CN104557511B - A kind of method of acrylic acid from vinylformic acid sour water - Google Patents
A kind of method of acrylic acid from vinylformic acid sour water Download PDFInfo
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- CN104557511B CN104557511B CN201510037102.5A CN201510037102A CN104557511B CN 104557511 B CN104557511 B CN 104557511B CN 201510037102 A CN201510037102 A CN 201510037102A CN 104557511 B CN104557511 B CN 104557511B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/50—Use of additives, e.g. for stabilisation
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- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method of acrylic acid from vinylformic acid sour water, comprise the following steps: introduced in extraction tower by vinylformic acid sour water, add extraction agent, extraction tower normal pressure and temperature operates, and sour water and extraction agent part by weight are 1:0.5-1:1; In extraction tower, organic phase is proposed from sour water, then obtain by-product vinylformic acid through distillation and concentration process; Described distillation and concentration process adopts single-tower continuous rectification, and hydrocone type reboiler take water vapor as thermal source; Beneficial effect of the present invention is 1) selected extraction agent extraction efficiency is high, and after extraction, organic phase concentration is higher, is beneficial to concentrated; 2) extraction agent heat enthalpy value is low, and rectifying energy consumption is little, and energy consumption is less than the half of former azeotropic concentration process energy consumption; 3) after extraction, waste water can through biochemical treatment qualified discharge; 4) final obtained by-product vinylformic acid is anhydrous, and quality index reaches esterification grade requirement, can be used for producing the products such as butyl acrylate, has obvious price advantage.
Description
Technical field
The present invention relates to a kind of method of acrylic acid from vinylformic acid sour water.
Background technology
Domestic and international propenal production technique generally adopts oxidation of propylene, and while propylene oxidation generates propenal, small part is vinylformic acid by deep oxidation.Mixed reaction product through washing, absorb, rectifying obtains propenal, by product vinylformic acid is in washing and absorb the molten water of operation and generate vinylformic acid sour water, and due to the difference of technique and catalyst selectivity, sour water concentration is generally 7% ~ 9%.
Vinylformic acid concentrates by the by-product acid hydromining methylbenzene azeotropic dewatering process in present most propenal production, can be used for producing vinylformic acid or butyl ester; Minority adopts in sour water and rear as sewage discharge.Above two schemes: because acrylic acid aqueous solution concentration is very low, concentration and evaporation moisture content needs to consume a large amount of energy; And concentrate process difficulty is larger; Entrainer toluene has certain toxicity; Final enriched product still moisture about 50%.If as sewage discharge, because vinylformic acid has certain bio-toxicity, not easily biochemical treatment, pre-treatment difficulty is very large, and environmental pollution is serious.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of method of acrylic acid from vinylformic acid sour water, employing acetates is extraction agent, environmental protection.
To achieve these goals, the present invention adopts following technical scheme:
Propenal production technique generally adopts oxidation of propylene, and while propylene oxidation generates propenal, small part is vinylformic acid by deep oxidation.Mixed reaction product obtains propenal through washing, absorption, rectifying, and by product vinylformic acid is in washing and absorb operation molten water generation vinylformic acid sour water.
Acryllic acid water component and degree: vinylformic acid about 6.5 ~ 7.5%, acetic acid about 0.5%, propenal is about 500PPM, and all the other are water.
1) introduced in extraction tower by vinylformic acid sour water, add extraction agent, extraction tower normal pressure and temperature operates, and sour water and extraction agent part by weight are 1/0.5 ~ 1/1; ; Described extraction agent is that acetates or MIBK etc. are miscible but be insoluble in the organic solvent of water with vinylformic acid;
2) in extraction tower, organic phase (vinylformic acid) is proposed from sour water, then obtain by-product vinylformic acid through distillation and concentration process.Sour water concentration 7 ~ 8% before extraction, after extraction, organic phase concentration is 8% ~ 15%, and waste water acid content <1.0%, wherein comprises the impurity such as acetic acid.
