CN1500739A - Method of polymerization and coagulation for treating sewage participating of heavy concentration acrylonitrile - Google Patents
Method of polymerization and coagulation for treating sewage participating of heavy concentration acrylonitrile Download PDFInfo
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- CN1500739A CN1500739A CNA021386374A CN02138637A CN1500739A CN 1500739 A CN1500739 A CN 1500739A CN A021386374 A CNA021386374 A CN A021386374A CN 02138637 A CN02138637 A CN 02138637A CN 1500739 A CN1500739 A CN 1500739A
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- Prior art keywords
- acrylonitrile
- waste water
- coagulation
- concentration
- wastewater
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000015271 coagulation Effects 0.000 title claims abstract description 13
- 238000005345 coagulation Methods 0.000 title claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 10
- 239000010865 sewage Substances 0.000 title 1
- 239000002351 wastewater Substances 0.000 claims abstract description 63
- 239000007787 solid Substances 0.000 claims abstract description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 14
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 7
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 7
- 231100000719 pollutant Toxicity 0.000 claims abstract description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 7
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000701 coagulant Substances 0.000 claims abstract description 6
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 230000001112 coagulating effect Effects 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 7
- 239000003999 initiator Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000004065 wastewater treatment Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000000575 pesticide Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 239000005754 Cyazofamid Substances 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- YXKMMRDKEKCERS-UHFFFAOYSA-N cyazofamid Chemical compound CN(C)S(=O)(=O)N1C(C#N)=NC(Cl)=C1C1=CC=C(C)C=C1 YXKMMRDKEKCERS-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000005059 solid analysis Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The pollutant acrylonitrile in high concentration waste water with acrylonitrile content of 2800-7603 mg/L is polymerized with solid ammonium persulfate, solid potassium persulfate, solid sodium chlorate or hydrogen peroxide as polymerization initiator at the reaction temperature of 10-70 deg.c while stirring electromagnetically or mechanically. The polymerized pollutant acrylonitrile is then eliminated through coagulation with polyaluminium chloride or polyferric sulfate as coagulant. When the polymerization time is 105 min, acrylonitrile eliminating rate as high as 96 % may be obtained and CODCr eliminating rate is 66-99 %. The present invention has simple and reasonable technological process, high waste water treating effect and low treating cost.
Description
Technical Field
The invention relates to a pretreatment technology of high-concentration acrylonitrile wastewater, which changes the environmental pollution and high-cost treatment conditions caused by the lack of the pretreatment technology to a certain extent.
Background
Industrial wastewater is a main pollution source causing environmental pollution, the discharge water amount of high-concentration organic wastewater is large, the distribution range of related industries and regions is wide, and particularly when high-concentration organic matters or toxic substances exist in the wastewater, the wastewater treatment difficulty is higher. From the treatment practice, the key point of the treatment of the high-concentration organic wastewater lies in the practical pretreatment technology which is effective, feasible and economically reasonable in technology.
The existing methods for treating high-concentration organic wastewater mainly comprise an extraction method, an anaerobic biochemical treatment method, a WAO (anaerobic-anoxic-oxic) method, an adsorption method, an incineration method and the like. These methods have advantages, but also have problems of secondary pollution, excessive treatment cost, and the like. Therefore, in actual wastewater treatment, a large amount of clear water is often used for diluting high-concentration organic wastewater and then performing further biochemical treatment, so that the wastewater treatment facility is large, the treatment cost is high, and the reduction rate of the total amount of pollutants is low.
From the viewpoint of the working idea of wastewater treatment, the existing treatment methods of high-concentration organic wastewater are all various degradation methods, namely, under certain conditions, the molecular chainsof pollutants are broken, and macromolecules are changed into micromolecules until mineralization is achieved. The treatment method comprises the steps of firstly polymerizing refractory organic matters, toxic matters and the like in high-concentration industrial organic wastewater to form low, medium and high polymerization degree substances with larger molecular weights, then removing the low polymerization degree pollutants by utilizing the net catching and rolling sweeping actions of a coagulant, achieving the purposes of removing the toxicity of the wastewater and reducing the COD of the wastewater, creating favorable conditions for further thorough treatment, and changing the environmental pollution and high-cost treatment conditions caused by the lack of the pretreatment technology of the high-concentration industrial organic wastewater at present.
