阅读说明：本技术 一种酶法制备环氧烷烃的工艺 (Process for preparing epoxyalkane by enzyme method ) 是由 汪昌国 苏桂珍 其他发明人请求不公开姓名 于 2019-11-01 设计创作，主要内容包括：本发明涉及环氧烷烃制备领域,公开了一种酶法制备环氧烷烃的工艺,解决了传统制备方法中使用大量的有机溶剂,生产过程中存在较大安全风险,对环境污染较大等问题,其技术方案要点是在烯烃中加入氧化剂、催化剂以及助剂,在35℃～65℃下混合搅拌反应,再进行过滤分层,将分层得到的有机层进行减压蒸馏后得到1,2-环氧烷烃,助剂包括长链脂肪酸,达到不采用有机溶剂,便可以高效的制备出环氧烷烃的效果。(The invention relates to the field of preparation of alkylene oxide, and discloses a process for preparing alkylene oxide by an enzyme method, which solves the problems that a large amount of organic solvent is used in the traditional preparation method, the production process has higher safety risk, the environmental pollution is higher and the like.)

1. A process for preparing epoxy alkane by an enzyme method is characterized in that: adding an oxidant, a catalyst and an auxiliary agent into olefin, wherein the auxiliary agent comprises long-chain fatty acid, mixing and stirring for reaction at the temperature of 35-65 ℃, filtering and layering, and carrying out reduced pressure distillation on an organic layer obtained by layering to obtain the 1, 2-epoxyalkane.

2. The process for preparing alkylene oxide by enzyme method according to claim 1, which is characterized in that: the oxidant comprises carbamide peroxide or aqueous hydrogen peroxide solution with the concentration of 20-50%, wherein the molar ratio of the olefin to the oxidant is 1: 1.0-2.5.

3. The process for preparing alkylene oxide by enzyme method according to claim 2, which is characterized in that: the preferable molar ratio of the olefin to the oxidant is 1: 1.2-2.

4. The process for preparing alkylene oxide by enzyme method according to claim 1, which is characterized in that: the catalyst comprises lipase, and the ratio of the mass of the lipase to the mass of the olefin is 2-150%.

5. The process for preparing alkylene oxide by enzyme method according to claim 4, wherein: the preferable ratio of the mass of the lipase to the mass of the olefin is 10% -80%.

6. The process for preparing alkylene oxide by enzyme method according to claim 1, which is characterized in that: the ratio of the mass of the long-chain fatty acid to the mass of the olefin is 5-150%.

7. The process for preparing alkylene oxide by enzyme method according to claim 6, wherein: the preferable ratio of the mass of the long-chain fatty acid to the mass of the olefin is 10-70%.

8. The process for preparing alkylene oxide by enzyme method according to claim 1, which is characterized in that: the 1, 2-alkylene oxide has the structure:wherein R1 is CnH2n +1, and n = 3-18.

9. The process for preparing alkylene oxide by enzyme method according to claim 8, wherein: the alkene is a 1-alkene with a carbon chain length corresponding to the corresponding 1, 2-alkylene oxide.

10. The process for preparing alkylene oxide by enzyme method according to claim 1, which is characterized in that: the molecular formula of the long-chain fatty acid is CmH2m +1COOH, wherein m is 8-18.

Technical Field

The invention relates to the field of preparation of alkylene oxide, and more particularly relates to a process for preparing alkylene oxide by an enzymatic method.

Background

The epoxy alkane is cyclic ether with a structure of-C, and the epoxide has high reaction activity due to the existence of ring tension, is an organic chemical raw material and a synthetic intermediate with wide application, is a raw material for synthesizing beta-halohydrin, 1, 2-diol, beta-hydroxylamine, polyether and higher alcohol, is an important intermediate for organic synthesis, and is widely applied to the fields of organic synthesis, fine chemical engineering, material science and the like;

in the prior art, chemical methods for preparing alkylene oxide mainly comprise a peracid method, a halohydrin method and an indirect oxidation method, and have the defects of complex process, high production cost, high safety risk of using a large amount of organic solvent and environment-friendliness of a large amount of waste water;

also enzymatic catalytic epoxidation reactions can be used for the preparation of alkylene oxides. Compared with the traditional chemical method, the enzyme catalysis synthesis compound has the advantages of mild reaction condition, good selectivity, environmental friendliness and the like. The method for preparing 1, 2-alkylene oxide by an enzyme method mainly uses an enzyme catalyst to catalyze olefin, uses lipase Nov435 as a catalyst and urea peroxide as an oxidant by people such as Horacio F.Oliva (Green chem.,2006,8,923-936) and the like, and epoxidizes styrene in the presence of an organic solvent, wherein the reaction time is 161h, and the yield is 73%. Moreira et al (synthetic communications,2005,35: 2107-. In the methods, a large amount of organic solvent is used to promote reaction conversion, a great safety risk exists in the production process, VOC has environmental pollution, and meanwhile, the reaction concentration is reduced due to the large amount of the solvent, so that the production efficiency is reduced, and the defects of high production cost and the like are caused.

