CN101450317A - Carbonic allyl ester preparation catalyst through catalyzing urea and 1,2-propylene glycol - Google Patents
Carbonic allyl ester preparation catalyst through catalyzing urea and 1,2-propylene glycol Download PDFInfo
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- CN101450317A CN101450317A CNA2008101816859A CN200810181685A CN101450317A CN 101450317 A CN101450317 A CN 101450317A CN A2008101816859 A CNA2008101816859 A CN A2008101816859A CN 200810181685 A CN200810181685 A CN 200810181685A CN 101450317 A CN101450317 A CN 101450317A
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- propane diols
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000004202 carbamide Substances 0.000 title claims abstract description 28
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 title claims abstract description 6
- -1 allyl ester Chemical class 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 11
- 239000001294 propane Substances 0.000 claims description 25
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 15
- 239000000376 reactant Substances 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 13
- 239000011964 heteropoly acid Substances 0.000 claims description 10
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 3
- 229940072033 potash Drugs 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- PCHQDTOLHOFHHK-UHFFFAOYSA-L zinc;hydrogen carbonate Chemical group [Zn+2].OC([O-])=O.OC([O-])=O PCHQDTOLHOFHHK-UHFFFAOYSA-L 0.000 claims description 2
- 125000005587 carbonate group Chemical group 0.000 claims 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 abstract description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000006136 alcoholysis reaction Methods 0.000 abstract description 5
- 150000005676 cyclic carbonates Chemical class 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000011667 zinc carbonate Substances 0.000 description 6
- 235000004416 zinc carbonate Nutrition 0.000 description 6
- 229910000010 zinc carbonate Inorganic materials 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to a novel catalyst for synthesizing cyclic carbonate, and in particular relates to a catalyst for synthesizing propene carbonate (vinyl carbonate) in reaction of urea and 1,2-propylene glycol or ethylene glycol. Compared with other catalysts, the catalyst has the advantages that the catalyst has simple preparation process and higher catalytic activity, is directly recycled after separated from a reaction system for synthesizing the propene carbonate (vinyl carbonate) through alcoholysis of the urea, does not need to add any auxiliary agent during reaction, and does not pollute the environment.
Description
Technical field
The invention belongs to a kind of new catalyst of synthesizing annular carbonate, specifically a kind of urea and 1 of relating to, the catalyst of 2-propane diols or glycol reaction carbonate synthesis third (second) alkene ester.
Background technology
Cyclic carbonate (Cyclic Carbonates) is a kind of organic solvent of function admirable and important organic chemical industry's product, medicine separate with fine chemicals, organic synthesis, weaving, cosmetics, gas and natural gas and syngas for synthetic ammonia in carbon dioxide and the fields such as absorption of hydrogen sulfide gas, wherein propene carbonate (Propylene Carbonate) electrolyte that can be used as lithium batteries such as mobile phone bears more abominable light, heat and chemical change.Synthetic method mainly contains phosgenation, oxidative carbonylation of methanol method, carbon dioxide and expoxy propane addition process and alcoholysis of urea.Phosgenation is eliminated gradually owing to use extremely toxic substance; Use nitrogen-containing oxide in the reaction of methanol oxidation carbonyl process, serious to equipment corrosion, catalyst is not only relatively more expensive, and the life-span does not reach the suitability for industrialized production requirement; The raw material expoxy propane of carbon dioxide and expoxy propane addition process is subjected to the restriction of petroleum industry, and by-product 1, the constraint of 2-propane diols purity and market conditions.
