CN105399621A - Wastewater-free type monomer production method - Google Patents
Wastewater-free type monomer production method Download PDFInfo
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- CN105399621A CN105399621A CN201510774496.2A CN201510774496A CN105399621A CN 105399621 A CN105399621 A CN 105399621A CN 201510774496 A CN201510774496 A CN 201510774496A CN 105399621 A CN105399621 A CN 105399621A
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- water
- acrylic acid
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- type monomer
- waste water
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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
- C07C51/48—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
- C07C51/50—Use of additives, e.g. for stabilisation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a wastewater-free type monomer production method. The method is characterized by comprising the following steps: S1, extracting acrylic acid from esterification generation water and first washing water in five times at an extraction temperature of 50-60 DEG C by adopting an acrylic acid extracting agent, stirring for 30 minutes, standing for 30 minutes, layering, collecting an extract of the previous time, collecting an extract, and performing negative pressure distillation in a distillation column to obtain acrylic acid; S2, performing negative pressure distillation on lower layer wastewater of the extract in the distillation column, performing condensation to obtain an acrylic acid aqueous solution for later use as secondary washing water, and filtering the obtained concentrated solution by virtue of a 25-micron filter bag to obtain a yellow green transparent solution; and S3, performing negative pressure distillation on alkali washing water and the washing water of the last time in the distillation column to obtain a distillate. The invention discloses a new acrylic acid extraction recycling technology and a catalyst recycling technology.
Description
Technical field
The present invention relates to monomer production field, more specifically, relate to a kind of without waste water type monomer production method.
Background technology
In the last few years, photocuring reactive thinner obtained tremendous expansion.Research rate of polymerization is fast, transformation efficiency is high, toxicity is low, moderate monomer making great efforts for people, does a lot of work in their preparation and polymerization.In addition in order to broadened application scope, people are also finding the monomer or monomer synthesize raw material that occurring in nature existing material is polymerized as photocuring.In application aspect, photocuring technology development is very rapid.Photocuring technology can be applicable to special field such as printing, coating, tamanori, microelectronics and rapid shaping, photoresist material etc.
The monomer of current more than 90%, production method is generally by direct esterification, after esterification, through alkali lye neutralization, extraction, washing and solvent removed by vacuum, finally obtains product.Specifically by alcohol and vinylformic acid, catalyzer (as methylsulphonic acid, p-methyl benzenesulfonic acid, inorganic heteropolyacid) and stopper (as Resorcinol, MEHQ, phenol, copper sulfate, cupric chloride, cuprous chloride etc. one or more) effect under, by use band water solvent (as toluene, normal heptane, normal hexane, hexanaphthene etc. one or more) constantly carry out esterification dehydration, after esterification terminates, with excessive acid, an acidic catalyst and extract stopper in low-concentration alkali liquor and in esterifying liquid, finally vacuumize and remove band water solvent.In actual production, in order to increase esterification degree, usual vinylformic acid is excessive 10-15%, and excessive unreacted vinylformic acid, catalyzer and stopper must be removed, prior art unique method is the technique adopting above-mentioned neutralization, extraction, washing, sometimes in order to ensure that product colour is good, how severally all over weak lye washing need, so, the product producing one ton about produces the waste water of 1.4-1.8 ton, a large amount of vinylformic acid of loss simultaneously, and not only cost for wastewater treatment is high, product yield is also low, is a kind of pole production technique not environmentally.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art part, and providing a kind of can utilize by waste water reclamation, and improves the method for preparing monomer of product yield.
There is provided a kind of without waste water type monomer production method, comprise following production stage:
S1. acrylic acid extraction agent (1 is adopted, the mixture of 4-butyrolactone and isopropyl ether) points of five times extracting, esterifyings generate water and first time washing water vinylformic acid, extraction temperature 50-60 degree, stirs 30 minutes, static 30 minutes, layering, collect extraction liquid last time, collect extraction liquid, enter distillation tower vacuum distillation, obtain vinylformic acid
S2. extraction liquid lower floor waste water is entered distillation tower vacuum distillation, through condensation, obtain acrylic acid aqueous solution, for subsequent use, as second time water scouring water; Concentrated solution, filter through 25 micron filter bag, obtain yellow-green colour clear solution, (main component is catalyzer methylsulphonic acid and a small amount of vinylformic acid and stopper) for subsequent use;
S3. soda-wash water and last washing are thrown into distillation tower, vacuum distillation, obtain overhead product.
Described acrylic acid extraction agent is the mixture of GBL and isopropyl ether.
Yellow-green colour clear solution described in S2 is catalyzer methylsulphonic acid and a small amount of vinylformic acid and stopper.
Overhead product described in S3 is water.
The object of the invention realizes, after mainly producing monomer, and the waste water that classification process monomer produces.
The waste water of monomer is divided into four kinds:
1. esterification generates water: strongly-acid, composition is vinylformic acid and water, and wherein acrylic acid content is between 8%-12%.
