CN103833537A - Absorption and refining method for high-purity methylacrolein - Google Patents
Absorption and refining method for high-purity methylacrolein Download PDFInfo
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- CN103833537A CN103833537A CN201410071066.XA CN201410071066A CN103833537A CN 103833537 A CN103833537 A CN 103833537A CN 201410071066 A CN201410071066 A CN 201410071066A CN 103833537 A CN103833537 A CN 103833537A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/79—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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Abstract
The invention belongs to the field of fine chemicals and chemical intermediates, and particularly discloses an absorption and refining method for high-purity methylacrolein. The invention provides a methylacrolein product which is prepared through two-step rectification by taking alkane containing six to eight carbon atoms as an absorbent for absorbing MA, and the content of the methylacrolein product is 99.5wt%, and the moisture content of the methylacrolein product is less than 0.1wt%. The method utilizes the characteristics of weak polarity of six to eight carbon atoms and the mutual solubility of water, the high-purity methylacrolein has higher absorption efficiency as an absorbent, the moisture content in absorption liquid is only about 0.5wt%, the burden of dehydration in the follow-up rectification operation can be greatly lightened, and the energy consumption can be saved. The absorption and refining method is simple in technological process, low in cost, and the methylacrolein is high in purity, low in the content of water and other impurities, and low in energy consumption, and can meet the application situation having high requirement on the quality of the methylacrolein.
Description
(1) technical field
The invention belongs to fine chemistry industry and chemical intermediate field, particularly a kind of absorption process for purification of high-purity methyl propenal.
(2) background technology
Methylacrylaldehyde (MA) is a kind of important chemical intermediate, can further be oxidized and produce methacrylic acid (MAA), all right direct and methyl alcohol and oxygen effect production methyl methacrylate (MMA), MMA is the principal monomer raw material of producing synthetic glass, has application very widely in fields such as national defence, aviation, building, home decoration and coating; Methylacrylaldehyde is still prepared the raw material of thermoplastics monomer, multiple spices and medicine intermediate.Produce Methylacrylaldehyde with the trimethyl carbinol (iso-butylene) oxidation and aspect Technology, economy and environmental protection, be a desirable operational path.
In order to meet the requirement of the further processing and utilization of MA, MA need to be absorbed and refine, but the absorption of MA is difficult with separating.Traditional Methylacrylaldehyde absorption process is to adopt water as absorption agent, because the polarity of water is stronger, to polarity, weak MA is difficult to absorb, need a large amount of water cycles, cause energy consumption to rise, and because water and MA can form azeotrope, the MA product purity obtaining is only for 90wt% left and right, comprising the acetaldehyde of suitable content, acetone and water.
Patent GP2110031 has proposed a kind of separation method that absorbs and extract for this reason, utilizes methyl alcohol as absorption agent, MA to be absorbed, and recycles water as extraction agent by methanol extraction out, recycle after methyl alcohol separates with water.The subject matter that the method exists is that the quantity of methyl alcohol of required use is very large, and the extraction agent water consumption matching is also very large, causes that facility investment is large, supplies consumption is large; And because methyl alcohol and MA, water and MA all exist azeotropism, thereby in MA product, inevitably affect next step use of MA with a small amount of methyl alcohol.Patent US3957880 proposes to adopt the alcohols of low-carbon (LC), comprise that methyl alcohol, ethanol, n-propyl alcohol or Virahol are as absorption agent, MA is absorbed from mixed gas, then water carries out extracting rectifying as extraction agent, but water and MA can form azeotrope to be caused containing moisture in MA product, cannot meet the service requirements of MA oxidative esterification catalyzer.Patent US5969178 reported that a kind of washing, methanol dehydration, MA absorb and and four towers associating absorption techniques of Methanol Recovery, but can not obtain the MA product that content is higher, only be suitable for oxidative esterification and produce MMA, but be further processed into the other products such as spices inapplicable for MA.4 of disclosed employings of patent CN101844973 alcohols more than carbon atom, as absorption agent, adopts the method for two step rectifying, and the MA product purity obtaining is 98wt%, but still the water that contains 1wt% left and right and other light constituent impurity of 1wt%.
