CN100425554C - Treatment method of acrylic acid production waste water - Google Patents
Treatment method of acrylic acid production waste water Download PDFInfo
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- CN100425554C CN100425554C CNB2006100974199A CN200610097419A CN100425554C CN 100425554 C CN100425554 C CN 100425554C CN B2006100974199 A CNB2006100974199 A CN B2006100974199A CN 200610097419 A CN200610097419 A CN 200610097419A CN 100425554 C CN100425554 C CN 100425554C
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000011282 treatment Methods 0.000 title claims abstract description 25
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- 238000000034 method Methods 0.000 title claims abstract description 18
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- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 3
- 238000007865 diluting Methods 0.000 abstract 1
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
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- 235000013619 trace mineral Nutrition 0.000 description 3
- 239000011573 trace mineral Substances 0.000 description 3
- MUZDXNQOSGWMJJ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-2-enoic acid Chemical class OC(=O)C=C.CC(=C)C(O)=O MUZDXNQOSGWMJJ-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
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- 239000011780 sodium chloride Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000009279 wet oxidation reaction Methods 0.000 description 2
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
The present invention discloses a method for treating waste water produced by acrylic acid production, belonging to the field of organic waste water treatment technology. It includes the following main steps: firstly, electrolyzing said waste water, regulating pH value to 5-7, controlling voltage and making it b 8-9V, controlling current and making it be 20-40 A, electrolyzing time is 10-30 min; diluting the electrolyzed waste water to make COD concentration be 2000-8000 mg/L, regulating pH value to 6.5-8, then feeding said waste water into anaerobic reactor to make treatment, controlling COD concentration of waste water discharged from said anaerobic reactor and making it be 200-1000 mg/L, then making said waste water be fed into an aerobic reactor, its residence time is 18-28 h and organic load is 0.5-5 kg COD/(cu.m d), then said treated waste water can be directly discharged.
Description
Technical field
This patent relates to a kind of treatment process of high concentrated organic wastewater, specifically the treatment process of acrylic acid production waste water.
Background technology
Acrylic acid production waste water is a kind of high-concentration organic industrial waste water, contains vinylformic acid, unreacted raw material such as propylene, byproduct such as formaldehyde, propenal, furfural, phenyl aldehyde, formic acid, acetate, toxilic acid, acrylic acid dimer and additive such as polymerization retarder.The waste water incineration device is a main flow device of handling high density vinylformic acid (methacrylic acid) and ester class waste water thereof at present both at home and abroad, the Catalytic Wet Oxidation device, and this two covering devices treatment effect is good, but the energy consumption height.The bioremediation that patent CN 1600706 A the announce wastewater treatment expense of pausing is 1/3rd of a burning method, but reactor residence time is long, processing efficiency is not high.
The waste water incineration device: acid waste water and alkaline waste water that vinylformic acid (methacrylic acid) and ester class production equipment thereof produce store respectively, entering neutralization tank through preheating mixes, and neutralize with sodium hydroxide, waste water after the neutralization is heated and enters distillation tower, carry dense with steam heating, recovery part process water, heavy constituent (debris) are sent into incinerator and are burned.Water outlet pH10-11 after the burning, COD＜100mg/L.Though treatment effect is fine, contain a large amount of Na in the waste discharge
2SO
4, Na
2CO
3, salt such as NaCl, this part waste water salt concentration about 6% causes to a certain degree environment and to pollute.The waste water incineration final vacuum contains Na
2SO
4, the NaCl xln, adopt that general technology is difficult to capture, atmosphere pollution the most important thing is that processing costs is than higher.
