CN1267428C - Supported catalyst for preparing alkene carbonate and preparation method thereof - Google Patents
Supported catalyst for preparing alkene carbonate and preparation method thereof Download PDFInfo
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- CN1267428C CN1267428C CN 03145916 CN03145916A CN1267428C CN 1267428 C CN1267428 C CN 1267428C CN 03145916 CN03145916 CN 03145916 CN 03145916 A CN03145916 A CN 03145916A CN 1267428 C CN1267428 C CN 1267428C
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- tetraethylammonium bromide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- -1 alkene carbonate Chemical class 0.000 title description 12
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical group [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 230000002194 synthesizing effect Effects 0.000 claims abstract 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 8
- 239000004480 active ingredient Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011949 solid catalyst Substances 0.000 abstract description 4
- QQUZYDCFSDMNPX-UHFFFAOYSA-N ethene;4-methyl-1,3-dioxolan-2-one Chemical compound C=C.CC1COC(=O)O1 QQUZYDCFSDMNPX-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 9
- 230000009466 transformation Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229910001508 alkali metal halide Inorganic materials 0.000 description 2
- 150000008045 alkali metal halides Chemical class 0.000 description 2
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- PLHJDBGFXBMTGZ-WEVVVXLNSA-N furazolidone Chemical compound O1C([N+](=O)[O-])=CC=C1\C=N\N1C(=O)OCC1 PLHJDBGFXBMTGZ-WEVVVXLNSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000009418 renovation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a supported solid catalyst for synthesizing ethylene (propylene) carbonate, which comprises the following components in part by weight: the carrier is active carbon, and the active component is tetraethyl ammonium bromide. The preparation method of the catalyst comprises the following steps: soaking activated carbon into 10-70% tetraethylammonium bromide solution for 10-50 h, filtering, and drying at 100-200 deg.C for 20-50 h.
Description
Technical field
The present invention relates to a kind ofly prepare ethylene (third) alkene ester Catalysts and its preparation method by epoxy second (third) alkane and carbon dioxide reaction.
Background technology
NSC 11801 is a kind of solvent of excellent property and the raw material of tensio-active agent, especially better to many polymkeric substance and dissolving resin effect, NSC 11801 also can be used as organic synthesis intermediate, alternative oxyethane is used for ethoxylation, raw material as synthetic Nifurazolidone, as water glass is slurry, the machining agent of fibre finish agent and other fiber etc.In addition, NSC 11801 also can be done the high tension battery electrolytic solution of high added value.
Before the present invention, the known method for preparing ethylene (third) alkene ester is to adopt alkali metal halide, alkaline earth metal halide, ammonium halide, Phosphorates phosphorus Halides.As U.S.Pat.No.4,881,555, U.S.Pat.No.4,931,571,, catalyzer is organic tetravalence ammonium halide, organic tetravalence Phosphorates phosphorus Halides, organic halogenation sulphur and organic halogenation antimony among the Japanese Laid-Open Pat.No.7-206846; Japan Laid-Open Pat.No.9-067365 and No.8-059557 catalyzer are alkali metal halide and alkaline earth metal halide; U.S.Pat.No.2,773,070 employings contain tetravalence Phosphorates phosphorus Halides ion-exchange resin catalyst; U.S.Pat.No.4,233,221 adopt DOWEX and Amberlite ion-exchange resin catalyst; U.S.Pat.No.4,665,467 and U.S.Pat.No.5,283,356 adopt and contain the phthalocyanine of Co, Cr, Fe, Mn, Ni, Ti, V, Zr or the catalyzer of porphyrin; U.S.Pat.No.6,156,909 usefulness indium halide and lead halide are catalyzer; U.S.Pat.No.6,160,130 adopt the manganese halide catalyzer; U.S.Pat.No.6,258,962 adopt the solid carrier that contains alkaline-earth metal.In industrial production, adopt homogeneous catalyst long reaction time (above 5 hours), epoxy second (third) alkane transformation efficiency is low, reaction process is high temperature (180 ℃) high pressure (10MPa) reactions, because catalyst dissolution is in NSC 11801, existence is from product separating catalyst problem, thereby makes catalyst loss.
Summary of the invention
The object of the present invention is to provide and a kind ofly prepare ethylene (third) alkene ester with solid catalyst and preparation method thereof by epoxy second (third) alkane and carbon dioxide reaction.
Particular content of the present invention is as follows:
Preparation ethylene provided by the invention (third) alkene ester supported solid catalyzer, carrier is a gac, active ingredient is the alkyl brometo de amonio.
Alkyl brometo de amonio in present method can be tetraethylammonium bromide.
Said gac is common commercial goods.
The present invention also provides a kind of preparation method of this loaded catalyst: gac is impregnated in the alkyl bromination ammonium solution that concentration is 10-70% 10-50 hour, filter, 100-200 ℃ dry 20-50 hour down.
The preferred 30-60% of alkyl bromination ammonium concentration in this preparation method, the preferred 20-40 of dipping time hour, the preferred 100-150 of drying temperature ℃, preferred 30-40 hour time of drying.
In realizing process of the present invention, can adopt one or more fixed-bed reactor intermittences or carry out prepared in reaction ethylene (third) alkene ester continuously.In fixed bed, the upper and lower filling porcelain ring of catalyst reactor bed, reactant carbonic acid gas and epoxy second (third) alkane enter and produce the minimum pressure drop in the reactor.
