CN111036293A - Preparation method of heteropoly acid catalyst - Google Patents
Preparation method of heteropoly acid catalyst Download PDFInfo
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- CN111036293A CN111036293A CN202010000360.7A CN202010000360A CN111036293A CN 111036293 A CN111036293 A CN 111036293A CN 202010000360 A CN202010000360 A CN 202010000360A CN 111036293 A CN111036293 A CN 111036293A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 21
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 230000001590 oxidative effect Effects 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 230000014759 maintenance of location Effects 0.000 claims abstract description 9
- 238000005086 pumping Methods 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 6
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- -1 quaternary ammonium salt cation Chemical group 0.000 claims description 4
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 4
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 4
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- 229940098424 potassium pyrophosphate Drugs 0.000 claims description 3
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 238000006735 epoxidation reaction Methods 0.000 abstract description 9
- 238000011084 recovery Methods 0.000 abstract description 6
- 150000001336 alkenes Chemical class 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 28
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 12
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 description 9
- SSZWWUDQMAHNAQ-UHFFFAOYSA-N 3-chloropropane-1,2-diol Chemical compound OCC(O)CCl SSZWWUDQMAHNAQ-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- CXTVRRQAGHQLGV-UHFFFAOYSA-M [NH4+].[Cl-].[Cl-].CCCCCCCCCCCCCCCCCCCCCC[N+](C)(C)C Chemical compound [NH4+].[Cl-].[Cl-].CCCCCCCCCCCCCCCCCCCCCC[N+](C)(C)C CXTVRRQAGHQLGV-UHFFFAOYSA-M 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/72—Epoxidation
Abstract
The invention provides a preparation process of a heteropoly acid catalyst, which comprises the following steps: adding a certain amount of sodium tungstate and deionized water into a four-neck flask with a stirring thermometer and a condensing tube at the temperature of 20-30 ℃, stirring and dissolving, adding a certain amount of hydrochloric acid, adding a certain amount of hydrogen peroxide, oxidizing to generate a peroxytungstic acid solution, then adding a certain amount of phosphorus source, and stirring for 20min at the temperature of 20-30 ℃ to define an oxidizing solution; pumping the oxidation liquid and a certain amount of quaternary ammonium salt water solution into a tubular reactor at a certain flow rate, reacting at a certain reaction temperature for a certain retention time to obtain a powdery catalyst, and centrifuging to obtain the heteropoly acid catalyst. The catalyst is used in the process of catalyzing olefin epoxidation, not only shows better activity, but also has higher catalyst recovery rate.
Description
Technical Field
The invention belongs to the field of chemical catalysis, and particularly relates to a preparation method of heteropoly acid and a method for preparing epoxy resin key intermediate epichlorohydrin by catalytic epoxidation.
Background
Olefin epoxidation is one of the very important reactions in the chemical industry, and the traditional processes for preparing epichlorohydrin mainly comprise a propylene high-temperature chlorination method and a glycerol method. The disadvantages of the propylene high-temperature chlorination method are mainly high temperature in the reaction process, more byproducts, large amount of saline wastewater and serious equipment corrosion; the glycerol method is clean in process, but the raw material glycerol is a byproduct of biodiesel, so that enterprises for producing epichlorohydrin by the glycerol method are often limited by the raw material supply of glycerol, and large-scale production cannot be expanded. With the advancement of the national sustainable development strategy, the method needs to provide a method which has the advantages of wide raw material source, short reaction time and high yield and can realize the green and environment-friendly process for preparing the epichlorohydrin. At present, the research at home and abroad mainly focuses on the process for preparing epoxy chloropropane by directly epoxidizing chloropropene by using hydrogen peroxide as an oxygen source and heteropoly acid as a catalyst, and the process route only contains water generated by reaction, does not contain salt, has high atom utilization rate and is green and environment-friendly. The performance of the catalyst is the core of the epoxidation synthesis of chloropropene and the industrial application thereof.