The alcoholysis of urea synthesizing annular carbonate is raw materials used cheap and easy to get, is the non-petroleum path of competitive cleaning.By urea and 1, the catalyst that 2-propane diols or ethylene glycol carbonate synthesis third (second) alkene ester are adopted mainly contains metal oxide, organic tin, carbonate etc.(US Patent 5003084) such as Su Weiyan investigated the situation that is reflected at ester exchange reaction under catalyst and the catalyst-free condition.Under the catalyst-free condition, amount of urea is 60g, 1, and 2-propane diols consumption is 102g, 170 ℃ of reaction temperatures, reaction time 3h, the selectivity of propene carbonate is 84%, 1, the conversion ratio of 2-propane diols is 43%.Add dibutyl tin dilaurate and make catalyst, the selectivity of propene carbonate is 99%, 1, and the conversion ratio of 2-propane diols is 64%.Kanbara etc. (EP Patent 0638541) adopt ZnO to make catalyst, catalyzing urea and glycol reaction use the mode that vacuumizes to discharge the ammonia of generation, react 2h down at 145 ℃, the conversion ratio of ethylene glycol is 80.1%, and the selectivity of ethylene carbonate is 97.5%.Jia Zhiguang (petroleum journal, 2006, when 22:77-83) having investigated the zinc-iron mixed oxide and make catalyst, catalyst accounts for 1.4% of reactant gross mass, 1,2-propane diols/urea mol ratio is 4,170 ℃ of reaction temperatures, under the optimal condition of reaction time 2h, the highest yield of propene carbonate is 78.4%, but catalyst has formed new crystalline phase in the course of reaction, causes catalyst life shorter.(petrochemical industry, 2006,35 (1): 12) investigated divalence Mg such as Shu Ting
2+, Cu
2+, Zn
2+, Ni
2+With trivalent Al
3+, Fe
3+, Cr
3+Etc. the houghite of several different cation compositions to urea and 1, the catalytic activity of 2-propane diols synthesizing acrylic ester.Experiment shows that houghite is to urea and 1, and the alcoholysis reaction of 2-propane diols has certain catalytic activity, the catalytic activity of houghite obviously improves after the roasting, wherein best with the catalytic activity of Zn-A1 product of roasting, the yield of propene carbonate is 98.7%, but Preparation of catalysts is comparatively loaded down with trivial details.
Summary of the invention
The object of the invention provides a kind of by urea and 1, the novel catalyst of 2-propane diols or glycol reaction carbonate synthesis third (second) alkene ester.
The object of the present invention is achieved like this, and adopting heteropoly acid and corresponding salt is raw material, and carbonate solution slowly is added drop-wise in the heteropolyacid salt solution.
Aforesaid heteropoly acid is phosphomolybdic acid, phosphotungstic acid, silico-tungstic acid.
Aforesaid carbonate is zinc carbonate, basic magnesium carbonate, potash, magnesium carbonate, calcium carbonate.
Preparation method of the present invention is as follows:
Method one: heteropoly acid is dissolved in a certain amount of distilled water, (mol ratio is 1:1～1:10) slowly to add the carbonate of design flow under the mechanical agitation, vacuum filtration is removed unreacted raw material and impurity, filtrate places 60～100 ℃ of waters bath with thermostatic control, evaporating water, 200～400 ℃ of following roastings 3～6 hours, obtain catalyst.
Method two: heteropoly acid is dissolved in a certain amount of distilled water, (heteropoly acid and carbonate mol ratio are 1:1～1:10) slowly to add the carbonate of design flow under mechanical agitation, reacted 1～5 hour, and filtered, filtrate places 60～100 ℃ of waters bath with thermostatic control to concentrate, when solution amount is reduced to a half, be placed in-5～0 ℃ of refrigerators 3～8 hours, centrifugation, be deposited in 60～100 ℃ dry down, in 200～400 ℃ of following roastings 3～6 hours, obtain catalyst.
Catalyst of the present invention is in urea and 1, the process conditions of 2-propane diols (ethylene glycol) carbonate synthesis third (second) alkene ester are that to account for reactant gross mass mark be 1.0～5.0% to catalyst, control reaction system vacuum 0.06～0.07MPa, 140～170 ℃ of reaction temperatures, 3～7 hours reaction time.
Catalyst of the present invention has been compared following advantage with other catalyst:
Preparation of catalysts technology is simple, and catalytic activity is higher, and catalyst directly recycles after separating from urea alcoholysis carbonate synthesis third (second) alkene ester reaction system, need not to add any auxiliary agent in the course of reaction, environmentally safe.
The specific embodiment
Embodiment 1
Add 10.735g phosphomolybdic acid and the reaction of 1.346g zinc carbonate in the reactor, filter, solution in 200 ℃ of following roastings 3 hours, obtains catalyst behind 80 ℃ of evaporates to dryness.
The urea, 1 that in reactor, adds design proportion, 2-propane diols and catalyst, the amount of catalyst accounts for 3.6% of reactant gross mass, vacuum 0.06～0.07MPa, 140 ℃ of reaction temperatures, 4.5 hours reaction time, cooled and filtered, catalyst circulation is used, and product chromatogram ration analysis, propene carbonate yield are 74.31%.
Embodiment 2
Add 25.844g phosphomolybdic acid and 8.683g basic carbonate reactive magnesium in the reactor, filter, solution in 200 ℃ of following roastings 4 hours, obtains catalyst behind 80 ℃ of evaporates to dryness.
