CN102267890B - Method for extracting and recovering acrylic acid from acrylic ester production wastewater - Google Patents
Method for extracting and recovering acrylic acid from acrylic ester production wastewater Download PDFInfo
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- CN102267890B CN102267890B CN201010546817.0A CN201010546817A CN102267890B CN 102267890 B CN102267890 B CN 102267890B CN 201010546817 A CN201010546817 A CN 201010546817A CN 102267890 B CN102267890 B CN 102267890B
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Abstract
The invention discloses a method for recovering acrylic acid from acrylic ester production wastewater. The method comprises steps that: (1) suspending particles in the wastewater are removed through a pretreatment process; (2) a pH value of the pretreated wastewater is regulated to 2.5 or less; a primary extraction process is carried out; back extraction is carried out upon an extract phase obtained from the first extraction by using NaOH, such that an acrylic acid concentrate is obtained, an extracting agent is recovered; and an extraction residual phase of the first extraction is discharged after neutralization and oil separation treatments; (3) a pH value of the obtained acrylic acid concentrate is regulated to 2.5 or less; a secondary extraction process is carried out; an extract phase obtained from the second extraction is rectified and refined, or is directly refined, such that acrylic acid is obtained; and an extraction residual phase of the second extraction is delivered back to the step (2). With the acrylic acid recovering method provided by the invention, content of acrylic acid in the wastewater can be substantially reduced, treatment difficulties and treatment burdens of subsequent treatment units can be reduced, and acrylic acid can be recovered from acrylic ester production wastewater.
Description
Technical field
The present invention relates to extract the method for acrylic acid from acrylate industrial wastewater.
Background technology
In the production process of acrylicacidandesters etc., can produce a large amount of waste water containing higher concentration vinylformic acid or acrylate (1%～5%).Because vinylformic acid and salt pair microorganism thereof have certain toxicity, directly carry out biochemical treatment, often there is sludge loss, process the problems such as effluent quality is unstable.
Adopt the techniques such as heating power burning method, biological process to process containing acrylic acid wastewater at present more.Heating power burning process is about to containing the acrylic acid waste water of high density after gas stripping column is concentrated, under combustion-supporting compressed-air actuated help, be the vaporific waster water incinerator that sprays into, fuel gas or oil fuel also enter roasting kiln burning simultaneously, burning gas temperature can reach 950 DEG C, under the high temperature of 950 DEG C, organism complete reaction in waste water becomes carbonic acid gas and water, and processing efficiency is very high.But heating power burning process initial cost is large, consume a large amount of fuel gas or oil fuel, energy consumption and running cost are high, and in the waste water such as acrylate, conventionally contain the sodium salt of high density, easily cause the corrosion of incinerator, stove brick etc. needs periodic replacement, has further increased running cost.Vinylformic acid is biodegradable organic, but due to the toxicity of vinylformic acid (salt), biological treatment needs to carry out processing after Macrodilution containing sanitary sewage, water coolant etc. for acrylic acid wastewater conventionally again, its shortcoming is that wastewater dilution wastes a large amount of water coolants, bioprocess technology floor space is large, operational management requires high, fluctuation of service etc.
At present domestic for mainly contain containing the patent of acrylic acid waste water treatment " electrolysis-biochemical process " (CN1948189A), " electrodialysis-biochemistry-extraction-rectification method " (CN101269899A), " reverse osmosis-rectification method " (CN1903738A) etc.The method that patent CN1948189A announces has only been carried out conventional electrolysis treatment to waste water, is conceived to the oxidation of pollutent; After the method that CN1903738A announces is concentrated to waste water reverse osmosis, carry out rectifying, reclaim vinylformic acid, toluene and acetic acid wherein, the method is more suitable for the acrylic acid production waste water that saltiness is low; The method that patent CN101269899A announces adopts traditional electrodialysis to concentrate waste water, after concentrating, carries out extraction-rectification, reclaims acetic acid wherein, and the method is more suitable for the acrylic acid production waste water that saltiness is low, does not relate to acrylic acid recovery in waste water.In patent CN1546453A, CN1249739A, CN1683309A, propose the method for acrylic acid the multiple water absorption liquid from propylene oxidation gas (high density acrylic acid solution), but there is no the method reclaiming for vinylformic acid under acrylic ester wastewater low concentration vinylformic acid (<5%) and high saliferous condition.