Document j.org.chem., 1988, 53: 1553 and 1557, discloses a basic structure and a preparation process of a phosphotungstic heteropoly acid catalyst, wherein tungstic acid, phosphoric acid, hydrogen peroxide, quaternary ammonium salt and the like are reacted and dried in the presence of an organic solvent to obtain the phosphotungstic heteropoly acid quaternary ammonium salt catalyst Q3PW4O24, wherein Q is quaternary ammonium salt cation.
CN103880779 discloses a more detailed preparation method of phosphotungstic heteropoly acid: 2.50g of tungstic acid was weighed into 10ml of 30% by mass H2O2, heated to 60 ℃ with stirring, and a colorless transparent solution was obtained after 60 minutes. To this solution, 0.29g of phosphoric acid having a mass concentration of 85% was added, and 20mL of distilled water was added and stirring was continued for 30 min. 2.5g of cetyltrimethylammonium chloride was weighed out and dissolved in 40ml of dichloroethane, and this solution was quickly dropped into the above-mentioned hydrogen peroxide solution, and stirring was continued for 60min to obtain a precipitate. The precipitate was washed with distilled water until the filtrate had a pH of about 4. And (3) drying the filtrate in vacuum at 50-60 ℃ to obtain the phosphotungstic heteropoly acid quaternary ammonium salt catalyst QmHnPMxOy, wherein Q is quaternary ammonium salt cation, M is W and/or Mo, M is more than or equal to 1 and less than or equal to 7, x is more than or equal to 1 and less than or equal to 12, n is more than or equal to 0 and less than or equal to 4, and y is more than or equal to 10 and less than or equal to 40.
Although the synthesis of epichlorohydrin by heteropoly acid catalysis is an environment-friendly process and has good catalytic activity, several key problems still exist, which restrict the industrialization of the process. (1) At present, organic solvents cannot be used in the preparation process of heteropoly acid catalysts, so that a great deal of pollution is generated in the preparation process of the catalysts, and safety problems are easily caused in the decomposition process of hydrogen peroxide or peroxide; (2) the heteropoly acid is easy to hydrolyze in the process of catalyzing the synthesis of epoxy chloropropane, inevitably causes a small amount of catalyst to be dissolved in an epoxy chloropropane oil layer and a water layer, influences the recovery rate of the catalyst, and further causes the activity of the recovered catalyst to be unstable. Therefore, the preparation process of the heteropolyacid catalyst with good stability, safety, environmental protection and high performance is developed, the recovery rate of the catalyst is improved, and the preparation process has very important significance for promoting petrochemical production and the like.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a safe and environment-friendly heteropoly acid catalyst preparation process, and the catalyst has the characteristics of high preparation yield, good catalytic activity and strong stability.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme: adding a certain amount of sodium tungstate and deionized water into a four-neck flask with a stirring thermometer and a condensing tube at the temperature of 20-30 ℃, stirring and dissolving, adding a certain amount of hydrochloric acid, adding a certain amount of hydrogen peroxide, oxidizing to generate a peroxytungstic acid solution, then adding a certain amount of phosphorus source, and stirring for 20min at the temperature of 20-30 ℃ to define an oxidizing solution; pumping the oxidation liquid and a certain amount of quaternary ammonium salt water solution into a tubular reactor at a certain flow rate, reacting at a certain reaction temperature for a certain retention time to obtain a powdery catalyst, and centrifuging to obtain the heteropoly acid catalyst.
The structure of the heteropoly acid catalyst is QmHnP2WxOyWherein Q is quaternary ammonium salt cation, m is more than or equal to 1 and less than or equal to 7, n is more than or equal to 0 and less than or equal to 4, x is more than or equal to 1 and less than or equal to 12, and y is more than or equal to 10 and less than or equal to 40.
