WO2019196681A1 - 一种氯丙烯直接环氧化制备环氧氯丙烷的工艺、改性杂多酸固载化催化剂及制备方法 - Google Patents

一种氯丙烯直接环氧化制备环氧氯丙烷的工艺、改性杂多酸固载化催化剂及制备方法 Download PDF

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WO2019196681A1
WO2019196681A1 PCT/CN2019/080417 CN2019080417W WO2019196681A1 WO 2019196681 A1 WO2019196681 A1 WO 2019196681A1 CN 2019080417 W CN2019080417 W CN 2019080417W WO 2019196681 A1 WO2019196681 A1 WO 2019196681A1
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chloropropene
epichlorohydrin
reaction
hydrogen peroxide
catalyst
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PCT/CN2019/080417
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English (en)
French (fr)
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黄杰军
徐林
丁克鸿
顾咸建
徐志斌
徐文轩
张晓谕
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江苏扬农化工集团有限公司
江苏瑞祥化工有限公司
江苏瑞恒新材料科技有限公司
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Priority to JP2021504564A priority Critical patent/JP7061227B2/ja
Publication of WO2019196681A1 publication Critical patent/WO2019196681A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals

Definitions

  • the invention relates to a process for preparing epichlorohydrin by direct epoxidation of chloropropene, a modified heteropolyacid catalyzed catalyst and a preparation method thereof, and more particularly to a modified heteropolyacid solid of chloropropene.
  • Epichlorohydrin is an important petrochemical product used primarily in the production of epoxy resins and synthetic glycerin.
  • the industrial synthesis methods of epichlorohydrin mainly include acrylic acid propylene ester method, propylene method and glycerin method, and the propylene method is further divided into a chlorohydrin method and a direct epoxidation method.
  • the propylene acetate method, the glycerol method and the chlorohydrin method are both dichloropropanol and then saponified and cyclized to form epichlorohydrin. Both processes bring a large amount of wastewater containing calcium chloride, and more and more Not suitable for the development of green chemistry.
  • scientists have studied the direct epoxidation of chloropropene to produce epichlorohydrin.
  • the commonly used catalysts are mainly titanium silicalite and heteropolyacid salts.
  • CN1769277A discloses a process for producing epichlorohydrin, which uses titanium silicalite as a catalyst to continuously add liquid phase or gas phase chloropropene and hydrogen peroxide to a special spiral channel type rotary bed or rotary packed bed supergravity reactor.
  • the epichlorohydrin is prepared by directly performing an epoxidation reaction.
  • Heteropolyacids are composed of heteroatoms (such as P, Si, Fe, Co, etc.) and polyatoms (such as Mo, W, V, Nb, Ta, etc.) which are bridged by oxygen atoms in a certain structure.
  • Oxygen acid It is not only acidic, but also redox, it is a multifunctional new catalyst; it can be used to catalyze reactions such as homogeneous, heterogeneous and phase transfer. These catalysts have good stability and no pollution to the environment, and are a promising green catalyst.
  • the existing heteropoly acid preparation methods mainly include an ether acid extraction method and an ion exchange method. The acidification extraction process requires more stringent requirements, and the acidification pH is very high.
  • the ether is characterized by low boiling point, toxic, flammable and extremely volatile, and the use process is dangerous. polluted environment.
  • the ion exchange method avoids the use of diethyl ether and has high production safety, but the production cycle is long, the energy consumption is extremely large, and the production capacity is limited, which becomes a bottleneck of industrial production.
  • CN102744088A discloses a preparation method of phosphotungstic heteropoly acid: dissolving sodium tungstate and disodium hydrogen phosphate in water, producing a mixed solution of phosphotungstic acid and sodium phosphotungstate under heating and acidic conditions, and then C n H The organic solution of 2n+1 N + Cl - is added to a mixed solution of phosphotungstic acid and sodium phosphotungstate. After the reaction, the product is centrifuged, washed, dried and calcined to obtain a phosphotungstic heteropoly acid.
  • CN107282106 discloses a preparation method and application of a weak water-soluble supported phosphotungstic heteropoly acid: dissolving sodium tungstate in water and adding it to dilute hydrochloric acid to obtain a yellow-green solid; adding a yellow-green solid to the phosphoric acid solution a plurality of times, Stirring water-soluble phosphotungstic heteropoly acid; adding citric acid, titanium silicon molecular sieve (TS-1) and potassium chloride solution; centrifuging and drying the precipitate to obtain the supported tungsten-phosphorus heteropoly acid of TS-1. The yield was 79.85%.
  • Heteropolyacids have good water solubility, poor solubility in organic phase, which makes catalyst recovery difficult, and there is unstable catalytic activity due to uneven distribution in practical application; compared with other acid catalysts, the price is high, Cannot be applied to industrial production. Therefore, research on heteropoly acid immobilization methods and improvement of catalyst recovery rate are of great significance for promoting petrochemical production.
  • the invention describes a process for preparing epichlorohydrin by direct epoxidation of chloropropene with hydrogen peroxide in a modified heteropolyacid supported catalyst.
  • the main advantages of this process are: 1 low ratio of chloropropene to hydrogen peroxide, less chloropropene; 2 coupling of reaction and separation process, saving equipment, simple process; 3 avoiding hydrolysis of epichlorohydrin under acidic conditions with water The side reaction, the epichlorohydrin yield and selectivity are high.
  • the main object of the present invention is to provide a method for preparing epichlorohydrin by direct epoxidation of chloropropene, a modified heteropolyacid supported catalyst and a preparation method thereof, so as to solve the preparation of epichlorohydrin chloride in the prior art.
  • One of the technical problems to be solved by the present invention is to provide a method for preparing epichlorohydrin by direct epoxidation of chloropropene in the presence of a catalyst using hydrogen peroxide as an oxygen source, which has a low ratio of chloropropene to hydrogen peroxide, chlorine.
  • the amount of propylene is low; the reaction and the separation process are coupled to avoid the side reaction of epichlorohydrin under acidic conditions, hydrolysis with water, and the high yield and selectivity of epichlorohydrin.
  • the present invention employs the following experimental method: in a reduced pressure system, a metering pump is used to pump chloropropene from the bottom into a fixed bed containing a modified heteropolyacid supported catalyst at a certain space velocity.
  • a metering pump is used to pump chloropropene from the bottom into a fixed bed containing a modified heteropolyacid supported catalyst at a certain space velocity.
  • hydrogen peroxide and chloropropene are pumped from the top into the fixed bed reactor at a certain molar ratio, and reacted at a certain temperature and pressure; while the reaction, the chloropropene, epichlorohydrin and water are stripped from the top of the reactor.
  • the system monochloropropanediol and another part of water from the bottom of the reactor out of the system; the top reaction liquid oil moisture layer, the oil layer is cooled to determine the composition, the water layer is incorporated into the bottom reaction liquid and then cooled to determine the composition, calculate the hydrogen peroxide conversion rate, epoxy Chloropropane and monochloropropanediol yield, epichlorohydrin selectivity and hydrogen peroxide utilization.
  • the chloropropene and hydrogen peroxide according to the present invention have a molar ratio of 0.85 to 2.00:1, preferably 0.95 to 1.50:1;
  • the chloropropene feed mass space velocity of the present invention is 1.5 to 10.0 h -1 , preferably 3.0 to 6.0 h -1 ;
  • the reaction temperature according to the present invention is 30 to 90 ° C, preferably 40 to 80 ° C; and the vacuum degree of the reduced pressure system is 5 to 65 kPa, preferably 20 to 60 kPa.
  • modified heteropolyacid supported catalyst has the following structural formula I:
  • n is any one of 3 to 20, preferably any one of 7 to 14, and a is an integer of 250 to 300, and b is an integer of 10 to 50, and R 1 and R 2 And R 3 are each independently selected from any one of C 1 to C 10 hydrocarbon groups, and further preferably each of R 1 , R 2 and R 3 is independently selected from a C 1 -C 4 alkyl group.
  • a process for the direct epoxidation of chloropropene to produce epichlorohydrin which comprises: catalyzing the reaction of chloropropene and hydrogen peroxide with a modified heteropolyacid supported catalyst; The epoxidation reaction produces epichlorohydrin, wherein the modified heteropolyacid supported catalyst has the following structural formula I:
  • n is any one of 3 to 20
  • a is an integer of 250 to 300
  • b is an integer of 10 to 50
  • R 1 , R 2 and R 3 are each independently selected from C 1 Any one of -C 10 hydrocarbon groups.
  • n is an integer of any one of 7 to 14, and R 1 , R 2 and R 3 are each independently selected from any one of C 1 to C 4 alkyl groups.
  • the molar ratio of the above chloropropene to hydrogen peroxide is from 0.85 to 2.00:1, preferably from 0.95 to 1.50:1.
  • chloropropene feed mass space velocity is 1.5 to 10.0 h -1 , preferably 3.0 to 6.0 h -1 .
  • reaction temperature of the above epoxidation reaction is 30 to 90 ° C; preferably 40 to 80 ° C.
  • the epoxidation reaction is carried out in a reduced pressure system, and the vacuum degree of the reduced pressure system is preferably 5 to 65 kPa, and more preferably 20 to 60 kPa.
  • the above method comprises: in a reduced pressure system, feeding chloropropene from the bottom into a reactor containing a modified heteropolyacid supported catalyst, and sending hydrogen peroxide from the top to the reactor to make chloropropene and hydrogen peroxide
  • the epoxidation reaction takes place to obtain epichlorohydrin, and preferably the reactor is a fixed bed reactor.
  • n is any one of 3 to 20
  • a is an integer of 250 to 300
  • b is an integer of 10 to 50
  • R 1 , R 2 and R 3 are each independently selected from C 1 Any one of -C 10 hydrocarbon groups.
  • n is an integer of any one of 7 to 14, and R 1 , R 2 and R 3 are each independently selected from any one of C 1 to C 4 alkyl groups.
  • a method for preparing a modified heteropolyacid supported catalyst comprising: Step S1, mixing an organic solution of a quaternary ammonium salt with peroxophosphoric acid and reacting to form
  • the heteropolyacid monomer of the formula II has the structural formula II: Wherein n is any one of 3 to 20, and R 1 , R 2 and R 3 are each independently selected from any one of C 1 to C 4 alkyl groups; and step S2, heteropoly acid monomer and N are - Isopropyl acrylamide is subjected to a polymerization reaction to obtain a modified heteropoly acid supported catalyst.
  • the organic solvent of the above organic solution is any one or more selected from the group consisting of methyl chloride, dichloromethane, chloroform, carbon tetrachloride and dichloroethane.
