WO2019196681A1 - Procédé de préparation d'épichlorhydrine par époxydation directe de chloropropène, catalyseur immobilisé hétéropolyacide modifié et procédé de préparation associé - Google Patents

Procédé de préparation d'épichlorhydrine par époxydation directe de chloropropène, catalyseur immobilisé hétéropolyacide modifié et procédé de préparation associé 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)
Chinese (zh)
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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/fr

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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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Epoxy Compounds (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé de préparation d'épichlorhydrine par époxydation directe de chloropropène, un catalyseur immobilisé hétéropolyacide modifié et un procédé de préparation associé ; plus particulièrement, l'invention concerne un procédé de préparation d'épichlorhydrine par époxydation directe de chloropropène en présence d'un catalyseur immobilisé hétéropolyacide modifié à l'aide de peroxyde d'hydrogène en tant que source d'oxygène. Le procédé selon l'invention présente des avantages en termes : ① d'un faible rapport entre le chloropropène et le peroxyde d'hydrogène, et d'une faible quantité de chloropropène ; ② d'un couplage des processus de réaction et de séparation afin de sauvegrader l'équipement, et d'une simplicité du procédé ; ③ le procédé permet également d'empêcher une réaction latérale d'hydrolyse entre l'épichlorhydrine et l'eau dans des conditions acides, permettant ainsi d'obtenir un rendement élevé et une haute sélectivité en épichlorhydrine.
PCT/CN2019/080417 2018-04-10 2019-03-29 Procédé de préparation d'épichlorhydrine par époxydation directe de chloropropène, catalyseur immobilisé hétéropolyacide modifié et procédé de préparation associé WO2019196681A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110833866A (zh) * 2019-11-14 2020-02-25 江苏扬农化工集团有限公司 一种提高环氧化反应催化剂回收率的方法
CN111068781A (zh) * 2020-01-02 2020-04-28 江苏扬农化工集团有限公司 一种杂多酸催化剂的制备及其在氯丙烯环氧化中的应用
CN114824648A (zh) * 2022-03-18 2022-07-29 扬州大学 Pw12@pdadmac/wmcnt修饰聚丙烯隔膜及其在锂硫电池中的应用
CN115894400A (zh) * 2022-12-01 2023-04-04 中国科学院大连化学物理研究所 一种应用液固循环流化床反应器直接氧化氯丙烯制环氧氯丙烷的工艺

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108395418A (zh) * 2018-04-10 2018-08-14 江苏扬农化工集团有限公司 一种氯丙烯直接环氧化制备环氧氯丙烷的工艺
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CN110575809A (zh) * 2019-09-27 2019-12-17 江苏扬农化工集团有限公司 一种连续化合成环氧氯丙烷的反应器及方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003033659A (ja) * 2001-07-26 2003-02-04 Tokyo Kasei Kogyo Kk 新規タングステン触媒，およびそれを用いるアリル型アルコールのエポキシ化法
CN101092406A (zh) * 2006-06-21 2007-12-26 中国石油化工股份有限公司 丙烯环氧化制备环氧丙烷的方法
CN101891711A (zh) * 2010-07-23 2010-11-24 上海化工研究院 一种使用相转移催化剂催化环氧化制备环氧化合物的方法
CN103159703A (zh) * 2011-12-16 2013-06-19 中国科学院大连化学物理研究所 一种氯丙烯直接环氧化连续生产环氧氯丙烷的方法
CN105712955A (zh) * 2014-12-05 2016-06-29 中国科学院大连化学物理研究所 一种氯丙烯环氧化生产环氧氯丙烷的工艺流程
CN108395418A (zh) * 2018-04-10 2018-08-14 江苏扬农化工集团有限公司 一种氯丙烯直接环氧化制备环氧氯丙烷的工艺

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4113573A (en) * 1973-09-20 1978-09-12 Fmc Corporation Method of and apparatus for steam stripping immiscible materials
CN103240127A (zh) * 2013-05-21 2013-08-14 新疆大学 一种温敏型水凝胶负载钨催化剂及其制备方法
CN103351364A (zh) * 2013-07-01 2013-10-16 太仓市恒益医药化工原料厂 一种制备环氧氯丙烷的方法
CN104557784B (zh) * 2013-10-29 2017-09-29 中国石油化工股份有限公司 一种生产环氧丙烷的方法
CN105777671B (zh) * 2014-12-17 2021-01-15 长春人造树脂厂股份有限公司 利用固载杂多酸将烯烃类环氧化的连续式制程
TWI518077B (zh) * 2014-12-17 2016-01-21 長春人造樹脂廠股份有限公司 利用固載雜多酸將烯烴類環氧化的連續式製程

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003033659A (ja) * 2001-07-26 2003-02-04 Tokyo Kasei Kogyo Kk 新規タングステン触媒，およびそれを用いるアリル型アルコールのエポキシ化法
CN101092406A (zh) * 2006-06-21 2007-12-26 中国石油化工股份有限公司 丙烯环氧化制备环氧丙烷的方法
CN101891711A (zh) * 2010-07-23 2010-11-24 上海化工研究院 一种使用相转移催化剂催化环氧化制备环氧化合物的方法
CN103159703A (zh) * 2011-12-16 2013-06-19 中国科学院大连化学物理研究所 一种氯丙烯直接环氧化连续生产环氧氯丙烷的方法
CN105712955A (zh) * 2014-12-05 2016-06-29 中国科学院大连化学物理研究所 一种氯丙烯环氧化生产环氧氯丙烷的工艺流程
CN108395418A (zh) * 2018-04-10 2018-08-14 江苏扬农化工集团有限公司 一种氯丙烯直接环氧化制备环氧氯丙烷的工艺

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110833866A (zh) * 2019-11-14 2020-02-25 江苏扬农化工集团有限公司 一种提高环氧化反应催化剂回收率的方法
CN111068781A (zh) * 2020-01-02 2020-04-28 江苏扬农化工集团有限公司 一种杂多酸催化剂的制备及其在氯丙烯环氧化中的应用
CN114824648A (zh) * 2022-03-18 2022-07-29 扬州大学 Pw12@pdadmac/wmcnt修饰聚丙烯隔膜及其在锂硫电池中的应用
CN115894400A (zh) * 2022-12-01 2023-04-04 中国科学院大连化学物理研究所 一种应用液固循环流化床反应器直接氧化氯丙烯制环氧氯丙烷的工艺
CN115894400B (zh) * 2022-12-01 2024-02-02 中国科学院大连化学物理研究所 一种应用液固循环流化床反应器直接氧化氯丙烯制环氧氯丙烷的工艺

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