The high-concentration acrylonitrile wastewater is high-concentration industrial organic wastewater and is commonly used in fine chemical production processes of acrylic fibers, pesticides and the like. Because the waste water has certain biological toxicity, the waste water can enter a biological reaction tank for degradation treatment after being pretreated. At present, an economic and effective pretreatment technology is lacked, and only a multi-effect evaporation, incineration or dilution method is used for treatment, so that the treatment cost of waste water is high, and the treatment is not thorough.
Disclosure of Invention
The invention aims at overcoming the defects of lack of pretreatment technology, high treatment cost and the like in the treatment process of high-concentration acrylonitrile wastewater at present, and according to the chemical characteristics of pollution components acrylonitrile, ammonium persulfate or potassium persulfate or sodium chlorate or hydrogen peroxide is used as an initiator to polymerize the acrylonitrile pollution components in the wastewater at the temperature of 10-70 ℃, and then polyaluminium chloride or polyferric sulfate is used for coagulating and removing the polymerized acrylonitrile in the wastewater. The method not only effectively removes the acrylonitrile pollution components with biological toxicity in the high-concentration acrylonitrile wastewater, but also greatly reduces the CODcr value of the wastewater.
A polymerizing-coagulating process for treating high-concentration acrylonitrile waste water features that inorganic polymerizing trigger is added to high-concentration acrylonitrile waste water to polymerize the acrylonitrile pollutant in waste water, and the coagulating agent-polyaluminium chloride or polyferric sulfate is used to coagulate and remove the polymerized acrylonitrile in waste water. The inorganic type polymerization initiator used was solid ammonium persulfate or solid potassium persulfate or solid sodium chlorate or hydrogen peroxide at a concentration of 30% by weight. The dosage of the inorganic polymerization initiator is 0.05 per mill to 8 per mill of the weight of the acrylonitrile wastewater. The coagulant is a polymeric ferric sulfate aqueous solution with the weight concentration of 12% or a polymeric aluminum chloride aqueous solution with the weight concentration of 10%. The coagulant is used in an amount of 0.5-1 wt% of the acrylonitrile waste water. The polymerization reaction formula is as follows:
the method has the advantages that the method can be directly used for removing most of toxic pollutants-acrylonitrile in the high-concentration acrylonitrile wastewater with different temperatures and concentrations, and is favorable for normal operation of subsequent biochemical procedures. Simple treatment equipment, reasonable process, low waste water treatment cost, good treatment effect, and great implementation value and social and economic benefits.
The specific implementation mode is as follows:
example 1
The implementation takes the configured high-concentration acrylonitrile wastewater as an example
Acrylonitrile (chemical pure reagent) and distilled water are used for preparing acrylonitrile waste water with a certain concentration. 500ml of wastewater is put into a 1000ml beaker, a small amount (0.05-8 per mill) of solid analytically pure ammonium persulfate is added, and the mixture is electromagnetically stirred and reacted for 30-180 minutes at the temperature of 35 +/-2 ℃. Cooling to room temperature, adjusting the pH value of the wastewater to 7-8 by using solid NaOH, adding 0.5% of polyaluminium chloride (10% aqueous solution) for coagulation, and standing to precipitate water. The treatment effect was detected as follows:
TABLE 1 Acrylonitrile removal Effect of ammonium persulfate as initiator
Reaction time (min) 03045607590105120150180
Waste water quality CODcr 7603544737643468162750749446613685
(unit: mg/l)
Wastewater kCODcr removal rate%/285154799394949899
Acrylonitrile content 75944171256925271744892312//, in the waste water
(unit: mg/l)
Acrylonitrile removal%/456667778896///H
Note 1: the CODcr value of the wastewater was measured by the potassium dichromate method (the same applies hereinafter).