Described distillation and concentration process adopts single-tower continuous rectification, and adopting hydrocone type reboiler, take water vapor as thermal source.The organic phase of extraction is by throat-fed in the middle part of rectifying tower, and more than described opening for feed adopting structured packing, is dual-flow tray below opening for feed, working pressure is-0.085Mpa, tower top temperature controls 30 ~ 40 DEG C, and column bottom temperature controls 80 ~ 90 DEG C, inlet temperature 70 ~ 75 DEG C.Because vinylformic acid is easily polymerized, be add reflux pipeline after stopper extraction agent is mixed with 10% solution to be polymerized in tower body to prevent vinylformic acid with Resorcinol.Vinylformic acid mean residence time about 2 hours.
Further, in technique scheme, described acetates is Iso Butyl Acetate (IPAC).
Further, in technique scheme, step 1) in will extract the aqueous phase obtained and introduce solvent recovery tower and reclaim, the waste water of generation draws as treatment center of sewage.After solvent recovery tower process, vinylformic acid 0.5 ~ 0.6% in waste water, acetic acid 0.3 ~ 0.4%, solvent 200PPM, propenal is about 200ppm.
Further, in technique scheme, recycling step 2) middle extraction agent, add in extraction tower and use.
The beneficial effect of the invention
1) the extraction agent extraction efficiency selected by is high, and after extraction, organic phase concentration is higher, is beneficial to concentrated.
2) extraction agent heat enthalpy value is low, and rectifying energy consumption is little, and energy consumption is less than the half of former azeotropic concentration process energy consumption.
3) after extraction, waste water can through biochemical treatment qualified discharge.
4) final obtained by-product vinylformic acid is anhydrous, and quality index reaches esterification grade requirement, can be used for producing the products such as butyl acrylate, has obvious price advantage.
Accompanying drawing explanation
Fig. 1 is present invention process schema;
Embodiment
Further illustrate with reference to the accompanying drawings.
Embodiment 1
As shown in Figure 1, propenal production technique generally adopts oxidation of propylene, and while propylene oxidation generates propenal, small part is vinylformic acid by deep oxidation.Mixed reaction product obtains propenal through washing, absorption, rectifying, and by product vinylformic acid is in washing and absorb operation molten water generation vinylformic acid sour water.
Acryllic acid water component and degree: vinylformic acid about 7%, acetic acid about 0.5%, propenal is about 500PPM, and all the other are water.
1) introduced in extraction tower by vinylformic acid sour water, add extraction agent, extraction tower normal pressure and temperature operates, and sour water and extraction agent part by weight are 1:0.7; Extraction tower is rotating disc contactor; Extraction agent is acetates; After extraction, organic phase acrylic acid concentration is about 11%, and waste water acid content <1.0%, wherein comprises the impurity such as acetic acid.
2) in extraction tower, organic phase (vinylformic acid) is proposed from sour water, then obtain by-product vinylformic acid through distillation and concentration process.
Distillation and concentration process adopts single-tower continuous rectification, and adopting hydrocone type reboiler, take water vapor as thermal source.The organic phase of extraction is by throat-fed in the middle part of rectifying tower, and more than opening for feed adopting structured packing, is dual-flow tray below opening for feed, working pressure is-0.085Mpa, tower top temperature controls 30 ~ 40 DEG C, and column bottom temperature controls 80 ~ 90 DEG C, inlet temperature 70 ~ 75 DEG C.Because vinylformic acid is easily polymerized, be add reflux pipeline after stopper extraction agent is mixed with 10% solution to be polymerized in tower body to prevent vinylformic acid with Resorcinol.Vinylformic acid mean residence time about 2 hours.
Acetates is Iso Butyl Acetate (IPAC).
Step 1) in will extract the aqueous phase that obtains and introduce solvent recovery tower and reclaim, the waste water of generation draws as treatment center of sewage.After solvent recovery tower process, vinylformic acid 0.5 ~ 0.6% in waste water, acetic acid 0.3 ~ 0.4%, solvent 200PPM, propenal is about 200ppm.
Recycling step 2) middle extraction agent, add in extraction tower and use.