The weight ratio of the sodium tungstate to the deionized water can be any ratio, and the sodium tungstate can be dissolved in water;
the concentration of the hydrochloric acid is 0.1-36.5%, preferably 10-30%; the molar ratio of the hydrochloric acid to the sodium tungstate is 1.5-3.0: 1, preferably 2.0-2.5: 1;
the concentration of the hydrogen peroxide is 10-70%, preferably 30-50%; the molar ratio of hydrogen peroxide to sodium tungstate is 1-20: 1, preferably 4-12: 1;
the phosphorus source is one or a combination of two of sodium pyrophosphate, potassium pyrophosphate and pyrophosphoric acid, and the molar ratio of the phosphorus source to sodium tungstate is 0.2-1.0: 1, preferably 0.4-0.8: 1;
the molecular formula of the quaternary ammonium salt is [ R ]1R2R3R4N+]Wherein R1, R2, R3 and R4 are C5-C22 linear or branched alkyl groups; the molar ratio of the quaternary ammonium salt to the sodium tungstate is 3-5: 4, preferably 3.5-4.5: 4;
the reaction temperature is 10-60 ℃, and preferably 20-40 ℃; the residence time is 1-5 h, preferably 2-4 h.
Compared with the prior art, the invention has the advantages that: (1) the preparation process of the catalyst does not use an organic solvent, uses hydrogen peroxide which is easy to decompose into oxygen, is safe and clean, and has high preparation yield; (2) due to the catalyst structure QmHnP2WxOyThe structure of P2 is not easy to hydrolyze, and the catalyst not only shows better activity but also has higher catalyst recovery rate when being used for catalyzing olefin epoxidation, especially chloropropene epoxidation.
Detailed Description
Example 1
Adding 40g of sodium tungstate (containing two crystal waters) and 200g of deionized water into a four-neck flask with a stirrer, a thermometer and a condenser at the temperature of 20-30 ℃, stirring and dissolving, adding 87.6g of 10% hydrochloric acid, adding 81.6g of 10% hydrogen peroxide, oxidizing to generate a peroxytungstic acid solution, adding 159.6g of 5% sodium pyrophosphate aqueous solution, and continuously stirring for 0.5h to define the oxidized solution; and pumping 126.5g of the oxidizing solution and 25% of dodecyl trimethyl ammonium chloride aqueous solution into a tubular reactor simultaneously, reacting under the condition of controlling the temperature of the tubular reactor to be 10 ℃ and the retention time to be 5 hours to obtain a powdery catalyst I, centrifuging to obtain 80.6g of a catalyst wet base (containing 25% of moisture), wherein the preparation yield is 97.9%, and the molar ratio of W to P of the catalyst is 2.2.
Example 2
Adding 40g of sodium tungstate (containing two crystal waters) and 100g of deionized water into a four-neck flask with a stirrer, a thermometer and a condenser at the temperature of 20-30 ℃, stirring and dissolving, adding 65.7g of 20% hydrochloric acid, adding 81.6g of 50% hydrogen peroxide, oxidizing to generate a peroxytungstic acid solution, adding 264.0g of 5% potassium pyrophosphate aqueous solution, and continuously stirring for 0.5h to define the oxidized solution; pumping 169.0g of oxidizing solution and 25% hexadecyl trimethyl ammonium chloride aqueous solution into a tubular reactor simultaneously, reacting under the condition of controlling the temperature of the tubular reactor to be 30 ℃ and the retention time to be 3 hours to obtain powdery catalyst II, centrifuging the powdery catalyst II to obtain 88.7g of catalyst wet base (containing 25% of moisture), wherein the preparation yield is 99.0%, and the molar ratio of catalyst W to P is 2.3.
Example 3
Adding 40g of sodium tungstate (containing two crystal waters) and 500g of deionized water into a four-neck flask with a stirrer, a thermometer and a condenser at the temperature of 20-30 ℃, stirring and dissolving, adding 30g of 36.5% hydrochloric acid, adding 81.6g of 50% hydrogen peroxide, oxidizing to generate a peroxytungstic acid solution, adding 71.2g of 5% pyrophosphoric acid aqueous solution, and continuously stirring for 0.5h to define the solution as an oxidized solution; and (2) simultaneously pumping 150.3g of the oxidation solution and 25% of octadecyl trimethyl ammonium chloride aqueous solution into a tubular reactor, reacting under the condition that the temperature of the tubular reactor is controlled to be 60 ℃ and the retention time is 4 hours to obtain a powdery catalyst III, centrifuging to obtain 89.3g of a catalyst wet base (with the moisture content of 25%), wherein the preparation yield is 94.9%, and the molar ratio of W to P of the catalyst is 2.0.
