicomolybdic acid catalyst HSM / SiO 2 was charged into the middle of a stainless steel tubular fixed-bed reactor, and the upper and lower sides of the catalyst were respectively filled with quartz sand.
  • the reactor temperature was raised to 120 ° C and the reaction pressure was 2.0 MPa.
  • the reactants cyclohexene and acetic acid were respectively fed into the reactor, and the molar ratio of acetic acid to cyclohexene was 4: 1.
  • the feed space velocity of cyclohexene was 1.0 g ⁇ g -1 ⁇ h -1 .
  • the reaction was run continuously for 250 hours. After the reaction products were collected, the composition of the products was analyzed by gas chromatography.
  • the conversion of cyclohexene was 85.4%, and the selectivity to cyclohexyl acetate was 96.9%.
  • the addition reaction product was rectified to obtain cyclohexyl acetate with a purity of greater than 99.5%.
  • the cyclohexyl acetate is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 110.3 g of 50% nitric acid is added to a 250 ml reaction kettle, and 3.3 g of cobalt nitrate hexahydrate and 0.1 g of ammonium metavanadate are added.
  • the reactor temperature was raised to 70 ° C.
  • the catalyst was dissolved by vigorous stirring. 17.8 g of cyclohexyl acetate obtained in the addition reaction was added to the reaction solution. The reaction was stirred for 40 minutes.
  • the addition reaction product was rectified to obtain cyclohexyl acetate with a purity of greater than 99.5%.
  • the cyclohexyl acetate is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 110.3 g of 50% nitric acid is added to a 250 ml reaction kettle, and 2.9 g of ferric nitrate and 0.1 g of ammonium metavanadate are added.
  • the reactor temperature was raised to 70 ° C.
  • the catalyst was dissolved by vigorous stirring. 17.8 g of cyclohexyl acetate obtained in the addition reaction was added to the reaction solution.
  • the reaction was stirred for 40 minutes. Then, the temperature of the reaction kettle was lowered to room temperature, and the reaction was stopped.
  • the reaction product was analyzed by liquid chromatography for product composition.
  • the conversion of cyclohexyl acetate was 100%, the yield of adipic acid was 90.4%, the yield of glutaric acid was 6.9%, and the yield of succinic acid was 1.9%.
  • HY molecular sieve catalyst 60 ml of HY molecular sieve catalyst was charged into the middle of a stainless steel tubular fixed bed reactor, and the upper and lower sides of the catalyst were filled with quartz sand, respectively.
  • the reactor temperature was raised to 80 ° C and the reaction pressure was 0.1 MPa.
  • the reactants cyclohexene and acetic acid were respectively fed into the reactor, and the molar ratio of acetic acid to cyclohexene was 4: 1.
  • the feed space velocity of cyclohexene was 1.0 g ⁇ g -1 ⁇ h -1 .
  • the reaction was run continuously for 250 hours. After the reaction products were collected, the composition of the products was analyzed by gas chromatography. The conversion of cyclohexene was 62.3%, and the selectivity to cyclohexyl acetate was 98.4%.
  • the addition reaction product was rectified to obtain cyclohexyl acetate with a purity of greater than 99.5%.
  • the cyclohexyl acetate is further subjected to an oxidation reaction, and the specific reaction steps are as follows: 99.2 g of 20% hydrogen peroxide is added to a 250 ml reaction kettle, and 2.3 g of phosphomolybdic acid are added respectively.
  • the reactor temperature was raised to 80 ° C.
  • the catalyst was dissolved by vigorous stirring. 17.8 g of cyclohexyl acetate obtained in the addition reaction was added to the reaction solution. The reaction was stirred for 60 minutes. Then, the temperature of the reaction kettle was lowered to room temperature, and the reaction was stopped.
  • the reaction product was analyzed by liquid chromatography for product composition.
  • the conversion of cyclohexyl acetate was 100%, the yield of adipic acid was 85.6%, the yield of glutaric acid was 9.8%, and the yield of succinic acid was 2.3%.
  • HZSM-5 molecular sieve catalyst 60 ml of HZSM-5 molecular sieve catalyst was charged into the middle of a stainless steel tubular fixed bed reactor, and the upper and lower sides of the catalyst were respectively filled with quartz sand.
  • the reactor temperature was raised to 80 ° C and the reaction pressure was 0.1 MPa.
  • the reactants cyclohexene and acetic acid were respectively fed into the reactor, and the molar ratio of acetic acid to cyclohexene was 4: 1.
  • the feed space velocity of cyclohexene was 1.0 g ⁇ g -1 ⁇ h -1 .
  • the reaction was run continuously for 250 hours. After the reaction products were collected, the composition of the products was analyzed by gas chromatography. The conversion of cyclohexene was 71.4%, and the selectivity to cyclohexyl acetate was 98.9%.
  • the addition reaction product was rectified to obtain cyclohexyl acetate with a purity of greater than 99.5%.
  • the cyclohexyl acetate is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 99.2 g of 20% hydrogen peroxide is added to a 250 ml reaction kettle, and 3.8 g of ammonium tungstate are added respectively.
  • the reactor temperature was raised to 80 ° C.
  • the catalyst was dissolved by vigorous stirring. 17.8 g of cyclohexyl acetate obtained in the addition reaction was added to the reaction solution.
  • the reaction was stirred for 60 minutes. Then, the temperature of the reaction kettle was lowered to room temperature, and the reaction was stopped.
  • the reaction product was analyzed by liquid chromatography for product composition.
  • the conversion of cyclohexyl acetate was 100%, the yield of adipic acid was 82.1%, the yield of glutaric acid was 10.4%, and the yield of succinic acid was 3.6%.
  • the unreacted cyclohexene was separated from the addition reaction product to obtain a mixture mainly composed of acetic acid and cyclohexyl acetate, wherein the molar ratio of acetic acid to cyclohexyl acetate was 3.7.
  • the acetic acid / cyclohexyl acetate mixture is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 110.3 g of 50% nitric acid is added to a 250 ml reaction kettle, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate are added.
  • the reactor temperature was raised to 70 ° C.
  • the catalyst was dissolved by vigorous stirring.
  • the unreacted cyclohexene was separated from the addition reaction product to obtain a mixture mainly composed of acetic acid and cyclohexyl acetate, wherein the molar ratio of acetic acid to cyclohexyl acetate was 6.4.
  • the acetic acid / cyclohexyl acetate mixture is further subjected to oxidation reaction.
  • the specific reaction steps are as follows: 110.3 g of 50% nitric acid is added to a 250 ml reaction kettle, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate are added. The reactor temperature was raised to 70 ° C. The catalyst was dissolved by vigorous stirring.
  • the addition reaction product was rectified to obtain cyclohexyl acetate with a purity of 99.5%.
  • the cyclohexyl acetate is further subjected to an oxidation reaction, and the specific reaction steps are as follows: 110.3 g of 50% nitric acid is added to a 250 ml reaction kettle, and 1.1 g (NH 4 ) 6 Mo 7 O 24 and 0.1 g of metavanadic acid are added respectively. Ammonium.
  • the reactor temperature was raised to 70 ° C.
  • the catalyst was dissolved by vigorous stirring. 17.8 g of cyclohexyl acetate obtained in the addition reaction was added to the reaction solution. The reaction was stirred for 40 minutes.
  • the addition reaction product was rectified to obtain cyclohexyl acetate with a purity of greater than 99.5%.
  • the cyclohexyl acetate is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 110.3 g of 50% nitric acid is added to a 250 ml reaction kettle, and 1.4 g (NH 4 ) 2 MoO 4 and 0.1 g of ammonium metavanadate are added.
  • the reactor temperature was raised to 70 ° C.
  • the catalyst was dissolved by vigorous stirring. 17.8 g of cyclohexyl acetate obtained in the addition reaction was added to the reaction solution.
  • the reaction was stirred for 40 minutes. Then, the temperature of the reaction kettle was lowered to room temperature, and the reaction was stopped.
  • the reaction product was analyzed by liquid chromatography for product composition.
  • the conversion of cyclohexyl acetate was 100%, the yield of adipic acid was 93.4%, the yield of glutaric acid was 5.2%, and the yield of succinic acid was 0.7%.
  • Unreacted cyclohexene was separated from the addition reaction product to obtain a mixture mainly composed of acetic acid and cyclohexyl acetate, wherein the molar ratio of acetic acid to cyclohexyl acetate was 1.6.
  • the acetic acid / cyclohexyl acetate mixture is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 110.3 g of 50% nitric acid is added to a 250 ml reaction kettle, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate are added. The reactor temperature was raised to 70 ° C. The catalyst was dissolved by vigorous stirring.
  • the addition reaction product was rectified to obtain cyclohexyl acetate with a purity of greater than 99.5%.
