CN105084608B - A kind of preprocess method of acrylic ester wastewater biochemical treatment - Google Patents
A kind of preprocess method of acrylic ester wastewater biochemical treatment Download PDFInfo
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Abstract
The embodiment of the invention discloses a kind of preprocess method of acrylic ester wastewater biochemical treatment, the COD of acrylic ester wastewater is 60000~120000mg/L, is comprised the following steps：1) pH value of acrylic ester wastewater, is adjusted to 1~3.5 with sulfuric acid solution；2), solubility calcium salting liquid is added in the acrylic ester wastewater for mixing up pH value, is vibrated or 10~60min of stir process, separating liquid is collected in separation of solid and liquid treatment；The dosage of soluble calcium salt is the 0.1%~0.35% of the acrylic ester wastewater quality；Soluble calcium salt is at least one in calcium chloride, calcium nitrate and calcium acetate；3), to step 2) obtain filtrate carry out extraction processing, raffinate phase is pretreatment water outlet.The method process is simple that the present invention is provided, and energy consumption is low.The biodegradability of the acrylic ester wastewater processed by the method is more than 0.5, can directly carry out biochemical treatment.
Description
Technical field
The present invention relates to technical field of waste water processing, more particularly to a kind of pretreatment side of acrylic ester wastewater biochemical treatment
Method.
Background technology
Acrylic ester wastewater refers to produce the waste water that acrylate is produced.N-butanol, acrylic acid are mainly contained in the waste water
The pollutants such as sodium, p-methyl benzenesulfonic acid, NaOH.Acrylic ester wastewater is mainly derived from technique waste water, equipment cleaning water, random
Rule discharge water etc., its water quality is complicated, and hardly degraded organic substance content is (COD ＞ 100000mg/L) high, and salt content is high, and treatment is tired
It is difficult.
When processing acrylic ester wastewater using biochemical technology, it usually needs waste water is pre-processed, acrylate is reduced
The content of useless Organic substance in water, makes the biodegradability (B/C) of acrylic ester wastewater more than 0.4, then carry out biochemical treatment.Existing rank
Section, the preprocess method of acrylic ester wastewater biochemical treatment has electroosmose process, electrolysis, is required for consuming electric energy, in actual life
High energy consumption in product.
The content of the invention
It is existing for solving the embodiment of the invention discloses a kind of preprocess method of acrylic ester wastewater biochemical treatment
The problem of the preprocess method high energy consumption of acrylic ester wastewater biochemical treatment.Technical scheme is as follows：
A kind of preprocess method of acrylic ester wastewater biochemical treatment, the COD of the acrylic ester wastewater for 60000~
120000mg/L, comprises the following steps：
1) pH value of acrylic ester wastewater, is adjusted to 1~3.5 with sulfuric acid solution；
2), solubility calcium salting liquid is added in the acrylic ester wastewater for mixing up pH value, vibration or stir process 10~
60min, separation of solid and liquid treatment, collects separating liquid；The dosage of the soluble calcium salt is the acrylic ester wastewater quality
0.1%~0.35%；The soluble calcium salt is at least one in calcium chloride, calcium nitrate and calcium acetate；
3), to step 2) filtrate that obtains carries out extraction processing, obtains extraction phase and raffinate phase, and raffinate phase is pretreatment
Water outlet；Extractant is one or more in mixed solution, benzene, toluene and the hexamethylene of tributyl phosphate and kerosene；The extraction
Taking agent and step 2) volume ratio of filtrate that obtains is (0.5~2.5):1.
In the preferred embodiment of the present invention, step 1) in sulfuric acid solution by the pH of the acrylic ester wastewater
Value is adjusted to 1.5~3.
In one kind of the invention is more highly preferred to implementation method, step 1) in sulfuric acid solution by the acrylic ester wastewater
PH value be adjusted to 1.5~2.5.
In one kind of the invention is more highly preferred to implementation method, the dosage of the soluble calcium salt is the acrylate
The 0.2%~0.3% of wastewater quality.
In one kind of the invention is more highly preferred to implementation method, the extractant and step 2) volume ratio of filtrate that obtains
It is (1~1.5):1.
In one kind of the invention is more highly preferred to implementation method, the extractant is that tributyl phosphate is molten with the mixing of kerosene
At least one in liquid, benzene and toluene.
In one kind of the invention is more highly preferred to implementation method, also including acrylic acid in recovery extraction phase.
In the preferred embodiment of the present invention, the tributyl phosphate and tricresyl phosphate fourth in the mixed solution of kerosene
The volume fraction of ester is 20%~50%.