Catalytic wet air oxidation: on the basis of wet oxidation process, grow up, petrochemical complex, pharmacy, papermaking, food, the contour concentration C OD waste water of fiber can not added the dilution primary treatment and be reduced to COD＜100mg/L, simultaneously to water decolour, deodorization, germicidal treatment, emission gases is N
2, CO
2, H
2Innoxious substances such as O.Catalyzer has particular requirement to waste water quality: containing mineral ion (Na, Ca, Fe etc.) in the waste water must be less than 20mg/L, otherwise will cause that catalyzer forever poisons, and can not use.This technology belongs to high temperature, high pressure and uses heavy metal catalyst, requires equipment, operating procedure complexity, energy consumption height, processing costs height.
The bioremediation that patent CN 1600706 A announce: (COD＞30000mg/L) at first carries out evenly modified, acid-base neutralisation to the high density organic chemical waste water, control pH value 6.5-7.5, add microbiological culture media, under normal temperature or high temperature, enter conventional acidification hydrolization pond, under the anaerobism/oxygen condition of holding concurrently, macromolecular substance acidification hydrolization in the high concentrated organic wastewater is a small-molecule substance, COD clearance about 35%.Subsequently, waste water successively enters the first step and second stage anaerobic treatment device.First step treater organic loading 14-22kgCOD/ (m
3D), residence time 50h, the COD clearance is greater than 90%; The maximum organic loading 5-6kgCOD/ of second stage treater (m
3D), residence time 60h, organic removal rate 60%.Enter the aerobic treatment device subsequently, the sludge retention time of 24h, water outlet COD＜100mg/L.
Summary of the invention
1. invent the technical problem that will solve
The invention provides a kind of treatment process of acrylic acid production waste water, not only concentration height but also kind are many at organism in the acrylic acid production waste water, though waste water incineration technology and catalytic wet air oxidation treatment effect are pretty good at present, but energy consumption height, processing simultaneously itself also is accompanied by corresponding pollution and produces, though the bioremediation processing costs is not high, but the treatment time is long, the handling procedure complexity, the load low, the present invention can handle acrylic acid production waste water fast and efficiently, and treated water outlet can reach the sewage drainage standard of national regulation.
2. technical scheme of the present invention
Principle of the present invention is at first to improve the biodegradability of hardly degraded organic substance by electrolysis, remove portion C OD simultaneously, remove most of organism by anaerobic biological treatment then, be converted into methane, carbonic acid gas and water, remove remaining organic substance by aerobic treatment at last.
Technical scheme of the present invention is as follows:
A kind of treatment process of acrylic acid production waste water, its step comprises:
(1) at first acrylic acid production waste water is carried out electrolysis, regulating the pH value is 5-7, control voltage 8-9V, electric current 20-40A, electrolysis time 10-30min;
(2) with the acrylic acid wastewater after the electrolysis, dilution COD concentration is at 2000-8000mg/L, and regulating the pH value is 6.5-8, and it is 20～80mg/L that interpolation phosphoric acid salt makes phosphate concn, enters anaerobic reactor then and handles;
(3) after being controlled at 200-1000mg/L, the effluent COD concentration of anaerobic reactor enters aerobic reactor, hydraulic detention time 18-28h, organic loading 0.5-5kgCOD/ (m
3D), water outlet after treatment can directly be discharged.
Anaerobic reactor described in the step (2) is anaerobic grain bed bioreactor, UASB reactor, IC reactor or EGSB reactor.UASB is that waste water flows through reactor from bottom to top, and mud need not special whipping device, and reactor head has special three-phase (gas, liquid, solid) separator.Whole reactor is made up of the cloth pool of bottom, the reaction zone at middle part and the disengaging zone at top.Mud can adopt anaerobic grain sludge, ordinary activated sludge.IC is about to biogas and is divided into two stages for to be formed by stacking by two UASB reactors, and the bottom is in high loading, the top underload.High liquid upflow velocity (6-12m/h), granule sludge is in swelling state.EGSB has high liquid upflow velocity (6-12m/h), and granule sludge is in a kind of novel UASB reactor of swelling state.The anaerobic grain bed bioreactor is for being the reactor of microorganism fixed form with granule sludge or the microbial film that is attached on the filler (gac, sand grains, polyethylene filler etc.), and waste water flows through reactor from top to bottom or from bottom to top.Before regulating the pH value in the step (2), it is 1～80 μ g/L:FeCl that the adding following compounds makes its concentration
34H
2O, CoCl
26H
2O, MnCl
24H
2O, ZnCl
2, NiCl
26H
2O, CuCl
22H
2O or (NH
4)
6Mo
7O
24
Anaerobic reactor initial start stage volumetric loading 0.1-0.5kgCOD/ (m in the step (3)
3D), when the COD clearance reaches 85% and when stable, the mode that progressively reduces hydraulic detention time or increase water inlet COD concentration promotes load, and the highest volumetric loading reaches 25-30kgCOD/ (m
3D).