Note 2: acrylonitrile content in the wastewater was determined using VARIAN prosar 230 liquid chromatograph.
Example 2
Acrylonitrile (chemical pure reagent) and distilled water are used for preparing acrylonitrile waste water with a certain concentration. 500ml of wastewater is put into a 1000ml beaker, a small amount (0.05-8 per mill) of solid analytically pure potassium persulfate is added, and the mixture is electromagnetically stirred for 30-180 minutes at the temperature of 35 +/-2 ℃. Cooling to room temperature, adjusting the pH value of the wastewater to 7-8 by using solid NaOH, adding 0.5% of polyaluminium chloride (10% aqueous solution) for coagulation, and standing to precipitate water. The treatment effect was detected as follows:
TABLE 2 Acrylonitrile removal effect of Potassium persulfate as initiator
Reaction time (min) 03045607590105
Waste water quality CODcr 76034299321617641012496192
(unit: mg/l)
Removal%/395877869397
Example 3
Acrylonitrile (chemical pure reagent) and distilled water are used for preparing acrylonitrile waste water with a certain concentration. 500ml of wastewater is put into a 1000ml beaker, a small amount (0.05-8 per mill) of solid analysis pure sodium chloride is added, and the mixture is electromagnetically stirred for 30-180 minutes at the temperature of 35 +/-2 ℃. Cooling to room temperature, adjusting the pH value of the wastewater to 7-8 by using solid NaOH, adding 0.5% of polyaluminium chloride (10% aqueous solution) for coagulation, and standing to precipitate water. The treatment effect was detected as follows:
TABLE 3 Acrylonitrile removal effectiveness of sodium chlorate as initiator
Reaction time (min) 03045607590105
Waste water quality CODcr 760351434583399523021247578
(unit: mg/l)
Removal%/324047708492
Example 4
Acrylonitrile (chemical pure reagent) and distilled water are used for preparing acrylonitrile waste water with a certain concentration. 500ml of wastewater is put into a 1000ml beaker, a small amount (0.05-8 per mill) of 30 percent of analytically pure hydrogen peroxide is added, and the mixture is electromagnetically stirred for 30-180 minutes at the temperature of 35 +/-2 ℃. Cooling to room temperature, adjusting the pH value of the wastewater to 7-8 by using solid NaOH, adding 0.5% of polyaluminium chloride (10% aqueous solution) for coagulation, and standing to precipitate water. The treatment effect was detected as follows:
TABLE 430% Acrylonitrile removal Effect of Hydrogen peroxide as initiator
Reaction time (min) 03045607590105
Waste water quality CODcr 7603484134123004248921131123
(unit: mg/l)
Removal%/365560677285
Example 5
The implementation takes the high-concentration acrylonitrile wastewater discharged by a cyclization process section in the production of the Duxiaoling pesticide as an example
Putting high-concentration acrylonitrile wastewater discharged from cyclization process stage in production of Duxiaoling pesticide at normal temperature of 50kg into 100m3Solid ammonium persulfate or solid potassium persulfate or solid sodium chlorate or 30 percent hydrogen peroxide which is 0.05 to 8 thousandths of the weight of the waste water is added into the enamel reaction kettle under stirring to be used as an initiator. Mechanically stirring for 30-180 minutes at thetemperature of 65 +/-5 ℃. After the reaction is finished, cooling the mixture to room temperature by cooling water, and adding solid Na2CO3Adjusting the pH value of the wastewater to 7-8, adding 1% polyaluminium chloride (10% aqueous solution) for coagulation, discharging the wastewater to a sedimentation tank, and standing to precipitate water.