The urea, 1 that in reactor, adds design proportion, 2-propane diols and catalyst, the amount of catalyst accounts for 3.0% of reactant gross mass, vacuum 0.06～0.07MPa, 140 ℃ of reaction temperatures, 3 hours reaction time, all the other conditions are with embodiment 1, and the propene carbonate yield is 71.82%.
Embodiment 3
Add 9.402g phosphotungstic acid and 4.546g basic carbonate reactive magnesium in the reactor, filter, solution in 300 ℃ of following roastings 4 hours, obtains catalyst behind 80 ℃ of evaporates to dryness.
Adding mol ratio in reactor is the urea and 1 of 1:2,2-propane diols and catalyst, and the amount of catalyst accounts for 5.5% of reactant gross mass, about vacuum 0.02MPa, 140 ℃ of reaction temperatures, 5 hours reaction time, all the other conditions are with embodiment 1, and the propene carbonate yield is 43.83%.
Embodiment 4
Add 10.735g phosphomolybdic acid and 3.578g potash in the reactor, after reaction is finished solution is evaporated down at 100 ℃, treat that solution amount reduces to a half, solution is positioned in the refrigerator, cooling is after 12 hours down at-3 ℃, and centrifugation separates, 100 ℃ of following evaporating water, in 200 ℃ of following roastings 4 hours, obtain catalyst.
The urea, 1 that in reactor, adds design flow, 2-propane diols and catalyst, the amount of catalyst accounts for 5.5% of reactant gross mass, vacuum is about 0.02MPa, 150 ℃ of reaction temperatures, 3 hours reaction time, all the other conditions are with embodiment 1, and the propene carbonate yield is 54.48%.
Embodiment 5
Add 11.512g silico-tungstic acid and the reaction of 2.967g zinc carbonate in the reactor, filter, solution in 300 ℃ of following roastings 4 hours, obtains catalyst behind 80 ℃ of following evaporates to dryness.
At the urea, 1 of reactor adding design flow, 2-propane diols and catalyst, the amount of catalyst accounts for 5.5% of reactant gross mass, vacuum is 0.06～0.07MPa, is warming up to 150 ℃ under mechanical agitation, reacts 3 hours, all the other conditions are with embodiment 1, and the propene carbonate yield is 62.78%.
Embodiment 6
Add 10.375g phosphomolybdic acid and the reaction of 2.019g zinc carbonate in the reactor, filter, solution in 300 ℃ of following roastings 3 hours, obtains catalyst behind 80 ℃ of following evaporates to dryness.
The urea, 1 that in reactor, adds design flow, 2-propane diols and catalyst, the amount of catalyst accounts for 3.7% of reactant gross mass, vacuum is 0.06～0.07MPa, 150 ℃ of reaction temperatures, 4.5 hours reaction time, all the other conditions are with embodiment 1, and the propene carbonate yield is 71.71%.
Embodiment 7
Add 10.375g phosphomolybdic acid and the reaction of 2.019g zinc carbonate in the reactor, filter, solution in 400 ℃ of following roastings 3 hours, obtains catalyst behind 80 ℃ of following evaporates to dryness.
The urea, 1 that in reactor, adds design flow, 2-propane diols and catalyst, the amount of catalyst accounts for 3.7% of reactant gross mass, vacuum is 0.06～0.07MPa, 140 ℃ of reaction temperatures, 6 hours reaction time, all the other conditions are with embodiment 1, and the propene carbonate yield is 58.74%.
Embodiment 8
Add 10.375g phosphomolybdic acid and the reaction of 2.019g zinc carbonate in the reactor, filter, solution in 250 ℃ of following roastings 4 hours, obtains catalyst behind 100 ℃ of following evaporates to dryness.
The urea, 1 that in reactor, adds design flow, 2-propane diols and catalyst, the amount of catalyst accounts for 3.0% of reactant gross mass, vacuum is 0.06～0.07MPa, 150 ℃ of reaction temperatures, 4.5 hours reaction time, all the other conditions are with embodiment 1, and the propene carbonate yield is 74.22%.
Embodiment 9
Add 10.375g phosphomolybdic acid and the reaction of 2.019g zinc carbonate in the reactor, filter, solution in 200 ℃ of following roastings 4 hours, obtains catalyst behind 100 ℃ of following evaporates to dryness.
The urea, 1 that in reactor, adds design flow, 2-propane diols and catalyst, the amount of catalyst accounts for 2.5% of reactant gross mass, vacuum is 0.06～0.07MPa, 150 ℃ of reaction temperatures, 4.5 hours reaction time, all the other conditions are with embodiment 1, and the propene carbonate yield is 78.71%.