  • the cyclohexyl acetate is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 110.3 g of 50% nitric acid is added to a 250 ml reaction kettle, and 2.5 g of copper nitrate trihydrate is added.
  • the reactor temperature was raised to 70 ° C.
  • the catalyst was dissolved by vigorous stirring. 17.8 g of cyclohexyl acetate obtained in the addition reaction was added to the reaction solution.
  • the reaction was stirred for 40 minutes.
  • the temperature of the reaction kettle was lowered to room temperature, and the reaction was stopped.
  • the reaction product was analyzed by liquid chromatography for product composition.
  • the conversion of cyclohexyl acetate was 100%, the yield of adipic acid was 83.3%, the yield of glutaric acid was 12.4%, and the yield of succinic acid
  • the addition reaction product was rectified to obtain cyclohexyl acetate with a purity of greater than 99.5%.
  • the cyclohexyl acetate is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 110.3 g of 50% nitric acid is added to a 250 ml reaction kettle, and 0.1 g of ammonium metavanadate is added.
  • the reactor temperature was raised to 70 ° C.
  • the catalyst was dissolved by vigorous stirring. 17.8 g of cyclohexyl acetate obtained in the addition reaction was added to the reaction solution.
  • the reaction was stirred for 40 minutes. Then, the temperature of the reaction kettle was lowered to room temperature, and the reaction was stopped.
  • the reaction product was analyzed by liquid chromatography for product composition.
  • the conversion of cyclohexyl acetate was 100%, the yield of adipic acid was 81.2%, the yield of glutaric acid was 13.5%, and the yield of succinic acid was 2.6%.
  • the addition reaction product was rectified to obtain cyclohexyl acetate with a purity of greater than 99.5%.
  • the cyclohexyl acetate is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 110.3 g of 50% nitric acid is added to a 250 ml reaction kettle, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate are added.
  • the reactor temperature was raised to 70 ° C.
  • the catalyst was dissolved by vigorous stirring. 17.8 g of cyclohexyl acetate obtained in the addition reaction was added to the reaction solution.
  • the reaction was stirred for 40 minutes. Then, the temperature of the reaction kettle was lowered to room temperature, and the reaction was stopped.
  • the reaction product was analyzed by liquid chromatography for product composition.
  • the conversion of cyclohexyl acetate was 100%, the yield of adipic acid was 96.7%, the yield of glutaric acid was 2.7%, and the yield of succinic acid was 0.1%.
  • the addition reaction product was rectified to obtain cyclopentyl acetate with a purity of greater than 99.5%.
  • the cyclopentyl acetate is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 110.3 g of 50% nitric acid is added to a 250 ml reaction kettle, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate are added.
  • the reactor temperature was raised to 70 ° C.
  • the catalyst was dissolved by vigorous stirring. 16.0 g of cyclopentyl acetate obtained in the addition reaction was added to the reaction solution.
  • the reaction was stirred for 40 minutes.
  • the temperature of the reaction kettle was lowered to room temperature, and the reaction was stopped.
  • the reaction product was analyzed by liquid chromatography for product composition. The conversion of cyclopentyl acetate was 100%, the yield of glutaric acid was 96.7%, and the yield of succinic acid was 2.9%.
  • the addition reaction product was rectified to obtain cyclohexyl acetate with a purity of greater than 99.5%.
  • the cyclohexyl acetate is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 78.8 g of 50% nitric acid is added to a 250 ml reaction kettle, and 0.96 g of copper nitrate trihydrate and 0.07 g of ammonium metavanadate are added.
  • the reactor temperature was raised to 70 ° C.
  • the catalyst was dissolved by vigorous stirring. 17.8 g of cyclohexyl acetate obtained in the addition reaction was added to the reaction solution. The reaction was stirred for 40 minutes.
  • the addition reaction product was rectified to obtain cycloheptyl formate with a purity of greater than 99.5%.
  • the cycloheptyl formate is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 110.3 g of 50% nitric acid is added to a 250 ml reaction kettle, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate are added.
  • the reactor temperature was raised to 70 ° C.
  • the catalyst was dissolved by vigorous stirring. 17.8 g of cycloheptyl formate obtained in the addition reaction was added to the reaction solution.
  • the reaction was stirred for 40 minutes. Then, the temperature of the reaction kettle was lowered to room temperature, and the reaction was stopped.
  • the reaction product was analyzed by liquid chromatography for product composition.
  • the conversion of cycloheptyl formate was 100%, the yield of pimelic acid was 95.6%, the yield of adipic acid was 3.4%, and the yield of glutaric acid was 0.5%.
  • the addition reaction product was rectified to obtain cyclohexyl acrylate having a purity of more than 99.5%.
  • the cyclohexyl acrylate is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 110.3 g of 50% nitric acid is added to a 250 ml reaction kettle, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate are added.
  • the reactor temperature was raised to 70 ° C.
  • the catalyst was dissolved by vigorous stirring. 19.3 g of cyclohexyl acrylate obtained in the addition reaction was added to the reaction solution.
  • the reaction was stirred for 40 minutes. Then, the temperature of the reaction kettle was lowered to room temperature, and the reaction was stopped.
  • the reaction product was analyzed by liquid chromatography for product composition.
  • the conversion of cyclohexyl acrylate was 100%, the yield of adipic acid was 95.1%, the yield of glutaric acid was 3.5%, and the yield of succinic acid was 0.6%.
  • the addition reaction product was rectified to obtain cyclohexyl trifluoroacetate with a purity of greater than 99.5%.
  • the cyclohexyl trifluoroacetate is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 110.3 g of 50% nitric acid is added to a 250 ml reaction kettle, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate are added.
  • the reactor temperature was raised to 70 ° C.
  • the catalyst was dissolved by vigorous stirring.
  • To the reaction solution was added 24.5 g of cyclohexyl trifluoroacetate obtained in the addition reaction. The reaction was stirred for 40 minutes.
  • the addition reaction product was rectified to obtain chlorocyclohexyl acetate having a purity of more than 99.5%.
  • the chlorocyclohexyl acetate is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 110.3 g of 50% nitric acid is added to a 250 ml reaction kettle, 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate are added.
  • the reactor temperature was raised to 70 ° C.
  • the catalyst was dissolved by vigorous stirring.
  • To the reaction solution was added 22.1 g of chlorocyclohexyl acetate obtained in the addition reaction. The reaction was stirred for 40 minutes. Then, the temperature of the reaction kettle was lowered to room temperature, and the reaction was stopped.
  • the reaction product was analyzed by liquid chromatography for product composition.
  • the conversion rate of chlorocyclohexyl acetate was 100%
  • the yield of chloroadipate was 96.2%
  • the yield of glutaric acid was 3.0%
  • the yield of succinic acid was 0.1%.
  • the addition reaction product was distilled to obtain methylcyclohexyl acetate having a purity of more than 99.5%.
  • the methyl cyclohexyl acetate is further subjected to an oxidation reaction, and the specific reaction steps are as follows: 110.3 g of 50% nitric acid is added to a 250 ml reaction kettle, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate are added.
  • the reactor temperature was raised to 70 ° C.
  • the catalyst was dissolved by vigorous stirring.
  • To the reaction solution was added 19.5 g of methyl cyclohexyl acetate obtained in the addition reaction. The reaction was stirred for 40 minutes.
  • the addition reaction product was rectified to obtain cyclohexyl acetate with a purity of greater than 99.5%.
  • the cyclohexyl acetate is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 78.8 g of 50% nitric acid is added to a 250 ml reaction kettle, and 0.48 g of copper nitrate trihydrate and 0.07 g of ammonium metavanadate are added. The temperature of the reaction kettle was raised to 60 ° C. The catalyst was dissolved by vigorous stirring. 17.8 g of cyclohexyl acetate obtained in the addition reaction was added to the reaction solution. The reaction was stirred for 60 minutes.
  • the addition reaction product was rectified to obtain cyclohexyl acetate with a purity of greater than 99.5%.
  • the cyclohexyl acetate is further subjected to an oxidation reaction.
  • the specific reaction steps are as follows: 110.3 g of 50% nitric acid is added to a 250 ml reaction kettle, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate are added.
  • the reactor temperature was raised to 70 ° C.
  • the catalyst was dissolved by vigorous stirring. 17.8 g of cyclohexyl acetate obtained in the addition reaction was added to the reaction solution.
  • the reaction was stirred for 40 minutes. Then, the temperature of the reaction kettle was lowered to room temperature, and the reaction was stopped.
  • the reaction product was analyzed by liquid chromatography for product composition.
  • the conversion of cyclohexyl acetate was 100%, the yield of adipic acid was 96.8%, the yield of glutaric acid was 2.6%, and the yield of succinic acid was 0.1%.