Patent US4618709 discloses the aqueous solution that a kind of utilization contains MAA and has absorbed as absorption agent the method for MA, although the method has good assimilated efficiency, the MA reclaiming contains the by products such as water, acetaldehyde and acetone, can affect next step use of MA product.Research shows, in the method, assimilated efficiency improves along with the increase of MAA concentration, increases, thereby limited the application of the method but the side effect that the increase of MAA concentration brings is polymerization tendency.
Patent CN101020625 also discloses and has adopted ionic liquid to absorb the method for MA as absorption agent, although described assimilated efficiency is higher, but being not easy to separate with ionic liquid, the high boiling substance producing in absorption process cause ionic liquid quality to decline, and ionic liquid cost is higher, therefore the industrial application value of the method is limited.
Therefore, aforesaid method has certain limitation, especially needs to use the occasion of high-purity methyl propenal, for example, apply Methylacrylaldehyde and produce isobutyric aldehyde etc. as monomer, the hydrogenation of thermoplastic polymer, and aforesaid method is all inapplicable.
(3) summary of the invention
The present invention, in order to make up the deficiencies in the prior art, provides the absorption process for purification of the high-purity methyl propenal that a kind of production energy consumption is low, product purity is high.
The present invention is achieved through the following technical solutions:
An absorption process for purification for high-purity methyl propenal, comprises the steps:
(1) adopt the alkane of one or more 6-8 carbon atom as absorption agent, under in absorption tower, the Methylacrylaldehyde in quench tower overhead gas being absorbed;
(2) by the process of the mixed solution containing the Methylacrylaldehyde water-and-oil separator after absorbing, occur that, after layering, upper oil phase enters lightness-removing column, lightness-removing column tower top part material is as backflow, and a part is as light constituent extraction, and materials at bottom of tower enters weight-removing column;
(3) material that enters weight-removing column is through rectifying separation, and a tower top material part refluxes, and a part is as Methylacrylaldehyde product, and materials at bottom of tower returns to top, absorption tower and recycles as absorption agent.
The invention provides the alkane that a kind of use contains 6-8 carbon atom and absorb MA as absorption agent, and obtain content by two step rectifying and be greater than the Methylacrylaldehyde product that 99.5wt%, water-content are less than 0.1wt%.The method has been utilized the low-pole of 6-8 carbon atom and the feature little with water mutual solubility, use it to have higher assimilated efficiency as absorption agent, water-content in absorption liquid is only 0.5wt% left and right, has greatly alleviated the burden of dewatering in follow-up distillation operation, has saved energy consumption.
The classical group that the reactant gases of Methylacrylaldehyde is produced in the trimethyl carbinol or selective isobutene oxidation becomes MA15wt%-18wt%, H
2o13wt%-15wt%, N
260wt%-65wt%, O
26wt%-8wt% and carbonic acid gas, carbon monoxide and a small amount of acetaldehyde, methacrylic acid, acetone etc.
More excellent scheme of the present invention is:
In step (1), absorption agent is one or more in hexanaphthene, 2-methyl hexane, 3-methyl hexane, normal heptane, methylcyclohexane, ethyl cyclopentane, ethylcyclohexane, 2-methylheptane, 3-methylheptane, trimethylpentane and octane; Be preferably one or more in 2-methyl hexane, 3-methyl hexane, normal heptane, methylcyclohexane and ethyl cyclopentane.
In step (1), the absorption agent temperature on absorption tower is 0-30 ℃, and working pressure is 20-100KPa, and column bottom temperature is 5-35 ℃, and absorption liquid gas mass ratio is 0.5-10.
