CN102276416A - Method for refining methanol - Google Patents
Method for refining methanol Download PDFInfo
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- CN102276416A CN102276416A CN2010101999912A CN201010199991A CN102276416A CN 102276416 A CN102276416 A CN 102276416A CN 2010101999912 A CN2010101999912 A CN 2010101999912A CN 201010199991 A CN201010199991 A CN 201010199991A CN 102276416 A CN102276416 A CN 102276416A
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- methylcarbonate
- methanol
- methyl alcohol
- refining methanol
- zeolite
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Abstract
The invention relates to a method for refining methanol. The method mainly solves the technical problem that based on the prior technology, methanol is separated from dimethyl carbonate difficultly and thus methanol purity is low. The method of the invention comprises that mixed liquor containing dimethyl carbonate and methanol passes through a adsorption bed under the conditions of a temperature of 10 to 100 DEG C, pressure of 0.1 to 3.0 MPa and an airspeed of 0.2 to 5.0 hours <-1> to contact with at least one adsorbent and thus methanol-rich effluent is obtained after adsorption, wherein the at least one adsorbent is selected form ZSM-5 zeolite, Y type zeolite or beta zeolite and a mole ratio of silicon to aluminum is (200 to 1000): 1. The method solves the technical problem well and can be utilized for industrial production of methanol refining.
Description
Technical field
The present invention relates to a kind of method of refining methanol, particularly about in CO coupling system dimethyl oxalate or the oxalic acid diethyl ester reaction absorption product, the method for refining methanol.
Background technology
Barkite is important Organic Chemicals, is used for fine chemistry industry in a large number and produces various dyestuffs, medicine, important solvent, extraction agent and various intermediate.Enter 21 century, barkite is subjected to international extensively attention as degradable environment-friendly engineering plastics monomer.In addition, the barkite ordinary-pressure hydrolysis can get oxalic acid, and normal pressure ammonia is separated and can be got high-quality slow chemical fertilizer oxamyl.Barkite can also be used as solvent, produces medicine and dyestuff intermediate etc., for example carries out various condensation reactions with fatty acid ester, hexamethylene phenyl methyl ketone, amido alcohol and many heterogeneous ring compounds.It can also synthesize at the chest acyl alkali that pharmaceutically is used as hormone.In addition, the barkite low-voltage hydrogenation can prepare crucial industrial chemicals ethylene glycol, and ethylene glycol mainly relies on petroleum path to prepare at present, and cost is higher, and China needs a large amount of import ethylene glycol every year, and import volume was nearly 4,800,000 tons in 2007.
The production route of tradition barkite utilizes oxalic acid to prepare with alcohol generation esterification, production technique cost height, and energy consumption is big, and is seriously polluted, and prepared using is unreasonable.For many years, people are seeking an operational path that cost is low, environment is good always.The sixties in last century, the D.F.Fenton of U.S. Associated Oil Company finds, carbon monoxide, pure and mild oxygen can pass through the direct synthesis of oxalic acid dialkyl of oxidation carbonylation, and company of Ube Industries Ltd. and U.S. ARCO company have carried out research and development in succession in this field since then.
Divide from development course for carbon monoxide oxidative coupling method synthesis of oxalate and can be divided into liquid phase method and vapor phase process.Wherein, carbon monoxide liquid phase method synthesis of oxalate condition is relatively harsher, and reaction is under high pressure carried out, the liquid-phase system corrosive equipment, and catalyzer easily runs off in the reaction process.The tool advantage of the vapor phase process of CO coupling producing oxalic ester, external company of Ube Industries Ltd. and Italian Montedisons SPA carried out vapor phase process research in succession in 1978.Wherein, the synthesis of oxalic ester by gaseous catalysis technology of emerging product company of space portion exploitation, reaction pressure 0.5MPa, temperature is 80 ℃～150 ℃.
The reaction process of synthesis of oxalate is as follows:
Linked reaction 2CO+2RONO → 2NO+ (COOR) 2 (1)
Regenerative response 2ROH+0.5O
2+ 2NO → 2RONO+H
2O (2)
By said process as can be known the key problem in technology of this system be to make the high efficiency reasonable use of NO, RONO, ROH highly selective in the two-step reaction process.
