CN1817844A - Method for separating methyl-acrolein in methyl-methyl acrylate - Google Patents
Method for separating methyl-acrolein in methyl-methyl acrylate Download PDFInfo
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- CN1817844A CN1817844A CN 200610011379 CN200610011379A CN1817844A CN 1817844 A CN1817844 A CN 1817844A CN 200610011379 CN200610011379 CN 200610011379 CN 200610011379 A CN200610011379 A CN 200610011379A CN 1817844 A CN1817844 A CN 1817844A
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- methylacrylaldehyde
- mal
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- methyl
- methyl methacrylate
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Abstract
Separation of methylacrolein in methyl methacrylate production is carried out by reacting to obtain mixed gas containing MAL, cooling and absorbing for MAL by 0~60 degrees C water, azeotropic rectifying with methanol as azeotropic agent, and separating MAL from mixed gas to obtain azeotropic mixture of MAL and methanol with water content lower 500pp. It is simple.
Description
Technical field:
The invention belongs to volatile polymerization single polymerization monomer absorption extraction technical field, particularly relate to the technology and method of Methylacrylaldehyde separation with synthesizing methylmethacrylate.
Background technology:
Methyl methacrylate (MMA) has a wide range of applications in many-sides such as national defence, building and fine chemistry industries, as production of production, modifying plastics, high grade paint and the tackiness agent of organic glass etc.Though produce the traditional acetone cyanalcohol method technical maturity of MMA, cost of material is higher, and uses highly toxic product and strong acid, cause serious problems such as environmental pollution and murder by poisoning human body.In the last few years, various countries carried out the research of MMA new process of production route unexpectedly mutually, wherein with C
4Cut is that the operational path of raw material system MMA reaches attractive economically in environmental protection.Competitive process for cleanly preparing is iso-butylene (or trimethyl carbinol) two-step oxidation method.The volume content of Methylacrylaldehyde in the first step oxidation products (MAL) is about 6%, and water vapor accounts for about 17.9%, also has a large amount of rare gas elementes such as N in addition
2, CO
2With CO etc., the water in the product must be removed, otherwise can influence the second step oxidative esterification reaction.Make the separation difficulty relatively of the MAL in the first step reaction product like this.U.S.Pat.No.3,957,880 methods that propose are to absorb with ethanol, and water carries out extracting rectifying as extraction agent then, and what obtain like this is the azeotrope of water and Methylacrylaldehyde, can not satisfy the requirement of the second step oxidative esterification reaction.U.S.Pat.No.2,514,966 methods that propose are that water absorbs, but the MAL that obtains can not satisfy the requirement of the second step oxidative esterification reaction equally.U.S.Pat.No.5, the washing of 969,178 reports, methyl alcohol drying, methyl alcohol absorb and reclaim the technology industrialization of rectifying four towers associating, but complex process.
Summary of the invention:
The present invention propose a kind of new MMA produce in process for separating and purifying and the working method thereof of MAL.Water carries out cooling and absorbing to the first step oxidation reaction product, a large amount of N
2, CO
2, CO and unreacted hydro carbons discharge, the product that absorbs mainly is MAL, acetone etc.Add a certain amount of methyl alcohol and carry out azeotropic distillation in this solution, the azeotrope that MAL and methyl alcohol are formed steams from cat head, makes MAL obtain separating and purifies, water-content is lower than 500ppm, entrainer methyl alcohol is the reaction raw materials in second step, does not influence follow-up oxidative esterification reaction, need not separate.Simplified U.S.Pat.No.5 like this, the complicated technology of 969,178 reports has reduced facility investment and process cost, has reduced environmental pollution.
Compare with existing processing method, the present invention has following advantage and positively effect: present method makes water absorb easy realization, has played the function of washing simultaneously, helps the removing of impurity.Carry out azeotropic distillation with methyl alcohol, simple and easy to operate, solved the high problem of water-content among the MAL well.Simplify technical process, thereby reduced facility investment and process cost, reduced environmental pollution.