A kind of preprocess method process is simple of acrylic ester wastewater biochemical treatment that the present invention is provided, and energy consumption is low.
The biodegradability of the acrylic ester wastewater processed by the method is more than 0.49, can directly carry out biochemical treatment.
Specific embodiment
Technical scheme：A kind of preprocess method of acrylic ester wastewater biochemical treatment, the acrylate gives up
The COD of water is 60000~120000mg/L, is comprised the following steps：
1) pH value of acrylic ester wastewater, is adjusted to 1~3.5 with sulfuric acid solution；
2), solubility calcium salting liquid is added in the acrylic ester wastewater for mixing up pH value, vibration or stir process 10~
60min, separation of solid and liquid treatment, collects separating liquid；The dosage of the soluble calcium salt is the acrylic ester wastewater quality
0.1%~0.35%；The soluble calcium salt is at least one in calcium chloride, calcium nitrate and calcium acetate；
3), to step 2) filtrate that obtains carries out extraction processing, obtains extraction phase and raffinate phase, and raffinate phase is pretreatment
Water outlet；Extractant is one or more in mixed solution, benzene, toluene and the hexamethylene of tributyl phosphate and kerosene；The extraction
Taking agent and step 2) volume ratio of filtrate that obtains is (0.5~2.5):1.
In experimentation, inventor it was unexpectedly observed that with sulfuric acid solution adjust acrylic ester wastewater pH value value 1~
After 3.5, soluble calcium salt is added thereto to, substantial amounts of white precipitate can be produced, that is, be slightly soluble in the calcium sulfate of water, at the same time,
Suspended particulate and some water insoluble organic substances in acrylic ester wastewater can together be precipitated with the generation of calcium sulfate
Get off, processed through separation of solid and liquid, collect separating liquid, then separating liquid is carried out into extraction processing, raffinate is pretreatment water outlet, can
Reach the standard (biodegradability is more than 0.4) of biochemical treatment.
It should be noted that the separation of solid and liquid treatment described in the present invention can be using technological means such as centrifugation, filterings.Centrifugation
1000~4000 revs/min are typically set at, 10~30min is centrifuged.Filtering generally includes suction filtration, husky filter, plate compression etc..Solid-liquid
This area conventional technical means is separated into, the present invention is not especially limited herein.
With sulfuric acid solution by the pH of the acrylic ester wastewater in the inventive solutions, it is preferable that step 1)
Value is adjusted to 1.5~3, it is highly preferred that pH value is adjusted to 1.5~2.5.
In the inventive solutions, the dosage of the soluble-salt is the acrylic ester wastewater quality
0.2%~0.3%, the suspended particulate and water insoluble organic substance that can effectively go in water removal.
In the inventive solutions, the extractant and step 2) volume ratio of filtrate that obtains is (1~1.5):
1, can be by the most of acrylic acid extraction in acrylic ester wastewater out.
In actual applications, technical scheme can also include reclaiming acrylic acid in extraction phase.Can specifically use
Mass fraction is 20%~50% NaOH solution back extraction acquisition PAA, or distillation treatment recovery is carried out to extraction phase
Acrylic acid.According to acrylic acid boiling point, the temperature for distilling treatment can be 141 DEG C~150 DEG C, and those skilled in the art can be voluntarily
It is determined that, the present invention is not especially limited herein.In actual applications, the tributyl phosphate and phosphoric acid in the mixed solution of kerosene
The volume fraction of tributyl is 20%~50%.
In the inventive solutions, described sulfuric acid solution is aqueous sulfuric acid.Described solubility calcium salting liquid
It is water-soluble calcium saline solution.In actual applications, soluble calcium salt mass concentration in the solution can be 100g/L
~350g/L, those skilled in the art can voluntarily determine that the present invention is not especially limited herein according to practical experience.
Technical scheme is described below in conjunction with specific embodiment, described embodiment is only this
A part of embodiment is invented, rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art exist
The every other embodiment obtained under the premise of creative work is not made, the scope of protection of the invention is belonged to.
Reagent used in embodiment is commercially available.
Embodiment 1
The Raw performance of acrylic ester wastewater：COD is 119000mg/L, pH value 13.2.
1000ml acrylic ester wastewaters are measured, its pH value to 3.5 is adjusted with the sulfuric acid solution that mass fraction is 98%.Again plus
Enter the calcium chloride solution 10ml of 350g/L, vibrate 30min, suction filtration obtains filtrate.