  • the structural formula of the quaternary ammonium salt is n is an integer of any one of 3 to 20, preferably any one of 7 to 14; preferably, the reaction temperature of the reaction of the quaternary ammonium salt with the peroxophosphoric acid is 10 to 60 ° C, preferably 20 to 40 ° C, and the reaction is carried out.
  • the time is from 1 to 10 h, preferably from 3 to 5 h.
  • step S2 includes:
  • the heteropoly acid monomer and N-isopropyl acrylamide are polymerized in the presence of a radical initiator and a solvent, preferably the radical initiator is azobisisobutyronitrile, azobisisoheptonitrile or uncle Butyl hydrogen peroxide or the like; the solvent is N,N-dimethylformamide, N,N-dimethylacetamide or dimethyl sulfoxide; preferably the polymerization temperature is 60 to 80 ° C; preferably N-isopropyl
  • the molar ratio of the acrylamide to the quaternary ammonium salt is from 5 to 25:1, preferably from 7 to 10:1.
  • the present invention adopts a modified heteropoly acid supported catalyst having the above formula, and it is verified by experiments that the catalyst can catalyze the epoxidation of chloropropene and hydrogen peroxide to avoid epichlorohydrin under acidic conditions.
  • the catalyst can be used to reduce the amount of chloropropene, even if the molar ratio of chloropropene to hydrogen peroxide is less than 4:1 It is also possible to achieve a higher yield of epichlorohydrin, thus lowering the cost of the raw material; further, since the catalyst of the present application is a supported catalyst, the recovery rate of the catalyst is high, and the catalyst cost is saved.
  • Figure 1 is a reaction flow diagram of the present invention.
  • the present application provides a method for preparing epichlorohydrin by direct epoxidation of chloropropene, a modified heteropoly acid supported catalyst, and a preparation method thereof.
  • a process for the direct epoxidation of chloropropene to produce epichlorohydrin which comprises: catalyzing the reaction of chloropropene and hydrogen peroxide with a modified heteropolyacid supported catalyst.
  • the oxidation reaction produces epichlorohydrin, wherein the modified heteropolyacid supported catalyst has the following structural formula I: Wherein n is any one of 3 to 20, a is an integer of 250 to 300, b is an integer of 10 to 50, and R 1 , R 2 and R 3 are each independently selected from C 1 Any one of -C 10 hydrocarbon groups.
  • the present invention adopts a modified heteropolyacid supported catalyst having the above formula, and it is verified by experiments that the catalyst can catalyze the epoxidation of chloropropene and hydrogen peroxide, and can avoid the side reaction of epichlorohydrin with water under acidic conditions. Therefore, the yield and selectivity of epichlorohydrin are improved; at the same time, the amount of chloropropene can be reduced when the catalyst is used, even if the molar ratio of chloropropene to hydrogen peroxide is less than 4:1, a higher ring can be realized.
  • the oxychloropropane yield thus reducing the cost of the raw material; further, since the catalyst of the present application is a supported catalyst, the recovery rate of the catalyst is high, and the catalyst cost is saved.
  • n is any one of 7 to 14, and R 1 , R 2 and R 3 are each independently selected from C 1 to C 4 alkyl groups.
  • n is any one of 7 to 14
  • R 1 , R 2 and R 3 are each independently selected from C 1 to C 4 alkyl groups.
  • the amount of the chloropropene used in the present application is reduced, and it is preferred that the molar ratio of the above chloropropene to hydrogen peroxide is from 0.85 to 2.00:1, more preferably from 0.95 to 1.50:1. In the above molar ratio range, a low amount of chloropropene is ensured, and a high yield and selectivity of epichlorohydrin can be ensured.
  • the above-mentioned chloropropene feed mass space velocity is from 1.5 to 10.0 h -1 , preferably from 3.0 to 6.0 h -1 .
  • the temperature of the epoxidation reaction of the present application may be a temperature conventionally used in the prior art, and it is preferred that the reaction temperature of the above epoxidation reaction is 30 to 90 ° C; more preferably 40 to 80 ° C. To further ensure the efficient and stable reaction.
  • the epoxidation reaction is carried out in a reduced pressure system, and preferably, the vacuum degree of the reduced pressure system is 5 to 65 kPa, and more preferably 20 to 60 kPa.
  • the method comprises: feeding chloropropene from a bottom into a reactor containing a modified heteropolyacid supported catalyst in a reduced pressure system, and sending hydrogen peroxide from the top to the reaction.
  • the epoxidation reaction of chloropropene and hydrogen peroxide is carried out to obtain epoxy chloropropene.
  • the reactor is a fixed bed reactor. The above epoxidation reaction is carried out in the reactor, and the obtained product and by-products can be directly separated from the reactor.
  • a modified heteropolyacid supported catalyst is provided, and the modified heteropolyacid supported catalyst has the following structural formula I:
  • n is any one of 3 to 20
  • a is an integer of 250 to 300
  • b is an integer of 10 to 50
  • R 1 , R 2 and R 3 are each independently selected from C 1 Any one of -C 10 hydrocarbon groups.
  • the above catalyst can catalyze the epoxidation of chloropropene and hydrogen peroxide to avoid the side reaction of epichlorohydrin hydrolysis with water under acidic conditions, thereby improving the yield and selectivity of epichlorohydrin;
  • the amount of chloropropene can be reduced, even if the molar ratio of chloropropene to hydrogen peroxide is less than 4:1, a higher yield of epichlorohydrin can be achieved, thereby reducing the cost of raw materials; further due to the application of the present application
  • the catalyst is a supported catalyst, so the recovery rate of the catalyst is high, and the catalyst cost is saved.
  • n is any one of 7 to 14, and R 1 , R 2 and R 3 are each independently selected from C 1 to C 4 alkyl groups.
  • n is any one of 7 to 14
  • R 1 , R 2 and R 3 are each independently selected from C 1 to C 4 alkyl groups.
  • a method for preparing a modified heteropolyacid supported catalyst comprising: Step S1, the organic solution of the quaternary ammonium salt and the peroxophosphoric acid After mixing, the reaction is carried out to form a heteropolyacid monomer having the structural formula II, and the structural formula II is: Wherein n is any one of 3 to 20, and R 1 , R 2 and R 3 are each independently selected from any one of C 1 to C 4 alkyl groups; and step S2, heteropoly acid monomer and N are - Isopropyl acrylamide is subjected to a polymerization reaction to obtain a modified heteropoly acid supported catalyst.
  • the heteropoly acid monomer having the above structural formula II is formed by using an organic solution of a quaternary ammonium salt and peroxophosphoric acid as a raw material, and then performing a polymerization reaction, and the process is simple and easy to implement.
  • the organic solvent of the organic solution is any one or more selected from the group consisting of methyl chloride, dichloromethane, chloroform, carbon tetrachloride and dichloroethane.
  • the structural formula of the quaternary ammonium salt is n is an integer of any one of 3 to 20, preferably any one of 7 to 14; preferably, the reaction temperature of the reaction of the quaternary ammonium salt with the peroxophosphoric acid is 10 to 60 ° C, preferably 20 to 40 ° C, and the reaction is carried out.
  • the time is from 1 to 10 h, preferably from 3 to 5 h.
  • the peroxyphosphoric acid of the present application can be prepared by a prior art preparation method.
  • the above step S1 includes a preparation process of peroxophosphoric acid, the preparation The process comprises: reacting sodium tungstate and phosphoric acid in an acidic aqueous solution to form a phosphotungstic acid solution under normal temperature and normal pressure; and oxidizing the phosphotungstic acid solution with hydrogen peroxide to form a peroxophosphoric acid solution, wherein the sodium tungstate and the phosphoric acid are moles
  • the ratio is 3.0 to 5.0:1, preferably 3.5 to 4.5:1; preferably, the amount of water in the acidic aqueous solution is 3 to 10 times, more preferably 5 to 8 times the weight of the sodium tungstate; preferably the acid in the acidic aqueous solution is hydrochloric acid, preferably HCl.
  • the molar ratio to sodium tungstate is from 1.5 to 3.0:1, more preferably from 2.0 to 2.5:1; preferably the molar ratio of hydrogen peroxide to sodium tungstate is from 1 to 10:1, more preferably from 3 to 8:1; preferably quaternary ammonium salt
  • the molar ratio to sodium tungstate is 2.8 to 3.3:4, more preferably 3.0 to 3.2:4.
  • the resulting peroxophosphoric acid solution is directly subjected to the next step of monomer preparation without purification.
  • the step S2 includes: polymerizing the heteropoly acid monomer and the N-isopropyl acrylamide in the presence of a radical initiator and a solvent, preferably the radical initiator is Nitrogen diisobutyronitrile, azobisisoheptanenitrile or t-butyl hydroperoxide, the solvent is N,N-dimethylformamide, N,N-dimethylacetamide or dimethyl sulfoxide; preferably polymerization
  • the temperature is 60 to 80 ° C; preferably, the molar ratio of N-isopropylacrylamide to quaternary ammonium salt is 5 to 25:1, preferably 7 to 10:1.
  • the polymerization reaction is carried out under the above conditions, whereby the polymerization efficiency can be improved, and the molecular weight of the obtained catalyst can be easily adjusted.