Above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (4)
1. the method for acrylic acid from vinylformic acid sour water, is characterized in that comprising the following steps:
1) introduced in extraction tower by vinylformic acid sour water, add extraction agent, extraction tower normal pressure and temperature operates, and sour water and extraction agent part by weight are 1:0.5 ~ 1:1; Described extraction agent is Iso Butyl Acetate;
2) in extraction tower, organic phase is proposed from sour water, then obtain by-product vinylformic acid through distillation and concentration process; Described distillation and concentration process adopts single-tower continuous rectification, and hydrocone type reboiler take water vapor as thermal source; The organic phase of extraction is by throat-fed in the middle part of rectifying tower, and more than described opening for feed adopt structured packing, be dual-flow tray below opening for feed, working pressure is-0.085Mpa, tower top temperature 30 ~ 40 DEG C, column bottom temperature 80 ~ 90 DEG C, inlet temperature 70 ~ 75 DEG C; Containing inhibition solution in distillation tower reflux pipeline, described inhibition solution is take Resorcinol as the solution that stopper extraction agent is mixed with that massfraction is 10%;
Step 1) acryllic acid water component and degree: vinylformic acid 6.5 ~ 7.5%, acetic acid 0.5%, propenal 500PPM, all the other are water.
2. method according to claim 1, is characterized in that: step 2) in vinylformic acid mean residence time 2 hours.
3. method according to claim 1, is characterized in that: step 1) in will extract the aqueous phase that obtains and introduce solvent recovery tower and reclaim.
4. method according to claim 1, is characterized in that: recycling step 2) middle extraction agent, add in extraction tower and use.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105061193B (en) * | 2015-08-10 | 2017-03-22 | 蓝星（北京）技术中心有限公司 | Method for recycling organic matters in methionine production wastewater treatment |
| CN105399620A (en) * | 2015-11-13 | 2016-03-16 | 惠州市长润发涂料有限公司 | Acrylic acid extraction recovery technology |
| CN105399621A (en) * | 2015-11-13 | 2016-03-16 | 惠州市长润发涂料有限公司 | Wastewater-free type monomer production method |
| CN106748749B (en) * | 2016-11-10 | 2019-06-18 | 万华化学集团股份有限公司 | A method of triisobutylene in separation tert-butyl acrylate reaction solution |
| CN110551020A (en) * | 2018-05-30 | 2019-12-10 | 中国石油集团东北炼化工程有限公司吉林设计院 | Method for recovering acrylic acid in wastewater |
| CN115448834A (en) * | 2022-09-16 | 2022-12-09 | 卫星化学股份有限公司 | Method for refining acrylic acid aqueous solution |
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| CN100374406C (en) * | 2006-02-28 | 2008-03-12 | 上海华谊丙烯酸有限公司 | Methylacrylic acid extracting and refining process |
| CN100554237C (en) * | 2006-06-30 | 2009-10-28 | 上海华谊丙烯酸有限公司 | A kind of method of purification of methacrylic acid |
| US20110201842A1 (en) * | 2008-10-15 | 2011-08-18 | Arkema Inc. | Method for recovering carboxylic acids from dilute aqueous streams |
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Address after: 250000 Xinglu Avenue 788, Zhoucun District, Zibo City, Shandong Province Patentee after: Shandong Lu Biotechnology Co., Ltd. Address before: 250000 Xinglu Avenue 788, Zhoucun District, Zibo City, Shandong Province Patentee before: ZIBO XINGLU CHEMICAL INDUSTRY CO., LTD. |
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Denomination of invention: A method of recovering acrylic acid from acrylic acid water Effective date of registration: 20210120 Granted publication date: 20160413 Pledgee: Hengfeng Bank Co.,Ltd. Zibo Branch Pledgor: SHANDONG XINGLU BIOTECHNOLOGY Co.,Ltd. Registration number: Y2021980000524 |
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Date of cancellation: 20220307 Granted publication date: 20160413 Pledgee: Hengfeng Bank Co.,Ltd. Zibo Branch Pledgor: SHANDONG XINGLU BIOTECHNOLOGY CO.,LTD. Registration number: Y2021980000524 |