The treatment effect was detected as follows:
TABLE 5 Effect of coagulation polymerization on treatment of high-concentration cyazofamid pesticide cyclized wastewater
Index CODcr (unit: mg/l) acrylonitrile concentration (unit: mg/l)
Quality of inlet water 530002800
Effluent quality 18000140
Removal Rate% 6695
Claims (5)
1. A polymerizing-coagulating process for treating high-concentration acrylonitrile waste water features that inorganic polymerizing trigger is added to high-concentration acrylonitrile waste water to polymerize the acrylonitrile pollutant in waste water, and the coagulating agent-polyaluminium chloride or polyferric sulfate is used to coagulate and remove the polymerized acrylonitrile in waste water.
2. The polymerization coagulation process according to claim 1, wherein the inorganic type polymerization initiator used is solid ammonium persulfate or solid potassium persulfate or solid sodium chlorate or hydrogen peroxide at a concentration of 30% by weight.
3. The coagulation polymerization method according to claim 2, wherein the amount of the inorganic type polymerization initiator is 0.05 to 8% by weight based on the acrylonitrilewaste water.
4. The coagulation method according to claim 1, wherein the coagulant is a 12% by weight aqueous solution of iron polysulfate or a 10% by weight aqueous solution of aluminum polychloride.
5. The polymerization coagulation method according to claim 4, wherein the amount of the coagulant used is 0.5 to 1% by weight based on the acrylonitrile waste water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02138637 CN1218885C (en) | 2002-11-19 | 2002-11-19 | Method of polymerization and coagulation for treating sewage participating of heavy concentration acrylonitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02138637 CN1218885C (en) | 2002-11-19 | 2002-11-19 | Method of polymerization and coagulation for treating sewage participating of heavy concentration acrylonitrile |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1500739A true CN1500739A (en) | 2004-06-02 |
| CN1218885C CN1218885C (en) | 2005-09-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02138637 Expired - Fee Related CN1218885C (en) | 2002-11-19 | 2002-11-19 | Method of polymerization and coagulation for treating sewage participating of heavy concentration acrylonitrile |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092266B (en) * | 2006-06-21 | 2010-05-12 | 中国石油化工股份有限公司 | Method for treating wastewater of dilute thiamine containing acrylonitrile |
| CN102219324A (en) * | 2011-04-07 | 2011-10-19 | 清华大学 | Method for processing acrylonitrile waste water with high concentration by nanofiltration membrane |
| CN103159374A (en) * | 2011-12-16 | 2013-06-19 | 王炜 | Treatment process for organic waste water with acrylonitrile materials |
| CN104556538A (en) * | 2013-10-18 | 2015-04-29 | 中国石油化工股份有限公司 | Treatment method for nitrile rubber production wastewater |
| CN110963647A (en) * | 2019-12-19 | 2020-04-07 | 安徽工程大学 | Treatment method of acrylic acid and lipid wastewater |
-
2002
- 2002-11-19 CN CN 02138637 patent/CN1218885C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092266B (en) * | 2006-06-21 | 2010-05-12 | 中国石油化工股份有限公司 | Method for treating wastewater of dilute thiamine containing acrylonitrile |
| CN102219324A (en) * | 2011-04-07 | 2011-10-19 | 清华大学 | Method for processing acrylonitrile waste water with high concentration by nanofiltration membrane |
| CN103159374A (en) * | 2011-12-16 | 2013-06-19 | 王炜 | Treatment process for organic waste water with acrylonitrile materials |
| CN103159374B (en) * | 2011-12-16 | 2014-12-03 | 上海洗霸科技股份有限公司 | Treatment process for organic waste water with acrylonitrile materials |
| CN104556538A (en) * | 2013-10-18 | 2015-04-29 | 中国石油化工股份有限公司 | Treatment method for nitrile rubber production wastewater |
| CN104556538B (en) * | 2013-10-18 | 2016-06-29 | 中国石油化工股份有限公司 | A kind of nitrile rubber produces the processing method of waste water |
| CN110963647A (en) * | 2019-12-19 | 2020-04-07 | 安徽工程大学 | Treatment method of acrylic acid and lipid wastewater |
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| Publication number | Publication date |
|---|---|
| CN1218885C (en) | 2005-09-14 |
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