CN100387338C - Ester exchange catalyst and its use - Google Patents
Ester exchange catalyst and its use Download PDFInfo
- Publication number
- CN100387338C CN100387338C CNB021338914A CN02133891A CN100387338C CN 100387338 C CN100387338 C CN 100387338C CN B021338914 A CNB021338914 A CN B021338914A CN 02133891 A CN02133891 A CN 02133891A CN 100387338 C CN100387338 C CN 100387338C
- Authority
- CN
- China
- Prior art keywords
- catalyst
- triethanolamine
- sodium methoxide
- ester exchange
- ethanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 125000004185 ester group Chemical group 0.000 title 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims abstract description 32
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000002148 esters Chemical group 0.000 claims abstract description 11
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 15
- 239000007788 liquid Substances 0.000 description 11
- 239000000376 reactant Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- UCVQOIPQDBZRMG-UHFFFAOYSA-N [C].COC(C=1C(C(=O)OC)=CC=CC1)=O Chemical compound [C].COC(C=1C(C(=O)OC)=CC=CC1)=O UCVQOIPQDBZRMG-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- VXSIXFKKSNGRRO-MXOVTSAMSA-N [(1s)-2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate;[(1s)-2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-3-[(e)-3-methoxy-2-methyl-3-oxoprop-1-enyl Chemical class CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1.CC1(C)[C@H](/C=C(\C)C(=O)OC)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1 VXSIXFKKSNGRRO-MXOVTSAMSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- DDBREPKUVSBGFI-UHFFFAOYSA-N phenobarbital Chemical compound C=1C=CC=CC=1C1(CC)C(=O)NC(=O)NC1=O DDBREPKUVSBGFI-UHFFFAOYSA-N 0.000 description 1
- 229960002695 phenobarbital Drugs 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- HYJYGLGUBUDSLJ-UHFFFAOYSA-N pyrethrin Natural products CCC(=O)OC1CC(=C)C2CC3OC3(C)C2C2OC(=O)C(=C)C12 HYJYGLGUBUDSLJ-UHFFFAOYSA-N 0.000 description 1
- 229940070846 pyrethrins Drugs 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Abstract
The present invention relates to a catalyst for preparing diethyl carbonate by the ester exchange reactions of dimethyl carbonate and ethanol, which comprises sodium methoxide and triethanolamine, wherein the molar ratio of the sodium methoxide to the triethanolamine is from 0.005 to 0.1. The catalyst has the advantages of high catalytic activity, long service life, circular use, good dissolvability in reaction solutions, no precipitation, no scale formation and easy use, and the catalyst activity keeps high through the reactions of seven periods.
Description
Technical field
The present invention relates to a kind of ester exchange catalyst and application thereof, particularly catalyzed carbon dimethyl phthalate and ethanol generation ester exchange reaction prepare the catalyst of diethyl carbonate, belong to chemical field.
Technical background
Diethyl carbonate is an a kind of purposes organic compound very widely, contains alkoxyl and carbonyl in its molecule, and chemical property is active, can with reactions such as multiple alcohol, phenol, amine and ester.It is a kind of solvent of function admirable, is widely used in cellulose nitrate, cellulose ether, natural or industries such as synthetic fibers, pharmacy; Also be the important intermediate of organic synthesis, can be used for synthetic phenobarbital and pyrethrins etc.In addition, it still is a kind of gasoline additive of function admirable, therefore has very high industrial application value.
The catalyst that ester-interchange method prepares the carbonic diester employing mostly is alkaline matter.That US3803201 adopts is highly basic NaOH, KOH, NaOCH
3, KOCH
3Catalyst, product yield are 96%, and be active higher.CN1320594A (2001) also adopts this class catalyst, and reaction speed is very high.But find that in actual application this class catalyst is poorly soluble in reactant liquor, easily precipitate, easily fouling, it is very fast to reuse the active decline in back, has influenced catalyst life, and has separated out in destilling tower easily, blocking pipe.
US4691041 discloses several heterogeneous catalysis, as quaternary amine type strong alkali resin, and the sulfonic acid type strong resin, the carboxylic acid type weak acid resin has flooded the SiO of alkali metal or alkaline-earth-metal silicate
2, wherein quaternary amine type strong alkali resin activity is the highest, and there is not the later separation problem in this class catalyst, but their general activity are not high.
US4734518 has proposed organophosphor catalyst such as tributylphosphine and triphenylphosphine, but activity is not high yet.
CN1320594A (2001) has proposed a kind of K
2CO
3With the homogeneous complex catalyst that polyethylene glycol forms, this catalyst activity is higher, and this complex compound favorable solubility in reactant liquor, and the life-span is long.But this catalyst later separation work is trouble, must be discharged by pump and again by pump return reactor after reactor is handled outward.