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Abstract

提供了一种二元羧酸的制备方法，所述方法包括如下步骤：1)使含有环状烯烃和一元羧酸的原料体系在加成催化剂作用下发生加成反应，生成含有羧酸环酯的中间产物体系；2)使所述中间产物体系在氧化催化剂作用下发生开环氧化反应，生成相应二元羧酸产物。该二酸合成路线中的加成反应单程转化率高，相应羧酸环酯选择性好；该加成-氧化合成路线中，加成和氧化反应速率均较快，并且相应二酸产品收率高。该基于加成-氧化合成路线，适于连续、稳定大规模的生产相应二酸产品。

Description

一种二元羧酸的制备方法 技术领域
本申请涉及一种二元羧酸的制备方法，属于化学品生产与制造新技术领域。
背景技术
二元羧酸是高分子化学工业和有机合成中的重要化工前体原料。己二酸是二元羧酸中的代表性物质，目前，其主要是经由环己醇/环己酮氧化的方法生产。代表性的路线有：1)环己烷氧化生成环己醇-环己酮(KA油)，KA油氧化生产己二酸；2)环己烯水合生成环己醇，环己醇氧化生产己二酸。第一条生产路线中，环己烷氧化生成KA油步骤中环己烷的单程转化率低(通常环己烷转化率低于6％)，反应工艺操条件不易控制，容易发生事故。第二条生产路线中环己烯水合路线在工艺操作安全性上具有显著的优势，但仍然存在以下问题：1)对环己烯、水原料纯度要求高。由于环己烯与环己烷等上游物料在水中溶解度接近，环己烯原料中的环己烷杂质的含量须尽可能降低，以减少环己烷杂质溶解效应对反应速率的负面影响；作为原料中水的氧含量对水合反应存在着影响，必须尽可能降低；2)水合反应速率慢。由于极性差异，环己烯在水中溶解度很小；造成反应浓度对反应速率的限制；3)单程转化率低。环己烯水合反应属于热力学平衡限制反应，据报道，即使延长环己烯原料在浆态反应器中的停留时间，环己烯单程反应转化率仍只能达到12％左右。4)反应操作和后续分离、循环成本较高。由于反应体系是“油相(环己烯)-水相-固相(分子筛)”三相复杂体系。需要强力搅拌形成乳化体系，以提高反应的传质；催化剂在搅拌过程中产生相应的磨损消耗，磨损产生的细小催化剂给后续物料分离带来困难；此外由于环己烯的单程转化率，大量未反应的环己烯物料需要进行循环。
除上述代表性路线之外，其他己二酸合成路线也有报道。US5166421报道了以丁二烯为原料，经过两次氢甲酰化制备己二酸的方法。该路线总的己二酸收率不高，并且使用的贵金属催化剂成本较高。GB1402480报道了先将环状单烯烃与含4-12个碳原子的饱和脂肪二元酸加成生成相应的二元酯，再将生成的酯氧化制得二元羧酸的方法。此方法由于加成反应步骤使用的反应原料为固液两相，因此只能进行间歇式操作，反应效率不高，最终产物与原料之间也不易分离。因此，基于目前技术现状，仍然需要发展新的二酸生产方法，使其具备工艺操作条件安全、反应速率快、反应转化率和原子利用率高的特点。
发明内容
根据本申请的一个方面，提供一种二元羧酸的制备方法，所述方法包括如下步骤：
1)使含有环状烯烃和低级一元羧酸的原料体系在加成催化剂的存在下发生加成反应，生成含有羧酸环酯的中间产物体系；
2)使所述含有羧酸环酯的中间产物体系在氧化剂和氧化催化剂的存在下发生开环氧化反应，生成相应二元羧酸产物。
优选地，所述环状烯烃含有五个及以上碳原子并且含有一个碳碳双键结构。
所述环状烯烃选自具有式I所示化学式的化合物、式II所示化学式的化合物、式III所示化学式的化合物、式IV所示化学式的化合物中的至少一种：
Figure PCTCN2018093445-appb-000001
其中，式I中的R 101、R 102、R 103、R 104、R 105、R 106、R 107、R 108分别独立地选自H、C 1～C 3的烃基、卤族元素或C 1～C 3的卤代烃基。优选地，式I中的R 101、R 102、R 103、R 104、R 105、R 106、R 107、R 108是C 1～C 3的烷基。
式II中的R 201、R 202、R 203、R 204、R 205、R 206、R 207、R 208、R 209、R 210分别独立地选自H、C 1～C 3的烃基、卤族元素或C 1～C 3的卤代烃基。优选地，式II中的R 201、R 202、R 203、R 204、R 205、R 206、R 207、R 208、R 209、R 210是C 1～C 3的烷基。
式III中的R 301、R 302、R 303、R 304、R 305、R 306、R 307、R 308、R 309、R 310、R 311、R 312分别独立地选自H、C 1～C 3的烃基、卤族元素或C 1～C 3的卤代烃基。优选地式III中的R 301、R 302、R 303、R 304、R 305、R 306、R 307、R 308、R 309、R 310、R 311、R 312是C 1～C 3的烷基。
式IV中的R 401、R 402、R 403、R 404、R 405、R 406、R 407、R 408、R 409、R 410、R 411、R 412、R 413、R 414分别独立地选自H、C 1～C 3的烃基、卤族元素或C 1～C 3的卤代烃基。优选地， 式IV中的R 401、R 402、R 403、R 404、R 405、R 406、R 407、R 408、R 409、R 410、R 411、R 412、R 413、R 414是C 1～C 3烷基。
所述低级一元羧酸选自具有式V所示化学式的化合物中的至少一种：
Figure PCTCN2018093445-appb-000002
其中，R 501选自H、C 1～C 3的烃基或C 1～C 3的卤代烃基。优选地，R 501是C 1～C 3的烷基或乙烯基。更优选地，所述低级一元羧酸选自乙酸、甲酸、三氟乙酸中的至少一种。
相应地，所述加成加成反应的产物如以下式VI、式VII、式VIII、式IX所示：
Figure PCTCN2018093445-appb-000003
并且，所述开环氧化反应的产物如以下式X、XI、XII和XIII所示。
Figure PCTCN2018093445-appb-000004
相对于使用的二元酸，低级一元羧酸尤其是乙酸与环状烯烃有更好的互溶性。反应物之间接触性更好，反应物比例可以有更宽的调整范围，从而可以有更高的反应活性和选择性。并且乙酸和环状烯烃的反应混合物为液相，所以本发明中的反应可以使用固定床连续操作，具有更高的效率。
使用本发明的的饱和一元羧酸为原料得到的加成中间产物为液体，例如乙酸环己酯。使用液体的乙酸环己酯更有利于后续的氧化操作，氧化反应步骤可连续操作，并且反应速度更快，选择性更高。本发明氧化反应后得到的二元羧酸产物更易与饱和一元羧酸分离。本发明使用的饱和一元羧酸更廉价。
优选地，步骤1)中所述加成催化剂含有负载型无机酸、阳离子交换树脂和分子筛中的至少一种。
优选地，所述酸性催化剂是固体酸催化剂。
固体酸催化剂具备以下优点：
a)更高的转化率和选择性；
b)可以使用固定床连续操作；
c)产物和催化剂易于分离；
d)对设备腐蚀性小。
优选地，所述负载型无机酸中的无机酸选自硫酸氢钠、磷酸氢钠、AlCl 3和杂多酸中的至少一种，所述负载型无机酸中的载体选自二氧化硅、硅藻土和高岭土中的至少一种；所述负载型无机酸中无机酸的重量百分含量为5～25％。
优选地，所述阳离子交换树脂为磺酸型强酸性大孔离子交换树脂，其酸强度的Hammett指数H 0<-10，离子交换树脂H +交换容量在1.0mmol/L以上；
所述分子筛选自拓扑结构为FAU、BEA、MFI的HY、Hβ和HZSM-5分子筛中的至少一种；以NH 3化学吸附测定衡量，所述分子筛的弱酸中心密度为0.005-0.35mmol/g、中等强度酸中心密度为0.01-0.5mmol/g、强酸中心密度为0.003-0.15mmol/g。
优选地，所述低级一元羧酸和所述环状烯烃的摩尔比值为0.2-10.0，所述环状烯烃的进料空速为0.6-3.0g·g -1·h -1。
所述加成反应中，酸烯摩尔比可以为0.2、1、2、3、4、5、6、7、8、9、10中的任意点值以及以上各点值中任意两个组成的范围中的任意点值。所述环状烯烃的进料空速可以为0.6g·g -1·h -1、1g·g -1·h -1、1.5g·g -1·h -1、2.0g·g -1·h -1、2.5g·g -1·h -1、3.0g·g -1·h -1或者以上各点值中任意两个组成的范围内的任意点值。
优选地，所述加成反应在一个或者多个反应器中进行，所述反应器选自固定床反应器、釜式反应器中的至少一种。
优选地，所述加成反应的条件为压力0.1-2.0MPa、反应温度50-150℃。
所述加成反应的压力可以为0.1MPa、0.5MPa、1.0MPa、1.5MPa、2.0MPa中的任意点值或者以上点值中任意两个组成的范围中的任意点值。
所述加成反应的温度下限选自50-60℃中的任意点值或范围，所述加成反应的温度上限选自130-150℃中的任意点值或范围。
优选地，步骤2)中所述氧化反应的反应条件为：反应温度40-120℃、反应压力0.1-0.5MPa。
所述氧化反应的温度下限选自40-50℃中的任意点值或范围，所述氧化反应的温度上限选自100-120℃中的任意点值或范围。
优选地，步骤2)中所述氧化剂选自HNO 3、亚硝酸盐、双氧水中的至少一种。
优选地，步骤2)中所述氧化催化剂选自NH 4VO 3、Cu(NO 3) 2、Co(NO 3) 2、Fe(NO 3) 3、钼酸铵、钨酸铵和杂多酸中的至少一种。
优选地，步骤2)中所述氧化剂和羧酸环酯的摩尔比为
氧化剂、羧酸环酯和催化剂＝3～15：1；