The mode that unattended operation carries out (intermittence or continuous) keeps enough pressure so that molecular balance moves right.General reaction pressure is 3.0-7.0Mpa (gauge pressure), temperature of reaction 100-200 ℃.Reaction times is 1-5 hour.After reaction finishes, NSC 11801 is separated, the carbonic acid gas separated and a spot of oxyethane can be circulated in the reactor and use by conventional separation method (as distillation).
Reaction product is identified with conventional vapor-phase chromatography.
The present invention's advantage compared with prior art is: utilize the mechanism of catalytic reaction of alkyl brometo de amonio, adopt the solid catalyst of loading type, Preparation of Catalyst renovation process simple economy; Overcome the shortcoming that the reaction process of direct employing homogeneous catalyst (tetraethylammonium bromide) exists, promptly low, the long reaction time of selectivity and in reaction process catalyst loss big.From the reaction process aspect, reaction pressure is lower than existing technology (10MPa), has saved facility investment.Oxyethane transformation efficiency of the present invention is 90-96%; Selectivity is 92-98%.
Embodiment
Content percentage ratio of the present invention is weight percentage.
Embodiment 1
It is in 40% the tetraethylammonium bromide 200g solution, to flood 30 hours that gac 20g joins concentration, filters, drying, and be 30 hours time of drying; Drying temperature is 150 ℃, obtains solid catalyst.
In the 1L high-pressure reactor, add the NSC 11801 of 420g, the oxyethane of 40mL; Activated-carbon catalyst is 17.7g, and reaction is 2 hours under 140 ℃, 5.25MPa condition, and cooling reactive system to 40 ℃, product analysis, ethylene oxide content are 2.10%, the content of NSC 11801 is 93.89%, and obtaining the oxyethane transformation efficiency is 95.72%; Selectivity is 93.19%.
Embodiment 2
Utilize the catalyzer among the embodiment 1, in reactor, add the NSC 11801 of 420g, the oxyethane of 40mL again; Reaction conditions is identical with embodiment 1, and product analysis, ethylene oxide content are 3.67%, ethylene carbonate content is 94.58%, and obtaining the oxyethane transformation efficiency is 92.81%; Selectivity is 97.04%.
Embodiment 3
Utilize the catalyzer among the embodiment 1, in reactor, add the NSC 11801 of 420g, the oxyethane of 40mL again; Reaction conditions is identical with embodiment 1, product analysis, and ethylene oxide content 3.71%, ethylene carbonate content are 92.47%, obtain oxyethane transformation efficiency 91.77%; Selectivity is 95.87%.
Embodiment 4
Adopt catalyzer 15g, the concentration of tetraethylammonium bromide is 17%, identical among other condition and the embodiment 1, product analysis, ethylene oxide content 4.47%, ethylene carbonate content are 90.70%, and obtaining the oxyethane transformation efficiency is 91.03%, and selectivity does evil 1.60%.
Embodiment 5
In the fixed-bed reactor of ф 32 * 2.5, contain excessive carbon dioxide and activated-carbon catalyst 35g, the concentration of active ingredient tetraethylammonium bromide is 30%, the flow of oxyethane is 40mL/hr, join in the reactor after oxyethane and 5.0MPa carbonic acid gas be preheating to 120 ℃, reaction is 100 hours under 140 ℃, the condition of 5.0-6.0MPa, product is extraction after cooling off, analytical results, ethylene oxide content is 2.41%, ethylene carbonate content is 92.62%, the transformation efficiency of oxyethane is 95.45%, and selectivity is 92.01%.
Claims (5)
1. synthesizing ethylene carbonate or propylene carbonate supported solid catalyzer, carrier is a gac, active ingredient is a tetraethylammonium bromide.
2. described Preparation of catalysts method of claim 1: gac is impregnated in the tetraethylammonium bromide solution that mass percentage concentration is 10-70% 10-50 hour, filter, 100-200 ℃ dry 20-50 hour down.
3. the described Preparation of catalysts method of claim 2 is characterized in that tetraethylammonium bromide mass percentage concentration wherein is 30-60%.
4. the described Preparation of catalysts method of claim 2 is characterized in that dipping time wherein is 20-40 hour.
5. the described Preparation of catalysts method of claim 2 is characterized in that be 30-40 hour time of drying wherein, and drying temperature is 100-150 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03145916 CN1267428C (en) | 2003-07-17 | 2003-07-17 | Supported catalyst for preparing alkene carbonate and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03145916 CN1267428C (en) | 2003-07-17 | 2003-07-17 | Supported catalyst for preparing alkene carbonate and preparation method thereof |
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| Publication Number | Publication Date |
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| CN1569851A CN1569851A (en) | 2005-01-26 |
| CN1267428C true CN1267428C (en) | 2006-08-02 |
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| CN 03145916 Expired - Fee Related CN1267428C (en) | 2003-07-17 | 2003-07-17 | Supported catalyst for preparing alkene carbonate and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103030623B (en) * | 2011-09-30 | 2016-09-07 | 中国石油化工股份有限公司 | Oxirane and carbon dioxide prepare the method for ethylene carbonate |
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Granted publication date: 20060802 Termination date: 20210717 |