CN100386302C - Method for extracting (methyl) acrylic acid aqueous solutior - Google Patents
Method for extracting (methyl) acrylic acid aqueous solutior Download PDFInfo
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- CN100386302C CN100386302C CNB2006100252116A CN200610025211A CN100386302C CN 100386302 C CN100386302 C CN 100386302C CN B2006100252116 A CNB2006100252116 A CN B2006100252116A CN 200610025211 A CN200610025211 A CN 200610025211A CN 100386302 C CN100386302 C CN 100386302C
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Abstract
The present invention relates to an extraction method of a methyl acrylic acid aqueous solution. Firstly, an addition agent is added in the methyl acrylic acid aqueous solution and is in contact with an extracting agent to realize the purpose of reduction of emulsified floccule generation on the point of an extraction interface, an organic phase and a hydrous phase containing methyl acrylic acid and the extracting agent are obtained, and the separation of the methyl acrylic acid and water is realized.
Description
Technical field
The present invention relates to the extracting process of (methyl) acrylic acid aqueous solution, this method is to add at least a auxiliary agent in raw material (methyl) acrylic acid aqueous solution, contact with extraction agent then, to reduce extraction emulsion at the interface, and contained the organic phase and the water of (methyl) vinylformic acid and extraction agent, realize the extracting and separating of (methyl) vinylformic acid and water.
Term among the present invention " (methyl) vinylformic acid " is meant acrylic or methacrylic acid.
Background technology
In the product that makes through molecular oxygen one step or two step catalytic gas phase oxidations by propane, propylene, iso-butylene, the trimethyl carbinol, isobutyric aldehyde or methacrylaldehyde etc., except that target product (methyl) vinylformic acid, also has carboxylic acid and aldehyde, as formic acid, acetic acid, toxilic acid, phenylformic acid, terephthalic acid, formaldehyde, acetaldehyde, methacrylaldehyde, phenyl aldehyde and furfural etc. as by product.The product water that catalytic gas phase oxidation obtains obtains (methyl) acrylic acid aqueous solution after absorbing as absorption agent.
Present many patents have proposed extraction separating method to (methyl) acrylic acid separation of water solution.EP-B 345083 has described a kind of method, and this method has comprised the extraction step of methacrylic acid, and use therein extraction agent is the stable hydrocarbon of 6～9 carbon atoms; EP-A 710643 describes by adding the method for organic solvent, the wherein aliphatic hydrocarbon of preferred 5～9 carbon atoms of organic solvent, aromatic hydrocarbons, ester or its mixture; Japanese Patent JP 57095938 has described and has used oxo solvent and TERTIARY BUTYL AMINE as the vinylformic acid in the extraction agent extraction water solution; The solvent of describing among the CN 98803154 of BASF Aktiengesellchaft is to be converted into (methyl) acrylic acid material or their mixture.Yet above-mentioned these extract from (methyl) acrylic acid aqueous solution and obtain (methyl) acrylic acid, all are imperfect.Produce the turbid liquid of emulsification because aldehydes in the oxidized byproduct and terephthalic acid are easy to emulsification takes place in the process of extraction, and on the interface, separate out; Turbid liquid is separated out on the interface simultaneously, will cause interface pollution, and the pool time of liquid is increased, and causes that organic phase and water are difficult for layering and separate, and has a strong impact on effect of extracting; And the turbid liquid that produces is difficult to reclaim, and increased the raw material consumption of producing.
In order to solve the emulsion that produces in the extraction process, the investigator of various countries has proposed many methods, attempts to solve emulsification problem.The GB-2045751 proposition as extraction agent, can reduce the generation of the turbid liquid of extraction process median surface place's emulsification with two or more solvents, still controls relatively difficulty of solvent ratios and solvent recuperation; The spy opens clear 54-90069 and proposes ventpipe is installed in extraction tower, utilizes air bubbling in tower, stops the accumulation of solid on dispersed phase interface, but the complex structure of such extraction tower.The none method has specifically described the emulsification that reduces the extraction interface with the method for adding auxiliary agent in the existing method.
Summary of the invention
The purpose of this invention is to provide a kind of extracting process that adds (methyl) acrylic acid aqueous solution of auxiliary agent, thereby reduce the generation that the extraction interface goes out the turbid liquid of emulsification.
Enforcement of the present invention is by add hydroquinone of polymerization retarder and at least a auxiliary agent in raw material (methyl) acrylic acid aqueous solution, and then contact with extraction agent toluene, contained the organic mutually aqeous of (methyl) vinylformic acid and extraction agent, and then realized the extracting and separating of (methyl) vinylformic acid and water.