氧化催化剂的加入量满足：加入所述氧化催化剂后，氧化反应体系中的每种氧化催化剂的质量浓度分别为0.01-1.0％。
氧化剂可以是一种或多种，在确定投入量时，每种氧化剂的质量浓度分别计算。
优选地，所述含有羧酸环酯的中间产物体系为加成反应结束后的混合体系或仅为羧酸环酯。
优选地，所述制备方法还包括步骤3)：
3)所述开环氧化反应结束后，分离得到产物中的低级一元羧酸循环至步骤1)中所述加成反应的原料中循环使用。
在一个优选实施方式中，原料环烯烃和羧酸分别进入固定床反应器，反应器内装填一定量的固体催化剂。反应操作压力：0.1-2.0MPa、反应温度50-150℃、环烯烃进料空速0.6-3.0g·g -1·h -1、酸烯摩尔比0.2-10.0，较佳的操作条件：反应压力0.1-1.1MPa、反应温度70-125℃，环烯烃进料空速0.6-2.0g·g -1·h -1、酸烯摩尔比1-6。反应结束后，将得到的产物精馏分离，得到纯度大于99.5％的羧酸环酯产品或羧酸环酯与相应羧酸的混合物。
在一个优选实施方式中，氧化反应步骤如下：一定量的氧化剂加入釜式反应器中，加入一定量的催化剂，并在一定转速下(100-300rmp/min)搅拌溶解。每种催化剂在溶液中的质量浓度范围0.01-1.0％。将反应器温度升至反应温度，然后加入羧酸环酯，或羧酸环酯与相应羧酸混合物。反应温度范围40-120℃，硝酸与羧酸环酯的摩尔比为3-15。反应10-60分钟后，停止反应。将物料冷却、结晶分离、洗涤纯化，获取相应二酸产品。
本申请能产生的有益效果包括：
1)本申请所提供的加成-氧化合成路线中，加成反应使用环状烯烃和低级一元羧酸为原料。所使用的反应物之间可以互溶，因此既可以方便的提高反应物中的酸烯比例，提高环状烯烃的转化率(环状烯烃转化率可达到95％以上)，又使反应物分子之间能够更好的接触，提高反应速率。
2)本申请加成反应使用的低级一元酸酸性较强，相对于酸性较弱的高碳数羧酸，加成反应的反应速率和转化率都有明显提高。
3)本申请所优选的固体酸催化剂具备适宜的酸强度和酸中心数分布，具备优良的孔道系统和较大的比表面积。因此在加成反应中显示出较高的单程转化率和目标产物选择性。催化剂和产物之间易于分离并且对设备腐蚀性小。
4)本申请加成反应可采用固定床反应工艺，加成反应可以连续操作，提高了反应效率，反应的时空收率可达到2.0kg·kg -1·h -1以上。
5)本申请所提供的加成-氧化合成路线中，加成反应的产物可不经分离，直接用于随后的氧化反应，可以节省分离成本，操作较为灵活。
6)本申请加成反应生成的相应酯均为液体，避免了固体产物在后续的氧化反应中操作的不便。
7)本申请所提供的加成-氧化合成路线，二元酸的收率高。以环状烯烃计算，相应二元酸的收率可达到95％以上
8)本申请所提供的加成-氧化合成路线反应条件温和，适于连续、稳定大规模生产。
附图说明
图1为实施例32中环己烯转化率与乙酸环己酯选择性随时间的变化。
具体实施方式
下面结合实施例对本发明予以进一步的说明，但本申请并不局限于这些实施例。如无特别说明，本申请的实施例中的原料和催化剂均通过商业途径购买。
产物具体方法如下：
加成产物分析：将收集到的加成反应产物在装有FID检测器的安捷伦7890B气相色谱上定量分析产物组成。气相色谱柱选用FFAP色谱柱。选用正丁醇为内标物对产物进行定量分析。
氧化产物分析：将收集到的氧化反应产物在华普S6000液相色谱上定量分析产物组成。液相色谱柱选用HSS-T3色谱柱分析。
实施例1
将60ml大孔强酸性离子交换树脂Amberlyst15装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至90℃，反应压力0.1MPa。将反应物环己烯和乙酸分别进入反应器，乙酸与环己烯的摩尔比为4：1。环己烯的进料空速为1.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环己烯转化率为85.5％，乙酸环己酯选择性98.1％。
将加成反应产物精馏得到纯度大于99.5％的乙酸环己酯。将该乙酸环己酯进一步进行氧化反应，具体反应步骤如下：将145.5g浓度为65％的硝酸加入250ml反应釜中，分别加入5.5g三水合硝酸铜和0.17g偏钒酸铵。将反应釜温度升至70℃。剧烈搅拌使催化剂溶解。在反应溶液中加入17.8g加成反应中得到的乙酸环己酯。搅拌反应40分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸环己酯的转化率为100％，己二酸收率96.9％，戊二酸收率2.8％，丁二酸收率0.1％。
实施例2
将60ml大孔强酸性离子交换树脂Amberlyst35装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至90℃，反应压力0.1MPa。将反应物环己烯和乙酸分别进入反应器，乙酸与环己烯的摩尔比为4：1。环己烯的进料空速为1.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环己烯转化率为84.2％，乙酸环己酯选择性98.2％。
将加成反应产物精馏得到纯度大于99.5％的乙酸环己酯。将该乙酸环己酯进一步进行氧化反应，具体反应步骤如下：将121.2g浓度为65％的硝酸加入250ml反应釜中，分别加入3.7g三水合硝酸铜和0.11g偏钒酸铵。将反应釜温度升至70℃。剧烈搅拌使催化剂溶解。在反应溶液中加入17.8g加成反应中得到的乙酸环己酯。搅拌反应40分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸环己酯的转化率为100％，己二酸收率96.6％，戊二酸收率3.1％，丁二酸收率0.1％。
实施例3
将60ml大孔强酸性离子交换树脂Amberlyst36装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至90℃，反应压力0.1MPa。将反应物环己烯和乙酸分别进入反应器，乙酸与环己烯的摩尔比为4：1。环己烯的进料空速为1.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环己烯转化率为81.5％，乙酸环己酯选择性98.1％。
将加成反应产物精馏得到纯度大于99.5％的乙酸环己酯。将该乙酸环己酯进一步进行氧化反应，具体反应步骤如下：将105.0g浓度为60％的硝酸加入250ml反应釜中，分别加入2.2g三水合硝酸铜和0.07g偏钒酸铵。将反应釜温度升至70℃。剧烈搅拌使催化剂溶解。在反应溶液中加入17.8g加成反应中得到的乙酸环己酯。搅拌反应40分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸环己酯的转化率为100％，己二酸收率96.1％，戊二酸收率3.5％，丁二酸收率0.1％。
实施例4
将60ml大孔强酸性离子交换树脂Amberlyst39装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至90℃，反应压力0.1MPa。将反应物环己烯和乙酸分别进入反应器，乙酸与环己烯的摩尔比为4：1。环己烯的进料空速为1.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环己烯转化率为81.9％，乙酸环己酯选择性98.8％。
将加成反应产物精馏得到纯度大于99.5％的乙酸环己酯。将该乙酸环己酯进一步进行氧化反应，具体反应步骤如下：将78.8g浓度为60％的硝酸加入250ml反应釜中，分别加入0.6g三水合硝酸铜和0.02g偏钒酸铵。将反应釜温度升至70℃。剧烈搅拌使催化剂溶解。在反应溶液中加入17.8g加成反应中得到的乙酸环己酯。搅拌反应40分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸环己酯的转化率为100％，己二酸收率94.2％，戊二酸收率6.5％，丁二酸收率0.4％。
实施例5
将60ml大孔强酸性离子交换树脂Amberlyst45装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至90℃，反应压力0.1MPa。将反应物环己烯和乙酸分别进入反应器，乙酸与环己烯的摩尔比为4：1。环己烯的进料空速为1.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。 环己烯转化率为83.2％，乙酸环己酯选择性98.9％。
将加成反应产物精馏得到纯度大于99.5％的乙酸环己酯。将该乙酸环己酯进一步进行氧化反应，具体反应步骤如下：将63.1g浓度为50％的硝酸加入250ml反应釜中，分别加入1.0g三水合硝酸铜和0.04g偏钒酸铵。将反应釜温度升至70℃。剧烈搅拌使催化剂溶解。在反应溶液中加入17.8g加成反应中得到的乙酸环己酯。搅拌反应40分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸环己酯的转化率为100％，己二酸收率93.1％，戊二酸收率6.0％，丁二酸收率0.4％。
实施例6
将60ml大孔强酸性离子交换树脂Amberlyst70装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至90℃，反应压力0.1MPa。将反应物环己烯和乙酸分别进入反应器，乙酸与环己烯的摩尔比为4：1。环己烯的进料空速为1.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环己烯转化率为82.6％，乙酸环己酯选择性98.5％。
