CN102442885A - Method of synthesizing glycol - Google Patents
Method of synthesizing glycol Download PDFInfo
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- CN102442885A CN102442885A CN201010501237XA CN201010501237A CN102442885A CN 102442885 A CN102442885 A CN 102442885A CN 201010501237X A CN201010501237X A CN 201010501237XA CN 201010501237 A CN201010501237 A CN 201010501237A CN 102442885 A CN102442885 A CN 102442885A
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- dimethyl oxalate
- mixed liquor
- component
- methyl alcohol
- components
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Abstract
The invention discloses a method of synthesizing glycol. The method comprises the following steps of: mixing dimethyl oxalate and methanol to obtain a mixed liquor I, wherein dimethyl oxalate accounts for 30-50 % of a total weight of the mixed liquor; gasifying the mixed liquor I; carrying out a reaction under catalysis of a copper silicon catalyst; condensing gas after the reaction; rectifying condensed liquid to recover glycol; washing other gas with a washing solvent methanol to form a mixed liquor II; rectifying the mixed liquor II under -0.03- -0.04 MPa and collecting a component at 130-150 DEG C to obtain dimethyl oxalate; storing other components I; substituting the methanol with the stored other components I as the washing solvent; when a mass ratio of methanol and dimethyl oxalate in the stored other components I equals to 9:1, rectifying the stored other components I under -0.03- -0.04 MPa and collecting a component at 130-150 DEG C to obtain dimethyl oxalate; using other components II as a washing solvent. The method of synthesizing glycol of the invention can gasify dimethyl oxalate under conditions of 2.5 MPa and 150 DEG C, so as to reduce cost of producing the glycol.
Description
Technical field
The present invention relates to a kind of method of synthesizing glycol.
Background technology
Dimethyl oxalate, molecular formula are C
4H
6O, structural formula (COOCH
3)
2, boiling point is 163.45 ℃ under the 0.1MPa pressure, boiling point is 300 ℃ under the 2.7MPa pressure, is dissolved in pure and mild ether.
During existing synthesizing glycol is produced, need to mix the back with hydrogen and get into reactor drum under the effect of Cu Si catalyst, generate terepthaloyl moietie and methyl alcohol with the gasiform dimethyl oxalate.Wherein required gasiform dimethyl oxalate adopts 3.8MPa with the HP steam of upward pressure or auxiliary electrical heating, heating system for oil; With more than the dimethyl oxalate liquid direct heating to 300 ℃; Be gasificated into gas, mix the back then with hydrogen and get into reactor drum generation terepthaloyl moietie.This gasification institute energy requirement is very big, and the equipment for gasification safety performance is required very high, causes the increasing of equipment cost.
Summary of the invention
The purpose of this invention is to provide the method that a kind of safety performance requires the synthesizing glycol low, that production cost is low.
The method of synthesizing glycol provided by the present invention comprises the steps:
Dimethyl oxalate and methanol mixed are obtained mixed liquor I, and dimethyl oxalate accounts for 30～50% of mixed solution total mass, and mixed liquor I gasifies; Reaction under the catalysis of copper Si catalyst; Reacted gas carries out condensation, and condensed liquid carries out rectifying, reclaims terepthaloyl moietie; Other gases are that cleaning solvent washs formation mixed liquor I I with methyl alcohol;
Said mixed liquor I I carries out rectifying ,-0.03～-0.04MPa, collect 130～150 ℃ of components, obtain dimethyl oxalate, other component I are stored;
It is cleaning solvent that said other component I of storing substitute said methyl alcohol;
When methyl alcohol and dimethyl oxalate mass ratio equal 9: 1 in said other component I of storing; Said other component I of storing are carried out rectifying ,-0.03～-0.04MPa, collect 130～150 ℃ of components; Obtain dimethyl oxalate, I is as cleaning solvent for other component I.
The method of synthesizing glycol of the present invention, wherein: the condition that said mixed liquor I gasifies is 2.5～3.0MPa, 130～150 ℃.