The auxiliary agent that the present invention adds is alcohol, lipid acid, fatty acid ester, acid amides, phosphoric acid ester, higher fatty acid salt or their mixture with branched structure.Wherein, the alcohol with branched structure is primary isoamyl alcohol, isooctyl alcohol, 2-Ethylhexyl Alcohol or 2-isobutyl carbinol; Lipid acid or fatty acid ester are stearic acid, lauric acid, palmitinic acid, triolein, triacetin, glycerol tripalmitate, tristearin, Diethylene Glycol laurate, Diethylene Glycol stearate, Diethylene Glycol mono-laurate, diethylene glycol monostearate or sorbitan monolaurate; Acid amides is ethylenedistearamide, two palmityl quadrols, two lauroyl quadrols or two oleic acid acyl quadrols; Phosphoric acid ester is tributyl phosphate, trioctyl phosphate, phosphoric acid pentyl ester or octyl phosphate; Higher fatty acid salt is Aluminum trilaurate, calcium laurate, Magnesium monolaurate, aluminum stearate, calcium stearate, Magnesium Stearate, aluminum palmitate, calcium palmitate or magnesium palmitate.
The present invention can use conventional extraction equipment to carry out, do not need special extraction equipment, for example adopt " chemical engineering handbook (volume such as Shi Jun, Chemical Industry Press, second edition, 93～110 pages in the first volume the 15th chapter) described mixer-settler, spraying and extracting tower, turntable extracting tower, stirring extraction tower, pulsed extraction tower, material filling type extraction tower and extraction plant that some are novel can be realized (methyl) acrylic acid extraction.
The present invention is 0.005～5.0% (weight) for the concentration requirement that adds auxiliary agent, look the concentration of aldehydes and terephthalic acid in (methyl) acrylic acid aqueous solution and different, but comparatively preferred concentration is about 0.01～3.0%, be preferably 0.02～0.5% especially, optimum is 0.05～0.1% (weight).Have no particular limits for (methyl) acrylic acid concentration in (methyl) acrylic acid aqueous solution, but be preferably 0.5～50% (weight), be preferably 1～40% (weight) especially.Particularly, if (methyl) acrylic acid aqueous solution is absorbed and obtains through water through a step or two-step catalysis oxidation and oxidation products with molecular oxygen by propane, propylene, iso-butylene, the trimethyl carbinol, isobutyric aldehyde or methacrylaldehyde, then this solution is except containing (methyl) vinylformic acid and water, can also contain and be less than being used for preparation (methyl) acrylic acid raw material and being less than the acetate of 6% (weight) of 3% (weight).
The present invention all has no particular limits for extraction agent and extracting operation temperature, mainly is to consider that two-phase forms the interface easily and separates under service temperature and pressure condition, and being generally extraction temperature is 15～60 ℃, is preferably 25～40 ℃.Extraction agent can be a kind of in varsol toluene, hexanaphthene or the heptane etc., also can be a kind of in esters solvent vinyl acetic monomer, N-BUTYL ACETATE, butyl propionate, ethyl propenoate, butyl acrylate, methyl methacrylate, butyl methacrylate, methyl isobutyrate, the M Cr etc., the perhaps a kind of mixture in a kind of and esters solvent in these varsols with arbitrary proportion; Extraction agent is 0.2～2.5 with (methyl) acrylic acid mass ratio, and the preferred mass ratio is 0.5～1.5.
In the present invention, can add used stopper usually, for example Resorcinol, thiodiphenylamine, pentanoic, copper dialkyldithiocarbamate salt etc., these stoppers can add a kind of, also can two or more mix adding, consumption is 30～3000ppm, is preferably 200～2000ppm.These stoppers can be pre-applied in (methyl) acrylic acid aqueous solution, also can be added in the extraction agent, can also directly be added in certain position of extraction equipment, preferably directly add in the acrylic acid aqueous solution of extraction feed (methyl).
After the present invention adds auxiliary agent, can significantly reduce extracting the generation of the turbid liquid of emulsification at the interface, but, promptly not influence effect of extracting for the not influence of distribution of methacrylic acid at organic phase and aqueous phase.
Specify below by embodiment, but protection scope of the present invention is not subjected to the qualification of embodiment content.
Embodiment 1
Diameter be 78mm, extraction section high be 34mm for the settling section at the bottom of 770mm, cat head, the tower is 250mm, disk diameter, to encircle internal diameter surely be 58mm, the compartment spacing is to carry out the extraction of methacrylic acid (MAA) aqueous solution in the turntable extracting tower of 26mm.Method by continuous countercurrent extracts the aqueous solution that contains 18.9% (weight) MAA and 3.9% (weight) acetate with toluene as extraction agent, and extraction is 1.0 with the mass ratio of MAA, and the feeding rate of the MAA aqueous solution is 0.015m
3/ h.Before the extraction, add extraction auxiliary agent triolein and hydroquinone of polymerization retarder in the MAA aqueous solution, triolein and the Resorcinol concentration in the MAA aqueous solution is respectively 0.08% (weight) and 500ppm.Extraction is carried out under 25 ℃, and rotary speed is 600 rev/mins.