But; practical situation are in the reaction process of step (1); except generating dialkyl oxalate; usually also with the side reaction that generates dialkyl carbonate; and dialkyl carbonate can enter in the regenerative response system along with the reactant flow circulation, at this moment, considers drawing up of the middle side reaction of step (2); and reduce influence to step (1) main reaction, need alkyl ester separates with oxalic acid with dialkyl carbonate.But methylcarbonate and methanol mixture can form azeotrope, and its normal pressure azeotropic temperature is 63.5 ℃, and weight consists of methyl alcohol 70%, methylcarbonate 30%; Azeotropic temperature is 138 ℃ during 1Mpa, and weight consists of methyl alcohol 87.6%, methylcarbonate 12.4%; Therefore be difficult to realize separation with general rectificating method to both.
In the prior art, several different methods has been proposed for their separation people, as freeze crystallization, compression rectification method, azeotropic distillation, membrane separation process, extraction process and extraction fractional distillation or the like.Wherein, extraction fractional distillation is relatively success on industrial application, can obtain the higher methylcarbonate product of purity, and realize effective purification of methyl alcohol, be the flat 4-27024 of TOHKEMY of extraction agent and to propose with the propylene carbonate be the CN 94112211.5 of extraction agent as proposing with the dimethyl oxalate.Yet the extraction agent that these patents are selected is not very good, and the boiling point of propylene carbonate is higher, requires vacuum operating.
How selecting more excellent method to realize that methylcarbonate and the effective of methyl alcohol separate, is valuable research topic, and especially the method with fractionation by adsorption realizes that methyl alcohol and the effective of methylcarbonate separate, and yet there are no report.
Summary of the invention
Technical problem to be solved by this invention is methyl alcohol that exists in the conventional art and the technical problem that the methylcarbonate difficulty is separated and methanol purity is low, and a kind of method of new refining methanol is provided.This method has the high advantage of methanol product purity.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of refining methanol, will contain the mixed solution of methylcarbonate and methyl alcohol, and 10～100 ℃ of temperature, pressure 0.1～3.0MPa, air speed 0.2～5.0 hour
-1Condition under by adsorption bed, contact with sorbent material, obtain being rich in the effluent of methyl alcohol after the absorption; Wherein at least a in sorbent material employing ZSM-5, y-type zeolite or the β zeolite, silica alumina ratio is 200～1000: 1.
Sorbent material is preferably from ZSM-5 type zeolite in the technique scheme, and the silica alumina ratio preferable range is 300～800: 1.The preferred operations condition of adsorption bed is: 20～80 ℃ of temperature; Pressure 0.1～2.0MPa; Air speed 0.5～3.0 hour
-1The content preferable range of methylcarbonate is greater than zero～20% in the mixed solution of methylcarbonate and methyl alcohol, in the mixed solution of methylcarbonate and methyl alcohol the content of methylcarbonate more preferably scope be greater than zero～10%, most preferred range is greater than zero～5%.
The mixed solution of methylcarbonate and methyl alcohol is from the product absorption liquid of CO coupling producing oxalic ester in the technique scheme.
As everyone knows, in CO coupling system dimethyl oxalate reaction process, except the dimethyl oxalate target product, also contain a certain amount of by product, as methylcarbonate etc., and methylcarbonate and methyl alcohol can form azeotrope, adopt conventional method to be difficult to separate, thereby influence the reuse of methyl alcohol, and cause the main reaction adverse influence.
The discovery that the present inventor is surprised under study for action, adopting ZSM-5, y-type zeolite or β zeolite is sorbent material, and the methylcarbonate in methylcarbonate and the methyl alcohol is had higher adsorption selectivity, especially the ZSM-5 zeolite is better.The inventive method, fractionation by adsorption efficient height, and also technology is simple, is easy to accomplish scale production.