Example 4
Adding 40g of sodium tungstate (containing two crystal waters) and 200g of deionized water into a four-neck flask with a stirrer, a thermometer and a condenser at 0-30 ℃, stirring to dissolve, adding 65.7g of 20% hydrochloric acid, adding 93.2g of 35% hydrogen peroxide to oxidize to generate a peroxytungstic acid solution, adding 60g of a mixed aqueous solution of 5% pyrophosphoric acid and sodium pyrophosphate (the weight ratio is 7:3), and continuously stirring for 0.5h to define the solution as an oxidized solution; and (2) simultaneously pumping 150.3g of the oxidation solution and 25% of octadecyl trimethyl ammonium chloride aqueous solution into a tubular reactor, reacting at 50 ℃ for 2 hours under the control of the temperature of the tubular reactor, so as to obtain a powdery catalyst IV, centrifuging to obtain 92.2g of a catalyst wet base (containing 25% of moisture), wherein the preparation yield is 98.0%, and the molar ratio of W to P of the catalyst is 2.4.
Example 5
Adding 40g of sodium tungstate (containing two crystal waters) and 200g of deionized water into a four-neck flask with a stirrer, a thermometer and a condenser at the temperature of 20-30 ℃, stirring and dissolving, adding 10.9g of 20% hydrochloric acid, adding 40.3g of 50% hydrogen peroxide, oxidizing to generate a peroxytungstic acid solution, adding 71.2g of 5% pyrophosphoric acid aqueous solution, and continuously stirring for 0.5h to define the solution as an oxidized solution; the oxidizing solution and 226.4g of 25% dodecyl trimethyl ammonium chloride aqueous solution are simultaneously pumped into a tubular reactor, and react under the condition of controlling the temperature of the tubular reactor to be 20 ℃ and the retention time to be 5 hours to obtain powdery catalyst V, the wet base (containing 25% of moisture) of the catalyst after centrifugation is 75.8g, the preparation yield is 99.6%, and the molar ratio of the catalyst W to the P is 2.7.
Example 6
Adding 40g of sodium tungstate (containing two crystal waters) and 200g of deionized water into a four-neck flask with a stirrer, a thermometer and a condenser at the temperature of 20-30 ℃, stirring and dissolving, adding 48.2g of 20% hydrochloric acid, adding 36.3g of 50% hydrogen peroxide, oxidizing to generate a peroxytungstic acid solution, adding 71.2g of 5% pyrophosphoric acid aqueous solution, and continuously stirring for 0.5h to define the solution as an oxidized solution; simultaneously pumping 180.5g of oxidizing solution and 25% of behenyl trimethyl ammonium chloride ammonium salt aqueous solution into a tubular reactor, reacting under the condition of controlling the temperature of the tubular reactor to be 20 ℃ and the retention time to be 5 hours to obtain powdery catalyst VI, centrifuging the powdery catalyst VI to obtain 97.1g of catalyst wet base (containing 25% of moisture), wherein the preparation yield is 98.5%, and the molar ratio of the catalyst W to the catalyst P is 1.9.
Comparative example 1
ECH synthesis was carried out with reference to patents CN1355067 and CN103880779, and with reference to catalyst [ pi-C5H 5NC16H33]3[ PW4O16], W/P molar ratio 4.1, and CN 1900071.
Comparative example 2
Referring to patents CN1355067 and CN103880779, the ECH synthesis was carried out with synthetic catalyst [ 70% C16H33N (CH3)3+ 30% C18H37N (CH3)3]3[ PW4O16] W/P molar ratio of 3.9, with reference to CN 1900071.