After extraction was stable, the concentration of MAA was 0.22% (weight) in the extracting phase (water), and the concentration of acetate is 4.25% (weight).Move after 2 hours, extraction begins to occur the emulsification floss at the interface, and the accumulation of floss highly is 40mm after 6 hours.
Embodiment 2～7
Carry out continuous countercurrent extraction in the turntable extracting tower in embodiment 1.The mass ratio of the feeding rate of the MAA aqueous solution, extraction agent, extraction agent and MAA, stopper and consumption thereof, extraction temperature, rotary speed be all with embodiment 1, and difference is the extraction auxiliary agent and the consumption difference thereof that add.Result of implementation is listed in the table below.
Under different auxiliary agents of table 1 and the consumption thereof in the extracting phase MAA content and extraction time of floss appears at the interface
| Embodiment | Raw material is formed (quality %) | The auxiliary agent title | Auxiliary dosage (quality %) | MAA concentration (quality %) in the extracting phase | Begin to occur the floss time (hour) | Floss reach 40 mm times (hour) |
| 1 | MAA 18.9 ACA 3.9 | Triacetin | 0.08 | 0.22 | 2.0 | 6.0 |
| 2 | MAA 12.5 ACA 2.5 | Season amylalcohol | 0.05 | 0.26 | 1.6 | 4.5 |
| 3 | MAA 12.5 ACA 2.5 | Tributyl phosphate | 0.10 | 0.28 | 2.0 | 5.0 |
| 4 | MAA 15.3 ACA 3.1 | Aluminum trilaurate | 0.12 | 0.21 | 2.5 | 6.0 |
| 5 | MAA 16.1 ACA 3.0 | Season amylalcohol and Aluminum trilaurate | 0.06 0.06 | 0.23 | 1.5 | 5.0 |
| 6 | MAA 18.2 ACA 3.4 | Two lauroyl quadrols | 0.10 | 0.31 | 1.7 | 5.5 |
| 7 | MAA 18.1 ACA 3.4 | Triacetin | 0.10 | 0.30 | 2.0 | 5.5 |
| 8 | MAA 18.1 ACA 3.4 | Triacetin | 0.80 | 0.29 | 2.3 | 5.5 |
| 9 | MAA 2.7 ACA 2.5 | Season amylalcohol | 0.10 | 0.15 | 1.8 | 5.0 |
| 10 | MAA 42.5 ACA 5.1 | Season amylalcohol | 0.10 | 0.51 | 1.5 | 5.0 |
| Comparative Examples 1 | MAA 18.2 ACA 4.0 | —— | —— | 0.28 | 0.33 | 1.0 |
Embodiment 8
Carry out continuous countercurrent extraction in the turntable extracting tower in embodiment 1.The mass ratio of the feeding rate of the MAA aqueous solution, extraction solvent, extraction agent and MAA, stopper and consumption, rotary speed etc. change extraction temperature and raw material MAA concentration of aqueous solution all with embodiment 1.
Extraction temperature is 45 ℃, and the concentration of MAA is 15.8% (weight) in the charging, and the concentration of acetate is 2.9%.After extraction was stable, the concentration of MAA was 0.46% (weight) in the extracting phase (water), and the concentration of acetate is 4.15%.Move after 2.5 hours, begin to occur the emulsification floss at the interface, the accumulation of floss highly is 40mm after 7 hours.
Embodiment 9～10
Carry out continuous countercurrent extraction in the turntable extracting tower in embodiment 1.The mass ratio of the feeding rate of the MAA aqueous solution, extraction solvent, extraction agent and MAA, extraction temperature, rotary speed etc. are all with embodiment 1, and different is the content of MAA in the charging.The results are shown in Table.
Comparative Examples 1
In the extraction tower of embodiment 1, carry out continuous countercurrent extraction.MAA aqueous solution feeding rate, extraction solvent, extraction solvent ratio, extraction temperature, rotary speed are all with embodiment 1.The concentration of MAA is 18.2% in the MAA aqueous solution, and the concentration of acetate is 4.0%.Do not add any auxiliary agent and extract, move 20 minutes rear interface places and the emulsification floss just occurred, the height of floss reaches 40mm after 1 hour.