将加成反应产物精馏得到纯度大于99.5％的乙酸环己酯。将该乙酸环己酯进一步进行氧化反应，具体反应步骤如下：将87.5g浓度为45％的硝酸加入250ml反应釜中，分别加入1.7g三水合硝酸铜和0.04g偏钒酸铵。将反应釜温度升至70℃。剧烈搅拌使催化剂溶解。在反应溶液中加入17.8g加成反应中得到的乙酸环己酯。搅拌反应60分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸环己酯的转化率为100％，己二酸收率95.1％，戊二酸收率4.5％，丁二酸收率0.3％。
实施例7
将60ml大孔强酸性离子交换树脂DA330装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至90℃，反应压力0.1MPa。将反应物环己烯和乙酸分别进入反应器，乙酸与环己烯的摩尔比为4：1。环己烯的进料空速为1.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环己烯转化率为84.5％，乙酸环己酯选择性98.5％。
将加成反应产物精馏得到纯度大于99.5％的乙酸环己酯。将该乙酸环己酯进一步进行氧化反应，具体反应步骤如下：将110.3g浓度为50％的硝酸加入250ml反应釜中，分别加入1.7g三水合硝酸铜和0.08g偏钒酸铵。将反应釜温度升至50℃。剧烈搅拌使催化剂溶解。在反应溶液中加入17.8g加成反应中得到的乙酸环己酯。搅拌反应60分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。 乙酸环己酯的转化率为100％，己二酸收率96.5％，戊二酸收率3.0％，丁二酸收率0.2％。
实施例8
将60ml大孔强酸性离子交换树脂DNW-II装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至90℃，反应压力0.1MPa。将反应物环己烯和乙酸分别进入反应器，乙酸与环己烯的摩尔比为4：1。环己烯的进料空速为1.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环己烯转化率为83.1％，乙酸环己酯选择性98.4％。
将加成反应产物精馏得到纯度大于99.5％的乙酸环己酯。将该乙酸环己酯进一步进行氧化反应，具体反应步骤如下：将110.3g浓度为50％的硝酸加入250ml反应釜中，分别加入2.5g三水合硝酸铜和0.1g偏钒酸铵。将反应釜温度升至40℃。剧烈搅拌使催化剂溶解。在反应溶液中加入17.8g加成反应中得到的乙酸环己酯。搅拌反应60分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸环己酯的转化率为100％，己二酸收率96.6％，戊二酸收率2.6％，丁二酸收率0.3％。
实施例9
将60ml大孔强酸性离子交换树脂D005装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至90℃，反应压力0.1MPa。将反应物环己烯和乙酸分别进入反应器，乙酸与环己烯的摩尔比为4：1。环己烯的进料空速为1.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环己烯转化率为85.2％，乙酸环己酯选择性98.2％。
将加成反应产物精馏得到纯度大于99.5％的乙酸环己酯。将该乙酸环己酯进一步进行氧化反应，具体反应步骤如下：将110.3g浓度为50％的硝酸加入250ml反应釜中，分别加入2.5g三水合硝酸铜和0.1g偏钒酸铵。将反应釜温度升至60℃。剧烈搅拌使催化剂溶解。在反应溶液中加入17.8g加成反应中得到的乙酸环己酯。搅拌反应40分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸环己酯的转化率为100％，己二酸收率96.1％，戊二酸收率3.0％，丁二酸收率0.3％。
实施例10
将60ml大孔强酸性离子交换树脂HNV-8装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至90℃，反应压力0.1MPa。将反应物环己烯和乙酸分别进入反应器，乙酸与环己烯的摩尔比为4：1。环己烯的进料空速为1.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环 己烯转化率为84.6％，乙酸环己酯选择性98.3％。
将加成反应产物精馏得到纯度大于99.5％的乙酸环己酯。将该乙酸环己酯进一步进行氧化反应，具体反应步骤如下：将110.3g浓度为50％的硝酸加入250ml反应釜中，分别加入2.5g三水合硝酸铜和0.1g偏钒酸铵。将反应釜温度升至80℃。剧烈搅拌使催化剂溶解。在反应溶液中加入17.8g加成反应中得到的乙酸环己酯。搅拌反应30分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸环己酯的转化率为100％，己二酸收率95.1％，戊二酸收率3.6％，丁二酸收率0.4％。
实施例11
将60ml负载型磷钨酸催化剂HPW/SiO 2装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至100℃，反应压力2.0MPa。将反应物环己烯和乙酸分别进入反应器，乙酸与环己烯的摩尔比为4：1。环己烯的进料空速为1.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环己烯转化率为80.7％，乙酸环己酯选择性97.8％。
将加成反应产物精馏得到纯度大于99.5％的乙酸环己酯。将该乙酸环己酯进一步进行氧化反应，具体反应步骤如下：将110.3g浓度为50％的硝酸加入250ml反应釜中，分别加入2.5g三水合硝酸铜和0.1g偏钒酸铵。将反应釜温度升至90℃。剧烈搅拌使催化剂溶解。在反应溶液中加入17.8g加成反应中得到的乙酸环己酯。搅拌反应30分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸环己酯的转化率为100％，己二酸收率93.3％，戊二酸收率4.1％，丁二酸收率0.6％。
实施例12
将60ml负载型磷钼酸催化剂HPM/SiO 2装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至100℃，反应压力2.0MPa。将反应物环己烯和乙酸分别进入反应器，乙酸与环己烯的摩尔比为4：1。环己烯的进料空速为1.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环己烯转化率为81.2％，乙酸环己酯选择性97.6％。
将加成反应产物精馏得到纯度大于99.5％的乙酸环己酯。将该乙酸环己酯进一步进行氧化反应，具体反应步骤如下：将110.3g浓度为50％的硝酸加入250ml反应釜中，分别加入2.5g三水合硝酸铜和0.1g偏钒酸铵。将反应釜温度升至100℃。剧烈搅拌使催化剂溶解。在反应溶液中加入17.8g加成反应中得到的乙酸环己酯。搅拌反应30分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。 乙酸环己酯的转化率为100％，己二酸收率92.1％，戊二酸收率4.6％，丁二酸收率0.7％。
实施例13
将60ml负载型硅钨酸催化剂HSW/SiO 2装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至120℃，反应压力2.0MPa。将反应物环己烯和乙酸分别进入反应器，乙酸与环己烯的摩尔比为4：1。环己烯的进料空速为1.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环己烯转化率为84.9％，乙酸环己酯选择性97.1％。
将加成反应产物精馏得到纯度大于99.5％的乙酸环己酯。将该乙酸环己酯进一步进行氧化反应，具体反应步骤如下：将110.3g浓度为50％的硝酸加入250ml反应釜中，分别加入2.5g三水合硝酸铜和0.1g偏钒酸铵。将反应釜温度升至120℃。剧烈搅拌使催化剂溶解。在反应溶液中加入17.8g加成反应中得到的乙酸环己酯。搅拌反应20分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸环己酯的转化率为100％，己二酸收率90.8％，戊二酸收率4.8％，丁二酸收率1.0％。
实施例14
将60ml负载型硅钼酸催化剂HSM/SiO 2装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至120℃，反应压力2.0MPa。将反应物环己烯和乙酸分别进入反应器，乙酸与环己烯的摩尔比为4：1。环己烯的进料空速为1.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环己烯转化率为85.4％，乙酸环己酯选择性96.9％。
将加成反应产物精馏得到纯度大于99.5％的乙酸环己酯。将该乙酸环己酯进一步进行氧化反应，具体反应步骤如下：将110.3g浓度为50％的硝酸加入250ml反应釜中，分别加入3.3g六水合硝酸钴和0.1g偏钒酸铵。将反应釜温度升至70℃。剧烈搅拌使催化剂溶解。在反应溶液中加入17.8g加成反应中得到的乙酸环己酯。搅拌反应40分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸环己酯的转化率为100％，己二酸收率91.2％，戊二酸收率6.1％，丁二酸收率1.5％。