The character parameter of granule sludge is in the anaerobic grain bed bioreactor: (VSS is that volatile suspended solid is represented organic matter or microorganism for 60～68gVSS/L, 70～80gSS/L, SS is a suspended solid, be to comprise VSS and ash content), particle diameter 0.2～2.5mm, the hydraulic detention time of waste water in reactor is 10～18h, keep the temperature room temperature (16-37 ℃) in the reactor, the pH value is controlled at 6.8～7.8.
The anaerobism water outlet directly or after the dilution enters aerobic reactor, water inlet COD concentration 200-1000mg/L, hydraulic detention time 18-28h, organic loading 0.5-5kgCOD/ (m
3D), COD clearance 85-95%, effluent COD concentration 40-50mg/L.Aerobic reactor includes but not limited to biological fluidized bed and SBR.
Aerobic reactor is biological fluidized bed or sbr reactor device in the step (3).
3. beneficial effect
The invention provides a kind of treatment process of acrylic acid production waste water, can be according to the many characteristics of concentration height but also kind not only of organism in the acrylic acid production waste water, can be handled fast and efficiently, water outlet reaches (GB8978-96) first discharge standard of country's " integrated wastewater discharge standard ", COD＜50mg/L wherein, pH 7～8.。
Embodiment
Embodiment 1:
At first acrylic acid wastewater is carried out electrolysis, regulate pH 5-6, control voltage 7-8V, electric current 20A, electrolysis time 30min.Acrylic acid wastewater after the electrolysis, dilution COD concentration is regulated pH 6.8-7.8 at 8000mg/L, and it is 80mg/L and trace element (μ g/L): CoCl that interpolation phosphoric acid salt makes concentration
26H
2O (80), MnCl
24H
2O (20), ZnCl
2(2), NiCl
26H
2O (2), (NH
4)
6Mo
7O
24(3).Enter the anaerobic grain bed bioreactor, the character parameter of granule sludge is: 60-68gVSS/L, 70-80gSS/L, particle diameter 0.2-2.5mm.The hydraulic detention time of waste water in reactor is 12h, keeps the temperature room temperature (16-37 ℃) in the reactor, and the pH value is controlled at 6.8-7.8.Anaerobic reactor initial start stage volumetric loading 0.1-0.5kgCOD/ (m
3D), when the COD clearance reaches 85% and when stable, the mode that progressively reduces hydraulic detention time or increase water inlet COD concentration promotes load, until with waste water directly as water inlet, loading is increased to 18-25kgCOD/ (m
3D).The anaerobism water outlet directly or after the dilution enters biological fluidized-bed reactor, control water inlet COD concentration 500-1000mg/L, hydraulic detention time 24-28h, organic loading 0.5-5kgCOD/ (m
3D), COD clearance 85-95%, effluent COD concentration 40-50mg/L.