Claims (4)
1. the extracting process of (methyl) acrylic acid aqueous solution, it is characterized in that adding in raw material (methyl) acrylic acid aqueous solution stopper and at least a auxiliary agent, the auxiliary agent that adds is alcohol, lipid acid, fatty acid ester, acid amides, phosphoric acid ester, higher fatty acid salt or their mixture with branched structure, and its concentration is 0.005 weight %～5.0 weight %; Contact with extraction agent then, extract the generation of emulsification floss at the interface, and contained the organic mutually aqeous of (methyl) vinylformic acid and extraction agent, realize the extracting and separating of (methyl) vinylformic acid and water with minimizing.
2. method according to claim 1, the alcohol that it is characterized in that having branched structure is primary isoamyl alcohol, isooctyl alcohol or 2-Ethylhexyl Alcohol; Lipid acid or fatty acid ester are stearic acid, lauric acid, palmitinic acid, triolein, triacetin, glycerol tripalmitate, tristearin, Diethylene Glycol laurate, Diethylene Glycol stearate, Diethylene Glycol mono-laurate, diethylene glycol monostearate or sorbitan monolaurate; Acid amides is ethylenedistearamide, two palmityl quadrols, two lauroyl quadrols or two oleic acid acyl quadrols; Phosphoric acid ester is tributyl phosphate, trioctyl phosphate, phosphoric acid pentyl ester or octyl phosphate; Higher fatty acid salt is Aluminum trilaurate, calcium laurate, Magnesium monolaurate, aluminum stearate, calcium stearate, Magnesium Stearate, aluminum palmitate, calcium palmitate or magnesium palmitate.
3. method according to claim 1, the concentration that it is characterized in that (methyl) acrylic acid aqueous solution is 0.2 weight %～80 weight %, inhibitor concentration is 30～3000ppm, assistant concentration is 0.02～0.5 weight %, extraction agent is 0.2～2.5 with (methyl) acrylic acid mass ratio, and the extracting operation temperature is 15～60 ℃.
4. method according to claim 3, the concentration that it is characterized in that (methyl) acrylic acid aqueous solution is 1 weight %～40 weight %, inhibitor concentration is 200～2000ppm, assistant concentration is 0.05～0.1 weight %, extraction agent is 0.5～1.5 with (methyl) acrylic acid mass ratio, and the extracting operation temperature is 25～40 ℃.
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| CNB2006100252116A CN100386302C (en) | 2006-03-29 | 2006-03-29 | Method for extracting (methyl) acrylic acid aqueous solutior |
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| CNB2006100252116A CN100386302C (en) | 2006-03-29 | 2006-03-29 | Method for extracting (methyl) acrylic acid aqueous solutior |
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| CN100386302C true CN100386302C (en) | 2008-05-07 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07118198A (en) * | 1993-09-03 | 1995-05-09 | Sumitomo Chem Co Ltd | Separation of methacrylic acid |
| CN1249739A (en) * | 1997-03-07 | 2000-04-05 | 巴斯福股份公司 | Method for extracting (meth) acrylic acid |
| CN1309628A (en) * | 1996-08-05 | 2001-08-22 | 巴斯福股份公司 | Process for separation of acrylic acid |
| JP2002128728A (en) * | 2000-10-19 | 2002-05-09 | Mitsubishi Rayon Co Ltd | Method for purifying methacrylic acid |
| CN1546453A (en) * | 2003-12-09 | 2004-11-17 | 上海华谊丙烯酸有限公司 | Method for purifying acrylic acid |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07118198A (en) * | 1993-09-03 | 1995-05-09 | Sumitomo Chem Co Ltd | Separation of methacrylic acid |
| CN1309628A (en) * | 1996-08-05 | 2001-08-22 | 巴斯福股份公司 | Process for separation of acrylic acid |
| CN1249739A (en) * | 1997-03-07 | 2000-04-05 | 巴斯福股份公司 | Method for extracting (meth) acrylic acid |
| JP2002128728A (en) * | 2000-10-19 | 2002-05-09 | Mitsubishi Rayon Co Ltd | Method for purifying methacrylic acid |
| CN1546453A (en) * | 2003-12-09 | 2004-11-17 | 上海华谊丙烯酸有限公司 | Method for purifying acrylic acid |
Non-Patent Citations (2)
| Title |
|---|
| 溶剂萃取法分离甲基丙烯酸水溶液的研究. 陈同芸，李倩英.石油化工，第24卷. 1995 |
| 溶剂萃取法分离甲基丙烯酸水溶液的研究. 陈同芸，李倩英.石油化工，第24卷. 1995 * |
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Effective date of registration: 20170222 Address after: 201424 Fengxian District Cang Road, lane, Lane 357, room 100, room 295 Patentee after: Shanghai Hua Yi new material Co., Ltd Address before: 200137 Pudong North Road, Shanghai, No. 2031, No. Patentee before: Shanghai Huayi Acrylic Acid Co., Ltd. |