To tributyl phosphate and kerosene mixed solution that addition 1500ml tributyl phosphate volume fractions in filtrate are 50%
Extracted as extractant.At 141 DEG C, extraction phase is distilled, acrylic acid, extractant can be recycled.Raffinate
Liquid is pretreatment water outlet, and the COD of raffinate is 10590mg/L, and COD clearances are that 91.2%, B/C ratios are 0.58, are adjusted with acid
After pH to 8.0, anaerobic biochemical treatment system can be directly entered.
Embodiment 2
The Raw performance of acrylic ester wastewater：COD is 61254mg/L, pH value 2.6.
1000ml acrylic ester wastewaters are measured, its pH value to 1.0 is adjusted with the sulfuric acid solution that mass fraction is 50%.Again plus
Enter the calcium chloride solution 10ml of 100g/L, vibrate 20min, suction filtration obtains filtrate.
Extracted as extractant to 500ml toluene is added in filtrate.Extraction phase is carried out with the 20%NaOH aqueous solution
Back extraction, acrylic acid sodium, extractant can be recycled.Raffinate is pretreatment water outlet, and the COD of raffinate is 5819mg/L,
COD clearances be 90.5%, B/C ratios be 0.54, with acid for adjusting pH to 7.6 after, anaerobic-aerobic biological respinse can be directly entered
Device.
Embodiment 3
The Raw performance of acrylic ester wastewater：COD is 89000mg/L, pH value 8.2.
1000ml acrylic ester wastewaters are measured, its pH value to 2.5 is adjusted with the sulfuric acid solution that mass fraction is 50%.Again plus
Enter the calcium acetate solution 10ml of 200g/L, vibrate 40min, suction filtration obtains filtrate.
Extracted as extractant to 2000ml toluene is added in filtrate.Extraction phase is carried out with the 30%NaOH aqueous solution
Back extraction, acrylic acid sodium, extractant can be recycled.Raffinate is pretreatment water outlet, and the COD of raffinate is 4895mg/L,
COD clearances are that 94.5%, B/C ratios are 0.53, can be directly entered anaerobic biological reactor.
Embodiment 4
The Raw performance of acrylic ester wastewater：COD is 102650mg/L, pH value 13.5.
1000ml acrylic ester wastewaters are measured, its pH value to 3 is adjusted with the sulfuric acid solution that mass fraction is 50%.Add
The calcium acetate solution 10ml of 300g/L, vibrates 40min, and suction filtration obtains filtrate.
Extracted as extractant to 2500ml hexamethylenes are added in filtrate.Extraction phase is entered with the 30%NaOH aqueous solution
Row back extraction, acrylic acid sodium, extractant can be recycled.Raffinate is pretreatment water outlet, and the COD of raffinate is 5670mg/
L, COD clearance are that 93.6%, B/C ratios are 0.52, can be directly entered anaerobic biological reactor.
Embodiment 5
The Raw performance of acrylic ester wastewater：COD is 60100mg/L, and pH value is 13.
1000ml acrylic ester wastewaters are measured, its pH value to 2 is adjusted with the sulfuric acid solution that mass fraction is 50%.Add
The calcium acetate solution 10ml of 250g/L, vibrates 40min, and suction filtration obtains filtrate.
To tributyl phosphate and kerosene mixed solution that addition 2500ml tributyl phosphate volume fractions in filtrate are 20%
Extracted as extractant.At 141 DEG C, extraction phase is distilled, acrylic acid, extractant can be recycled.Raffinate
Liquid is pretreatment water outlet, and the COD of raffinate is 5109mg/L, and COD clearances are that 91.5%, B/C ratios are 0.56, can be directly entered
Anaerobic biological reactor.
Comparative example 1
The Raw performance of acrylic ester wastewater：COD is 60100mg/L, pH value 13.
Waste water of the 1000ml containing acrylate is taken, with the sulphur acid for adjusting pH that mass fraction is 50% to 2；Add 250g/L sulphur
Sour calcium turbid solution 10ml, vibrates 40min, and suction filtration obtains filtrate.
To tributyl phosphate and kerosene mixed solution that addition 2500mL tributyl phosphate volume fractions in filtrate are 20%
Extracted as extractant.Raffinate is pretreatment water outlet, and the COD of raffinate is 31072mg/L, and COD clearances are
48.3%, B/C ratio are 0.28, it is impossible to be directly entered biochemical system.
Comparative example 2
The Raw performance of acrylic ester wastewater：COD is 60100mg/L, pH value 13.