2. washing water: the water using tap water cleaning monomer mixture material, strongly-acid, composition is catalyzer, vinylformic acid, reductive agent, stopper, water.Acrylic acid content is between 5%-8%, and catalyzer is between 15%-22%.
3. soda-wash water: alkalescence, use in low-concentration alkali liquor and the water of monomer material, composition is sodium salt class, monomeric oligomeric thing class and water, wherein sodium salt class, and monomeric oligomeric thing class content is greatly between 12%-15%.
4. washing water: weakly alkaline, as long as composition is sodium salt class and water, sodium salt class content is lower, is less than less than 0.5%.
In the present invention, first we adopt acrylic acid extraction agent (1, 4-butyrolactone, isopropyl ether etc.) extracting, esterifying generate water and first time washing water in vinylformic acid, percentage extraction is about 85%, contain in extraction liquid and only contain vinylformic acid, acid content generally remains on 8%-10% and has walked, with the reactor of 70 cubes, to feed intake calculating according to normally producing TPMTA (Viscoat 295), excessive vinylformic acid is greatly about about 2.2 tons, by extraction, we can acrylic acid about 1.6 tons, the extraction agent reclaimed, adopt the method for vacuum distillation, acrylic acid, the vinylformic acid reclaimed can be used further to monomer and produce.The waste water reclaimed, also adopt the method for vacuum distillation, slough the moisture of 80%, its debris is aqueous catalyst solution, can again for the catalyzed reaction that monomer is produced, and the water distilled, is used for carrying out the washing water that lower batch of monomer is produced, or configuration alkali lye.Soda-wash water and last washing water, we are suitable for the method for vacuum distillation equally, and water is steamed, and are used for producing lower batch of monomer.
The preparation method of monomer in the present invention, adopt extraction vinylformic acid technology first, recycling waste water technology, production for monomer will produce very large change, change the concept that monomer factory effluent is many, reach waste water reclamation to utilize, the object of catalyst recycle is a kind of energy-saving consumption-reducing environmental-protecting process.Secondly, because excessive propene acid recovery utilizes, catalyst recycle etc., greatly reduce the production cost of monomer, improve the market competitiveness.
Embodiment
The present invention is further described below in conjunction with specific embodiment.Unless stated otherwise, the present invention adopts reagent, equipment and method are conventional commercial reagent, equipment and the conventional method used of the art.
Embodiment 1
Long profit is sent out 69.3 cubes of esterifying kettles and is produced TMPTA, first batch of 21990 kilograms, the vinylformic acid that feeds intake, excessive 2244 kilograms, methylsulphonic acid 660 kilograms (concentration 70%). according to normal production, produce esterification and generate 6210 kilograms, water, acrylic acid content 16%, amounting to vinylformic acid is 993.6 kilograms.
Washing water for the first time, add water 5000 kilograms, after layering, quality is 6350 kilograms, wherein acrylic acid content 11.5%, amounts to 730 kilograms, vinylformic acid, methylsulphonic acid content 7%, amounts to methylsulphonic acid 440 kilograms.
Soda-wash water 10000 kilograms, after layering, the aqueous solution weighs 11000 kilograms.
Last washing water 4000 kilograms, after layering, washing water weight is constant.
Precipitation distills, and obtains product 25.612 tons.
Adopt acrylic acid extraction agent (1, the mixture of 4-butyrolactone and isopropyl ether) point five extracting, esterifyings generation water and the vinylformic acid of first time washing water, use extraction agent 1000 kilograms, extraction temperature 50-60 degree at every turn, stir 30 minutes, static 30 minutes, layering, collected extraction liquid last time, collect extraction liquid 6360 kilograms altogether, enter distillation tower vacuum distillation, obtain 1245 kilograms, vinylformic acid, content is greater than 98%.
Extraction liquid lower floor waste water is entered distillation tower vacuum distillation, through condensation, obtains acrylic acid aqueous solution 10200 kilograms, acrylic acid content 1.8%, amount to 180 kilograms, vinylformic acid, for subsequent use, as second time water scouring water; Concentrated solution 980 kilograms, filters through 25 micron filter bag, obtains yellow-green colour clear solution, (main component is catalyzer methylsulphonic acid and a small amount of vinylformic acid and stopper) for subsequent use.Soda-wash water and last washing are thrown into distillation tower, vacuum distillation, and obtain overhead product 13500 kilograms, after chemical examination, main component is water, and cyclohexane content is approximately 3000ppm, for subsequent use, is used for doing lower batch of configuration sodium hydroxide solution, and water scouring water.
Feed intake reaction for the second time, add 20490 kilograms, vinylformic acid, the transparent catalyst solution of yellow-green colour 600 kilograms of recovery, methylsulphonic acid 250 kilograms, normal esterification, washing precipitation, filters and packages, obtains product 25.683 tons, look 17.9#, ester content is greater than 98.5%, and three ester contents 92.4%, product is completely normal.The vinylformic acid reclaimed and catalyzer normally participate in reaction, and save 1500 kilograms, vinylformic acid, methylsulphonic acid 410 kilograms, amounts to total price 21000 yuan, and TMPTA cost declines 0.82 yuan/kilogram, and every still raw material production price reduces more than 21000 yuan.