Embodiment 10
Preparation of catalysts is with embodiment 9.
The urea, 1 that in reactor, adds design flow, 2-propane diols and catalyst, the amount of catalyst accounts for 2.5% of reactant gross mass, vacuum is 0.06～0.07MPa, 140 ℃ of reaction temperatures, 4 hours reaction time, all the other conditions are with embodiment 1, and the propene carbonate yield is 68.32%.
Claims (4)
1. one kind is used for urea and 1, and the heteropolyacid salt catalyst of 2-propane diols synthesizing acrylic ester is characterized in that: the synthetic of catalyst prepared by heteropoly acid and salts reaction.
2. the catalyst of a kind of synthesizing acrylic ester according to claim 1 is characterized in that described heteropoly acid is phosphomolybdic acid, phosphotungstic acid or silico-tungstic acid.
3. the catalyst of a kind of synthesizing acrylic ester according to claim 1 is characterized in that described salt is a carbonate, and carbonate is zinc carbonate, basic magnesium carbonate, potash or calcium carbonate.
4. urea and 1,2-propane diols reaction synthesizing acrylic ester, be characterised in that: with the described heteropolyacid salt of claim 1 is catalyst, catalyst amount is 2.0～5.5% of a reactant gross mass, 130～160 ℃ of reaction temperatures, reaction time 2～6h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101816859A CN101450317A (en) | 2007-12-03 | 2008-12-01 | Carbonic allyl ester preparation catalyst through catalyzing urea and 1,2-propylene glycol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710050687 | 2007-12-03 | ||
| CN200710050687.X | 2007-12-03 | ||
| CNA2008101816859A CN101450317A (en) | 2007-12-03 | 2008-12-01 | Carbonic allyl ester preparation catalyst through catalyzing urea and 1,2-propylene glycol |
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| CN101450317A true CN101450317A (en) | 2009-06-10 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110339867A (en) * | 2019-07-24 | 2019-10-18 | 河南大学 | Urea and polyol reaction prepare cyclic carbonate catalyst recovery method |
| CN111185230A (en) * | 2020-01-21 | 2020-05-22 | 山西中科惠安化工有限公司 | Method for separating and recovering catalyst in reaction liquid of urea and polyalcohol |
| CN114210273A (en) * | 2021-12-24 | 2022-03-22 | 常州化工设计院有限公司 | Preparation process of ethylene carbonate |
| CN115055196A (en) * | 2022-07-04 | 2022-09-16 | 中国科学院过程工程研究所 | Heteropolyacid salt catalyst and preparation method and application thereof |
| CN115518628A (en) * | 2021-06-25 | 2022-12-27 | 中国科学院成都有机化学有限公司 | Preparation method of carbon-based metal oxide catalyst for synthesizing cyclic carbonate through urea alcoholysis, catalyst and application |
-
2008
- 2008-12-01 CN CNA2008101816859A patent/CN101450317A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110339867A (en) * | 2019-07-24 | 2019-10-18 | 河南大学 | Urea and polyol reaction prepare cyclic carbonate catalyst recovery method |
| CN111185230A (en) * | 2020-01-21 | 2020-05-22 | 山西中科惠安化工有限公司 | Method for separating and recovering catalyst in reaction liquid of urea and polyalcohol |
| CN115518628A (en) * | 2021-06-25 | 2022-12-27 | 中国科学院成都有机化学有限公司 | Preparation method of carbon-based metal oxide catalyst for synthesizing cyclic carbonate through urea alcoholysis, catalyst and application |
| CN115518628B (en) * | 2021-06-25 | 2023-11-28 | 中国科学院成都有机化学有限公司 | Preparation method of carbon-based metal oxide catalyst for synthesizing cyclic carbonate through urea alcoholysis, catalyst and application |
| CN114210273A (en) * | 2021-12-24 | 2022-03-22 | 常州化工设计院有限公司 | Preparation process of ethylene carbonate |
| CN114210273B (en) * | 2021-12-24 | 2023-09-05 | 常州化工设计院有限公司 | Preparation process of ethylene carbonate |
| CN115055196A (en) * | 2022-07-04 | 2022-09-16 | 中国科学院过程工程研究所 | Heteropolyacid salt catalyst and preparation method and application thereof |
| CN115055196B (en) * | 2022-07-04 | 2023-10-03 | 中国科学院过程工程研究所 | Heteropoly acid salt catalyst and preparation method and application thereof |
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