Disclosure of Invention

The invention aims to provide a process for preparing alkylene oxide by an enzyme method, which can achieve the effect of efficiently preparing the alkylene oxide without adopting an organic solvent.

The technical purpose of the invention is realized by the following technical scheme: a process for preparing epoxy alkane by enzyme method includes adding oxidant, catalyst and assistant to olefin, mixing and stirring for reaction at 35-65 deg.C, filtering for layering, and vacuum distilling the layered organic layer to obtain 1, 2-epoxy alkane.

In a preferable embodiment of the invention, the oxidant comprises carbamide peroxide or aqueous hydrogen peroxide solution with the concentration of 20-50%, wherein the molar ratio of the olefin to the oxidant is 1: 1.0-2.5; further, the preferable molar ratio of the olefin to the oxidant is 1: 1.2-2.

In a preferred embodiment of the present invention, the catalyst comprises lipase, the ratio of the mass of lipase to the mass of olefin is 2% to 150%, and further, the preferred ratio of the mass of lipase to the mass of olefin is 10% to 80%.

In a preferred embodiment of the present invention, the ratio of the mass of the long-chain fatty acid to the mass of the olefin is 5 to 150%, and the preferred ratio of the mass of the long-chain fatty acid to the mass of the olefin is 10 to 70%.

As a preferred embodiment of the present invention, the 1, 2-alkylene oxide has the structure:wherein R1 is CnH2n +1, and n is 3-18; the alkene is a 1-alkene with a carbon chain length corresponding to the corresponding 1, 2-alkylene oxide.

The preferable scheme of the invention is that the molecular formula of the long-chain fatty acid is CmH2m +1COOH, wherein m is 8-18.

In conclusion, the invention has the following beneficial effects: the preparation process does not adopt an organic solvent, so that higher conversion rate and higher selectivity can be obtained, the safety and environmental protection risks caused by the organic solvent are avoided, more raw materials can be contained in the equipment due to the reduction of the participation of the organic solvent, the utilization rate of the equipment is greatly improved, the large-scale production is easier to realize, and the production cost is lower.

Detailed Description

The following is a further detailed description of the present invention.

A process for preparing epoxy alkane by enzyme method includes adding oxidant, catalyst and assistant into alkene, mixing and stirring at 35-65 deg.C for reaction, filtering for layering, vacuum distilling the layered organic layer to obtain 1, 2-epoxy alkane, recovering unreacted raw material and long-chain fatty acid, and recovering raw material and assistant.

The 1, 2-alkylene oxide has the structure:wherein R1 is CnH2n +1, n is 3-18, the alkene is 1-alkene, and the carbon chain length corresponds to the corresponding 1, 2-alkylene oxide.

The oxidant comprises carbamide peroxide or aqueous hydrogen peroxide solution with the concentration of 20-50%, wherein the molar ratio of the olefin to the oxidant is 1: 1.0-2.5, and further, the preferable molar ratio of the olefin to the oxidant is 1: 1.2-2.

The catalyst comprises Lipase, the Lipase is triacylglycerol hydrolase, the Lipase is an enzyme capable of hydrolyzing long-chain fatty glyceride into diglyceride, monoglyceride, glycerol and fatty acid, the ratio of the mass of the Lipase to the mass of olefin is 2-150%, further, the preferable ratio of the mass of the Lipase to the mass of the olefin is 10-80%, according to the enzyme dynamics principle, the low proportion of the catalyst is low in catalytic efficiency and high in enzyme dosage, the catalytic efficiency is high but the cost is high, and the economy is poor, so the dosage of the catalyst is selected according to the actual requirement in the actual production preparation, in the actual production, the Lipase can adopt commercial enzyme and engineering enzyme, the commercial enzyme can adopt Candida sp.99-125, Nov435, Lipase AY30G and the like, the Lipase is widely distributed in animals, plants and microorganisms, the preparation is easy, and the economy is higher;

the auxiliary agent comprises long-chain fatty acid, the molecular formula of the long-chain fatty acid is CmH2m +1COOH, wherein m is 8-18, the ratio of the mass of the long-chain fatty acid to the mass of olefin is 5-150%, further, the preferable ratio of the mass of the long-chain fatty acid to the mass of the olefin is 10-70%, the long-chain fatty acid can be capric acid, lauric acid, myristic acid, palmitic acid and isostearic acid, the fatty acid is usually derived from plants, animals and synthesis, and the derived fatty acid of vegetable oil is more common, economical and practical.