  • a phosphotungstic acid solution is formed under acidic conditions, and 54.4 g of a hydrogen peroxide solution of 50% hydrogen peroxide is added to the phosphotungstic acid solution to form a peroxophosphoric acid solution after oxidation; and the previously prepared mass concentration is 6 wt% [C 5 H 206.7 g of a solution of 11 N(CH 3 ) 3 ]Cl (linear quaternary ammonium salt) in dichloroethane (containing 12.4 g of quaternary ammonium salt) was added to the above-mentioned peroxophosphoric acid solution, and reacted at 20 ° C for 4 h. After the reaction, the product is centrifuged, washed, and dried to obtain 30.8 g of a heteropolyacid monomer I, and the yield is 86.9%;
  • a phosphotungstic acid solution is formed under acidic conditions, and 20.4 g of a hydrogen peroxide solution having a mass concentration of 50% hydrogen peroxide is added to the phosphotungstic acid solution to form a peroxophosphoric acid solution after oxidation; and the previously prepared mass concentration is 6 wt% [C 18 H 450.0 g of a solution of 35 N(CH 3 ) 3 ]Cl (linear quaternary ammonium salt) in dichloroethane (containing 27.0 g of quaternary ammonium salt) was added to a solution of peroxophosphoric acid and reacted at 30 ° C for 3 h. After the reaction, the product was centrifuged, washed and dried to obtain 45.9 g of heteropolyacid monomer II, and the yield was 95.2%;
  • Acid solution adding 68.0g of 50% hydrogen peroxide solution to the phosphotungstic acid solution, and oxidizing to form a peroxo-tungstic acid solution; and then pre-configured 6wt% [C 13 H 25 N(CH 3 ) 3 ]Cl (linear type) 328.3 g of a quaternary ammonium salt solution (containing 19.7 g of quaternary ammonium salt) was added to a solution of peroxophosphoric acid and reacted at 10 ° C for 1 h. After the reaction, the product was centrifuged, washed and dried to obtain a miscellaneous product. Polyacid monomer III 34.9g, the preparation yield was 79.3%;
  • Acid solution adding 6.8g of 50% hydrogen peroxide solution to the phosphotungstic acid solution, and oxidizing to form a peroxo-tungstic acid solution; and then pre-configured 6wt% [C 9 H 17 N(CH 3 ) 3 ]Cl (linear type) 310.0 g of a quaternary ammonium salt solution (containing quaternary ammonium salt 18.6 g) was added to a solution of peroxophosphoric acid and reacted at 60 ° C for 5 h. After the reaction, the product was centrifuged, washed and dried to obtain a miscellaneous product. Polyacid monomer IV 36.9g, the preparation yield was 92.7%;
  • Acid solution adding 34.0g of 50% hydrogen peroxide solution to the phosphotungstic acid solution, and oxidizing to form a peroxo-tungstic acid solution; and then pre-configured 6wt% [C 23 H 45 N(CH 3 ) 3 ]Cl (linear type) 508.3 g of a quaternary ammonium salt solution (containing 30.5 g of quaternary ammonium salt) was added to a solution of peroxophosphoric acid and reacted at 40 ° C for 10 h. After the reaction, the product was centrifuged, washed and dried to obtain a miscellaneous product. The polyacid monomer V 49.3g, the preparation yield is 90.4%;
  • heteropoly acid monomer 5.7 g of N-isopropyl acrylamide, 14.1 g of heteropoly acid monomer, and a radical initiator azobisisobutyronitrile (AIBN) were sequentially added to the pressure resistant reaction bottle. 0.1g and solvent N,N-dimethylformamide 200g, and stir to dissolve the substances, remove oxygen, and then carry out polymerization at 60 ° C for 5h. After the reaction is finished, the product is precipitated, centrifuged and dried to obtain a supported type. Heteropolyacid catalyst I 19.1 g.
  • heteropoly acid monomer 5.7 g of N-isopropyl acrylamide, 14.1 g of heteropoly acid monomer, and a radical initiator azobisisobutyronitrile (AIBN) were sequentially added to the pressure resistant reaction bottle. 0.1g and solvent N,N-dimethylformamide 200g, and stir to dissolve the substances, remove oxygen, and then carry out polymerization at 80 ° C for 4h. After the reaction is finished, the product is precipitated, centrifuged and dried to obtain a supported type. Heteropolyacid catalyst I 19.6 g.
  • Acid solution add 34.0g of 50% hydrogen peroxide solution to the phosphotungstic acid solution, and oxidize to form a peroxo-tungstic acid solution; then pre-configured 6wt% [C 23 H 45 N(C 4 H 9 ) 3 ]Cl (straight 508.3 g of a dichloroethane solution of a chain quaternary ammonium salt (containing 39.7 g of a quaternary ammonium salt) was added to a solution of peroxophosphoric acid and reacted at 40 ° C for 10 h. After the reaction, the product was centrifuged, washed, and dried. Obtaining 59.0 g of heteropoly acid monomer VI, the preparation yield is 92.5%;
  • heteropoly acid monomer 7.9 g of N-isopropyl acrylamide, 25.6 g of heteropoly acid monomer VI, and a radical initiator azobisisobutyronitrile (AIBN) were sequentially added to the pressure resistant reaction bottle. 0.1g and solvent N,N-dimethylformamide 200g, stir to dissolve the substance, remove oxygen, and then carry out polymerization at 70 ° C for 4h, after the end of the reaction, the product is precipitated, centrifuged and dried to obtain a supported type.
  • Heteropolyacid catalyst VI 33.2g.
  • the reaction solution is recovered by centrifugation, and the dry weight of the catalyst is recovered by vacuum drying; the catalyst dry basis is determined by ICP to determine P and W, and the catalyst recovery rate is obtained.
  • the specific results are shown in Table 1.
  • the chloropropene was pumped from the bottom into a fixed-bed reactor equipped with a self-modified heteropolyacid-supported catalyst I at a space velocity of 8.0 h -1 .
  • the ratio of hydrogen peroxide to chloropropene was 1:1.10.
  • the top is pumped into a fixed bed reactor and reacted at 30 ° C and a system vacuum of 5 KPa; while reacting, chloropropene, epichlorohydrin and water are stripped from the top of the reactor, monochloropropanediol and another portion of water from the reactor
  • the bottom of the reactor exits the system; the top reactant oil moisture layer, after the oil layer is cooled, the composition is chloropropene 26.1%, epichlorohydrin 73.5% and water 0.4%, and the water layer is combined into the bottom reaction liquid and then cooled to form hydrogen peroxide 0.5%.
  • the chloropropene was pumped from the bottom into a fixed-bed reactor equipped with a self-modified heteropolyacid supported catalyst II at a space velocity of 4.0 h -1 .
  • the ratio of hydrogen peroxide to chloropropene was 1:1.20.
  • the top is pumped into a fixed bed reactor and reacted at 60 ° C and a system vacuum of 20 kPa; while reacting, chloropropene, epichlorohydrin and water are stripped from the top of the reactor, monochloropropanediol and another portion of water from the reactor
  • the bottom of the reactor exits the system; the top reactant oil moisture layer, after the oil layer is cooled, the composition is 11.4% of chloropropene, 88.1% of epichlorohydrin and 0.5% of water.
  • the water layer is combined into the bottom reaction liquid and then cooled to form hydrogen peroxide 0.4%.
  • the chloropropene was pumped from the bottom into a fixed-bed reactor equipped with a self-modified heteropolyacid-supported catalyst IV at a space velocity of 10.0 h -1 .
  • the ratio of hydrogen peroxide to chloropropene was 1:0.90.
  • the top is pumped into a fixed bed reactor and reacted at 60 ° C and a system vacuum of 15 kPa; while reacting, chloropropene, epichlorohydrin and water are stripped from the top of the reactor, monochloropropanediol and another portion of water from the reactor
  • the bottom of the reactor exits the system; the top reactant oil moisture layer, after the oil layer is cooled, the composition is 21.9% of chloropropene, 77.5% of epichlorohydrin and 0.6% of water, and the water layer is combined into the bottom reaction liquid and then cooled to form hydrogen peroxide 0.3%.
  • the chloropropene was pumped from the bottom into a fixed-bed reactor equipped with a self-modified heteropolyacid supported catalyst III at a space velocity of 6.0 h -1 .
  • the ratio of hydrogen peroxide to chloropropene was 1:1.50.
  • the top is pumped into a fixed bed reactor and reacted at 50 ° C and a system vacuum of 15 kPa; while reacting, chloropropene, epichlorohydrin and water are stripped from the top of the reactor, monochloropropanediol and another portion of water from the reactor
  • the bottom of the reactor exits the system; the top reactant oil moisture layer, after the oil layer is cooled, the composition is 21.9% of chloropropene, 77.5% of epichlorohydrin and 0.6% of water.
  • the water layer is combined into the bottom reaction liquid and then cooled to form hydrogen peroxide 0.5%.
  • the chloropropene was pumped from the bottom into a fixed-bed reactor equipped with a self-modified heteropolyacid supported catalyst V at a space velocity of 3.0 h -1 .
  • the ratio of hydrogen peroxide to chloropropene was 1:2.00.
  • the top is pumped into a fixed bed reactor and reacted at 90 ° C and a system vacuum of 60 kPa; while reacting, chloropropene, epichlorohydrin and water are stripped from the top of the reactor, monochloropropanediol and another portion of water from the reactor
  • the bottom of the reactor exits the system; the top reactant oil moisture layer, after the oil layer is cooled, the composition is 46.4% of chloropropene, 52.9% of epichlorohydrin and 0.7% of water.
  • the water layer is combined into the bottom reaction liquid and then cooled to form hydrogen peroxide 0.1%.
  • the chloropropene was pumped from the bottom into a fixed-bed reactor equipped with a self-modified heteropolyacid-supported catalyst V at a space velocity of 2.0 h -1 .
  • the ratio of hydrogen peroxide to chloropropene was 1:1.30.
  • the top is pumped into a fixed bed reactor and reacted at 80 ° C and atmospheric pressure; while reacting, chloropropene, epichlorohydrin and water are stripped from the top of the reactor, monochloropropanediol and another portion of water from the reactor
  • the bottom outlet system the top reactant oil moisture layer, after the oil layer is cooled, the composition is chloropropene 15.9%, epichlorohydrin 83.3% and water 0.8%.
  • the water layer is combined into the bottom reaction liquid and then cooled to form hydrogen peroxide 0.1%, epoxy.
  • the chloropropene was pumped from the bottom into a fixed-bed reactor equipped with a self-modified heteropolyacid-supported catalyst II at a space velocity of 3.0 h -1 .
  • the ratio of hydrogen peroxide to chloropropene was 1:1.10.
  • the top is pumped into a fixed bed reactor and reacted at 60 ° C and a system vacuum of 20 kPa; while reacting, chloropropene, epichlorohydrin and water are stripped from the top of the reactor, monochloropropanediol and another portion of water from the reactor
  • the bottom of the reactor exits the system; the top reactant oil moisture layer, after the oil layer is cooled, the composition is chloropropene 3.1%, epichlorohydrin 96.5% and water 0.4%, and the water layer is combined into the bottom reaction liquid and then cooled to form hydrogen peroxide 0.2%.
  • the chloropropene was pumped from the bottom into a fixed-bed reactor equipped with a self-modified heteropolyacid-supported catalyst I at a space velocity of 4.0 h -1 .
  • the ratio of hydrogen peroxide to chloropropene was 1:1.20.
  • the top is pumped into a fixed bed reactor and reacted at 70 ° C and a system vacuum of 40 kPa; while reacting, chloropropene, epichlorohydrin and water are stripped from the top of the reactor, monochloropropanediol and another portion of water from the reactor
  • the bottom of the reactor was out of the system; for a total of 500 h, the catalyst activity was stable.
  • the top reactant oil moisture layer after the oil layer is cooled, the composition is chloropropene 9.6%, epichlorohydrin 89.9% and water 0.5%.