The catalyst that the present invention adopts is sodium methoxide and triethanolamine composition, and the existing high catalytic activity of this catalyst has good solubility again, can reuse, and the life-span is long, and be a kind of catalyst of ester-interchange method synthesizing diethyl carbonate.
Summary of the invention
For overcoming the shortcoming of above-mentioned prior art, the invention provides a kind of sodium methoxide and triethanolamine 0.005～0.1 catalyst of forming in molar ratio, the existing high catalytic activity of this catalyst, fine solubility is arranged again, can reuse, and the life-span is long, is a kind of catalyst of ester-interchange method synthesizing diethyl carbonate.The present invention also provides described Application of Catalyst.
Technical scheme of the present invention is: ester exchange catalyst is 0.005～0.1 to form by sodium methoxide and triethanolamine in molar ratio, is used for the catalyzed carbon dimethyl phthalate and ethanol generation ester exchange reaction prepares diethyl carbonate.
Sodium methoxide is active very high alkali catalyst, and because sodium methoxide has fine solubility in triethanolamine, the composition of sodium methoxide and triethanolamine also has fine solubility in reactant liquor.The beneficial effect of its generation is: reaction can remain homogeneous system, and after reaction finished, product and excess ethyl alcohol distillation, sodium methoxide remaining in the reactor was dissolved in the triethanolamine, does not precipitate, and non-scaling adds reactant liquor again, can repeat synthetic reaction again.Triethanolamine itself is an organic base simultaneously, and promoting catalysis is arranged.
Specific embodiments of the present invention is: catalyst is the composition of sodium methoxide and triethanolamine, and the mol ratio of sodium methoxide and triethanolamine is 0.005～0.1, preferred 0.01～0.05.The synthetic reaction of catalyst of the present invention institute catalysis is to be raw material with dimethyl carbonate and ethanol, in the presence of catalyst, carry out ester exchange and prepare diethyl carbonate, wherein, catalyst amount, count 0.001%～1% with the raw material total amount, preferred 0.05%～0.3%.Reaction temperature is 50 ℃～100 ℃, and the reaction time is 1h～5h, is reflected under the normal pressure and carries out.Reaction distills out product and excess ethyl alcohol after finishing, and remaining sodium methoxide and triethanolamine are stayed in the reactor, and sodium methoxide is dissolved in the triethanolamine, do not precipitate, and non-scaling, just reusable behind the adding reactant liquor, the active maintenance better.
Specific embodiment
The present invention is described further below in conjunction with embodiment.
Embodiment 1:
Dimethyl carbonate 20.5g, ethanol 84.5g, sodium methoxide 0.15g, triethanolamine 20.5g, mixed reaction solution are transparent liquid, and behind 78 ℃ of reaction 4h, 170 ℃ distill out product and excess ethyl alcohol, and still liquid is yellow transparent liquid.The results are shown in following table.
Embodiment 2: dimethyl carbonate 20.5g, and ethanol 84.5g, as catalyst, the remaining reaction condition is with example 1 with the still liquid of embodiment 1.The results are shown in following table.
Embodiment 3: dimethyl carbonate 20.5g, and ethanol 84.5g, as catalyst, the remaining reaction condition is with example 1 with the still liquid of embodiment 2.The results are shown in following table.
Embodiment 4: dimethyl carbonate 20.5g, and ethanol 84.5g, as catalyst, the remaining reaction condition is with example 1 with the still liquid of embodiment 3.The results are shown in following table.
Embodiment 5: dimethyl carbonate 20.5g, and ethanol 84.5g, as catalyst, the remaining reaction condition is with example 1 with the still liquid of embodiment 4.The results are shown in following table.
Embodiment 6: dimethyl carbonate 20.5g, and ethanol 84.5g, as catalyst, the remaining reaction condition is with example 1 with the still liquid of embodiment 5.The results are shown in following table.
Embodiment 7: dimethyl carbonate 20.5g, and ethanol 84.5g, as catalyst, the remaining reaction condition is with example 1 with the still liquid of embodiment 6.The results are shown in following table.
The content (quality) of embodiment 1-7 distillate and the conversion ratio of dimethyl carbonate see the following form.
| Distillate quality (g) | Dimethyl carbonate (%) | Methyl alcohol (%) | Ethanol (%) | Methyl ethyl carbonate (%) | Diethyl carbonate (%) | Dimethyl carbonate conversion ratio (%) | |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 | 101 100 97.5 100 102 103 102 | 0.55 0.71 0.79 0.79 0.80 0.75 0.85 | 13.6 7.7 7.8 7.8 7.9 7.7 7.7 | 70.5 70.3 70.9 70.5 70.1 69.5 69.7 | 7.0 9.9 8.6 8.9 9.1 7.4 7.3 | 8.4 11.4 11.9 12.0 12.1 14.7 14.5 | 97.3 96.5 96.2 96.1 96.0 96.2 95.8 |
Wherein the content of distillate is by the gas chromatograph analysis.(chromatographic condition: fixing is carbowax-20M mutually, and carrier is GDX-102,150 ℃ of column temperatures, 180 ℃ of TCD detector temperatures, 180 ℃ of vapourizing temperatures)
Through the experiment in seven cycles, still liquid still is transparent liquid, does not precipitate non-scaling, and active the maintenance better.