Example 7
309.0g of chloropropene and 30g of catalyst (the catalyst of examples 1-6 or the catalyst of comparative examples 1-2) are put into a 500mL four-neck flask, the temperature is raised to reflux, 69.6g of 49.1% hydrogen peroxide is dripped into the flask within 2h under the stirring state, and the reaction is continued for 2h at the reflux temperature; and after the reaction is finished, centrifuging, standing and layering to obtain an epichlorohydrin oil layer and a water layer, carrying out GC (gas chromatography) quantitative analysis on the epichlorohydrin and the 3-chloro-1, 2-propanediol content in the oil layer and the water layer, and measuring the residual hydrogen peroxide content in the water layer.
Table 1: data on catalytic performance
The above table shows that the catalyst provided by the invention is used for synthesizing epichlorohydrin by chloropropene epoxidation, the recovery rate of the catalyst is high, and the yield of the hydrolysis byproduct 3-chloro-1, 2-propanediol is controllable in the reaction environment of epichlorohydrin.
Example 8
309.0g of chloropropene and 30.0g of catalyst (example 1) are put into a 500mL four-neck flask, the temperature is raised to reflux, 69.6g of 49.1% hydrogen peroxide is dripped into the flask within 2h under the stirring state, and the mixture reacts for 2h at the reflux temperature; and after the reaction is finished, centrifuging, standing and layering to obtain an epichlorohydrin oil layer and a water layer, carrying out GC (gas chromatography) quantitative analysis on the epichlorohydrin and the 3-chloro-1, 2-propanediol content in the oil layer and the water layer, and measuring the residual hydrogen peroxide content in the water layer. The catalyst was recovered and 0.30g of fresh catalyst was added and recycled for 5 times, the catalytic conditions are shown in the table below.
Table 2 example 8 cyclic reaction performance data
Example 9
309.0g of chloropropene and 30.0g of catalyst (comparative example 2) are added into a 500mL four-neck flask, the temperature is raised to reflux, 69.6g of 49.1% hydrogen peroxide is dropwise added within 2h under the stirring state, and the reaction is carried out for 2h at the reflux temperature; and after the reaction is finished, centrifuging, standing and layering to obtain an epichlorohydrin oil layer and a water layer, carrying out GC (gas chromatography) quantitative analysis on the epichlorohydrin and the 3-chloro-1, 2-propanediol content in the oil layer and the water layer, and measuring the residual hydrogen peroxide content in the water layer. The catalyst was recovered and 0.30g of fresh catalyst was added and recycled for 5 times, the catalytic conditions are shown in the table below.
Table 3 example 9 cycle reaction performance data
As can be seen from tables 2 and 3, when the catalyst of comparative example 2 is used for synthesizing epichlorohydrin by epoxidation of chloropropene, the recovery rate of the catalyst gradually decreases and the yield of the hydrolysis byproduct 3-chloro-1, 2-propanediol of epichlorohydrin gradually increases with the increase of the cycle number of the catalyst. The catalyst provided by the scheme of the invention is used for representing better stability in the process of synthesizing epoxy chloropropane by the epoxidation of chloropropene, and the yield of a hydrolysis byproduct of the epoxy chloropropane, namely 3-chloro-1, 2-propanediol, is controllable.
Claims (9)
1. A preparation method of a heteropoly acid catalyst comprises the following steps: adding a certain amount of sodium tungstate and deionized water into a four-neck flask at the temperature of 20-30 ℃, stirring and dissolving, adding a certain amount of hydrochloric acid, adding a certain amount of hydrogen peroxide, oxidizing to generate a peroxytungstic acid solution, adding a certain amount of phosphorus source, and stirring at the temperature of 20-30 ℃ for 20min to define an oxidizing solution; pumping the oxidation liquid and a certain amount of quaternary ammonium salt water solution into a reactor at a certain flow rate, reacting at a certain reaction temperature for a certain retention time to obtain a powdery catalyst, and centrifuging to obtain the heteropoly acid catalyst.