  • the water layer is combined into the bottom reaction liquid and then cooled to form hydrogen peroxide 0.3% and epichlorohydrin 1.3%.
  • the chloropropene was pumped from the bottom into a fixed-bed reactor equipped with a self-modified heteropolyacid-supported catalyst V at a space velocity of 3.0 h -1 .
  • the ratio of hydrogen peroxide to chloropropene was 1:0.85.
  • the top is pumped into a fixed bed reactor and reacted at 50 ° C and a system vacuum of 50 kPa; while reacting, chloropropene, epichlorohydrin and water are stripped from the top of the reactor, monochloropropanediol and another portion of water from the reactor
  • the bottom of the reactor exits the system; the top reactant oil moisture layer, after the oil layer is cooled, the composition is epichlorohydrin 99.6% and water 0.4%.
  • the water layer is combined into the bottom reaction liquid and then cooled to form hydrogen peroxide 0.3%, epichlorohydrin.
  • the chloropropene was pumped from the bottom into a fixed-bed reactor equipped with a self-modified heteropolyacid supported catalyst III at a space velocity of 3.0 h -1 .
  • the ratio of hydrogen peroxide to chloropropene was 1:0.99.
  • the top is pumped into a fixed bed reactor and reacted at 60 ° C and a system vacuum of 20 kPa; while reacting, chloropropene, epichlorohydrin and water are stripped from the top of the reactor, monochloropropanediol and another portion of water from the reactor
  • the bottom of the reactor exits the system; the top reactant oil moisture layer, after the oil layer is cooled, the composition is 0.1% of chloropropene, 99.5% of epichlorohydrin and 0.4% of water.
  • the water layer is combined into the bottom reaction liquid and then cooled to form 0.5% hydrogen peroxide.
  • the chloropropene was pumped from the bottom into a fixed-bed reactor equipped with a self-modified heteropolyacid supported catalyst III at a space velocity of 3.0 h -1 .
  • the ratio of hydrogen peroxide to chloropropene was 1:0.99.
  • the top is pumped into a fixed bed reactor and reacted at 40 ° C and a system vacuum of 20 kPa; while reacting, chloropropene, epichlorohydrin and water are stripped from the top of the reactor, monochloropropanediol and another portion of water from the reaction
  • the bottom of the reactor exits the system; the top reactant oil moisture layer, after the oil layer is cooled, the composition is 0.21% of chloropropene, 99.5% of epichlorohydrin and 0.34% of water.
  • the aqueous layer is combined into the bottom reaction liquid and then cooled to form 0.8% hydrogen peroxide.
  • the chloropropene was pumped from the bottom into a fixed-bed reactor equipped with a self-modified heteropolyacid-supported catalyst VI at a space velocity of 1.5 h -1 .
  • the ratio of hydrogen peroxide to chloropropene was 1:0.95.
  • the top is pumped into a fixed bed reactor and reacted at 30 ° C and a system vacuum of 65 kPa; while reacting, chloropropene, epichlorohydrin and water are stripped from the top of the reactor, monochloropropanediol and another portion of water from the reactor
  • the bottom of the reactor exits the system; the top reactant oil moisture layer, after the oil layer is cooled, the composition is 0.2% of chloropropene, 99.3% of epichlorohydrin and 0.5% of water.
  • the water layer is combined into the bottom reaction liquid and then cooled to form hydrogen peroxide 0.1%.

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Abstract

本发明公开了一种氯丙烯直接环氧化制备环氧氯丙烷的工艺、改性杂多酸催固载化催化剂及制备方法，更具体的是公开了一种氯丙烯在改性的杂多酸固载化催化剂存在下，以双氧水为氧源，直接环氧化制备环氧氯丙烷的工艺路线。该工艺主要的优点在于：①氯丙烯与双氧水的比例低，氯丙烯用量少；②反应和分离过程耦合，节省设备，过程简单；③避免环氧氯丙烷在酸性条件下，与水发生水解的副反应，环氧氯丙烷收率和选择性高。

Description

一种氯丙烯直接环氧化制备环氧氯丙烷的工艺、改性杂多酸固载化催化剂及制备方法 技术领域
本发明涉及一种氯丙烯直接环氧化制备环氧氯丙烷的工艺、改性杂多酸催固载化催化剂及制备方法，更具体的是涉及一种氯丙烯在改性的杂多酸固载化催化剂存在下，以双氧水为氧源，直接环氧化制备环氧氯丙烷的工艺路线。
背景技术
环氧氯丙烷是一种重要的石油化工产品，主要用于生产环氧树脂和合成甘油。目前环氧氯丙烷的工业合成方法主要有醋酸丙烯酯法、丙烯法和甘油法，其中丙烯法又分为氯醇法和直接环氧化法。醋酸丙烯酯法、甘油法和氯醇法都是先生成二氯丙醇，然后经过皂化环合生成环氧氯丙烷，这两种工艺都会带来大量的含氯化钙的废水，越来越不适应绿色化学的发展思路。为了解决大量含盐废水的问题，科学家们研究用氯丙烯直接环氧化制备环氧氯丙烷，常用的催化剂主要有钛硅分子筛和杂多酸盐类化合物。
CN1769277A公开了一种环氧氯丙烷生产工艺，以钛硅分子筛为催化剂，向一种特殊的螺旋通道型旋转床或旋转填充床超重力反应器中同时连续加入液相或气相氯丙烯及双氧水，直接进行环氧化反应制备环氧氯丙烷。
1985年Carlo Venturello等人提出了一种[PW 4O 24] 3-型季铵盐磷钨杂多酸催化剂的制备方法，并在1988年首次报道了以双氧水为氧源，磷钨杂多酸催化氯丙烯直接环氧化反应制备环氧氯丙烷，反应过程中杂多酸的[R 4N +] 3{PO 4[WO(O 2) 2] 4} 3-为催化活性物种，苯为溶剂，反应2.5h，环氧氯丙烷的产率为85％。1988年，日本人Yasutaka Ishii在J.Org.Chem.上详细研究了不同季铵盐修饰的磷钨杂多酸催化剂在催化剂双键环氧化方面的应用，同时提出了反应机理，即反应前为催化剂为不溶解的固体，反应中由于双氧水的作用而溶于反应体系进行均相催化反应；当双氧水耗尽，催化剂又可以从反应体系中析出，通过分离可以循环使用。2000年以后的中国专利CN101205219、CN101045717和CN100532371均提供了以磷钨杂多酸季铵盐为催化剂，双氧水为氧源，氯丙烯环氧化制备环氧氯丙烷的工艺方法，分别研究了双氧水浓度、溶剂种类和助剂种类等克服水相存在对环氧化反应带来的不利影响。