Summary of the invention
The object of this invention is to provide a kind of one side and can significantly reduce the pollutant load in waste water, on the other hand the method for acrylic acid from acrylate industrial wastewater.
Provided by the present invention from acrylic ester wastewater the method for acrylic acid, comprise the following steps:
1) suspended particulate in waste water is removed in pre-treatment;
2) after premenstrual waste water furnishing acidity after treatment, carry out one-level extraction, one-level extraction extraction phase carries out back extraction with NaOH solution, obtains sodium acrylate concentrated solution, reclaims extraction agent simultaneously, and one-level extraction extracting phase is discharged after neutralization, oil removal are processed;
3) after described sodium acrylate concentrated solution furnishing acidity, carry out secondary extraction, secondary extraction extraction phase carries out re-refining or directly refining acquisition vinylformic acid after rectifying; Secondary extraction extracting phase returns to step 2).
The method of the present invention's acrylic acid from acrylic ester wastewater, wherein said extraction agent is any one or several in heptane, methylcyclohexane, toluene, Iso Butyl Acetate, isobutyl acetate and ethyl isobutyl ether.
The method of the present invention's acrylic acid from acrylic ester wastewater, the throughput ratio of wherein said extraction agent and described acrylate industrial wastewater is (1～6): 1.
The method of the present invention's acrylic acid from acrylic ester wastewater, the mass percent concentration of wherein said sodium hydroxide solution is 10%～20%.
The method of the present invention's acrylic acid from acrylic ester wastewater, the throughput ratio of wherein said extraction agent and sodium acrylate concentrated solution is (1～6): 1.
The method of the present invention's acrylic acid from acrylic ester wastewater, wherein said directly refining be to carry out in the case of extraction agent is identical with entrainer in vinylformic acid production process or extraction agent.
The method of the present invention's acrylic acid from acrylic ester wastewater, wherein said pre-treatment comprises coagulation, precipitation, filtration and/or cooling.
The method of the present invention's acrylic acid from acrylic ester wastewater can significantly reduce acrylic acid content in waste water, reduces the intractability of subsequent disposal unit and processes load; Can be from acrylate industrial wastewater acrylic acid.The present invention's method of acrylic acid from acrylic ester wastewater adopts two step extraction processs to process acrylic ester wastewater, extracting by one-level the vinylformic acid making in waste water is concentrated, and under lower energy consumption, realize the recovery of extraction agent by alkali lye back extraction, be conducive to improve the efficiency of second stage extraction simultaneously, reduce Solvent quantity and extraction agent and reclaim energy consumption, thereby reduce the processing cost of waste water.
Brief description of the drawings
Fig. 1 is the schema that extracts acrylic acid in embodiment 1 from acrylate industrial wastewater.
Fig. 2 is the schema that extracts acrylic acid in embodiment 3 from acrylate industrial wastewater.
Embodiment
Percentage composition in following embodiment is quality percentage composition.
Embodiment 1:
As shown in Figure 1, taking acrylate concentration as 4%(is taking vinylformic acid) acrylic ester wastewater as handling object, after coagulation, precipitation, filtration, cooling pre-treatment, adjust wastewater pH=2.5 at pH regulator tank 1 use sulfuric acid, carry out first step extraction taking toluene as extraction agent at one-level extraction tower 2, extraction agent dosage is 5 times of wastewater flow rate, adopt turntable extracting tower to carry out counter-current extraction, obtain containing acrylic acid extraction phase, extraction agent reclaims in extraction agent recovery tower 3, in extraction phase, acrylic acid concentration is 0.75%, and the vinylformic acid rate of recovery reaches 93.7%; Then use 15%NaOH solution reextraction extraction phase, obtain 27%(in vinylformic acid) sodium acrylate concentrated solution.Sodium acrylate concentrated solution is adjusted after pH=2.5 at pH regulator tank 4 use sulfuric acid, in secondary extraction tower 5, carry out second stage extraction taking toluene as extraction agent, extraction agent dosage is 3.5 times of the sodium acrylate concentrated solution water yield, extraction phase is for containing the acrylic acid toluene solution of higher concentration, its acrylic acid concentration is about 7.5%, this extraction phase directly enters the refining workshop section (carrying out component distillation taking toluene as extraction agent) of acrylic acid production device and further refines, obtaining mean concns is more than 90% vinylformic acid, toluene is wherein realized its recovery as azeotropy dehydrant in the refining workshop section of vinylformic acid.First step extraction extracting phase neutralization tank 8 through neutralization, at oil separation tank 8 after oil removal is processed, in waste water, remaining acrylate concentration is about 0.25%(in vinylformic acid), second stage extraction extracting phase returns to one-level extraction step circular treatment.