Description of drawings
Fig. 1: separation method process principle figure.
Embodiment:
Embodiment 1: MAL separates a kind of process operation parameter of purifying in the product gas mixture
Reaction product stream is fed the water absorption tower, and stage number is 10, atmospheric operation, and 110 ℃ of import product gas temperature, gas composition is IB (iso-butylene) 0.22%, O
21.51%, N
268.11%, H
2O 12.30%, CO
24.25%, CO 1.77%, and MAL 10.97%, and MAA 0.50%, C
3H
6O 0.1%, and mass rate is 15.44kg/h, absorbs 44.6 ℃ of tower still temperature, 2.3 ℃ of tower top temperatures with 2 ℃ water 42.00kg/h.Overhead gas after the absorption consists of IB 0.03%, O
21.96%, N
289.6%, H
2O 0.5%, CO
25.5%, CO 2.32%, MAL trace, C
3H
6The O trace.
The MAL aqueous solution and methyl alcohol are squeezed in the rectifying tower, and the rectifying tower stage number is 25 blocks of plates, and atmospheric operation, feed entrance point are 13 blocks of plates, and the inlet feed temperature is 25 ℃, and the raw material MAL aqueous solution consists of H
2O 95.63%, CO
20.10%, CO 0.003%, and MAL 3.70%, and MAA 0.30%, and mass rate is 45.85kg/h, the add-on 1.20kg/h of methyl alcohol, 100.3 ℃ of tower still temperature, 55.6 ℃ of tower top temperatures.Cat head consists of H
2O0.20%, CO
21.5%, MAL 54.6%, CH
4O 38.7%.Consist of H at the bottom of the tower
2O 99.7%, MAL trace, CH
4The O trace, MAA 0.30%.
Embodiment 2: MAL separates the another kind of process operation parameter of purifying in the product gas mixture
Reaction product stream is fed the water absorption tower, and stage number is 10, atmospheric operation, and 130 ℃ of import product gas temperature, gas composition is IB 0.22%, O
21.51%, N
268.11%, H
2O 12.30%, CO
24.25%, CO 1.77%, and MAL 10.97%, and MAA 0.50%, C
3H
6O 0.1%, and mass rate is 15.44kg/h, absorbs 52.0 ℃ of tower still temperature, 22.3 ℃ of tower top temperatures with 20 ℃ water 48.00kg/h.Overhead gas after the absorption consists of IB 0.20%, O
21.97%, N
285.20%, H
2O 1.7%, CO
25.21%, CO2.12%, MAL 3.4%, C
3H
6The O trace.
The MAL aqueous solution and methyl alcohol are squeezed in the rectifying tower, and the rectifying tower stage number is 25 blocks of plates, and atmospheric operation, feed entrance point are 13 blocks of plates, and the inlet feed temperature is 25 ℃, and the raw material MAL aqueous solution consists of H
2O 97.00%, CO
20.10%, CO 0.003%, and MAL 2.5%, and MAA 0.25%, and mass rate is 50.24kg/h, the add-on 2.20kg/h of methyl alcohol, 102.2 ℃ of tower still temperature, 51.9 ℃ of tower top temperatures.Cat head consists of IB 1.1%, O
20.2%, N
23.2%, CO
22.8%, H
2The O trace, MAL 79.0%, CH
4O 10.8%.Consist of H at the bottom of the tower
2O 99.7%, MAL trace, CH
4O 0.1%, and MAA 0.20%.
Embodiment 3: MAL separates the third process operation parameter of purifying in the product gas mixture
Reaction product stream is fed the water absorption tower, and stage number is 10, and working pressure is 2atm, 120 ℃ of import product gas temperature, and gas composition is IB 0.22%, O
21.51%, N
268.11%, H
2O 12.30%, CO
24.25%, CO 1.77%, and MAL 10.97%, and MAA 0.50%, C
3H
6O 0.1%, and mass rate is 15.44kg/h, absorbs 52.2 ℃ of tower still temperature, 10.5 ℃ of tower top temperatures with 10 ℃ water 42.00kg/h.Overhead gas after the absorption consists of IB trace, O
22%, N
290.00%, H
2O 0.4%, CO
25.21%, CO 2.30%, and MAL 0.23%, C
3H
6O 0.004%.