The processing condition that absorb affect assimilated efficiency.After above-mentioned absorption agent is determined, assimilated efficiency depends primarily on the consumption of temperature, pressure and absorption agent.Temperature is higher, more unfavorable to absorbing, but reduces absorption temperature to sacrifice energy consumption as cost.Consider assimilation effect and energy consumption, the service temperature on absorption tower is at 0-30 ℃, preferably 5-15 ℃.The working pressure on absorption tower also affects assimilated efficiency, and working pressure is high, favourable to absorbing, but the energy consumption of system compresses machine before increasing considers assimilated efficiency and energy consumption, and the working pressure on absorption tower is in 20-100kPa(gauge pressure, lower same), preferably 30-70kPa.The consumption of absorption agent is also very large on assimilation effect impact, and absorption agent consumption is larger, and assimilated efficiency is higher, but the needed energy consumption of desorb and solvent loss are also larger.The consumption of the absorption agent ratio of the mass rate of gas phase (absorption agent with) is generally 0.5-10, preferably 2-5.
In step (2), at the bottom of the tower of lightness-removing column, service temperature is 70-120 ℃, and operating reflux ratio is 1-10, atmospheric operation.
In step (3), at the bottom of the tower of weight-removing column, service temperature is 80-130 ℃, and operating reflux ratio is 0.5-5, negative-pressure operation, and tower top pressure is controlled at the absolute pressure of 60-90KPa.
The structure type of described absorption tower, lightness-removing column and weight-removing column adopts in sieve-tray tower, packing tower, bubble-plate column and valve tray column one or more.
The be absorbed mixed solution of agent and Methylacrylaldehyde of absorption tower tower reactor.Because selected absorption agent is (ring) alkane solvents of 6-8 carbon atom, therefore, the water in absorption liquid can be separated the overwhelming majority by water-and-oil separator.The phase-splitting time between water and many carbon (ring) alkane is very short, and the general residence time is at 10-20 minute.
The oil phase of water-and-oil separator enters Methylacrylaldehyde lightness-removing column.The lightness-removing column effect of Methylacrylaldehyde is acetaldehyde, acetone, propenal and the water removing in absorption liquid.Tower top discharging is light constituent, is mainly acetaldehyde, acetone and Methylacrylaldehyde, and water is removed by the separatory bag of return tank of top of the tower; At the bottom of tower, be the mixture of Methylacrylaldehyde and (ring) alkane, enter weight-removing column and take off heavily separation.
In the above-mentioned operation that takes off light and weight-removing column, adding of stopper is very necessary.
Adopt above-mentioned absorption and process for purification and suitable processing condition, the Methylacrylaldehyde product purity obtaining is greater than 99.5wt%, water-content is less than 0.1wt%.
Technical process of the present invention is simple, with low cost, and the Methylacrylaldehyde purity obtaining is high, and the foreign matter contents such as water are low, and energy consumption is low, meets the application scenario high to Methylacrylaldehyde specification of quality.
(4) accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is further illustrated.
Fig. 1 is absorption rectification flow schematic diagram of the present invention.
In figure, 1 reaction mixer that contains Methylacrylaldehyde, 2 absorption towers, 3 water-and-oil separators, 4 waste gas, 5 oil phases, 6 waste water, 7 lightness-removing columns, 8 light constituents, 9 weight-removing column chargings, 10 weight-removing columns, 11 products pots, 12 heat exchangers.
(5) embodiment
Accompanying drawing is a kind of process flow diagram of the present invention, and its concrete technology process description is as follows:
The reaction mixture gas 1 that contains Methylacrylaldehyde enters 2 bottoms, Methylacrylaldehyde absorption tower, enters 2 tops, absorption tower, counter-current absorption from the solvent of weight-removing column 9 tower reactors after heat exchanger cooling.Top, absorption tower waste gas 4 emptying after removing organism processing; Bottom, absorption tower absorption liquid enters water-and-oil separator 3.