The method of synthesizing glycol of the present invention, wherein: said reaction pressure is that 2.5～3.0MPa, temperature are 200～210 ℃.
The method of synthesizing glycol of the present invention, wherein: said copper Si catalyst is for being that raw material precipitation from homogeneous solution(PFHS) sedimentation prepares with cupric nitrate and alkaline silica sol.
The method of synthesizing glycol of the present invention, wherein: the CuO quality accounts for 20～50% in the said copper Si catalyst, and surplus is SiO
2
The method of synthesizing glycol of the present invention at 2.5～3.0MPa, can gasify dimethyl oxalate under 130～150 conditions, has reduced the production cost of synthesizing glycol.Dimethyl oxalate is dissolved in the methyl alcohol, also can prevent dimethyl oxalate crystallization disabling facility and pipeline.
The method of synthesizing glycol of the present invention, technical process is simple, recycles as cleaning solvent with the azeotrope of methyl alcohol and dimethyl oxalate, and behind the circulation cleaning, dimethyl oxalate content will increase, and can obtain dimethyl oxalate through rectifying.
Embodiment
Embodiment 1,
Dimethyl oxalate and methanol mixed are obtained mixed liquor I, and dimethyl oxalate accounts for 30% of mixed liquor I total mass, and mixed liquor I gets in the gasifier; 2.5MPa 150 ℃ of gasification mixed liquor I, gas gets into the reactor drum that is filled with the copper Si catalyst, 3.0MPa, 200 ℃ of reactions; Reacted gaseous product flows out through pipeline, and the cooling back gets into condensing surface, liquefies such as terepthaloyl moietie, methyl alcohol, dimethyl oxalate in condensing surface; Get in the rectifying tower, noncondensable gases such as hydrogen are discharged; Pressure is-0.04MPa in the rectifying tower; 130 ℃ of column bottom temperatures; From the extraction of tower still, the light constituent of methyl alcohol and dimethyl oxalate gets into washing tower from cat head to terepthaloyl moietie as heavy constituent, in washing tower, is that with methyl alcohol the cleaning solvent scrubbing exhaust gas forms the mixed liquor I I of methyl alcohol, dimethyl oxalate; The mixed liquor I I that comes out at the bottom of the washing Tata gets into knockout tower to be separated; In knockout tower, carry out rectifying, pressure is-0.03MPa in the rectifying tower, 150 ℃ of column bottom temperatures; Tower still extraction dimethyl oxalate, the mixture of cat head extraction methyl alcohol and dimethyl oxalate gets into storage tank; The mixture of methyl alcohol and dimethyl oxalate is sent into the washing of washing tower replacement methanol loop through topping-up pump in the storage tank; When methyl alcohol in the storage tank and dimethyl oxalate mass ratio during more than or equal to 9: 1, with methyl alcohol in the storage tank and dimethyl oxalate mixture through being pumped into knockout tower; In the knockout tower, methyl alcohol and dimethyl oxalate mixture carry out rectifying under-0.03Mpa, and pressure is-0.03MPa in the rectifying tower, and 150 ℃ of column bottom temperatures are taked the part dimethyl oxalate at the bottom of the tower, and cat head forms the azeotrope of methyl alcohol and dimethyl oxalate; The azeotrope of methyl alcohol and dimethyl oxalate gets into the azeotrope storage tank, through being pumped in the washing tower as the cleaning solvent recycle.