Adopt technical scheme of the present invention, for being raw material greater than zero～20% the methylcarbonate and the mixed solution of methyl alcohol, adopting ZSM-5, y-type zeolite or β zeolite is sorbent material, 10～100 ℃ of temperature with the content of methylcarbonate, pressure 0.1～3.0MPa, air speed 0.2～5.0 hour
-1Condition under by adsorption bed, contact with sorbent material, the purity of the methyl alcohol that obtains after the absorption has obtained better technical effect greater than 99.8%.
The invention will be further elaborated below by embodiment, but be not limited only to present embodiment.
Embodiment
[embodiment 1～9]
Filling 500 gram ZSM-5 type zeolite (its silica alumina ratio is 600: 1) sorbent materials feed methyl alcohol weight content 95% in adsorption bed, and the solution of methylcarbonate weight content 5% adsorbs under the condition shown in the following table, adsorb saturated after, the result who obtains is as follows:
Table 1
| Sequence number | Temperature ℃ | Air speed hour -1 | Pressure MPa | The weight content of methyl alcohol, % | The weight content of methylcarbonate, % |
| 1 | 22 | 0.25 | 1.0 | 99.92 | 0.08 |
| 2 | 31 | 0.40 | 0.5 | 99.88 | 0.12 |
| 3 | 52 | 0.61 | 5.0 | 99.82 | 0.18 |
| 4 | 75 | 0.80 | 3.5 | 99.70 | 0.30 |
| 5 | 30 | 1.6 | 0.5 | 99.66 | 0.34 |
| 6 | 55 | 1.3 | 2.5 | 99.69 | 0.31 |
| 7 | 61 | 2.4 | 0.1 | 99.82 | 0.18 |
| 8 | 44 | 0.67 | 2.0 | 99.80 | 0.20 |
| 9 | 50 | 0.48 | 1.5 | 99.76 | 0.24 |
[embodiment 10～18]
Filling 500 gram ZSM-5 type zeolite (its silica alumina ratio is 350: 1) sorbent materials feed the absorption raw material shown in the following table in adsorption bed, 40 ℃ of temperature, and pressure 0.2MPa, air speed 0.8 hour
-1Condition under by adsorption bed, contact with sorbent material and to adsorb, adsorb saturated after, the result who obtains is as shown in the table:
Table 2
| Sequence number | The weight content of methyl alcohol in the raw material, % | The weight content of methylcarbonate in the raw material, % | The weight content of absorption back methyl alcohol, % | The weight content of absorption back methylcarbonate, % |
| 10 | 81 | 19 | 99.52 | 0.48 |
| 11 | 73 | 27 | 99.48 | 0.52 |
| 12 | 91 | 9 | 99.64 | 0.36 |
| 13 | 94 | 6 | 99.82 | 0.18 |
| 14 | 99 | 1 | 99.86 | 0.14 |
| 15 | 96 | 4 | 99.90 | 0.10 |
| 16 | 99.5 | 0.5 | 99.95 | 0.05 |
| 17 | 86 | 14 | 99.56 | 0.44 |
| 18 | 88 | 12 | 99.61 | 0.39 |
[embodiment 19]
Filling 500 gram ZSM-5 type zeolite (its silica alumina ratio is 800: 1) sorbent materials feed methyl alcohol weight content 94% in adsorption bed, the absorption raw material of methylcarbonate weight content 6%, and 20 ℃ of temperature, pressure 2.8MPa, air speed 4.8 hours
-1Condition under by adsorption bed, contact with sorbent material and to adsorb, adsorb saturated after, the adsorbent solution that obtains is: methyl alcohol weight content 99.92%, methylcarbonate weight content 0.08%.
[embodiment 20]
Filling 500 gram ZSM-5 type zeolite (its silica alumina ratio is 500: 1) sorbent materials feed methyl alcohol weight content 97% in adsorption bed, the absorption raw material of methylcarbonate weight content 3%, and 90 ℃ of temperature, pressure 2.0MPa, air speed 3.5 hours
-1Condition under by adsorption bed, contact with sorbent material and to adsorb, adsorb saturated after, the adsorbent solution that obtains is: methyl alcohol weight content 99.86%, methylcarbonate weight content 0.14%.