The oil phase 5 on water-and-oil separator upper strata enters lightness-removing column 7 middle parts.Lightness-removing column 7 tower tops are light constituent 8, are the mixture 9 of Methylacrylaldehyde and absorption agent at the bottom of tower, enter weight-removing column 10.
A tower top material part for weight-removing column 10 refluxes, and a part directly enters products pot 11 as product extraction, and materials at bottom of tower recycles as absorption agent after overcooling.
The embodiment of this invention is described below by concrete case study on implementation, but protection domain is not subject to the restriction of case study on implementation.
Methylacrylaldehyde mixed gas (composition is in sequence number in table 1 1) to be absorbed relies on pressure to send into Methylacrylaldehyde absorption tower with the flow of 2000kg/h, and absorption agent is heptane.Tower top temperature is 7 ℃, and column bottom temperature is 15 ℃.Absorbing liquid-gas ratio (mass ratio) is 1.0, and tower top waste gas is directly emptying after heating power burning disposal, and at the bottom of tower, absorption liquid enters water-and-oil separator and carries out layering, and upper strata is oil phase (composition is in table 1 sequence number 2), and as the charging of lightness-removing column, flow is 1980kg/h.
The major function of lightness-removing column is to utilize azeotropic distillation to remove moisture, utilizes conventional distillation to remove the light constituent such as acetaldehyde and acetone.Lightness-removing column atmospheric operation, 64 ℃ of tower top temperatures, 95 ℃ of tower reactor temperature, reflux ratio 4, tower top discharging is 206kg/h, tower top material forms in sequence number in table 13.Materials at bottom of tower is sent into weight-removing column 10 by pump.
The major function of weight-removing column is to remove absorption agent heptane, obtains highly purified Methylacrylaldehyde.
The composition table look-up of each material in table 1 case study on implementation
Claims (8)
1. an absorption process for purification for high-purity methyl propenal, is characterized by, and comprises the steps: that (1) adopts the alkane of one or more 6-8 carbon atom as absorption agent, under in absorption tower, the Methylacrylaldehyde in quench tower overhead gas being absorbed; (2) by the process of the mixed solution containing the Methylacrylaldehyde water-and-oil separator after absorbing, occur that, after layering, upper oil phase enters lightness-removing column, lightness-removing column tower top part material is as backflow, and a part is as light constituent extraction, and materials at bottom of tower enters weight-removing column; (3) material that enters weight-removing column is through rectifying separation, and a tower top material part refluxes, and a part is as Methylacrylaldehyde product, and materials at bottom of tower returns to top, absorption tower and recycles as absorption agent.
2. the absorption process for purification of high-purity methyl propenal according to claim 1, it is characterized in that: in step (1), absorption agent is one or more in hexanaphthene, 2-methyl hexane, 3-methyl hexane, normal heptane, methylcyclohexane, ethyl cyclopentane, ethylcyclohexane, 2-methylheptane, 3-methylheptane, trimethylpentane and octane.
3. the absorption process for purification of high-purity methyl propenal according to claim 1, it is characterized in that: in step (1), the absorption agent temperature on absorption tower is 0-30 ℃, and working pressure is 20-100KPa, column bottom temperature is 5-35 ℃, and absorption liquid gas mass ratio is 0.5-10.
4. the absorption process for purification of high-purity methyl propenal according to claim 1, is characterized in that: in step (2), at the bottom of the tower of lightness-removing column, service temperature is 70-120 ℃, and operating reflux ratio is 1-10, atmospheric operation.
5. the absorption process for purification of high-purity methyl propenal according to claim 1, it is characterized in that: in step (3), at the bottom of the tower of weight-removing column, service temperature is 80-130 ℃, and operating reflux ratio is 0.5-5, negative-pressure operation, tower top pressure is controlled at the absolute pressure of 60-90KPa.