Embodiment 2:
Taking acrylate concentration as 1.0%(is taking vinylformic acid) acrylic ester wastewater as handling object, waste water is after coagulation, filtration pre-treatment, adjust pH=2 with sulfuric acid, carry out first step extraction taking heptane as extraction agent, when extraction agent dosage is 6 times of wastewater flow rate, adopt turntable extracting tower to carry out counter-current extraction, obtain containing acrylic acid extraction phase, in extraction phase, acrylic acid concentration is 0.15%, and the vinylformic acid rate of recovery reaches 90.5%.Adopt 10% NaOH solution back extraction extraction phase, obtain about 18%(in vinylformic acid) sodium acrylate concentrated solution.Sodium acrylate concentrated solution is adjusted after pH=2.5 with sulfuric acid, carries out second stage extraction taking heptane as extraction agent, and extraction agent dosage is 6 times of the sodium acrylate concentrated solution water yield, and extraction phase is for containing the acrylic acid n-heptane solution of higher concentration, and its acrylic acid concentration is about 2.9%.This extraction phase enters rectifying tower and reclaims extraction agent, and tower reactor is more than 90% crude acrylic acid of concentration, and tower top is for reclaiming extraction agent heptane, and crude acrylic acid can enter acrylic acid production device and further refine, and reclaims extraction agent and returns to second stage extraction.First step extraction extracting phase is after neutralization, oil removal are processed, and in waste water, remaining acrylate concentration is about 0.095%(in vinylformic acid), second stage extraction extracting phase is with returning to first step extraction step circular treatment.
Embodiment 3:
As shown in Figure 2, taking acrylate concentration as 5.0%(is taking vinylformic acid) acrylic ester wastewater as handling object, waste water is after coagulation, filtration treatment, adjust pH=6 at pH regulator tank 1 use sulfuric acid, in one-level extraction tower 2 taking toluene and isobutyl acetate (mass ratio 1:1) as extraction agent, carry out first step extraction, when extraction agent dosage is 1 times of wastewater flow rate, adopt perforated-plate extraction tower to carry out counter-current extraction, obtain containing acrylic acid extraction phase, extraction agent reclaims in extraction agent recovery tower 3, and in extraction phase, acrylic acid concentration is 4.62%, and the vinylformic acid rate of recovery reaches 92.3%.Adopt 20% NaOH solution back extraction extraction phase, obtain about 36%(in vinylformic acid) sodium acrylate concentrated solution.Sodium acrylate concentrated solution is adjusted after pH=2.5 at pH regulator tank 4 use sulfuric acid, in secondary extraction tower 5, carry out second stage extraction with toluene and isobutyl acetate (mass ratio 1:1), extraction agent dosage is 1 times of the sodium acrylate concentrated solution water yield, extraction phase is that middle acrylic acid concentration is about 33%, this extraction phase enters rectifying tower (extraction agent recovery tower 6) and reclaims extraction agent, solvent overhead enters in receiving tank 7 mutually, solvent overhead is mutually containing 0.30% vinylformic acid, water is containing 0.15% vinylformic acid, tower reactor is crude acrylic acid solution, containing vinylformic acid 95.6%, water 0.15%, isobutyl acetate 3.2%, toluene 0.02%.First step extraction extracting phase neutralization tank 8 through neutralization, at oil separation tank 8 after oil removal is processed, in waste water, remaining acrylate concentration is about 0.30%(in vinylformic acid), second stage extraction extracting phase returns to first step extraction step circular treatment.
Above embodiment is described the preferred embodiment of the present invention; not scope of the present invention is limited; design under the prerequisite of spirit not departing from the present invention; various distortion and improvement that the common engineering technical personnel in this area make technical scheme of the present invention, all should fall in the definite protection domain of claims of the present invention.
