CN1095395C - Catalyst for synthesizing dimethyl carbonate and its preparing process - Google Patents
Catalyst for synthesizing dimethyl carbonate and its preparing process Download PDFInfo
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- CN1095395C CN1095395C CN00117793A CN00117793A CN1095395C CN 1095395 C CN1095395 C CN 1095395C CN 00117793 A CN00117793 A CN 00117793A CN 00117793 A CN00117793 A CN 00117793A CN 1095395 C CN1095395 C CN 1095395C
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- Prior art keywords
- carbonate
- catalyst
- catalyzer
- dimethyl carbonate
- alkaline earth
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 title abstract description 14
- 230000002194 synthesizing effect Effects 0.000 title abstract description 3
- 238000000034 method Methods 0.000 title description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 7
- -1 alkaline earth metal carbonate Chemical class 0.000 claims abstract description 7
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical group [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 229960001708 magnesium carbonate Drugs 0.000 claims description 4
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000007789 gas Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000004587 chromatography analysis Methods 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 5
- 238000010792 warming Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
一种合成碳酸二甲酯的催化剂及其制备方法，采用碱土金属碳酸盐在氮气氛围下，以5-12℃/分钟的升温速率，升温至600-1000℃进行焙烧2-6小时，即得产品。本发明的催化剂具有活性、选择性较高，用量少，对反应器无腐蚀等特点。反应结束后，催化剂通过过滤得到分离，且其可重复使用。A catalyst for synthesizing dimethyl carbonate and its preparation method, using alkaline earth metal carbonate in a nitrogen atmosphere, at a heating rate of 5-12 °C/min, heating up to 600-1000 °C for 2-6 hours, that is get the product. The catalyst of the invention has the characteristics of high activity, high selectivity, less dosage, no corrosion to the reactor and the like. After the reaction, the catalyst is separated by filtration, and it can be reused.
Description
The invention belongs to from the Catalysts and its preparation method of methyl alcohol and propylene carbonate Synthesis of dimethyl carbonate.
As a kind of eco-friendly organic synthesis intermediate and gasoline dope, methylcarbonate (Dimethyl Carbonate letter DMC) synthetic be subjected in recent years paying attention to widely with using (Y.Ono., Appl.Catal.A:, 1997,155,133).Synthesizing DMC from propylene carbonate and methyl alcohol through transesterify, because process is simple, and can generate dibasic alcohol, thereby is competitive method (A.G.Shaikh, S.Sivaram, Chem.Rev., 1996,96,951).
Propylene carbonate (being called for short PC) is as follows with the methyl alcohol reaction formula:
In this reaction, much more general with (Jiang Qi etc., gas chemical industry, 1997,22 (5), 1) such as alkali metal hydroxide, alkaline carbonate, alkali metal alcoholates as catalyzer.But, cause difficulty for the separation and the repeated use of catalyzer because of it is a homogeneous reaction.
Goal of the invention of the present invention provides a kind of catalyzer from methyl alcohol and propylene carbonate Synthesis of dimethyl carbonate, and this catalyzer has high reactivity and is easy to be separated from product.
Goal of the invention of the present invention is achieved in that and adopts alkaline earth metal carbonate roasting and getting under nitrogen atmosphere.
The mol ratio of catalyzer of the present invention:
Alkaline earth metal oxide: alkaline earth metal carbonate=1: 0.5-10.
Aforesaid alkaline earth metal carbonate is magnesiumcarbonate, lime carbonate, Strontium carbonate powder or barium carbonate.
As mentioned above the Preparation of catalysts method be with alkaline earth metal carbonate under nitrogen protection with 3-10 ml/min flow velocity, with 5-12 ℃/minute temperature rise rate, be warming up to 600-1000 ℃ and carried out roasting 2-6 hour.
Aforesaid catalyzer and other catalyzer relatively have higher activity and selectivity, and consumption is few, and reactor is not had corrosion, belongs to environment-friendly catalyst.After reaction finished, catalyzer can obtain separating by filtration, and it is reusable.
Embodiments of the invention are as follows:
Embodiment 1
Lime carbonate roasting 4 hours under nitrogen atmosphere, 600 ℃ of maturing temperatures, its temperature rise rate are 10 ℃/min, and nitrogen flow rate 4ml/min obtains this catalysts, and it consists of CaO: CaCO
3=1: 5.Add methyl alcohol and propylene carbonate by certain mole proportioning in reaction vessel, the add-on of catalyzer is 4% of a reaction mixture weight, under agitation condition, is warming up to 120 ℃, 2 hours reaction times.Cooling is filtered, and catalyzer is separated with reaction solution, the reaction solution gas chromatographic analysis, and the productive rate of DMC is 35.8%, the transformation efficiency of PC is 41.1%.