[embodiment 21]
Filling 500 gram y-type zeolite ((its silica alumina ratio is 200: 1)) sorbent materials feed methyl alcohol weight content 96% in adsorption bed, the absorption raw material of methylcarbonate weight content 4%, and 70 ℃ of temperature, pressure 1.5MPa, air speed 1.5 hours
-1Condition under by adsorption bed, contact with sorbent material and to adsorb, adsorb saturated after, the adsorbent solution that obtains is: methyl alcohol weight content 99.80%, methylcarbonate weight content 0.20%.
[embodiment 22]
Filling 500 gram zeolite beta ((its silica alumina ratio is 280: 1)) sorbent materials feed methyl alcohol weight content 98% in adsorption bed, the absorption raw material of methylcarbonate weight content 2%, and 50 ℃ of temperature, pressure 0.8MPa, air speed 0.5 hour
-1Condition under by adsorption bed, contact with sorbent material and to adsorb, adsorb saturated after, the adsorbent solution that obtains is: methyl alcohol weight content 99.88%, methylcarbonate weight content 0.12%.
Claims (7)
1. the method for a refining methanol will contain the mixed solution of methylcarbonate and methyl alcohol, 10～100 ℃ of temperature, and pressure 0.1～3.0MPa, air speed 0.2～5.0 hour
-1Condition under by adsorption bed, contact with sorbent material, obtain being rich in the effluent of methyl alcohol after the absorption; It is at least a to it is characterized in that sorbent material adopts in ZSM-5, y-type zeolite or the β zeolite, and silica alumina ratio is 200～1000: 1.
2. according to the method for the described refining methanol of claim 1, it is characterized in that sorbent material adopts ZSM-5 type zeolite, its silica alumina ratio is 300～800: 1.
3. according to the method for the described refining methanol of claim 1, it is characterized in that 20～80 ℃ of the temperature of adsorption bed; Pressure 0.1～2.0MPa; Air speed 0.5～3.0 hour
-1
4. according to the method for the described refining methanol of claim 1, the content that it is characterized in that methylcarbonate in the mixed solution of methylcarbonate and methyl alcohol is for greater than zero～20%.
5. according to the method for the described refining methanol of claim 4, the content that it is characterized in that methylcarbonate in the mixed solution of methylcarbonate and methyl alcohol is for greater than zero～10%.
6. according to the method for the described refining methanol of claim 5, the content that it is characterized in that methylcarbonate in the mixed solution of methylcarbonate and methyl alcohol is for greater than zero～5%.
7. according to the method for the described refining methanol of claim 1, it is characterized in that the product absorption liquid of the mixed solution of methylcarbonate and methyl alcohol from CO coupling producing oxalic ester.
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| CN2010101999912A CN102276416A (en) | 2010-06-11 | 2010-06-11 | Method for refining methanol |
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| CN2010101999912A CN102276416A (en) | 2010-06-11 | 2010-06-11 | Method for refining methanol |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020143050A (en) * | 2019-02-28 | 2020-09-10 | 三菱ケミカル株式会社 | Method of separating methanol |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0139442A1 (en) * | 1983-10-04 | 1985-05-02 | Imperial Chemical Industries Plc | Carbonate production |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0139442A1 (en) * | 1983-10-04 | 1985-05-02 | Imperial Chemical Industries Plc | Carbonate production |
Non-Patent Citations (2)
| Title |
|---|
| > 20100115 范雯雯等 碳酸二甲酯-甲醇共沸物的吸附分离 10-13 1-7 第38卷, 第1期 * |
| 范雯雯等: "碳酸二甲酯-甲醇共沸物的吸附分离", <<化学工程>> * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020143050A (en) * | 2019-02-28 | 2020-09-10 | 三菱ケミカル株式会社 | Method of separating methanol |
| JP7463761B2 (en) | 2019-02-28 | 2024-04-09 | 三菱ケミカル株式会社 | Method for separating methanol |
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Application publication date: 20111214 |