The MAL aqueous solution and methyl alcohol are squeezed in the rectifying tower, and the rectifying tower stage number is 25 blocks of plates, and atmospheric operation, feed entrance point are 10 blocks of plates, and the inlet feed temperature is 25 ℃, and the raw material MAL aqueous solution consists of H
2O 95.40%, CO
20.20%, CO 0.003%, and MAL 3.70%, and MAA 0.30%, and mass rate is 45.96kg/h, the add-on 0.60kg/h of methyl alcohol, 102.3 ℃ of tower still temperature, 50.7 ℃ of tower top temperatures.Cat head consists of IB 1.5%, O
20.2%, N
23.8%, CO
23.5%, H
2The O trace, MAL 66.5%, CH
4O 21.6%.Consist of H at the bottom of the tower
2O 99.7%, MAL trace, CH
4O 0.1%, and MAA 0.10%.
Embodiment 4: MAL separates the 4th kind of process operation parameter of purifying in the product gas mixture
Reaction product stream is fed the water absorption tower, and stage number is 10, and working pressure is 2atm, 100 ℃ of import product gas temperature, and gas composition is IB 0.22%, O
21.51%, N
268.11%, H
2O 12.30%, CO
24.25%, CO 1.77%, and MAL 10.97%, and MAA 0.50%, C
3H
6O 0.1%, and mass rate is 11.20kg/h, absorbs 63.2 ℃ of tower still temperature, 15.6 ℃ of tower top temperatures with 15 ℃ water 38.00kg/h.Overhead gas after the absorption consists of IB trace, O
22.00%, N
289.5%, H
2O 0.6%, CO
25.40%, CO 2.30%, and MAL 0.06%, C
3H
6O 0.001%.
The MAL aqueous solution and methyl alcohol are squeezed in the rectifying tower, and the rectifying tower stage number is 25 blocks of plates, and atmospheric operation, feed entrance point are 13 blocks of plates, and the inlet feed temperature is 25 ℃, and the raw material MAL aqueous solution consists of H
2O 94.80%, and MAL 4.30%, and MAA 0.30%, and mass rate is 38.85kg/h, the add-on 0.7kg/h of methyl alcohol, 102.1 ℃ of tower still temperature, 58.4 ℃ of tower top temperatures.Cat head consists of H
2The O trace, MAL 72.0%, CH
4O27.9%.Consist of H at the bottom of the tower
2O 99.5%, MAL trace, CH
4O 0.20%, and MAA 0.30%.Annotate: above composition is mass percent.
Claims (6)
1. one kind is used for the separation method that methyl methacrylate is produced Methylacrylaldehyde, it is characterized in that Methylacrylaldehyde being absorbed from the first step reaction product, add entrainer then and adopt the azeotropic distillation technology that the Methylacrylaldehyde purification is separated by a kind of absorption agent.
2. according to a kind of separation method that is used for methyl methacrylate production Methylacrylaldehyde described in the claim 1 coupling technique of absorption and azeotropic distillation.
3. be water according to the absorption agent in the described a kind of separation method that is used for methyl methacrylate production Methylacrylaldehyde of claim 1, entrainer is a methyl alcohol.
4. produce absorption agent in the separation method of Methylacrylaldehyde according to the described a kind of methyl methacrylate that is used for of claim 1, according to flow rate of reactive gas and its add-on of temperature regulation and temperature, the absorption agent add-on is 0.1-10 a times of reaction gas mass rate, and temperature is between 0-60 ℃.
5. produce entrainer in the separation method of Methylacrylaldehyde according to the described a kind of methyl methacrylate that is used for of claim 1, consumption is according to the concentration difference of Methylacrylaldehyde, add-on be the Methylacrylaldehyde mass content 0.01-20 doubly.