Embodiment 2
Lime carbonate roasting 5 under nitrogen atmosphere is advanced for a short time, and 900 ℃ of maturing temperatures, its temperature rise rate are 7 ℃/min, and nitrogen flow rate 9ml/min obtains this catalysts, and it consists of CaO: CaCO
3=1: 3.5.All the other are with embodiment 1, the reaction solution gas chromatographic analysis, and the productive rate of DMC is 39.5%, the transformation efficiency of PC is 42.1%.
Embodiment 3
Magnesiumcarbonate roasting 6 hours under nitrogen atmosphere, 700 ℃ of maturing temperatures, its temperature rise rate are 5 ℃/min, and nitrogen flow rate 5ml/min obtains this catalysts, and it consists of MgO: MgCO
3=1: 0.5.All the other are with embodiment 1, the reaction solution gas chromatographic analysis, and the productive rate of DMC is 32.2%, the transformation efficiency of PC is 34.5%.
Embodiment 4
Barium carbonate roasting 3 hours under nitrogen atmosphere, 800 ℃ of maturing temperatures, its temperature rise rate are 9 ℃/min, and nitrogen flow rate 8ml/min obtains this catalysts, and it consists of BaO: BaCO
3=1: 10.All the other are with embodiment 1.It is 40.9% that gas chromatographic analysis, the productive rate of DMC are used in reaction, and the transformation efficiency of PC is 44.1%.
Embodiment 5
Strontium carbonate powder roasting 4 under nitrogen atmosphere is advanced for a short time, and 900 ℃ of maturing temperatures, its temperature rise rate are 12 ℃/min, and nitrogen flow rate 7ml/min obtains this catalysts, and it consists of SrO: SrCO
3=1: 8.All the other are with embodiment 1, the reaction solution gas chromatographic analysis, and the productive rate of DMC is 37.1%, the transformation efficiency of PC is 45.3%.
Embodiment 6
Magnesiumcarbonate roasting 2 under nitrogen atmosphere is advanced for a short time, and 600 ℃ of maturing temperatures, its temperature rise rate are 10 ℃/min, and nitrogen flow rate 10ml/min obtains this catalysts, and its level becomes MgO: MgCO
3=1: 1.All the other are with embodiment 1, the reaction solution gas chromatographic analysis, and the productive rate of DMC is 28.5%, the transformation efficiency of PC is 31.1%.
Claims (2)
1. the catalyzer of a Synthesis of dimethyl carbonate is characterized in that the mol ratio of catalyzer is:
Alkaline earth metal oxide: alkaline earth metal carbonate=1: 0.5-10.
2. the catalyzer of a kind of Synthesis of dimethyl carbonate as claimed in claim 1 is characterized in that described alkaline earth metal carbonate is magnesiumcarbonate, lime carbonate, Strontium carbonate powder or barium carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00117793A CN1095395C (en) | 2000-06-21 | 2000-06-21 | Catalyst for synthesizing dimethyl carbonate and its preparing process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00117793A CN1095395C (en) | 2000-06-21 | 2000-06-21 | Catalyst for synthesizing dimethyl carbonate and its preparing process |
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| Publication Number | Publication Date |
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| CN1304790A CN1304790A (en) | 2001-07-25 |
| CN1095395C true CN1095395C (en) | 2002-12-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00117793A Expired - Fee Related CN1095395C (en) | 2000-06-21 | 2000-06-21 | Catalyst for synthesizing dimethyl carbonate and its preparing process |
Country Status (1)
| Country | Link |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115463675A (en) * | 2022-10-26 | 2022-12-13 | 高化学（江苏）化工新材料有限责任公司 | Novel catalyst for synthesizing dimethyl carbonate and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS517410A (en) * | 1974-07-08 | 1976-01-21 | Hitachi Ltd | BOSUIGATA DENDOKI |
| CN1103862A (en) * | 1993-07-15 | 1995-06-21 | 拜尔公司 | Process for the preparation of dimethyl carbonate |
| CN1107834A (en) * | 1993-11-24 | 1995-09-06 | 拜尔公司 | Process for working up the liquid reaction products from the Cu-catalysted preparation of dimethyl carbonate |
-
2000
- 2000-06-21 CN CN00117793A patent/CN1095395C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS517410A (en) * | 1974-07-08 | 1976-01-21 | Hitachi Ltd | BOSUIGATA DENDOKI |
| CN1103862A (en) * | 1993-07-15 | 1995-06-21 | 拜尔公司 | Process for the preparation of dimethyl carbonate |
| CN1107834A (en) * | 1993-11-24 | 1995-09-06 | 拜尔公司 | Process for working up the liquid reaction products from the Cu-catalysted preparation of dimethyl carbonate |
Non-Patent Citations (1)
| Title |
|---|
| 化工辞典 1996.9.1 化学工业出版社，第三版，王箴主编 * |
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| CN1304790A (en) | 2001-07-25 |
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