Claims (3)
1. ester exchange catalyst is characterized in that: by sodium methoxide and triethanolamine is 0.005～0.1 to form in molar ratio.
2. ester exchange catalyst according to claim 1 is characterized in that: the mol ratio of sodium methoxide and triethanolamine is 0.01～0.05.
3. the application of an ester exchange catalyst as claimed in claim 1 or 2 is characterized in that: this catalyst is used for preparing diethyl carbonate by dimethyl carbonate and ethanol ester exchange.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021338914A CN100387338C (en) | 2002-10-11 | 2002-10-11 | Ester exchange catalyst and its use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021338914A CN100387338C (en) | 2002-10-11 | 2002-10-11 | Ester exchange catalyst and its use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1488439A CN1488439A (en) | 2004-04-14 |
| CN100387338C true CN100387338C (en) | 2008-05-14 |
Family
ID=34145706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021338914A Expired - Lifetime CN100387338C (en) | 2002-10-11 | 2002-10-11 | Ester exchange catalyst and its use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100387338C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100435951C (en) * | 2003-09-17 | 2008-11-26 | 中国科学院成都有机化学有限公司 | Preparing methyl ethyl carbonate catalyst by ester exchange |
| CN102115437B (en) * | 2010-04-12 | 2014-05-07 | 上海海嘉诺医药发展股份有限公司 | Method for preparing gamma and delta unsaturated ketone |
| CN108728249A (en) * | 2018-06-15 | 2018-11-02 | 成都恒润高新科技股份有限公司 | A method of preparing biodiesel using swill |
| CN113769770B (en) * | 2020-06-09 | 2024-04-02 | 中国科学院成都有机化学有限公司 | Preparation method of catalyst for synthesizing dimethyl carbonate by transesterification, catalyst and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4062884A (en) * | 1975-04-09 | 1977-12-13 | Anic, S.P.A. | Process for the preparation of dialkylcarbonates |
| HU214302B (en) * | 1994-04-21 | 1998-04-28 | CAOLA Kozmetikai és Háztartásvegyipari Rt. | Process for producing quaternary triethanolamine fattyacid diesters having textile-rinsing features |
| CN1314338A (en) * | 2001-04-05 | 2001-09-26 | 华东理工大学 | Process for preparing diethyl carbonate |
| CN1320594A (en) * | 2001-04-03 | 2001-11-07 | 华东理工大学 | Process for continuously preparing diethyl carbonate |
-
2002
- 2002-10-11 CN CNB021338914A patent/CN100387338C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4062884A (en) * | 1975-04-09 | 1977-12-13 | Anic, S.P.A. | Process for the preparation of dialkylcarbonates |
| HU214302B (en) * | 1994-04-21 | 1998-04-28 | CAOLA Kozmetikai és Háztartásvegyipari Rt. | Process for producing quaternary triethanolamine fattyacid diesters having textile-rinsing features |
| CN1320594A (en) * | 2001-04-03 | 2001-11-07 | 华东理工大学 | Process for continuously preparing diethyl carbonate |
| CN1314338A (en) * | 2001-04-05 | 2001-09-26 | 华东理工大学 | Process for preparing diethyl carbonate |
Non-Patent Citations (1)
| Title |
|---|
| "碳酸二乙酯合成方法综述". 潘鹤林等.上海化工，第20期. 2001 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1488439A (en) | 2004-04-14 |
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Owner name: AOKE CHEMICAL YANGZHOU CO., LTD. Effective date: 20130802 |
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Effective date of registration: 20130802 Address after: 610041 Chengdu South Road, Sichuan, No. four, No. nine Patentee after: Chengdu Institute of Organic Chemistry Chinese Academy of Sciences Patentee after: OXIRANCHEM (YANGZHOU) Co.,Ltd. Address before: 610041 Chengdu South Road, Sichuan, No. four, No. nine Patentee before: Chengdu Institute of Organic Chemistry Chinese Academy of Sciences |
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Address after: 610041 Chengdu South Road, Sichuan, No. four, No. nine Co-patentee after: JIANGSU OXIRANCHEM Co.,Ltd. Patentee after: CHENGDU ORGANIC CHEMICALS Co.,Ltd. CHINESE ACADEMY OF SCIENCES Address before: 610041 Chengdu South Road, Sichuan, No. four, No. nine Co-patentee before: OXIRANCHEM (YANGZHOU) Co.,Ltd. Patentee before: Chengdu Institute of Organic Chemistry Chinese Academy of Sciences |
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