1988年至今的近30年，研究过渡金属杂多酸的文献和专利比较多，但是公开的报道中基本无实现工业化的实例。现有氯丙烯环氧化制备环氧氯丙烷工艺存在的以下不足：①以钛硅分子筛为催化剂制备环氧氯丙烷的工艺，绝大多数需使用甲醇，甲醇一方面作为溶剂，另一方面活化催化剂；且催化剂需经常再生使用；②以磷钨杂多酸为催化剂制备环氧氯丙烷的工艺，氯丙烯与双氧水的摩尔比为4:1以上，用量较大；③反应生成的环氧氯丙烷在酸性条件下，在水相中易发生水解，环氧氯丙烷收率及选择性均不高。
杂多酸是由杂原子(如P、Si、Fe和Co等)和多原子(如Mo、W、V、Nb和Ta等)按一定的结构通过氧原子配位桥联组成的一类含氧多酸。它不但具有酸性，而且具有氧化还原性，是一种多功能的新型催化剂；可用于催化均相、非均相以及相转移等反应。该类催化剂稳定性好，对环境无污染，是一类大有前途的绿色催化剂。现有的杂多酸制备方法主要有***酸化萃取法和离子交换法等。***酸化萃取法工艺过程要求比较苛刻，对酸化pH要求很高，即使相差0.01所得产物结构就完全不同，同时***的特点是沸点低、有毒、易燃和极易挥发，使用过程较危险性且污染环境。离子交换法避免了使用***，生产安全性高，但生产周期长，能耗极大，生产能力有限，成为工业化生产的瓶颈。
CN102744088A公开一种磷钨杂多酸的制备方法：将钨酸钠和磷酸氢二钠溶于水中，在加热和酸性条件下生产磷钨酸和磷钨酸钠的混合溶液，然后将C nH 2n+1N +Cl -的有机溶液加入到磷钨酸和磷钨酸钠的混合溶液中，反应后，产物经离心、洗涤、干燥和焙烧，即得到磷钨杂多酸。
CN107282106公开一种弱水溶性负载型磷钨杂多酸制备方法及应用：将钨酸钠溶于水后滴加入稀盐酸中，得黄绿色固体；将黄绿色固体少量多次加入磷酸溶液中，搅拌得水溶性磷钨杂多酸；加入柠檬酸、钛硅分子筛(简称TS-1)和氯化钾溶液；将沉淀离心、烘干后即得负载型TS-1的磷钨杂多酸，产率79.85％。
杂多酸水溶性好，在有机相中溶解性差，造成催化剂回收困难，且在实际应用过程中存在因分布不均匀所造成的不稳定的催化活性；与其它酸催化剂相比，价格偏高，无法应用于工业化生产。因此，开展杂多酸固载化方法的研究，提高催化剂的回收率，对促进石油化工生产等具有非常重要的意义。
本发明介绍了在一种改性杂多酸固载化催化剂中，氯丙烯与双氧水直接环氧化制备环氧氯丙烷的工艺。该工艺主要的优点在于：①氯丙烯与双氧水的比例低，氯丙烯用量少；②反应和分离过程耦合，节省设备，过程简单；③避免环氧氯丙烷在酸性条件下，与水发生水解的副反应，环氧氯丙烷收率和选择性高。
发明内容
本发明的主要目的在于提供一种氯丙烯直接环氧化制备环氧氯丙烷的方法、改性杂多酸固载化催化剂及其制备方法，以解决现有技术中的制备环氧氯丙烷氯丙烯消耗量较多的问题。
本发明所要解决的技术问题之一是提供一种氯丙烯在催化剂存在下，以双氧水为氧源，直接环氧化制备环氧氯丙烷的方法，该方法具有氯丙烯与双氧水的比例低，氯丙烯用量低；反应和分离过程耦合，避免环氧氯丙烷在酸性条件下，与水发生水解的副反应，环氧氯丙烷收率和选择性高等优点。
为达到本发明的目的，本发明采用如下实验方法：在减压体系中，用计量泵按一定的空速将氯丙烯从底部泵入装有改性的杂多酸固载化催化剂的固定床反应器内，双氧水与氯丙烯按一定的摩尔比从顶部泵入固定床反应器，在一定温度和压力下反应；反应的同时，氯丙烯、 环氧氯丙烷和水从反应器的顶部汽提出***，一氯丙二醇和另一部分水从反应器的底部出***；顶部反应液油水分层，油层冷却后测定组成，水层并入底部反应液后冷却后测定组成，计算双氧水转化率、环氧氯丙烷和一氯丙二醇收率、环氧氯丙烷选择性和双氧水利用率。
本发明所述的氯丙烯和双氧水按一定的摩尔比为0.85～2.00:1，优选0.95～1.50:1；
本发明所述的氯丙烯进料质量空速为1.5～10.0h -1，优选3.0～6.0h -1；
本发明所述的反应温度为30～90℃，优选40～80℃；减压体系真空度为5～65kPa，优选20～60kPa。
进一步地，上述改性杂多酸固载化催化剂具有如下结构通式I：
Figure PCTCN2019080417-appb-000001
其中，n为3～20中的任意一个整数，优选为7～14中任意一个整数，a为250～300中的任意一个整数，b为10～50中的任意一个整数，R 1、R 2和R 3各自独立地选自C 1～C 10的烃基中的任意一种，进一步优选R 1、R 2和R 3各自独立地选自C 1～C 4的烷基中的任意一种。
为了实现上述目的，根据本发明的另一方面，提供了一种氯丙烯直接环氧化制备环氧氯丙烷的方法，方法包括：利用改性杂多酸固载化催化剂催化氯丙烯和双氧水进行环氧化反应，得到环氧氯丙烷，其中改性杂多酸固载化催化剂具有如下结构通式I：
Figure PCTCN2019080417-appb-000002
其中，n为3～20中的任意一个整数，a为250～300中的任意一个整数，b为10～50中的任意一个整数，R 1、R 2和R 3各自独立地选自C 1～C 10的烃基中的任意一种。
进一步地，上述n为7～14中的任意一个整数,R 1、R 2和R 3各自独立地选自C 1～C 4的烷基中的任意一种。
进一步地，上述氯丙烯和双氧水的摩尔比为0.85～2.00:1，优选为0.95～1.50:1。
进一步地，上述氯丙烯进料质量空速为1.5～10.0h -1，优选为3.0～6.0h -1。
进一步地，上述环氧化反应的反应温度为30～90℃；优选为40～80℃。
进一步地，上述环氧化反应在减压体系中进行，优选减压体系的真空度为5～65kPa，进一步优选为20～60kPa。
进一步地，上述方法包括：在减压体系中，将氯丙烯从底部送入装有改性杂多酸固载化催化剂的反应器内，将双氧水从顶部送入反应器，使氯丙烯和双氧水发生环氧化反应，得到环氧氯丙烯，优选反应器为固定床反应器。
根据本发明的又一方面，提供了一种改性杂多酸固载化催化剂，该改性杂多酸固载化催化剂具有如下结构通式I：
Figure PCTCN2019080417-appb-000003
其中，n为3～20中的任意一个整数，a为250～300中的任意一个整数，b为10～50中的任意一个整数，R 1、R 2和R 3各自独立地选自C 1～C 10的烃基中的任意一种。
进一步地，上述n为7～14中的任意一个整数，R 1、R 2和R 3各自独立地选自C 1～C 4的烷基中的任意一种。
根据本发明的再一方面，提供了改性杂多酸固载化催化剂的制备方法，该制备方法包括：步骤S1，将季铵盐的有机溶液与过氧磷钨酸混合后反应，形成具有结构通式II的杂多酸单体，结构通式II为：
Figure PCTCN2019080417-appb-000004
其中n为3～20中的任意一个整数，R 1、R 2和R 3各自独立地选自C 1～C 4的烷基中的任意一种；步骤S2，将杂多酸单体与N-异丙基丙烯酰胺进行聚合反应，得到改性杂多酸固载化催化剂。
进一步地，上述有机溶液的有机溶剂为氯甲烷、二氯甲烷、氯仿、四氯化碳和二氯乙烷组成的组中的任意一种或多种，优选季铵盐的结构式为
Figure PCTCN2019080417-appb-000005
的n为3～20中的任意一个整数，优选7～14中的任意一个整数；优选季铵盐与过氧磷钨酸反应的反应温度为10～60℃，优选为20～40℃，反应时间为1～10h，优选为3～5h。
进一步地，上述步骤S2包括：
将杂多酸单体与N-异丙基丙烯酰胺在自由基引发剂和溶剂存在的条件下进行聚合反应，优选自由基引发剂为偶氮二异丁腈、偶氮二异庚腈或叔丁基过氧化氢等；溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或二甲亚砜；优选聚合反应的温度为60～80℃；优选N-异丙基丙烯酰胺与季铵盐的摩尔比为5～25:1，优选7～10:1。
应用本发明的技术方案，本申请采用具有上述通式的改性杂多酸固载化催化剂，经过试验验证该催化剂催化氯丙烯和双氧水环氧化时，可以避免环氧氯丙烷在酸性条件下与水发生水解的副反应，从而使得环氧氯丙烷的收率和选择性得到提高；同时，该催化剂使用时可以 使氯丙烯的用量减小，即使氯丙烯与双氧水的摩尔比不足4:1也能够实现较高的环氧氯丙烷收率，因此降低了原料成本；进一步地由于本申请的催化剂为固载化催化剂，因此催化剂的回收率较高，节约了催化剂成本。
附图说明
构成本申请的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。在附图中：
图1为本发明反应流程图。
具体实施方式
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将参考附图并结合实施例来详细说明本发明。
如本申请背景技术所分析的，现有技术的环氧氯丙烷的制备中氯丙烯的消耗量较多，导致成本较高。为了解决该问题，本申请提供了一种氯丙烯直接环氧化制备环氧氯丙烷的方法、改性杂多酸固载化催化剂及其制备方法。
在本申请一种典型的实施方式中，提供了一种氯丙烯直接环氧化制备环氧氯丙烷的方法，该方法包括：利用改性杂多酸固载化催化剂催化氯丙烯和双氧水进行环氧化反应，得到环氧氯丙烷，其中改性杂多酸固载化催化剂具有如下结构通式I：
Figure PCTCN2019080417-appb-000006
其中，n为3～20中的任意一个整数，a为250～300中的任意一个整数，b为10～50中的任意一个整数，R 1、R 2和R 3各自独立地选自C 1～C 10的烃基中的任意一种。
本申请采用具有上述通式的改性杂多酸固载化催化剂，经过试验验证该催化剂催化氯丙烯和双氧水环氧化时，可以避免环氧氯丙烷在酸性条件下与水发生水解的副反应，从而使得环氧氯丙烷的收率和选择性得到提高；同时，该催化剂使用时可以使氯丙烯的用量减小，即使氯丙烯与双氧水的摩尔比不足4:1也能够实现较高的环氧氯丙烷收率，因此降低了原料成本；进一步地由于本申请的催化剂为固载化催化剂，因此催化剂的回收率较高，节约了催化剂成本。