2. The method for producing a heteropoly acid catalyst according to claim 1, wherein the structure of the heteropoly acid catalyst is QmHnP2WxOyWherein Q is quaternary ammonium salt cation, m is more than or equal to 1 and less than or equal to 7, n is more than or equal to 0 and less than or equal to 4, x is more than or equal to 1 and less than or equal to 12, and y is more than or equal to 10 and less than or equal to 40.
3. The method for preparing the heteropoly acid catalyst according to claim 1, wherein the concentration of the hydrochloric acid is 0.1-36.5%, preferably 10-30%; the molar ratio of the hydrochloric acid to the sodium tungstate is 1.5-3.0: 1, preferably 2.0-2.5: 1.
4. The preparation method of the heteropoly acid catalyst according to claim 1, wherein the concentration of hydrogen peroxide is 10-70%, preferably 30-50%; the molar ratio of the hydrogen peroxide to the sodium tungstate is 1-20: 1, preferably 4-12: 1.
5. The preparation method of the heteropoly acid catalyst according to claim 1, wherein the phosphorus source is one or a combination of two of sodium pyrophosphate, potassium pyrophosphate and pyrophosphoric acid, and the molar ratio of the phosphorus source to sodium tungstate is 0.2-1.0: 1, preferably 0.4-0.8: 1.
6. According to claimThe method for preparing the heteropoly acid catalyst according to claim 1, wherein the molecular formula of the quaternary ammonium salt is R1R2R3R4N+Wherein R1, R2, R3 and R4 are C5-C22 linear or branched alkyl groups.
7. The method for preparing a heteropoly acid catalyst according to claim 1, wherein the molar ratio of the quaternary ammonium salt to the sodium tungstate is 3-5: 4, preferably 3.5-4.5: 4.
8. The preparation method of the heteropoly acid catalyst according to claim 1, wherein the reaction temperature is 10 to 60 ℃ and the residence time is 1 to 5 hours.
9. The method for preparing the heteropoly acid catalyst according to claim 8, wherein the reaction temperature is 20-40 ℃; the retention time is 2-4 h.
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| CN1355067A (en) * | 2000-11-29 | 2002-06-26 | 中国科学院大连化学物理研究所 | Reaction control phase transferring catalyst for oxidizing reaction and its oxidizing reaction process |
| JP2013032340A (en) * | 2011-07-01 | 2013-02-14 | Jnc Corp | Quaternary ammonium salt, oxidation catalyst obtained from the same, and method for producing epoxy derivative using the catalyst |
| JP2013112639A (en) * | 2011-11-29 | 2013-06-10 | Daicel Corp | Quaternary ammonium salt, catalyst for oxidation reaction containing the same, method for producing epoxy compound, and method for separating the catalyst for oxidation reaction |
| CN103880779A (en) * | 2012-12-20 | 2014-06-25 | 中国科学院大连化学物理研究所 | Method utilizing quaternary ammonium heteropolyate to catalyze alkene epoxidation |
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| CN1355067A (en) * | 2000-11-29 | 2002-06-26 | 中国科学院大连化学物理研究所 | Reaction control phase transferring catalyst for oxidizing reaction and its oxidizing reaction process |
| JP2013032340A (en) * | 2011-07-01 | 2013-02-14 | Jnc Corp | Quaternary ammonium salt, oxidation catalyst obtained from the same, and method for producing epoxy derivative using the catalyst |
| JP2013112639A (en) * | 2011-11-29 | 2013-06-10 | Daicel Corp | Quaternary ammonium salt, catalyst for oxidation reaction containing the same, method for producing epoxy compound, and method for separating the catalyst for oxidation reaction |
| CN103880779A (en) * | 2012-12-20 | 2014-06-25 | 中国科学院大连化学物理研究所 | Method utilizing quaternary ammonium heteropolyate to catalyze alkene epoxidation |
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