Claims (3)
1. the method for acrylic acid from acrylic ester wastewater, comprises the following steps:
1) suspended particulate in waste water is removed in pre-treatment;
2) after premenstrual waste water after treatment is adjusted pH≤2.5, carry out one-level extraction, one-level extraction extraction phase carries out back extraction with NaOH solution, obtains sodium acrylate concentrated solution, reclaims extraction agent simultaneously, and one-level extraction extracting phase is discharged after neutralization, oil removal are processed;
3) described sodium acrylate concentrated solution carries out secondary extraction after adjusting pH≤2.5, and secondary extraction extraction phase carries out re-refining or directly refining acquisition vinylformic acid after rectifying; Secondary extraction extracting phase returns to step 2);
Wherein, described extraction agent is any one or several in heptane, methylcyclohexane, toluene, Iso Butyl Acetate, isobutyl acetate;
The throughput ratio of described extraction agent and described acrylate industrial wastewater is (1～6): 1;
The mass percent concentration of described sodium hydroxide solution is 10%～20%;
The throughput ratio of described extraction agent and described sodium acrylate concentrated solution is (1～6): 1.
2. method according to claim 1, is characterized in that: described directly refining be to carry out in the case of extraction agent is identical with entrainer in vinylformic acid production process or extraction agent.
3. method according to claim 2, is characterized in that: described pre-treatment comprises coagulation, precipitation, filtration and/or cooling.
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| CN201010546817.0A CN102267890B (en) | 2010-11-16 | 2010-11-16 | Method for extracting and recovering acrylic acid from acrylic ester production wastewater |
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| CN201010546817.0A CN102267890B (en) | 2010-11-16 | 2010-11-16 | Method for extracting and recovering acrylic acid from acrylic ester production wastewater |
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| CN102267890A CN102267890A (en) | 2011-12-07 |
| CN102267890B true CN102267890B (en) | 2014-06-11 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515391A (en) * | 2011-12-15 | 2012-06-27 | 中蓝连海设计研究院 | Method for pre-treating wastewater from ultraviolet absorber production |
| 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 |
| CN105084608B (en) * | 2015-09-17 | 2017-05-31 | 博天环境集团股份有限公司 | A kind of preprocess method of acrylic ester wastewater biochemical treatment |
| CN105130060B (en) * | 2015-09-17 | 2017-07-14 | 博天环境集团股份有限公司 | A kind of method of 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 |
| CN110684470B (en) * | 2019-10-21 | 2022-03-01 | 江苏利田科技股份有限公司 | Method for preparing acrylate adhesive by using UV monomer wastewater and acrylate adhesive |
| JP2024515353A (en) * | 2021-04-22 | 2024-04-09 | ベーアーエスエフ・エスエー | Extraction Method |
| 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 |
| CN114349252B (en) * | 2022-01-24 | 2023-04-07 | 南通百川新材料有限公司 | Comprehensive utilization process method of acrylate washing wastewater |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1081095A (en) * | 1963-08-30 | 1967-08-31 | Union Carbide Corp | Separation of acrylic acid and acetic acid |
| CN1125219A (en) * | 1994-07-28 | 1996-06-26 | 埃勒夫阿托化学有限公司 | Process for the manufacture of butyl acrylate by direct esterification |
| JP2006213647A (en) * | 2005-02-03 | 2006-08-17 | Toagosei Co Ltd | Method for recovering unreacted acrylic acid |
| CN1948189A (en) * | 2006-11-07 | 2007-04-18 | 南京大学 | Treatment method of acrylic acid production waste water |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61243046A (en) * | 1985-04-19 | 1986-10-29 | Nippon Oil & Fats Co Ltd | Production of ester of acrylic acid or methacrylic acid |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1081095A (en) * | 1963-08-30 | 1967-08-31 | Union Carbide Corp | Separation of acrylic acid and acetic acid |
| CN1125219A (en) * | 1994-07-28 | 1996-06-26 | 埃勒夫阿托化学有限公司 | Process for the manufacture of butyl acrylate by direct esterification |
| JP2006213647A (en) * | 2005-02-03 | 2006-08-17 | Toagosei Co Ltd | Method for recovering unreacted acrylic acid |
| CN1948189A (en) * | 2006-11-07 | 2007-04-18 | 南京大学 | Treatment method of acrylic acid production waste water |
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