为了进一步提高催化剂的选择性，优选上述通式I中，n为7～14中的任意一个整数，R 1、R 2和R 3各自独立地选自C 1～C 4的烷基中的任意一种。
如前所描述的，本申请的氯丙烯用量减少，优选上述氯丙烯和双氧水的摩尔比为0.85～2.00:1，更优选为0.95～1.50:1。在上述摩尔比范围内，保证了氯丙烯的低用量，且能够保证环氧氯丙烷较高的收率和选择性。
为了进一步提高氯丙烯的转化率，优选上述氯丙烯进料质量空速为1.5～10.0h -1，优选为3.0～6.0h -1。
本申请的环氧化反应的温度可以采用现有技术中常用的温度，优选上述环氧化反应的反应温度为30～90℃；更优选为40～80℃。以进一步保证反应的高效稳定性。
在本申请一种实施例中，上述环氧化反应在减压体系中进行，优选减压体系的真空度为5～65kPa，进一步优选为20～60kPa。通过控制反应体系的压力，一方面提高反应的安全性，另一方面便于产物分离。
在本申请另一种实施例中，上述方法包括：在减压体系中，将氯丙烯从底部送入装有改性杂多酸固载化催化剂的反应器内，将双氧水从顶部送入反应器，使氯丙烯和双氧水发生环氧化反应，得到环氧氯丙烯，优选反应器为固定床反应器。将上述环氧化反应在反应器中反应，所得产物和副产物直接可以从反应器中分离出来，比如反应的同时，氯丙烯、环氧氯丙烷和水从反应器的顶部汽提出***，一氯丙二醇和另一部分水从反应器的底部出***；顶部反应液油水分层，油层冷却后测定组成，水层并入底部反应液后冷却后测定组成。由此可见，上述实施例中环氧化反应和产物分离过程耦合，因此可以节省设备，简化整个工艺过程。
在本申请另一种典型的实施方式中，提供了一种改性杂多酸固载化催化剂，改性杂多酸固载化催化剂具有如下结构通式I：
Figure PCTCN2019080417-appb-000007
其中，n为3～20中的任意一个整数，a为250～300中的任意一个整数，b为10～50中的任意一个整数，R 1、R 2和R 3各自独立地选自C 1～C 10的烃基中的任意一种。
经过试验验证上述催化剂催化氯丙烯和双氧水环氧化时，可以避免环氧氯丙烷在酸性条件下与水发生水解的副反应，从而使得环氧氯丙烷的收率和选择性得到提高；同时，该催化剂使用时可以使氯丙烯的用量减小，即使氯丙烯与双氧水的摩尔比不足4:1也能够实现较高的环氧氯丙烷收率，因此降低了原料成本；进一步地由于本申请的催化剂为固载化催化剂，因此催化剂的回收率较高，节约了催化剂成本。
为了进一步提高催化剂的选择性，优选上述通式I中，n为7～14中的任意一个整数，R 1、R 2和R 3各自独立地选自C 1～C 4的烷基中的任意一种。
在本申请又一种典型的实施方式中，提供了一种改性杂多酸固载化催化剂的制备方法，该制备方法包括：步骤S1，将季铵盐的有机溶液与过氧磷钨酸混合后反应，形成具有结构通式II的杂多酸单体，结构通式II为：
Figure PCTCN2019080417-appb-000008
其中n为3～20中的任意一个整 数，R 1、R 2和R 3各自独立地选自C 1～C 4的烷基中的任意一种；步骤S2，将杂多酸单体与N-异丙基丙烯酰胺进行聚合反应，得到改性杂多酸固载化催化剂。
以季铵盐的有机溶液和过氧磷钨酸为原料形成具有上述结构通式II的杂多酸单体，然后再进行聚合反应，过程简单，易于实现。
为了提高反应效率，优选有机溶液的有机溶剂为氯甲烷、二氯甲烷、氯仿、四氯化碳和二氯乙烷组成的组中的任意一种或多种，优选季铵盐的结构式为
Figure PCTCN2019080417-appb-000009
的n为3～20中的任意一个整数，优选7～14中的任意一个整数；优选季铵盐与过氧磷钨酸反应的反应温度为10～60℃，优选为20～40℃，反应时间为1～10h，优选为3～5h。
本申请的过氧磷钨酸可以采用现有技术的制备方法来制备，为了提高本申请的制备方法的易控性并降低成本，优选上述步骤S1包括过氧磷钨酸的制备过程，该制备过程包括：常温常压下，将钨酸钠和磷酸在酸性水溶液中反应生成磷钨酸溶液；利用双氧水氧化磷钨酸溶液后生成过氧磷钨酸溶液，其中，钨酸钠和磷酸的摩尔比为3.0～5.0:1，优选3.5～4.5:1；优选酸性水溶液中的水量为钨酸钠重量的3～10倍，更优选5～8倍；优选酸性水溶液为的酸为盐酸，优选HCl与钨酸钠的摩尔比为1.5～3.0:1，更优选2.0～2.5:1；优选双氧水与钨酸钠的摩尔比为1～10:1，更优选3～8:1；优选季铵盐与钨酸钠的摩尔比为2.8～3.3:4，更优选3.0～3.2:4。所得到的过氧磷钨酸溶液不需要经过提纯直接进行下一步的单体制备。
在本申请一种实施例中，上述步骤S2包括：将杂多酸单体与N-异丙基丙烯酰胺在自由基引发剂和溶剂存在的条件下进行聚合反应，优选自由基引发剂为偶氮二异丁腈、偶氮二异庚腈或叔丁基过氧化氢，溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或二甲亚砜；优选聚合反应的温度为60～80℃；优选N-异丙基丙烯酰胺与季铵盐的摩尔比为5～25:1，优选7～10:1。在上述条件下进行聚合反应，可以提高聚合反应效率，并且易于调整所得催化剂的分子量大小。
以下用具体的实施例来说明本发明的技术方案和技术效果，但本发明的保护范围不限于此。
催化剂合成实施例
实施例1-1
(1)杂多酸单体制备：常温常压下，将钨酸钠33.0g和质量浓度为85％磷酸3.8g溶于198.0g的水中，加入质量浓度为30％盐酸28.0g，此时在酸性条件下生成磷钨酸溶液，向磷钨酸溶液中加入质量浓度为50％双氧水54.4g，氧化后生成过氧磷钨酸溶液；再将事先配置好的质量浓度为6wt％[C 5H 11N(CH 3) 3]Cl(直链型季铵盐)的二氯乙烷溶液206.7g(含季铵盐12.4g)加入至上述过氧磷钨酸溶液中，在20℃下反应4h，反应后，产物经离心、洗涤、干燥，得到杂多酸单体I 30.8g，制备收率86.9％；
(2)杂多酸单体聚合：向耐压反应瓶中依次加入N-异丙基丙烯酰胺5.7g、杂多酸单体I 14.1g、自由基引发剂偶氮二异丁腈0.1g和溶剂N,N-二甲基甲酰胺(或N,N-二甲基乙酰胺)200g，并搅拌使各物质溶解，除氧，然后在70℃下进行聚合反应4h，反应结束后将产物通过沉淀、离心、干燥得到固载型杂多酸催化剂I 19.4g。
实施例1-2
(1)杂多酸单体制备：常温常压下，将钨酸钠33.0g和质量浓度为85％磷酸3.3g溶于99.0g的水中，加入质量浓度为30％盐酸30.4g，此时在酸性条件下生成磷钨酸溶液，向磷钨酸溶液中加入质量浓度为50％双氧水20.4g，氧化后生成过氧磷钨酸溶液；再将事先配置好的质量浓度为6wt％[C 18H 35N(CH 3) 3]Cl(直链型季铵盐)的二氯乙烷溶液450.0g(含季铵盐27.0g)加入过氧磷钨酸的溶液中，在30℃下反应3h，反应后，产物经离心、洗涤、干燥，得到杂多酸单体II 45.9g，制备收率95.2％；
(2)杂多酸单体聚合：向耐压反应瓶中依次加入N-异丙基丙烯酰胺11.3g、杂多酸单体II19.3g、自由基引发剂偶氮二异丁腈(或偶氮二异庚腈)0.1g和溶剂N,N-二甲基甲酰胺200g，并搅拌使各物质溶解，除氧，然后在70℃下进行聚合反应4h，反应结束后将产物通过沉淀、离心、干燥得到固载型杂多酸催化剂II 30.0g。
实施例1-3
(1)杂多酸单体制备：常温常压下，将钨酸钠33.0g和85％磷酸2.3g溶于264.0g的水中，加入30％盐酸24.3g，此时在酸性条件下生成磷钨酸溶液，向磷钨酸溶液中加入50％双氧水68.0g，氧化后生成过氧钨酸溶液；再将事先配置好的6wt％[C 13H 25N(CH 3) 3]Cl(直链型季铵盐)的二氯乙烷溶液328.3g(含季铵盐19.7g)加入过氧磷钨酸的溶液中，在10℃下反应1h，反应后，产物经离心、洗涤、干燥，得到杂多酸单体III 34.9g，制备收率79.3％；
(2)杂多酸单体聚合：向耐压反应瓶中依次加入N-异丙基丙烯酰胺9.0g、杂多酸单体III17.6g、自由基引发剂偶氮二异丁腈0.1g和溶剂N,N-二甲基甲酰胺200g，并搅拌使各物质溶解，除氧，然后在70℃下进行聚合反应4h，反应结束后将产物通过沉淀、离心、干燥得到固载型杂多酸催化剂III 26.1g。
实施例1-4
(1)杂多酸单体制备：常温常压下，将钨酸钠33.0g和85％磷酸2.9g溶于165.0g的水中，加入30％盐酸36.5g，此时在酸性条件下生成磷钨酸溶液，向磷钨酸溶液中加入50％双氧水6.8g，氧化后生成过氧钨酸溶液；再将事先配置好的6wt％[C 9H 17N(CH 3) 3]Cl(直链型季铵盐)的二氯乙烷溶液310.0g(含季铵盐18.6g)加入过氧磷钨酸的溶液中，在60℃下反应5h，反应后，产物经离心、洗涤、干燥，得到杂多酸单体IV 36.9g，制备收率92.7％；
(2)杂多酸单体聚合：向耐压反应瓶中依次加入N-异丙基丙烯酰胺28.3g、杂多酸单体IV15.9g、自由基引发剂偶氮二异丁腈(或叔丁基过氧化氢)0.1g和溶剂N,N-二甲基甲酰胺(或 二甲亚砜)200g，搅拌使各物质溶解，除氧，然后在70℃下进行聚合反应4h，反应结束后将产物通过沉淀、离心、干燥得到固载型杂多酸催化剂IV 43.3g。
实施例1-5
(1)杂多酸单体制备：常温常压下，将钨酸钠33.0g和85％磷酸2.6g溶于330.0g的水中，加入30％盐酸18.3g，此时在酸性条件下生成磷钨酸溶液，向磷钨酸溶液中加入50％双氧水34.0g，氧化后生成过氧钨酸溶液；再将事先配置好的6wt％[C 23H 45N(CH 3) 3]Cl(直链型季铵盐)的二氯乙烷溶液508.3g(含季铵盐30.5g)加入过氧磷钨酸的溶液中，在40℃下反应10h，反应后，产物经离心、洗涤、干燥，得到杂多酸单体V 49.3g，制备收率90.4％；
(2)杂多酸单体聚合：向耐压反应瓶中依次加入N-异丙基基丙烯酰胺7.9g、杂多酸单体V 21.8g、自由基引发剂偶氮二异丁腈0.1g和溶剂N,N-二甲基甲酰胺200g，搅拌使各物质溶解，除氧，然后在70℃下进行聚合反应4h，反应结束后将产物通过沉淀、离心、干燥得到固载型杂多酸催化剂V 29.1g。
实施例1-6
(1)杂多酸单体制备同实施例1-1。