What needs to be explained in the present invention is: the long-chain fatty acid is used as an auxiliary agent, the conversion from olefin to an epoxy compound can be realized under the condition of not using an organic solvent or other special solvents, the safety risk caused by using the organic solvent can be avoided, the reaction concentration is improved, the production cost is reduced, the advantages are very obvious, the olefin epoxidation selectivity is very high, the subsequent separation is simple, and the method is very beneficial to improving the production efficiency and reducing the production cost;

the long-chain fatty acid generates peroxy acid under the action of aqueous hydrogen peroxide, and then oxidizes olefin, and meanwhile, the long-chain fatty acid not only has a cocatalyst effect, but also has an emulsification effect because a hydrophobic chain and a hydrophilic end exist in the structure, and the emulsification effect can be generated when the hydrophobic chain is long enough. Because olefin and hydrogen peroxide are oil-water two-phase systems, a large amount of solvent or similar cosolvent is needed to improve the dispersion sufficiency of two phases, and better reaction conversion rate can be realized. The long-chain fatty acid can play an emulsification role in a system to promote the area of an oil-water interface to be greatly increased, the lipase catalytic reaction has a unique interface activation role, the reaction is usually generated on the oil-water interface, and the catalytic efficiency of the interface activation role is higher than that of the lipase catalytic reaction in a water phase or an oil phase, so that the long-chain fatty acid can promote the lipase to catalyze and realize higher reaction conversion rate.

Detailed description of the preferred embodiment 1

100g (0.089mol) of octene and 250g of 30% H2O2(0.17mol) were added to a reaction flask, and 50g of novacin NOV435 lipase and 100g of lauric acid were added, stirred at 50 ℃ for 40H, and the conversion was 83% and the selectivity was 99% by gas chromatography. Filtering to remove enzyme, recovering enzyme, standing for layering, and distilling organic layer to obtain raw materials including octene, 1, 2-epoxyoctane and lauric acid, and recovering octene and lauric acid for reuse.

Specific example 2

75g (0.089mol) of hexene and 80g of 50% H2O2(0.12mol) were added to a reaction flask, and 50g of Candida sp.99-125, 20g of decanoic acid were added and stirred at 60 ℃ for 48H, with a conversion of 76% and a selectivity of 98% by gas chromatography. The layers were separated by filtration and the organic phase was distilled to give the product 1,2 epoxyhexane.

Specific example 3

252g (0.095mol) octene and 200g carbamide peroxide (0.17mol)200g water were added to a reaction flask, and 25g novicent NOV435 lipase, 30g decanoic acid were added, stirred at 40 ℃ for 30h, and tested by gas chromatography with 53% conversion and 99% selectivity. Filtering, layering and distilling the organic phase to obtain the product 1, 2-epoxyoctane.

Specific example 4

100g (0.089mol) of octene and 150g of 30% H2O2(0.13mol) were added to a reaction flask, 10g of Novovin NOV435 lipase and 60g of stearic acid were added, and the mixture was stirred at 63 ℃ for 24 hours, and the conversion was 56% and the selectivity was 98% by gas chromatography. Filtering, layering and distilling the organic phase to obtain the product 1, 2-epoxyoctane.

Specific example 5

100g (0.089mol) of hexene and 150g of 30% H2O2(0.13mol) were added to a reaction flask, and 50g of Novovin NOV435 lipase, 20g of capric acid, 20g of stearic acid were stirred at 50 ℃ for 48H, with a conversion of 76% and a selectivity of 99% by gas chromatography. The layers were separated by filtration and the organic phase was distilled to give the product 1,2 epoxyhexane.

Specific example 6

100g (0.089mol) of hexene and 150g of 30% strength H2O2(0.13mol) were added to the reaction flask, and 120g of lipase Candida sp.99-125, 40g of myristic acid were added, stirred at 50 ℃ for 24H, and the conversion was 70% and the selectivity was 99% by gas chromatography. The layers were separated by filtration and the organic phase was distilled to give the product 1,2 epoxyhexane.

In conclusion, the preparation process does not adopt an organic solvent, so that higher conversion rate and higher selectivity can be obtained, the safety and environmental protection risks caused by the organic solvent are avoided, and the participation of the organic solvent is reduced, so that more raw materials can be contained in the equipment, the utilization rate of the equipment is greatly improved, the large-scale production is easier to realize, and the production cost is lower.

The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.