6. the absorption process for purification of high-purity methyl propenal according to claim 1, is characterized in that: the structure type of described absorption tower, lightness-removing column and weight-removing column adopts in sieve-tray tower, packing tower, bubble-plate column and valve tray column one or more.
7. the absorption process for purification of high-purity methyl propenal according to claim 2, is characterized in that: described absorption agent is one or more in 2-methyl hexane, 3-methyl hexane, normal heptane, methylcyclohexane and ethyl cyclopentane.
8. the absorption process for purification of high-purity methyl propenal according to claim 3, is characterized in that: in step (1), the absorption agent temperature on absorption tower is 5-15 ℃, and working pressure is 30-70KPa, and absorption liquid gas mass ratio is 2-5.
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| CN201410071066.XA CN103833537B (en) | 2014-02-28 | 2014-02-28 | Absorption and refining method for high-purity methylacrolein |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467610A (en) * | 2018-11-27 | 2019-03-15 | 华南理工大学 | A kind of method for preparing high degree of substitution cross-linked starch concurrently in the production process of acetate starch |
| CN110256395A (en) * | 2019-07-02 | 2019-09-20 | 菏泽学院 | A kind of synthetic method of 4,4- dimethyl-2-isopropyl -1,3- dioxolane |
| CN113845409A (en) * | 2021-10-18 | 2021-12-28 | 浙江皇马科技股份有限公司 | Absorption and refining method of high-purity methacrolein |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003192627A (en) * | 2001-12-27 | 2003-07-09 | Mitsubishi Rayon Co Ltd | Method for producing methacrolein |
| CN101020625A (en) * | 2007-03-12 | 2007-08-22 | 中国科学院过程工程研究所 | Process of absorbing methyl acraldehyde with ionic liquid |
| CN101844973A (en) * | 2010-06-01 | 2010-09-29 | 上海华谊丙烯酸有限公司 | Method for absorbing and separating methacrolein |
| US8273313B2 (en) * | 2007-02-14 | 2012-09-25 | Saudi Basic Industries Corporation | System for producing methacrylic acid |
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2014
- 2014-02-28 CN CN201410071066.XA patent/CN103833537B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003192627A (en) * | 2001-12-27 | 2003-07-09 | Mitsubishi Rayon Co Ltd | Method for producing methacrolein |
| US8273313B2 (en) * | 2007-02-14 | 2012-09-25 | Saudi Basic Industries Corporation | System for producing methacrylic acid |
| CN101020625A (en) * | 2007-03-12 | 2007-08-22 | 中国科学院过程工程研究所 | Process of absorbing methyl acraldehyde with ionic liquid |
| CN101844973A (en) * | 2010-06-01 | 2010-09-29 | 上海华谊丙烯酸有限公司 | Method for absorbing and separating methacrolein |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467610A (en) * | 2018-11-27 | 2019-03-15 | 华南理工大学 | A kind of method for preparing high degree of substitution cross-linked starch concurrently in the production process of acetate starch |
| CN110256395A (en) * | 2019-07-02 | 2019-09-20 | 菏泽学院 | A kind of synthetic method of 4,4- dimethyl-2-isopropyl -1,3- dioxolane |
| CN113845409A (en) * | 2021-10-18 | 2021-12-28 | 浙江皇马科技股份有限公司 | Absorption and refining method of high-purity methacrolein |
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Application publication date: 20140604 Assignee: Zibo Qixian Tengda Chemical Co., Ltd. Assignor: Heze HOLLEY New Material Co Ltd Contract record no.: 2018370000065 Denomination of invention: Absorption and refining method for high-purity methylacrolein Granted publication date: 20150401 License type: Exclusive License Record date: 20181214 |
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Address after: No. 333, Haihe Road, Heze Development Zone, 274000 Shandong Province Patentee after: Qixiang Huali New Material Co., Ltd Address before: 274000 Shandong province Heze Development Zone Haihe road to the North Patentee before: HEZE HUALI NEW MATERIAL Co.,Ltd. |