实施例15
将60ml Hβ分子筛催化剂装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至80℃，反应压力0.1MPa。将反应物环己烯和乙酸分别进入反应器，乙酸与环己烯的摩尔比为4：1。环己烯的进料空速为1.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环己烯转化率为75.2％， 乙酸环己酯选择性98.2％。
将加成反应产物精馏得到纯度大于99.5％的乙酸环己酯。将该乙酸环己酯进一步进行氧化反应，具体反应步骤如下：将110.3g浓度为50％的硝酸加入250ml反应釜中，分别加入2.9g硝酸铁和0.1g偏钒酸铵。将反应釜温度升至70℃。剧烈搅拌使催化剂溶解。在反应溶液中加入17.8g加成反应中得到的乙酸环己酯。搅拌反应40分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸环己酯的转化率为100％，己二酸收率90.4％，戊二酸收率6.9％，丁二酸收率1.9％。
实施例16
将60ml HY分子筛催化剂装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至80℃，反应压力0.1MPa。将反应物环己烯和乙酸分别进入反应器，乙酸与环己烯的摩尔比为4：1。环己烯的进料空速为1.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环己烯转化率为62.3％，乙酸环己酯选择性98.4％。
将加成反应产物精馏得到纯度大于99.5％的乙酸环己酯。将该乙酸环己酯进一步进行氧化反应，具体反应步骤如下：将99.2g浓度为20％的双氧水加入250ml反应釜中，分别加入2.3g磷钼酸。将反应釜温度升至80℃。剧烈搅拌使催化剂溶解。在反应溶液中加入17.8g加成反应中得到的乙酸环己酯。搅拌反应60分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸环己酯的转化率为100％，己二酸收率85.6％，戊二酸收率9.8％，丁二酸收率2.3％。
实施例17
将60ml HZSM-5分子筛催化剂装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至80℃，反应压力0.1MPa。将反应物环己烯和乙酸分别进入反应器，乙酸与环己烯的摩尔比为4：1。环己烯的进料空速为1.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环己烯转化率为71.4％，乙酸环己酯选择性98.9％。
将加成反应产物精馏得到纯度大于99.5％的乙酸环己酯。将该乙酸环己酯进一步进行氧化反应，具体反应步骤如下：将99.2g浓度为20％的双氧水加入250ml反应釜中，分别加入3.8g钨酸铵。将反应釜温度升至80℃。剧烈搅拌使催化剂溶解。在反应溶液中加入17.8g加成反应中得到的乙酸环己酯。搅拌反应60分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸环己酯的转化率为 100％，己二酸收率82.1％，戊二酸收率10.4％，丁二酸收率3.6％。
实施例18
将60ml大孔强酸性离子交换树脂Amberlyst45装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至120℃，反应压力2.0MPa。将反应物环己烯和乙酸分别进入反应器，乙酸与环己烯的摩尔比为4：1。环己烯的进料空速为1.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环己烯转化率为85.5％，乙酸环己酯选择性98.1％。
将加成反应产物分离出未反应的环己烯，得到以乙酸和乙酸环己酯为主的混合物，其中乙酸与乙酸环己酯的摩尔比为3.7。将该乙酸/乙酸环己酯混合物进一步进行氧化反应，具体反应步骤如下：将110.3g浓度为50％的硝酸加入250ml反应釜中，分别加入2.5g三水合硝酸铜和0.1g偏钒酸铵。将反应釜温度升至70℃。剧烈搅拌使催化剂溶解。在反应溶液中加入45.7g上述乙酸/乙酸环己酯混合物。搅拌反应40分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸环己酯的转化率为100％，己二酸收率96.1％，戊二酸收率3.1％，丁二酸收率0.2％。
实施例19
将60ml大孔强酸性离子交换树脂DNW-II装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至140℃，反应压力2.0MPa。将反应物环己烯和乙酸分别进入反应器，乙酸与环己烯的摩尔比为6：1。环己烯的进料空速为2.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环己烯转化率为81.1％，乙酸环己酯选择性98.5％。
将加成反应产物分离出未反应的环己烯，得到以乙酸和乙酸环己酯为主的混合物，其中乙酸与乙酸环己酯的摩尔比为6.4。将该乙酸/乙酸环己酯混合物进一步进行氧化反应，具体反应步骤如下：将110.3g浓度为50％的硝酸加入250ml反应釜中，分别加入2.5g三水合硝酸铜和0.1g偏钒酸铵。将反应釜温度升至70℃。剧烈搅拌使催化剂溶解。在反应溶液中加入66.3g上述乙酸/乙酸环己酯混合物。搅拌反应40分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸环己酯的转化率为100％，己二酸收率96.4％，戊二酸收率3.0％，丁二酸收率0.1％。
实施例20
将60ml大孔强酸性离子交换树脂Amberlyst70装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至150℃，反应压力2.0MPa。 将反应物环己烯和乙酸分别进入反应器，乙酸与环己烯的摩尔比为6：1。环己烯的进料空速为3.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环己烯转化率为78.2％，乙酸环己酯选择性98.2％。
将加成反应产物精馏得到纯度为99.5％的乙酸环己酯。将该乙酸环己酯进一步进行氧化反应，具体反应步骤如下：将110.3g浓度为50％的硝酸加入250ml反应釜中，分别加入1.1g(NH 4) 6Mo 7O 24和0.1g偏钒酸铵。将反应釜温度升至70℃。剧烈搅拌使催化剂溶解。在反应溶液中加入17.8g加成反应中得到的乙酸环己酯。搅拌反应40分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸环己酯的转化率为100％，己二酸收率93.1％，戊二酸收率5.5％，丁二酸收率0.7％。
实施例21
将60ml负载三氯化铝的二氧化硅(AlCl 3-SiO2)催化剂装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至150℃，反应压力2.0MPa。将反应物环己烯和乙酸分别进入反应器，乙酸与环己烯的摩尔比为6：1。环己烯的进料空速为0.6g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环己烯转化率为50.3％，乙酸环己酯选择性97.6％。
将加成反应产物精馏得到纯度大于99.5％的乙酸环己酯。将该乙酸环己酯进一步进行氧化反应，具体反应步骤如下：将110.3g浓度为50％的硝酸加入250ml反应釜中，分别加入1.4g(NH 4) 2MoO 4和0.1g偏钒酸铵。将反应釜温度升至70℃。剧烈搅拌使催化剂溶解。在反应溶液中加入17.8g加成反应中得到的乙酸环己酯。搅拌反应40分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸环己酯的转化率为100％，己二酸收率93.4％，戊二酸收率5.2％，丁二酸收率0.7％。
实施例22
将60ml大孔强酸性离子交换树脂DA330装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至100℃，反应压力2MPa。将反应物环己烯和乙酸分别进入反应器，乙酸与环己烯的摩尔比为2：1。环己烯的进料空速为2.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环己烯转化率为76.5％，乙酸环己酯选择性98.6％。
将加成反应产物分离出未反应的环己烯，得到以乙酸和乙酸环己酯为主的混合物，其中乙酸与乙酸环己酯的摩尔比为1.6。将该乙酸/乙酸环己酯混合物进一步进行氧化反应，具体反应步骤如下：将110.3g浓度为50％的硝酸加入250ml反应釜中，分别加入 2.5g三水合硝酸铜和0.1g偏钒酸铵。将反应釜温度升至70℃。剧烈搅拌使催化剂溶解。在反应溶液中加入30.0g上述乙酸/乙酸环己酯混合物。搅拌反应40分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸环己酯的转化率为100％，己二酸收率96.9％，戊二酸收率2.7％，丁二酸收率0.1％。
实施例23
将60ml大孔强酸性离子交换树脂D 005装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至50℃，反应压力1.0MPa。将反应物环己烯和乙酸分别进入反应器，乙酸与环己烯的摩尔比为4：1。环己烯的进料空速为1.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环己烯转化率为67.2％，乙酸环己酯选择性98.2％。