Embodiment 2:
At first acrylic acid wastewater is carried out electrolysis, regulate pH 5-6, control voltage 7-8V, electric current 30A, electrolysis time 25min.Acrylic acid wastewater after the electrolysis, dilution COD concentration is regulated pH 6.8-7.8 at 2000mg/L, and it is 20mg/L and trace element (μ g/L): CoCl that interpolation phosphoric acid salt makes concentration
26H
2O (70), MnCl
24H
2O (10), ZnCl
2(4), NiCl
26H
2O (4), (NH
4)
6Mo
7O
24(5), enter the UASB reactor, the character parameter of granule sludge is: 60-68gVSS/L, 70-80gSS/L, particle diameter 0.2-2.5mm.The hydraulic detention time of waste water in reactor is 18h, keeps the temperature room temperature (16-37 ℃) in the reactor, and the pH value is controlled at 6.8-7.8.Anaerobic reactor initial start stage volumetric loading 0.1-0.5kgCOD/ (m
3D), when the COD clearance reaches 85% and when stable, the mode that progressively reduces hydraulic detention time or increase water inlet COD concentration promotes load, until with waste water directly as water inlet, loading is increased to 18-20kgCOD/ (m
3D).The anaerobism water outlet directly or after the dilution enters biological fluidized-bed reactor, control water inlet COD concentration 200-500mg/L, hydraulic detention time 18-24h, organic loading 0.5-5kgCOD/ (m
3D), COD clearance 85-95%, effluent COD concentration＜50mg/L.
Embodiment 3:
At first acrylic acid wastewater is carried out electrolysis, regulate pH 6-7, control voltage 8-9V, electric current 40A, electrolysis time 10min.Acrylic acid wastewater after the electrolysis, dilution COD concentration is regulated pH 6.5-7.8 at 5000mg/L, adds 50mg/L phosphoric acid salt and trace element (μ g/L): CoCl
26H
2O (60), MnCl
24H
2O (30), ZnCl
2(5), NiCl
26H
2O (4), (NH
4)
6Mo
7O
24(2), enter IC reactor (or EGSB), the character parameter of granule sludge is: 60-68gVSS/L, 70-80gSS/L, particle diameter 0.2-2.5mm.The hydraulic detention time of waste water in reactor is 10h, keeps the temperature room temperature (16-37 ℃) in the reactor, and the pH value is controlled at 6.8-7.8.Anaerobic reactor initial start stage volumetric loading 0.1-0.5kgCOD/ (m
3D), when the COD clearance reaches 85% and when stable, the mode that progressively reduces hydraulic detention time or increase water inlet COD concentration promotes load, until with waste water directly as water inlet, loading is increased to 20-25kgCOD/ (m
3D).The anaerobism water outlet directly or after the dilution enters SBR, control water inlet COD concentration 200-500mg/L, and hydraulic detention time 18h, wherein aeration 8h leaves standstill 6h, organic loading 0.5-5kgCOD/ (m
3D), COD clearance 85-95%, effluent COD concentration＜50mg/L.
Claims (6)
1. the treatment process of an acrylic acid production waste water, its step comprises:
(1) at first acrylic acid production waste water is carried out electrolysis, regulating the pH value is 5～7, control voltage 8～9V, electric current 20～40A, electrolysis time 10～30min;
(2) with the acrylic acid wastewater after the electrolysis, dilution COD concentration is at 2000～8000mg/L, and regulating the pH value is 6.5～8, and it is 20～80mg/L that adding phosphoric acid salt makes phosphate concn, enters anaerobic reactor then and handles;
(3) after being controlled at 200～1000mg/L, the effluent COD concentration of anaerobic reactor enters aerobic reactor, hydraulic detention time 18～28h, organic loading 0.5～5kg COD/ (m
3D), water outlet after treatment can directly be discharged.
2. the treatment process of acrylic acid production waste water according to claim 1 is characterized in that the anaerobic reactor described in the step (2) is anaerobic grain bed bioreactor, UASB reactor, IC reactor or EGSB reactor.