(2)杂多酸单体聚合：向耐压反应瓶中依次加入N-异丙基丙烯酰胺5.7g、杂多酸单体I 14.1g、自由基引发剂偶氮二异丁腈(AIBN)0.1g和溶剂N,N-二甲基甲酰胺200g，并搅拌使各物质溶解，除氧，然后在60℃下进行聚合反应5h，反应结束后将产物通过沉淀、离心、干燥得到固载型杂多酸催化剂I 19.1g。
实施例1-7
(1)杂多酸单体制备同实施例1-1。
(2)杂多酸单体聚合：向耐压反应瓶中依次加入N-异丙基丙烯酰胺5.7g、杂多酸单体I 14.1g、自由基引发剂偶氮二异丁腈(AIBN)0.1g和溶剂N,N-二甲基甲酰胺200g，并搅拌使各物质溶解，除氧，然后在80℃下进行聚合反应4h，反应结束后将产物通过沉淀、离心、干燥得到固载型杂多酸催化剂I 19.6g。
实施例1-8
(1)杂多酸单体制备：常温常压下，将钨酸钠33.0g和85％磷酸2.6g溶于330.0g的水中，加入30％盐酸18.3g，此时在酸性条件下生成磷钨酸溶液，向磷钨酸溶液中加入50％双氧水34.0g，氧化后生成过氧钨酸溶液；再将事先配置好的6wt％[C 23H 45N(C 4H 9) 3]Cl(直链型季铵盐)的二氯乙烷溶液508.3g(含季铵盐39.7g)加入过氧磷钨酸的溶液中，在40℃下反应10h，反应后，产物经离心、洗涤、干燥，得到杂多酸单体VI 59.0g，制备收率92.5％；
(2)杂多酸单体聚合：向耐压反应瓶中依次加入N-异丙基基丙烯酰胺7.9g、杂多酸单体VI 25.6g、自由基引发剂偶氮二异丁腈(AIBN)0.1g和溶剂N,N-二甲基甲酰胺200g，搅拌使 各物质溶解，除氧，然后在70℃下进行聚合反应4h，反应结束后将产物通过沉淀、离心、干燥得到固载型杂多酸催化剂VI 33.2g。
环氧化实施例
实施例2-1
向500mL四口烧瓶中投入氯丙烯309.0g和催化剂I 19.4g，升温至回流，在搅拌状态下2h内滴加49.1％双氧水69.6g，回流温度下继续反应3h；反应结束后离心、静置分层得环氧氯丙烷油层和水层，油层和水层进行GC定量分析环氧氯丙烷和3-氯-1,2-丙二醇含量，水层测定残留双氧水含量。
实施例2-2
向500mL四口烧瓶中投入氯丙烯309.0g和催化剂II 30.0g，升温至回流，在搅拌状态下2h内滴加49.1％双氧水69.6g，回流温度下继续反应5h；反应结束后离心、静置分层得环氧氯丙烷油层和水层，油层和水层进行GC定量分析环氧氯丙烷和3-氯-1,2-丙二醇含量，水层测定残留双氧水含量。
实施例2-3
向500mL四口烧瓶中投入氯丙烯309.0g和催化剂III 26.1g，升温至回流，在搅拌状态下2h内滴加49.1％双氧水69.6g，回流温度下继续反应1h；反应结束后离心、静置分层得环氧氯丙烷油层和水层，油层和水层进行GC定量分析环氧氯丙烷和3-氯-1,2-丙二醇含量，水层测定残留双氧水含量。
实施例2-4
向500mL四口烧瓶中投入氯丙烯309.0g和催化剂IV 43.3g，升温至回流，在搅拌状态下1h内滴加49.1％双氧水69.6g，回流温度下反应3h；反应结束后离心、静置分层得环氧氯丙烷油层和水层，油层和水层进行GC定量分析环氧氯丙烷和3-氯-1,2-丙二醇含量，水层测定残留双氧水含量。
实施例2-5
向500mL四口烧瓶中投入氯丙烯309.0g和催化剂V 29.1g，升温至回流，在搅拌状态下2h内滴加49.1％双氧水69.6g，回流温度下反应4h；反应结束后离心、静置分层得环氧氯丙烷油层和水层，油层和水层进行GC定量分析环氧氯丙烷和3-氯-1,2-丙二醇含量，水层测定残留双氧水含量。
实施例2-6
向500mL四口烧瓶中投入氯丙烯309.0g和催化剂VI 33.2g，升温至回流，在搅拌状态下2h内滴加49.1％双氧水69.6g，回流温度下反应4h；反应结束后离心、静置分层得环氧氯 丙烷油层和水层，油层和水层进行GC定量分析环氧氯丙烷和3-氯-1,2-丙二醇含量，水层测定残留双氧水含量。
对比实施例2-1
向500mL四口烧瓶中投入氯丙烯309.0g和杂多酸单体I 14.1g，升温至回流，在搅拌状态下2h内滴加49.1％双氧水69.6g，回流温度下继续反应3h；反应结束后离心、静置分层得环氧氯丙烷油层和水层，油层和水层进行GC定量分析环氧氯丙烷和3-氯-1,2-丙二醇含量，水层测定残留双氧水含量。
对比实施例2-2
向500mL四口烧瓶中投入氯丙烯309.0g和杂多酸单体V 21.8g，升温至回流，在搅拌状态下2h内滴加49.1％双氧水69.6g，回流温度下反应4h；反应结束后离心、静置分层得环氧氯丙烷油层和水层，油层和水层进行GC定量分析环氧氯丙烷和3-氯-1,2-丙二醇含量，水层测定残留双氧水含量。
通过上述所测定的环氧氯丙烷、3-氯-1,2-丙二醇、双氧水含量计算环氧氯丙烷的选择性、3-氯-1,2-丙二醇的选择性、双氧水的转化率和利用率。
反应液经离心回收催化剂，真空干燥后得回收催化剂干基重量；催化剂干基经ICP测定其中P和W，得催化剂回收率。具体结果见表1。
表1
Figure PCTCN2019080417-appb-000010
实施例2-7
向500mL四口烧瓶中投入氯丙烯309.0g和催化剂II 30.0g，升温至回流，在搅拌状态下2h内滴加49.1％双氧水69.6g，回流温度下反应2h；反应结束后离心、静置分层得环氧氯 丙烷油层和水层，油层和水层进行GC定量分析环氧氯丙烷和3-氯-1,2-丙二醇含量，水层测定残留双氧水含量。回收催化剂，补加0.24g新催化剂，循环使用5次，催化情况见下表2。
表2
Figure PCTCN2019080417-appb-000011
实施例3-1
用计量泵按空速为8.0h -1将氯丙烯从底部泵入装有自制改性的杂多酸固载化催化剂I的固定床反应器内，双氧水与氯丙烯按摩尔比1:1.10从顶部泵入固定床反应器，在30℃和体系真空度为5KPa下反应；反应的同时，氯丙烯、环氧氯丙烷和水从反应器的顶部汽提出***，一氯丙二醇和另一部分水从反应器的底部出***；顶部反应物油水分层，油层冷却后组成为氯丙烯26.1％、环氧氯丙烷73.5％和水0.4％，水层并入底部反应液后冷却后组成为双氧水0.5％、环氧氯丙烷1.5％、一氯丙二醇3.4％和水94.6％，双氧水转化率为99.0％、环氧氯丙烷和一氯丙二醇收率分别为69.0％和2.1％、环氧氯丙烷选择性为97.1％和双氧水利用率为71.7％。上述流程可参考图1。
实施例3-2
用计量泵按空速为4.0h -1将氯丙烯从底部泵入装有自制改性的杂多酸固载化催化剂II的固定床反应器内，双氧水与氯丙烯按摩尔比1:1.20从顶部泵入固定床反应器，在60℃和体系真空度为20kPa下反应；反应的同时，氯丙烯、环氧氯丙烷和水从反应器的顶部汽提出***，一氯丙二醇和另一部分水从反应器的底部出***；顶部反应物油水分层，油层冷却后组成为氯丙烯11.4％、环氧氯丙烷88.1％和水0.5％，水层并入底部反应液后冷却后组成为双氧水0.4％、环氧氯丙烷1.3％、一氯丙二醇4.5％和水93.8％，双氧水转化率为99.2％、环氧氯丙烷和一氯丙二醇收率分别为89.7％和2.7％、环氧氯丙烷选择性为97.0％和双氧水利用率为93.2％。
实施例3-3
用计量泵按空速为10.0h -1将氯丙烯从底部泵入装有自制改性的杂多酸固载化催化剂IV的固定床反应器内，双氧水与氯丙烯按摩尔比1:0.90从顶部泵入固定床反应器，在60℃和体系真空度为15kPa下反应；反应的同时，氯丙烯、环氧氯丙烷和水从反应器的顶部汽提出***，一氯丙二醇和另一部分水从反应器的底部出***；顶部反应物油水分层，油层冷却后组成为氯丙烯21.9％、环氧氯丙烷77.5％和水0.6％，水层并入底部反应液后冷却后组成为双氧 水0.3％、环氧氯丙烷1.6％、一氯丙二醇5.4％和水92.7％，双氧水转化率为99.4％、环氧氯丙烷和一氯丙二醇收率分别为59.7％和3.3％、环氧氯丙烷选择性为94.8％和双氧水利用率为63.4％。
实施例3-4
用计量泵按空速为6.0h -1将氯丙烯从底部泵入装有自制改性的杂多酸固载化催化剂III的固定床反应器内，双氧水与氯丙烯按摩尔比1:1.50从顶部泵入固定床反应器，在50℃和体系真空度为15kPa下反应；反应的同时，氯丙烯、环氧氯丙烷和水从反应器的顶部汽提出***，一氯丙二醇和另一部分水从反应器的底部出***；顶部反应物油水分层，油层冷却后组成为氯丙烯21.9％、环氧氯丙烷77.5％和水0.6％，水层并入底部反应液后冷却后组成为双氧水0.5％、环氧氯丙烷1.8％、一氯丙二醇4.1％和水93.6％，双氧水转化率为99.0％、环氧氯丙烷和一氯丙二醇收率分别为84.9％和2.5％、环氧氯丙烷选择性为97.2％和双氧水利用率为88.3％。
实施例3-5
用计量泵按空速为3.0h -1将氯丙烯从底部泵入装有自制改性的杂多酸固载化催化剂V的固定床反应器内，双氧水与氯丙烯按摩尔比1:2.00从顶部泵入固定床反应器，在90℃和体系真空度为60kPa下反应；反应的同时，氯丙烯、环氧氯丙烷和水从反应器的顶部汽提出***，一氯丙二醇和另一部分水从反应器的底部出***；顶部反应物油水分层，油层冷却后组成为氯丙烯46.4％、环氧氯丙烷52.9％和水0.7％，水层并入底部反应液后冷却后组成为双氧水0.1％、环氧氯丙烷1.1％、一氯丙二醇7.3％和水91.5％，双氧水转化率为99.8％、环氧氯丙烷和一氯丙二醇收率分别为89.6％和4.4％、环氧氯丙烷选择性为95.3％和双氧水利用率为94.2％。
实施例3-6
用计量泵按空速为2.0h -1将氯丙烯从底部泵入装有自制改性的杂多酸固载化催化剂V的固定床反应器内，双氧水与氯丙烯按摩尔比1:1.30从顶部泵入固定床反应器，在80℃和常压下反应；反应的同时，氯丙烯、环氧氯丙烷和水从反应器的顶部汽提出***，一氯丙二醇和另一部分水从反应器的底部出***；顶部反应物油水分层，油层冷却后组成为氯丙烯15.9％、环氧氯丙烷83.3％和水0.8％，水层并入底部反应液后冷却后组成为双氧水0.1％、环氧氯丙烷1.2％、一氯丙二醇6.4％和水92.3％，双氧水转化率为99.8％、环氧氯丙烷和一氯丙二醇收率分别为91.8％和3.9％、环氧氯丙烷选择性为95.9％和双氧水利用率为95.8％。
实施例3-7