将加成反应产物精馏得到纯度大于99.5％的乙酸环己酯。将该乙酸环己酯进一步进行氧化反应，具体反应步骤如下：将110.3g浓度为50％的硝酸加入250ml反应釜中，加入2.5g三水合硝酸铜。将反应釜温度升至70℃。剧烈搅拌使催化剂溶解。在反应溶液中加入17.8g加成反应中得到的乙酸环己酯。搅拌反应40分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸环己酯的转化率为100％，己二酸收率83.3％，戊二酸收率12.4％，丁二酸收率2.5％。
实施例24
将60ml大孔强酸性离子交换树脂Amberlyst45装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至80℃，反应压力0.1MPa。将反应物环己烯和乙酸分别进入反应器，乙酸与环己烯的摩尔比为0.5：1。环己烯的进料空速为0.8g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环己烯转化率为39.6％，乙酸环己酯选择性98.6％。
将加成反应产物精馏得到纯度大于99.5％的乙酸环己酯。将该乙酸环己酯进一步进行氧化反应，具体反应步骤如下：将110.3g浓度为50％的硝酸加入250ml反应釜中，加入0.1g偏钒酸铵。将反应釜温度升至70℃。剧烈搅拌使催化剂溶解。在反应溶液中加入17.8g加成反应中得到的乙酸环己酯。搅拌反应40分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸环己酯的转化率为100％，己二酸收率81.2％，戊二酸收率13.5％，丁二酸收率2.6％。
实施例25
将60ml大孔强酸性离子交换树脂Amberlyst45装入不锈钢管式固定床反应器的中 部，催化剂的上下分别用石英砂填充。将反应器温度升至80℃，反应压力0.1MPa。将反应物环己烯和乙酸分别进入反应器，乙酸与环己烯的摩尔比为0.2：1。环己烯的进料空速为0.6g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环己烯转化率为17.5％，乙酸环己酯选择性98.7％。
将加成反应产物精馏得到纯度大于99.5％的乙酸环己酯。将该乙酸环己酯进一步进行氧化反应，具体反应步骤如下：将110.3g浓度为50％的硝酸加入250ml反应釜中，分别加入2.5g三水合硝酸铜和0.1g偏钒酸铵。将反应釜温度升至70℃。剧烈搅拌使催化剂溶解。在反应溶液中加入17.8g加成反应中得到的乙酸环己酯。搅拌反应40分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸环己酯的转化率为100％，己二酸收率96.7％，戊二酸收率2.7％，丁二酸收率0.1％。
实施例26
将60ml大孔强酸性离子交换树脂DNW-II装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至80℃，反应压力0.1MPa。将反应物环戊烯和乙酸分别进入反应器，乙酸与环戊烯的摩尔比为4：1。环戊烯的进料空速为1.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环戊烯转化率为81.2％，乙酸环戊酯选择性98.2％。
将加成反应产物精馏得到纯度大于99.5％的乙酸环戊酯。将该乙酸环戊酯进一步进行氧化反应，具体反应步骤如下：将110.3g浓度为50％的硝酸加入250ml反应釜中，分别加入2.5g三水合硝酸铜和0.1g偏钒酸铵。将反应釜温度升至70℃。剧烈搅拌使催化剂溶解。在反应溶液中加入16.0g加成反应中得到的乙酸环戊酯。搅拌反应40分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸环戊酯的转化率为100％，戊二酸收率96.7％，丁二酸收率2.9％。
实施例27
将60ml大孔强酸性离子交换树脂Amberlyst45装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至80℃，反应压力0.1MPa。将反应物环己烯和乙酸混合进入反应器，乙酸与环己烯的摩尔比为10：1。环己烯的进料空速为1.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环己烯转化率为96.4％，己二酸二环己酯选择性98.3％。
将加成反应产物精馏得到纯度大于99.5％的乙酸环己酯。将该乙酸环己酯进一步进行氧化反应，具体反应步骤如下：将78.8g浓度为50％的硝酸加入250ml反应釜中，分 别加入0.96g三水合硝酸铜和0.07g偏钒酸铵。将反应釜温度升至70℃。剧烈搅拌使催化剂溶解。在反应溶液中加入17.8g加成反应中得到的乙酸环己酯。搅拌反应40分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸环己酯的转化率为100％，己二酸收率96.5％，戊二酸收率2.9％，丁二酸收率0.4％。
实施例28
将60ml大孔强酸性离子交换树脂Amberlyst45装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至100℃，反应压力0.1MPa。将反应物环庚烯和甲酸分别进入反应器，甲酸与环庚烯的摩尔比为4：1。环庚烯的进料空速为1.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环庚烯转化率为85.3％，甲酸环庚酯选择性98.5％。
将加成反应产物精馏得到纯度大于99.5％的甲酸环庚酯。将该甲酸环庚酯进一步进行氧化反应，具体反应步骤如下：将110.3g浓度为50％的硝酸加入250ml反应釜中，分别加入2.5g三水合硝酸铜和0.1g偏钒酸铵。将反应釜温度升至70℃。剧烈搅拌使催化剂溶解。在反应溶液中加入17.8g加成反应中得到的甲酸环庚酯。搅拌反应40分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。甲酸环庚酯的转化率为100％，庚二酸收率95.6％，己二酸收率3.4％，戊二酸收率0.5％。
实施例29
将60ml大孔强酸性离子交换树脂Amberlyst45装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至100℃，反应压力0.1MPa。将反应物环己烯和丙稀酸分别进入反应器，丙稀酸与环己烯的摩尔比为4：1。环己烯的进料空速为1.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环己烯转化率为84.3％，丙稀酸环己酯选择性98.6％。
将加成反应产物精馏得到纯度大于99.5％的丙稀酸环己酯。将该丙稀酸环己酯进一步进行氧化反应，具体反应步骤如下：将110.3g浓度为50％的硝酸加入250ml反应釜中，分别加入2.5g三水合硝酸铜和0.1g偏钒酸铵。将反应釜温度升至70℃。剧烈搅拌使催化剂溶解。在反应溶液中加入19.3g加成反应中得到的丙稀酸环己酯。搅拌反应40分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。丙稀酸环己酯的转化率为100％，己二酸收率95.1％，戊二酸收率3.5％，丁二酸收率0.6％。
实施例30
将60ml大孔强酸性离子交换树脂Amberlyst45装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至100℃，反应压力0.1MPa。将反应物环己烯和三氟乙酸分别进入反应器，三氟乙酸与环己烯的摩尔比为4：1。环己烯的进料空速为1.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。环己烯转化率为86.3％，三氟乙酸环己酯选择性98.5％。
将加成反应产物精馏得到纯度大于99.5％的三氟乙酸环己酯。将该三氟乙酸环己酯进一步进行氧化反应，具体反应步骤如下：将110.3g浓度为50％的硝酸加入250ml反应釜中，分别加入2.5g三水合硝酸铜和0.1g偏钒酸铵。将反应釜温度升至70℃。剧烈搅拌使催化剂溶解。在反应溶液中加入24.5g加成反应中得到的三氟乙酸环己酯。搅拌反应40分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。三氟乙酸环己酯的转化率为100％，己二酸收率95.8％，戊二酸收率3.3％，丁二酸收率0.1％。
实施例31
将60ml大孔强酸性离子交换树脂Amberlyst45装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至100℃，反应压力0.1MPa。将反应物3-氯代环己烯和乙酸混合进入反应器，乙酸与氯代环己烯的摩尔比为4：1。3-氯代环己烯的进料空速为1.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。氯代环己烯转化率为80.1％，乙酸氯代环己酯选择性98.1％。