The preparation method of copper Si catalyst: Cu (NO
3)
23H
2O is dissolved in the deionized water, fully after the dissolving, gets NH
3H
2O slowly joins Cu (NO
3)
2Stir in the solution and simultaneously, process copper ammon solution.Then JN-30 type alkaline silica sol is splashed into through separating funnel in the copper ammon solution that configures, stir 4h, elevated temperature; Fully stir, steaming removes ammonia and makes pH value of solution=6.5, and color is progressively precipitated by initial dark blue solution and is varied to sapphire selection suspension liquid; Wash vacuum-drying through suction filtration, washing, alcohol then, obtain the catalyzer powder, burn training 4h down at 500 ℃; Obtain graminaceous catalyst precursor, compressing tablet sieves out 40-60 purpose granules of catalyst.The CuO quality accounts for 50% in the copper Si catalyst, and surplus is SiO
2The preceding copper Si catalyst of use reduces 150 ℃ of reduction temperatures with hydrogeneous 1% hydrogen nitrogen mixed gas.
The transformation efficiency of dimethyl oxalate is 95%, and the productive rate of terepthaloyl moietie is 95%; The recovery of dimethyl oxalate is 99%.
Embodiment 2,
Dimethyl oxalate and methanol mixed are obtained mixed liquor I, and dimethyl oxalate accounts for 50% of mixed liquor I total mass, and mixed liquor I gets in the gasifier; 3.0MPa 130 ℃ of gasification mixed liquor I, gas gets into the reactor drum that is filled with the copper Si catalyst, 2.5MPa, 210 ℃ of reactions; Reacted gaseous product flows out through pipeline, and the cooling back gets into condensing surface, liquefies such as terepthaloyl moietie, methyl alcohol, dimethyl oxalate in condensing surface; Get in the rectifying tower, noncondensable gases such as hydrogen are discharged; Pressure is-0.03MPa in the rectifying tower; 150 ℃ of column bottom temperatures; From the extraction of tower still, the light constituent of methyl alcohol and dimethyl oxalate gets into washing tower from cat head to terepthaloyl moietie as heavy constituent, in washing tower, is that with methyl alcohol the cleaning solvent scrubbing exhaust gas forms the mixed liquor I I of methyl alcohol, dimethyl oxalate; The mixed liquor I I that comes out at the bottom of the washing Tata gets into knockout tower to be separated; In knockout tower, carry out rectifying, pressure is-0.03MPa in the rectifying tower, 150 ℃ of column bottom temperatures; Tower still extraction dimethyl oxalate, the mixture of cat head extraction methyl alcohol and dimethyl oxalate gets into storage tank; The mixture of methyl alcohol and dimethyl oxalate is sent into the washing of washing tower replacement methanol loop through topping-up pump in the storage tank; When methyl alcohol in the storage tank and dimethyl oxalate mass ratio during greater than 9: 1, with methyl alcohol in the storage tank and dimethyl oxalate mixture through being pumped into knockout tower; In the knockout tower, methyl alcohol and dimethyl oxalate mixture carry out rectifying, and pressure is-0.04MPa in the rectifying tower, and 130 ℃ of column bottom temperatures are taked the part dimethyl oxalate at the bottom of the tower, and cat head forms the azeotrope of methyl alcohol and dimethyl oxalate; The azeotrope of methyl alcohol and dimethyl oxalate gets into the azeotrope storage tank, through being pumped in the washing tower as the cleaning solvent recycle.
The preparation method of copper Si catalyst: Cu (NO
3)
23H
2O is dissolved in the deionized water, fully after the dissolving, gets NH
3H
2O slowly joins Cu (NO
3)
2Stir in the solution and simultaneously, process copper ammon solution; Then JN-30 type alkaline silica sol is splashed into through separating funnel in the copper ammon solution that configures, stir 4h, elevated temperature; Fully stir, steaming removes ammonia and makes pH value of solution=6.5, and color is progressively precipitated by initial dark blue solution and is varied to sapphire selection suspension liquid; Wash vacuum-drying through suction filtration, washing, alcohol then, obtain the catalyzer powder, burn training 4h down at 500 ℃; Obtain graminaceous catalyst precursor, compressing tablet sieves out 40-60 purpose granules of catalyst; The CuO quality accounts for 20% in the copper Si catalyst, and surplus is SiO
2The preceding copper Si catalyst of use reduces 500 ℃ of reduction temperatures with hydrogeneous 90% hydrogen nitrogen mixed gas.