3. the treatment process of acrylic acid production waste water according to claim 1, before it is characterized in that regulating pH value in the step (2), it is 1～80 μ g/L:FeCl that the adding following compounds makes its concentration
34H
2O, CoCl
26H
2O, MnCl
24H
2O, ZnCl
2, NiCl
26H
2O, CuCl
22H
2O or (NH
4)
6Mo
7O
24
4. the treatment process of acrylic acid production waste water according to claim 2 is characterized in that anaerobic reactor initial start stage volumetric loading 0.1～0.5kg COD/m
3D, when the COD clearance reaches 85% and when stable, the mode that progressively reduces hydraulic detention time or increase water inlet COD concentration promotes load.
5. according to the treatment process of right 1 or 2 or 3 or 4 described acrylic acid production waste waters, the character parameter that it is characterized in that granule sludge in the anaerobic grain bed bioreactor is: 60～68gVSS/L, 70～80gSS/L, particle diameter 0.2～2.5mm, the hydraulic detention time of waste water in reactor is 10～18h, keep the temperature room temperature in the reactor, the pH value is controlled at 6.8～7.8.
6. according to the treatment process of right 1 or 2 or 3 or 4 described acrylic acid production waste waters, it is characterized in that aerobic reactor is biological fluidized bed or sbr reactor device in the step (3).
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|---|---|---|---|
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269899B (en) * | 2008-05-13 | 2011-05-11 | 吉林大学 | Comprehensive approach for acrylic wastewater |
| CN101973653B (en) * | 2010-09-30 | 2012-07-04 | 南京大学 | Method for treating high-concentration PAM (Polyacrylamide) production wastewater by using composite coagulation method |
| 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 |
| CN102225976B (en) * | 2011-04-29 | 2012-10-10 | 张家港市德宝化工有限公司 | Method for preparing polyacrylic acid dispersing agents by adopting acrylic acid waste water as raw material |
| CN102491591B (en) * | 2011-12-09 | 2014-12-03 | 宜兴市荣盛达环保有限公司 | Sewage treating and recycling system and method for high-concentration polyester slices |
| CN103803741B (en) * | 2012-11-14 | 2015-05-13 | 中国石油天然气股份有限公司 | Method for treating acid wastewater of acrylic acid device |
| CN103058418A (en) * | 2013-01-18 | 2013-04-24 | 北京市环境保护科学研究院 | Pretreatment device and method for biochemically treating acrylic waste water |
| CN103739170A (en) * | 2014-01-22 | 2014-04-23 | 南京美泓环保科技有限公司 | Sewage treatment method |
| CN104556554A (en) * | 2014-12-04 | 2015-04-29 | 江门谦信化工发展有限公司 | Acrylic acid and ester wastewater deep treatment process method |
| CN105152447B (en) * | 2015-09-28 | 2017-11-03 | 博天环境集团股份有限公司 | A kind of method administered acrylic acid wastewater and reclaim sodium acetate |
| CN105859037B (en) * | 2016-05-13 | 2019-01-15 | 中国海洋石油集团有限公司 | A kind of combination treatment method of high concentration acrylic acid and ester waste water |
| CN108409044B (en) | 2018-04-04 | 2019-04-16 | 蓝星安迪苏南京有限公司 | For handling the method and device of acrolein reaction device waste water |
| CN114920489B (en) * | 2022-05-26 | 2024-02-09 | 昌德新材科技股份有限公司 | Cement raw material additive and application thereof and cement production process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1435594A (en) * | 2002-01-30 | 2003-08-13 | 株式会社日本触媒 | Method for treating waste from production of acrylic acid and polyacrylic acid |
| CN1600706A (en) * | 2004-10-12 | 2005-03-30 | 北京东方石油化工有限公司东方化工厂 | Biological treatment method for wastewater of containing acrylics and esters |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1435594A (en) * | 2002-01-30 | 2003-08-13 | 株式会社日本触媒 | Method for treating waste from production of acrylic acid and polyacrylic acid |
| CN1600706A (en) * | 2004-10-12 | 2005-03-30 | 北京东方石油化工有限公司东方化工厂 | Biological treatment method for wastewater of containing acrylics and esters |
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