将加成反应产物精馏得到纯度大于99.5％的乙酸氯代环己酯。将该乙酸氯代环己酯进一步进行氧化反应，具体反应步骤如下：将110.3g浓度为50％的硝酸加入250ml反应釜中，分别加入2.5g三水合硝酸铜和0.1g偏钒酸铵。将反应釜温度升至70℃。剧烈搅拌使催化剂溶解。在反应溶液中加入22.1g加成反应中得到的乙酸氯代环己酯。搅拌反应40分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸氯代环己酯的转化率为100％，氯代己二酸收率96.2％，戊二酸收率3.0％，丁二酸收率0.1％。
实施例32
将60ml大孔强酸性离子交换树脂Amberlyst45装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至100℃，反应压力0.1MPa。将反应物甲基环己烯和乙酸混合进入反应器，乙酸与甲基环己烯的摩尔比为4：1。甲基 环己烯的进料空速为1.0g·g -1·h -1。反应连续运转250小时。反应产物收集后，用气相色谱分析产物组成。甲基环己烯转化率为83.2％，乙酸甲基环己酯选择性98.5％。
将加成反应产物精馏得到纯度大于99.5％的乙酸甲基环己酯。将该乙酸甲基环己酯进一步进行氧化反应，具体反应步骤如下：将110.3g浓度为50％的硝酸加入250ml反应釜中，分别加入2.5g三水合硝酸铜和0.1g偏钒酸铵。将反应釜温度升至70℃。剧烈搅拌使催化剂溶解。在反应溶液中加入19.5g加成反应中得到的乙酸甲基环己酯。搅拌反应40分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸甲基环己酯的转化率为100％，甲基己二酸收率96.4％，戊二酸收率2.9％，丁二酸收率0.1％。
实施例33
将10ml大孔强酸性离子交换树脂Amberlyst45装入不锈钢反应釜中，然后在反应釜中加入20g环己烯和56g乙酸。反应釜密封后，将温度升至100℃。持续加热搅拌4小时后停止反应。然后将反应釜温度降至室温。取出反应产物，用气相色谱分析产物组成。环己烯转化率为91.2％，乙酸环己酯选择性98.2％。
将加成反应产物精馏得到纯度大于99.5％的乙酸环己酯。将该乙酸环己酯进一步进行氧化反应，具体反应步骤如下：将78.8g浓度为50％的硝酸加入250ml反应釜中，分别加入0.48g三水合硝酸铜和0.07g偏钒酸铵。将反应釜温度升至60℃。剧烈搅拌使催化剂溶解。在反应溶液中加入17.8g加成反应中得到的乙酸环己酯。搅拌反应60分钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸环己酯的转化率为100％，己二酸收率96.1％，戊二酸收率3.1％，丁二酸收率0.5％。
实施例34
将60ml大孔强酸性离子交换树脂Amberlyst45装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至90℃，反应压力0.1MPa。将反应物环己烯和乙酸分别进入反应器，乙酸与环己烯的摩尔比为4：1。环己烯的进料空速为1.0g·g -1·h -1。反应连续运转1000小时。反应产物收集后，用气相色谱分析产物组成。环己烯转化率83％-84％，乙酸环己酯选择性98％-99％。反应结果如图1。
将加成反应产物精馏得到纯度大于99.5％的乙酸环己酯。将该乙酸环己酯进一步进行氧化反应，具体反应步骤如下：将110.3g浓度为50％的硝酸加入250ml反应釜中，分别加入2.5g三水合硝酸铜和0.1g偏钒酸铵。将反应釜温度升至70℃。剧烈搅拌使催化剂溶解。在反应溶液中加入17.8g加成反应中得到的乙酸环己酯。搅拌反应40分 钟。然后将反应釜温度降至室温，停止反应。反应得到的产物用液相色谱分析产物组成。乙酸环己酯的转化率为100％，己二酸收率96.8％，戊二酸收率2.6％，丁二酸收率0.1％。
对比例1
将60ml大孔强酸性离子交换树脂Amberlyst45装入不锈钢管式固定床反应器的中部，催化剂的上下分别用石英砂填充。将反应器温度升至90℃，反应压力0.1MPa。将反应物环己烯和己酸分别进入反应器，己酸与环己烯的摩尔比为4：1。环己烯的进料空速为1.0g·g -1·h -1。反应连续运转24小时。反应产物收集后，用气相色谱分析产物组成。环己烯转化率为64.1％，己酸环己酯选择性98.1％。是用己酸为反应物，加成反应的转化率显著低于相同条件下实施例5。
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。

Claims (16)

  1. 一种二元羧酸的制备方法，其特征在于，所述方法包括如下步骤：
    1)使含有环状烯烃和低级一元羧酸的原料体系在加成催化剂的存在下发生加成反应，生成含有羧酸环酯的中间产物体系；
    2)使所述含有羧酸环酯的中间产物体系在氧化剂和氧化催化剂的存在下发生开环氧化反应，生成相应二元羧酸产物。
  2. 根据权利要求1所述的二元羧酸的制备方法，其特征在于，所述环状烯烃含有五个及以上碳原子并且含有一个碳碳双键结构。
  3. 根据权利要求1所述的二元羧酸的制备方法，其特征在于，所述环状烯烃选自具有式I所示化学式的化合物、式II所示化学式的化合物、式III所示化学式的化合物、式IV所示化学式的化合物中的至少一种：
    Figure PCTCN2018093445-appb-100001
    其中，式I中的R 101、R 102、R 103、R 104、R 105、R 106、R 107、R 108分别独立地选自H、C 1～C 3的烃基、卤族元素或C 1～C 3的卤代烃基；
    式II中的R 201、R 202、R 203、R 204、R 205、R 206、R 207、R 208、R 209、R 210分别独立地选自H、C 1～C 3的烃基、卤族元素或C 1～C 3的卤代烃基；
    式III中的R 301、R 302、R 303、R 304、R 305、R 306、R 307、R 308、R 309、R 310、R 311、R 312 分别独立地选自H、C 1～C 3的烃基、卤族元素或C 1～C 3的卤代烃基；
    式IV中的R 401、R 402、R 403、R 404、R 405、R 406、R 407、R 408、R 409、R 410、R 411、R 412、R 413、R 414分别独立地选自H、C 1～C 3的烃基、卤族元素或C 1～C 3的卤代烃基。
  4. 根据权利要求1所述的二元羧酸的制备方法，其特征在于，所述低级一元羧酸选自具有式V所示化学式的化合物中的至少一种：
    Figure PCTCN2018093445-appb-100002
    其中，R 501选自H、C 1～C 3的烃基或C 1～C 3的卤代烃基。
  5. 根据权利要求1所述的二元羧酸的制备方法，其特征在于，步骤1)中所述加成催化剂含有负载型无机酸、阳离子交换树脂和分子筛中的至少一种。
  6. 根据权利要求5所述的二元羧酸的制备方法，其特征在于，所述负载型无机酸中的无机酸选自硫酸氢钠、磷酸氢钠、AlCl 3和杂多酸中的至少一种，所述负载型无机酸中的载体选自二氧化硅、硅藻土和高岭土中的至少一种；所述负载型无机酸中无机酸的重量百分含量为5～25％。
  7. 根据权利要求5所述的二元羧酸的制备方法，其特征在于，所述阳离子交换树脂为磺酸型强酸性大孔离子交换树脂，其酸强度的Hammett指数H 0<-10，离子交换树脂H +交换容量在1.0mmol/L以上；
    所述分子筛选自拓扑结构为FAU、BEA、MFI的HY、Hβ和HZSM-5分子筛中的至少一种；以NH 3化学吸附测定衡量，所述分子筛的弱酸中心密度为0.005-0.35mmol/g、中等强度酸中心密度为0.01-0.5mmol/g、强酸中心密度为0.003-0.15mmol/g。
  8. 根据权利要求1所述的二元羧酸的制备方法，其特征在于，所述低级一元羧酸和所述环状烯烃的摩尔比值为0.2-10.0，所述环状烯烃的进料空速为0.6-3.0g·g -1·h -1。
  9. 根据权利要求1所述的二元羧酸的制备方法，其特征在于，所述加成反应在一个或者多个反应器中进行，所述反应器选自固定床反应器、釜式反应器中的至少一种。
  10. 根据权利要求1所述的二元羧酸的制备方法，其特征在于，所述加成反应的条件为压力0.1-2.0MPa、反应温度50-150℃。
  11. 根据权利要求1所述的二元羧酸的制备方法，其特征在于，步骤2)中所述氧 化反应的反应条件为：反应温度40-120℃、反应压力0.1-0.5MPa。
  12. 根据权利要求1所述的二元羧酸的制备方法，其特征在于，步骤2)中所述氧化剂选自HNO 3、亚硝酸盐、双氧水中的至少一种。
  13. 根据权利要求1所述的二元羧酸的制备方法，其特征在于，步骤2)中所述氧化催化剂选自NH 4VO 3、Cu(NO 3) 2、Co(NO 3) 2、Fe(NO 3) 3、钼酸铵、钨酸铵和杂多酸中的至少一种。
  14. 根据权利要求1所述的二元羧酸的制备方法，其特征在于，步骤2)中所述氧化剂和羧酸环酯的摩尔比为：
    氧化剂：羧酸环酯＝(3～15)：1；
    氧化催化剂的加入量满足：加入所述氧化催化剂后，氧化反应体系中的每种氧化催化剂的质量浓度分别为0.01-1.0％。
  15. 根据权利要求1所述的二元羧酸的制备方法，其特征在于，所述含有羧酸环酯的中间产物体系为加成反应结束后的混合体系或仅为羧酸环酯。
  16. 根据权利要求1所述的二元羧酸的制备方法，其特征在于，还包括步骤3)：
    3)所述开环氧化反应结束后，分离得到产物中的低级一元羧酸循环至步骤1)中所述加成反应的原料中循环使用。
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