用计量泵按空速为3.0h -1将氯丙烯从底部泵入装有自制改性的杂多酸固载化催化剂II的固定床反应器内，双氧水与氯丙烯按摩尔比1:1.10从顶部泵入固定床反应器，在60℃和体系真空度为20kPa下反应；反应的同时，氯丙烯、环氧氯丙烷和水从反应器的顶部汽提出***，一氯丙二醇和另一部分水从反应器的底部出***；顶部反应物油水分层，油层冷却后组成为 氯丙烯3.1％、环氧氯丙烷96.5％和水0.4％，水层并入底部反应液后冷却后组成为双氧水0.2％、环氧氯丙烷1.7％、一氯丙二醇4.8％和水93.3％，双氧水转化率为99.6％、环氧氯丙烷和一氯丙二醇收率分别为90.3％和2.9％、环氧氯丙烷选择性为96.9％和双氧水利用率为93.6％。
实施例3-8
用计量泵按空速为4.0h -1将氯丙烯从底部泵入装有自制改性的杂多酸固载化催化剂I的固定床反应器内，双氧水与氯丙烯按摩尔比1:1.20从顶部泵入固定床反应器，在70℃和体系真空度为40kPa下反应；反应的同时，氯丙烯、环氧氯丙烷和水从反应器的顶部汽提出***，一氯丙二醇和另一部分水从反应器的底部出***；共运行500h，催化剂活性稳定。顶部反应物油水分层，油层冷却后组成为氯丙烯9.6％、环氧氯丙烷89.9％和水0.5％，水层并入底部反应液后冷却后组成为双氧水0.3％、环氧氯丙烷1.3％、一氯丙二醇5.4％和水93.0％，双氧水转化率为99.4％、环氧氯丙烷和一氯丙二醇收率分别为91.5％和3.3％、环氧氯丙烷选择性为96.5％和双氧水利用率为95.3％。
实施例3-9
用计量泵按空速为3.0h -1将氯丙烯从底部泵入装有自制改性的杂多酸固载化催化剂V的固定床反应器内，双氧水与氯丙烯按摩尔比1:0.85从顶部泵入固定床反应器，在50℃和体系真空度为50kPa下反应；反应的同时，氯丙烯、环氧氯丙烷和水从反应器的顶部汽提出***，一氯丙二醇和另一部分水从反应器的底部出***；顶部反应物油水分层，油层冷却后组成为环氧氯丙烷99.6％和水0.4％，水层并入底部反应液后冷却后组成为双氧水0.3％、环氧氯丙烷1.8％、一氯丙二醇0.5％和水97.4％，双氧水转化率为99.4％、环氧氯丙烷和一氯丙二醇收率分别为77.2％和0.3％、环氧氯丙烷选择性为99.6％和双氧水利用率为77.9％。
实施例3-10
用计量泵按空速为3.0h -1将氯丙烯从底部泵入装有自制改性的杂多酸固载化催化剂III的固定床反应器内，双氧水与氯丙烯按摩尔比1:0.99从顶部泵入固定床反应器，在60℃和体系真空度为20kPa下反应；反应的同时，氯丙烯、环氧氯丙烷和水从反应器的顶部汽提出***，一氯丙二醇和另一部分水从反应器的底部出***；顶部反应物油水分层，油层冷却后组成为氯丙烯0.1％、环氧氯丙烷99.5％和水0.4％，水层并入底部反应液后冷却后组成为双氧水0.5％、环氧氯丙烷1.9％、一氯丙二醇5.7％和水91.9％，双氧水转化率为99.1％、环氧氯丙烷和一氯丙二醇收率分别为87.3％和3.3％、环氧氯丙烷选择性为96.3％和双氧水利用率为91.5％。
实施例3-11
用计量泵按空速为3.0h -1将氯丙烯从底部泵入装有自制改性的杂多酸固载化催化剂III的固定床反应器内，双氧水与氯丙烯按摩尔比1:0.99从顶部泵入固定床反应器，在40℃和体系真空度为20kPa下反应；反应的同时，氯丙烯、环氧氯丙烷和水从反应器的顶部汽提出***， 一氯丙二醇和另一部分水从反应器的底部出***；顶部反应物油水分层，油层冷却后组成为氯丙烯0.21％、环氧氯丙烷99.5％和水0.34％，水层并入底部反应液后冷却后组成为双氧水0.8％、环氧氯丙烷1.6％、一氯丙二醇5.6％和水91.9％，双氧水转化率为98.51％、环氧氯丙烷和一氯丙二醇收率分别为87.1％和3.1％、环氧氯丙烷选择性为96.5％和双氧水利用率为90.8％。
实施例3-12
用计量泵按空速为1.5h -1将氯丙烯从底部泵入装有自制改性的杂多酸固载化催化剂VI的固定床反应器内，双氧水与氯丙烯按摩尔比1:0.95从顶部泵入固定床反应器，在30℃和体系真空度为65kPa下反应；反应的同时，氯丙烯、环氧氯丙烷和水从反应器的顶部汽提出***，一氯丙二醇和另一部分水从反应器的底部出***；顶部反应物油水分层，油层冷却后组成为氯丙烯0.2％、环氧氯丙烷99.3％和水0.5％，水层并入底部反应液后冷却后组成为双氧水0.1％、环氧氯丙烷1.7％、一氯丙二醇5.5％和水92.7％，双氧水转化率为99.8％、环氧氯丙烷和一氯丙二醇收率分别为86.9％和2.8％、环氧氯丙烷选择性为96.9％和双氧水利用率为93.4％。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (20)

  1. 一种氯丙烯直接环氧化制备环氧氯丙烷的方法，其特征在于，在减压体系中，用计量泵按一定的空速将氯丙烯从底部泵入装有改性杂多酸固载化催化剂的固定床反应器内，双氧水与氯丙烯按一定的摩尔比从顶部泵入固定床反应器，在一定温度和压力下反应；反应的同时，氯丙烯、环氧氯丙烷和水从反应器的顶部汽提出***，一氯丙二醇和另一部分水从反应器的底部出***；顶部反应液油水分层，油层冷却后测定组成，水层并入底部反应液后冷却后测定组成。
  2. 根据权利要求1所述的方法，其特征在于，所述的氯丙烯和双氧水的摩尔比为0.85～2.00:1。
  3. 根据权利要求2所述的方法，其特征在于，所述的氯丙烯和双氧水的摩尔比为0.95～1.50:1。
  4. 根据权利要求1所述的方法，其特征在于，所述的氯丙烯进料质量空速为1.5～10.0h -1。
  5. 根据权利要求4所述的方法，其特征在于，所述的氯丙烯进料质量空速为3.0～6.0h -1。
  6. 根据权利要求1所述的方法，其特征在于，所述的反应温度为30-90℃；减压体系真空度为5～65kPa。
  7. 根据权利要求6所述的方法，其特征在于，所述的反应温度为40-80℃；减压体系真空度为20～60kPa。
  8. 根据权利要求1所述的方法，其特征在于，所述改性杂多酸固载化催化剂具有如下结构通式I：
    Figure PCTCN2019080417-appb-100001
    其中，n为3～20中的任意一个整数，优选为7～14中任意一个整数，a为250～300中的任意一个整数，b为10～50中的任意一个整数，R 1、R 2和R 3各自独立地选自C 1～C 10的烃基中的任意一种，进一步优选R 1、R 2和R 3各自独立地选自C 1～C 4的烷基中的任意一种。
  9. 一种氯丙烯直接环氧化制备环氧氯丙烷的方法，其特征在于，所述方法包括：
    利用改性杂多酸固载化催化剂催化氯丙烯和双氧水进行环氧化反应，得到环氧氯丙烷，其中所述改性杂多酸固载化催化剂具有如下结构通式I：
    Figure PCTCN2019080417-appb-100002
    其中，n为3～20中的任意一个整数，a为250～300中的任意一个整数，b为10～50中的任意一个整数，R 1、R 2和R 3各自独立地选自C 1～C 10的烃基中的任意一种。
  10. 根据权利要求9所述的方法，其特征在于，所述n为7～14中的任意一个整数,R 1、R 2和R 3各自独立地选自C 1～C 4的烷基中的任意一种。
  11. 根据权利要求9所述的方法，其特征在于，所述氯丙烯和所述双氧水的摩尔比为0.85～2.00:1，优选为0.95～1.50:1。
  12. 根据权利要求9所述的方法，其特征在于，所述氯丙烯进料质量空速为1.5～10.0h -1，优选为3.0～6.0h -1。
  13. 根据权利要求9所述的方法，其特征在于，所述环氧化反应的反应温度为30～90℃；优选为40～80℃。
  14. 根据权利要求9所述的方法，其特征在于，所述环氧化反应在减压体系中进行，优选所述减压体系的真空度为5～65kPa，进一步优选为20～60kPa。
  15. 根据权利要求9至14中任一项所述的方法，其特征在于，所述方法包括：在减压体系中，将所述氯丙烯从底部送入装有所述改性杂多酸固载化催化剂的反应器内，将所述双氧水从顶部送入所述反应器，使所述氯丙烯和所述双氧水发生环氧化反应，得到所述环氧氯丙烯，优选所述反应器为固定床反应器。
  16. 一种改性杂多酸固载化催化剂，其特征在于，所述改性杂多酸固载化催化剂具有如下结构通式I：
    Figure PCTCN2019080417-appb-100003
    其中，n为3～20中的任意一个整数，a为250～300中的任意一个整数，b为10～50中的任意一个整数，R 1、R 2和R 3各自独立地选自C 1～C 10的烃基中的任意一种。
  17. 根据权利要求16所述的改性杂多酸固载化催化剂，其特征在于，所述n为7～14中的任意一个整数，R 1、R 2和R 3各自独立地选自C 1～C 4的烷基中的任意一种。
  18. 权利要求16或17所述的改性杂多酸固载化催化剂的制备方法，其特征在于，所述制备方法包括：
    步骤S1，将季铵盐的有机溶液与过氧磷钨酸混合后反应，形成具有结构通式II的杂多酸单体，所述结构通式II为：
    Figure PCTCN2019080417-appb-100004
    其中n为3～20中的任意一个整数，R 1、R 2和R 3各自独立地选自C 1～C 4的烷基中的任意一种；
    步骤S2，将所述杂多酸单体与N-异丙基丙烯酰胺进行聚合反应，得到所述改性杂多酸固载化催化剂。
  19. 根据权利要求18所述的制备方法，其特征在于，所述有机溶液的有机溶剂为氯甲烷、二氯甲烷、氯仿、四氯化碳和二氯乙烷组成的组中的任意一种或多种，优选所述季铵盐的结构式为
    Figure PCTCN2019080417-appb-100005
    所述的n为3～20中的任意一个整数，优选7～14中的任意一个整数；优选季铵盐与所述过氧磷钨酸反应的反应温度为10～60℃，优选为20～40℃，反应时间为1～10h，优选为3～5h。
  20. 根据权利要求18所述的制备方法，其特征在于，所述步骤S2包括：
    将所述杂多酸单体与N-异丙基丙烯酰胺在自由基引发剂和溶剂存在的条件下进行所述聚合反应，优选所述自由基引发剂为偶氮二异丁腈、偶氮二异庚腈或叔丁基过氧化氢等；所述溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或二甲亚砜；优选所述聚合反应的温度为60～80℃；优选所述N-异丙基丙烯酰胺与所述季铵盐的摩尔比为5～25:1，优选7～10:1。
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