The transformation efficiency of dimethyl oxalate is 94%, and the productive rate of terepthaloyl moietie is 94%; The recovery of dimethyl oxalate is 98%.
Above embodiment describes preferred implementation of the present invention; Be not that scope of the present invention is limited; Design under the prerequisite of spirit not breaking away from the present invention; Various distortion and improvement that the common engineering technical personnel in this area make technical scheme of the present invention all should fall in the definite protection domain of claims of the present invention.
Claims (5)
1. the method for synthesizing glycol comprises the steps:
Dimethyl oxalate and methanol mixed are obtained mixed liquor I, and dimethyl oxalate accounts for 30～50% of mixed solution total mass, and mixed liquor I gasifies; Reaction under the catalysis of copper Si catalyst; Reacted gas carries out condensation, and condensed liquid carries out rectifying, reclaims terepthaloyl moietie; Other gases are that cleaning solvent washs formation mixed liquor I I with methyl alcohol;
Said mixed liquor I I carries out rectifying ,-0.03～-0.04MPa, collect 130～150 ℃ of components, obtain dimethyl oxalate, other component I are stored;
It is cleaning solvent that said other component I of storing substitute said methyl alcohol;
When methyl alcohol and dimethyl oxalate mass ratio equal 9: 1 in said other component I of storing; Said other component I of storing are carried out rectifying ,-0.03～-0.04MPa, collect 130～150 ℃ of components; Obtain dimethyl oxalate, I is as cleaning solvent for other component I.
2. method according to claim 1 is characterized in that: the condition that said mixed liquor I gasifies is 2.5～3.0MPa, 130～150 ℃.
3. method according to claim 1 and 2 is characterized in that: said reaction pressure is that 2.5～3.0MPa, temperature are 200～210 ℃.
4. method according to claim 1 and 2 is characterized in that: said copper Si catalyst is for being that raw material precipitation from homogeneous solution(PFHS) sedimentation prepares with cupric nitrate and alkaline silica sol.
5. method according to claim 1 and 2 is characterized in that: the CuO quality accounts for 20～50% in the said copper Si catalyst, and surplus is SiO
2
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|---|---|---|---|
| CN201010501237XA CN102442885A (en) | 2010-10-09 | 2010-10-09 | Method of synthesizing glycol |
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|---|---|---|---|
| CN201010501237XA CN102442885A (en) | 2010-10-09 | 2010-10-09 | Method of synthesizing glycol |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254030A (en) * | 2013-05-17 | 2013-08-21 | 天津天中福大科技发展有限公司 | Device and method for recycling byproduct residual liquid in coal-to-ethylene-glycol production process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101190884A (en) * | 2006-11-21 | 2008-06-04 | 上海焦化有限公司 | Method for synthesizing dimethyl oxalate and coproducing dimethyl carbonate |
| CN101648134A (en) * | 2009-08-27 | 2010-02-17 | 浙江大学 | Copper and silicon catalyst for preparing ethanediol by hydrogenating dimethyl oxalate and preparation method thereof |
-
2010
- 2010-10-09 CN CN201010501237XA patent/CN102442885A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101190884A (en) * | 2006-11-21 | 2008-06-04 | 上海焦化有限公司 | Method for synthesizing dimethyl oxalate and coproducing dimethyl carbonate |
| CN101648134A (en) * | 2009-08-27 | 2010-02-17 | 浙江大学 | Copper and silicon catalyst for preparing ethanediol by hydrogenating dimethyl oxalate and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254030A (en) * | 2013-05-17 | 2013-08-21 | 天津天中福大科技发展有限公司 | Device and method for recycling byproduct residual liquid in coal-to-ethylene-glycol production process |
| CN103254030B (en) * | 2013-05-17 | 2015-10-21 | 天津天中福大科技发展有限公司 | The recovery method of by-product raffinate in coal-ethylene glycol production process |
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Application publication date: 20120509 |