Waste water of the 1000ml containing acrylate is taken, with the sulphur acid for adjusting pH that mass fraction is 50% to 5.5, adds 0.5g to gather
Sulphation iron (PFS) is closed, is stirred 20 minutes, a small amount of flco is engendered in solution, filtered, obtain filtrate.
Filtrate pH to 2.0 is adjusted with the sulfuric acid that mass fraction is 50%, to addition 2500mL phosphorus in the filtrate for regulating pH
Sour tributyl volume fraction is that 20% tributyl phosphate kerosene mixed solution is extracted as extractant.Raffinate is pre- place
The COD for managing water outlet raffinate is 27886mg/L, and 53.6%, the B/C that COD clearances reach raw water compares 0.26, it is impossible to be directly entered
Biochemical system.
From comparative example 1 and 2 as can be seen that the solution and flocculant poly sulphur commonly used in the art directly prepared with calcium sulfate
Sour iron does not reach the COD removal effects of the acquisition of embodiment 1 to 5.
From above-described embodiment and comparative example, a kind of pretreatment of acrylic ester wastewater biochemical treatment disclosed by the invention
Method process is simple, generates unexpected technique effect, and the COD clearances of acrylic ester wastewater are pre- to locate more than 90%
The B/C ratios for managing water outlet are more than 0.5, have reached the standard of biochemical treatment.
It should be noted that the COD described in the present invention refers to the chemical oxygen demand determined as oxidant with potassium bichromate
Amount.
Detailed Jie has been carried out to a kind of preprocess method of acrylic ester wastewater biochemical treatment provided by the present invention above
Continue.Specific embodiment used herein is set forth to principle of the invention and implementation method, the explanation of above example
It is only intended to help and understands the method for the present invention and its central idea.It should be pointed out that coming for one of ordinary skill in the art
Say, under the premise without departing from the principles of the invention, some improvement and modification can also be carried out to the present invention, these improve and modify
Also fall into the protection of the claims in the present invention.
Claims (6)
1. a kind of preprocess method of acrylic ester wastewater biochemical treatment, the COD of the acrylic ester wastewater for 60000~
120000mg/L, it is characterised in that comprise the following steps：
1) pH value of acrylic ester wastewater, is adjusted to 1.5~3 with sulfuric acid solution；
2), solubility calcium salting liquid is added in the acrylic ester wastewater for mixing up pH value, vibration or stir process 10~
60min, separation of solid and liquid treatment, collects separating liquid；The dosage of the soluble calcium salt is the acrylic ester wastewater quality
0.1%~0.35%；The soluble calcium salt is at least one in calcium chloride, calcium nitrate and calcium acetate；
3), to step 2) filtrate that obtains carries out extraction processing, obtains extraction phase and raffinate phase, and raffinate phase is and pre-processes out
Water；Extractant is one or more in mixed solution, benzene and the hexamethylene of tributyl phosphate and kerosene；The extractant and step
The volume ratio of the rapid filtrate for 2) obtaining is (0.5~2.5):1.
2. preprocess method as claimed in claim 1, it is characterised in that step 1) in sulfuric acid solution by the acrylate
The pH value of waste water is adjusted to 1.5~2.5.
3. the preprocess method as described in any one of claim 1 to 2, it is characterised in that the dosage of the soluble-salt is
The 0.2%~0.3% of the acrylic ester wastewater quality.
4. preprocess method as claimed in claim 3, it is characterised in that the extractant and step 2) body of filtrate that obtains
Product is than being (1~1.5):1.
5. preprocess method as claimed in claim 1, it is characterised in that also including reclaiming acrylic acid in extraction phase.
6. preprocess method as claimed in claim 1, it is characterised in that in the tributyl phosphate and the mixed solution of kerosene
The volume fraction of tributyl phosphate is 20%~50%.
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| 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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| JP4654584B2 (en) * | 2004-03-01 | 2011-03-23 | 三菱化学株式会社 | Handling of (meth) acrylic ester-containing liquid |
| US20110021670A1 (en) * | 2009-07-25 | 2011-01-27 | Soil Net Llc | Integrated process for manufacturing a binder |
| CN102267890B (en) * | 2010-11-16 | 2014-06-11 | 中国环境科学研究院 | Method for extracting and recovering acrylic acid from acrylic ester production wastewater |
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Denomination of invention: Pretreatment method of acrylate wastewater biochemical treatment Effective date of registration: 20191127 Granted publication date: 20170531 Pledgee: Beijing urban construction and development branch of China Construction Bank Co., Ltd Pledgor: POTEN ENVIRONMENT GROUP CO., LTD. Registration number: Y2019990000597 |
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