The present invention mainly proposes acrylic acid extraction recovery and reuse technology, catalyst recovery reutilization technology.
Claims (4)
1., without a waste water type monomer production method, it is characterized in that, comprise following production stage:
S1. adopt acrylic acid extraction agent divide five extracting, esterifyings generate water and first time washing water vinylformic acid, extraction temperature 50-60 degree, stirs 30 minutes, static 30 minutes, layering, collects extraction liquid last time, and collection extraction liquid, enters distillation tower vacuum distillation, obtain vinylformic acid,
S2. extraction liquid lower floor waste water is entered distillation tower vacuum distillation, through condensation, obtain acrylic acid aqueous solution, for subsequent use, as second time water scouring water; Obtain concentrated solution, filter through 25 micron filter bag, obtain yellow-green colour clear solution;
S3. soda-wash water and last washing are thrown into distillation tower, vacuum distillation, obtain overhead product.
2. according to claim 1ly it is characterized in that without waste water type monomer production method, described acrylic acid extraction agent is the mixture of GBL and isopropyl ether.
3. according to claim 1ly it is characterized in that without waste water type monomer production method, the yellow-green colour clear solution described in S2 is catalyzer methylsulphonic acid and a small amount of vinylformic acid and stopper.
4. according to claim 1ly it is characterized in that without waste water type monomer production method, the overhead product described in S3 is water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510774496.2A CN105399621A (en) | 2015-11-13 | 2015-11-13 | Wastewater-free type monomer production method |
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| CN201510774496.2A CN105399621A (en) | 2015-11-13 | 2015-11-13 | Wastewater-free type monomer production method |
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| CN105399621A true CN105399621A (en) | 2016-03-16 |
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| CN201510774496.2A Pending CN105399621A (en) | 2015-11-13 | 2015-11-13 | Wastewater-free type monomer production method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113387493A (en) * | 2021-04-15 | 2021-09-14 | 佳化化学科技发展（上海）有限公司 | Wastewater treatment process in production of active diluent |
| CN114230072A (en) * | 2021-11-30 | 2022-03-25 | 江苏三木化工股份有限公司 | Efficient treatment method of acrylate monomer wastewater |
Citations (6)
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| CN101239909A (en) * | 2008-03-17 | 2008-08-13 | 上海华谊丙烯酸有限公司 | Method for preparing (methyl) acrylate and device used for the same |
| CN102267890A (en) * | 2010-11-16 | 2011-12-07 | 中国环境科学研究院 | Method for extracting and recovering acrylic acid from acrylic ester production wastewater |
| CN103214368A (en) * | 2012-01-19 | 2013-07-24 | 胜一化工股份有限公司 | Method for preparing alkyl diol alkyl ether (meth)acrylate |
| CN103842328A (en) * | 2011-10-03 | 2014-06-04 | 国际人造丝公司 | Processes for producing acrylic acids and acrylates |
| CN104492505A (en) * | 2014-12-03 | 2015-04-08 | 江门谦信化工发展有限公司 | Extraction method of butyl acrylate catalyst |
| CN104557511A (en) * | 2015-01-24 | 2015-04-29 | 淄博市兴鲁化工有限公司 | Method for recovering acrylic acid from acrylic acid water |
-
2015
- 2015-11-13 CN CN201510774496.2A patent/CN105399621A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101239909A (en) * | 2008-03-17 | 2008-08-13 | 上海华谊丙烯酸有限公司 | Method for preparing (methyl) acrylate and device used for the same |
| CN102267890A (en) * | 2010-11-16 | 2011-12-07 | 中国环境科学研究院 | Method for extracting and recovering acrylic acid from acrylic ester production wastewater |
| CN103842328A (en) * | 2011-10-03 | 2014-06-04 | 国际人造丝公司 | Processes for producing acrylic acids and acrylates |
| CN103214368A (en) * | 2012-01-19 | 2013-07-24 | 胜一化工股份有限公司 | Method for preparing alkyl diol alkyl ether (meth)acrylate |
| CN104492505A (en) * | 2014-12-03 | 2015-04-08 | 江门谦信化工发展有限公司 | Extraction method of butyl acrylate catalyst |
| CN104557511A (en) * | 2015-01-24 | 2015-04-29 | 淄博市兴鲁化工有限公司 | Method for recovering acrylic acid from acrylic acid water |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113387493A (en) * | 2021-04-15 | 2021-09-14 | 佳化化学科技发展（上海）有限公司 | Wastewater treatment process in production of active diluent |
| CN113387493B (en) * | 2021-04-15 | 2023-12-05 | 佳化化学科技发展（上海）有限公司 | Wastewater treatment process in reactive diluent production |
| CN114230072A (en) * | 2021-11-30 | 2022-03-25 | 江苏三木化工股份有限公司 | Efficient treatment method of acrylate monomer wastewater |
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Application publication date: 20160316 |
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