6. according to the adding of entrainer described in the claim 1, its adding method can add by storage tank is static, also can dynamically add with charging.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100113791A CN100368368C (en) | 2006-02-28 | 2006-02-28 | Method for separating methyl-acrolein in methyl-methyl acrylate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100113791A CN100368368C (en) | 2006-02-28 | 2006-02-28 | Method for separating methyl-acrolein in methyl-methyl acrylate |
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| Publication Number | Publication Date |
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| CN1817844A true CN1817844A (en) | 2006-08-16 |
| CN100368368C CN100368368C (en) | 2008-02-13 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015043861A1 (en) * | 2013-09-26 | 2015-04-02 | Evonik Industries Ag | Method for producing methacrolein and the conditioning/draining thereof for direct oxidative esterification |
| CN105683142A (en) * | 2013-10-28 | 2016-06-15 | 罗门哈斯公司 | Process for separating methacrolein |
| CN108863789A (en) * | 2018-06-14 | 2018-11-23 | 西京学院 | A kind of low-purity isobutene prepares the production system and method for methyl methacrylate |
| CN115974668A (en) * | 2022-12-02 | 2023-04-18 | 重庆道为低碳科技有限公司 | Method for separating methacrolein in methyl methacrylate production |
-
2006
- 2006-02-28 CN CNB2006100113791A patent/CN100368368C/en active Active
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI633082B (en) * | 2013-09-26 | 2018-08-21 | 贏創羅恩有限責任公司 | Process for preparing methacrolein and conditioning/dewatering thereof for direct oxidative esterification |
| KR20160061395A (en) * | 2013-09-26 | 2016-05-31 | 에보니크 룀 게엠베하 | Method for producing methacrolein and the conditioning/draining thereof for direct oxidative esterification |
| CN105683148A (en) * | 2013-09-26 | 2016-06-15 | 赢创罗姆有限公司 | Method for producing methacrolein and the conditioning/draining thereof for direct oxidative esterification |
| KR102282531B1 (en) | 2013-09-26 | 2021-07-27 | 룀 게엠베하 | Method for producing methacrolein and the conditioning/draining thereof for direct oxidative esterification |
| JP2016536277A (en) * | 2013-09-26 | 2016-11-24 | エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツングＥｖｏｎｉｋ Ｒｏｅｈｍ ＧｍｂＨ | Process for the preparation of methacrolein and its conditioning / dehydration for direct oxidative esterification |
| US9580374B2 (en) | 2013-09-26 | 2017-02-28 | Evonik Roehm Gmbh | Method for producing methacrolein and the conditioning/draining thereof for direct oxidative esterification |
| WO2015043861A1 (en) * | 2013-09-26 | 2015-04-02 | Evonik Industries Ag | Method for producing methacrolein and the conditioning/draining thereof for direct oxidative esterification |
| RU2645214C2 (en) * | 2013-09-26 | 2018-02-19 | Эвоник Рём ГмбХ | Method of producing methacrolein and its air-conditioning / dehydration for direct oxidative etherification |
| US9765007B2 (en) | 2013-10-28 | 2017-09-19 | Rohm And Haas Company | Dehydration process |
| CN105683142B (en) * | 2013-10-28 | 2018-11-13 | 罗门哈斯公司 | Method for detaching methacrolein |
| CN105683142A (en) * | 2013-10-28 | 2016-06-15 | 罗门哈斯公司 | Process for separating methacrolein |
| CN108863789A (en) * | 2018-06-14 | 2018-11-23 | 西京学院 | A kind of low-purity isobutene prepares the production system and method for methyl methacrylate |
| CN115974668A (en) * | 2022-12-02 | 2023-04-18 | 重庆道为低碳科技有限公司 | Method for separating methacrolein in methyl methacrylate production |
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| Publication number | Publication date |
|---|---|
| CN100368368C (en) | 2008-02-13 |
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