CN100526236C - Process for treating and recovering wastewater of coking - Google Patents
Process for treating and recovering wastewater of coking Download PDFInfo
- Publication number
- CN100526236C CN100526236C CNB2004100402152A CN200410040215A CN100526236C CN 100526236 C CN100526236 C CN 100526236C CN B2004100402152 A CNB2004100402152 A CN B2004100402152A CN 200410040215 A CN200410040215 A CN 200410040215A CN 100526236 C CN100526236 C CN 100526236C
- Authority
- CN
- China
- Prior art keywords
- coking
- waste water
- remove
- ammonia
- chemical waste
- Prior art date
- 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.)
- Expired - Fee Related
Links
- 238000004939 coking Methods 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims description 22
- 239000002351 wastewater Substances 0.000 title claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 19
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 9
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001311 chemical methods and process Methods 0.000 claims abstract description 5
- 239000002894 chemical waste Substances 0.000 claims description 25
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229920000620 organic polymer Polymers 0.000 claims description 5
- 159000000013 aluminium salts Chemical class 0.000 claims description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 4
- 238000007255 decyanation reaction Methods 0.000 claims description 4
- 239000008394 flocculating agent Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 238000009628 steelmaking Methods 0.000 claims description 4
- 231100000419 toxicity Toxicity 0.000 claims description 3
- 230000001988 toxicity Effects 0.000 claims description 3
- 229910017958 MgNH Inorganic materials 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims 1
- 150000003016 phosphoric acids Chemical class 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000571 coke Substances 0.000 abstract 1
- 238000010410 dusting Methods 0.000 abstract 1
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000003337 fertilizer Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000003851 biochemical process Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical class [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 2
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003471 mutagenic agent Substances 0.000 description 1
- 231100000707 mutagenic chemical Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052567 struvite Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Removal Of Specific Substances (AREA)
- Physical Water Treatments (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The coking effluent treating and reusing technology of the present invention features that coking effluent is treated in a physical and chemical process, so that the treated coking effluent has its ammonia nitrogen, phenol, cyanide, suspended matter and other pollutants eliminated to reach the reuse standard for dusting in converter, washing ammonia of coke, sintering and other inner systems and to reach zero exhaust radically. The present invention has low coking effluent treating cost and saves great amount of production water.
Description
The present invention relates to a kind of novel Treatment of Coking Effluent and reuse technology, belong to environmental technology field.
The coking chemical waste water water yield is big, pollutent is complicated, concentration is high, colourity is dark, wherein inorganics generally exists with ammonium salt, the phenolic compound of organic composition except that about 85%, also comprise hypertoxic carcinogenic mutagen matter such as prussiate, inorganic fluorion, polycyclic aromatic hydrocarbons and heterogeneous ring compound.Coking chemical waste water is a kind of trade effluent of generally acknowledged difficult for biological degradation, its intractability is that the biodegradability of waste water is very poor, prussiate, polycyclic aromatic hydrocarbons and heterogeneous ring compound are difficult to biological degradation, ammonia nitrogen in high density has very strong restraining effect to the activity of microbial bacterial in addition, and Nitrogen removal effect is not good.Therefore concerning enterprise, TREATMENT OF COKING is a very big difficult problem.
Along with China's water resources worsening shortages, State Economic and Trade Commission has classified the same oil of water, grain as national three great strategy resources together in the water conservation meeting of calendar year 2001, and for encouraging water saving and water conservation to put into effect a series of policies, the water cost will progressively improve.In the national water conservation meeting of holding recently, national departments concerned is emphasized " Constructing Water-saved Society is the basic outlet that solves China's shortage of water resources problem " once more, and spells out " advanced treatment and reuse that one of key problem of water saving is trade effluent ".Present domestic have hundreds of families coke-oven plant and producer gas plant, a year wastewater discharge reaches more than 100,000,000 tons.Many enterprises adopt traditional biological method Treatment of Wastewater in Coking, have obtained certain effect, but relatively poor to the treatment effect of organism and ammonia nitrogen, are difficult to qualified discharge.In addition, biochemical process need consume the Macrodilution water, has increased processing cost, adds that preliminary engineering investment is big, running cost is high, enterprise is difficult to bear, and presses for to seek less investment, working cost is low, treatment effect is good waste water treatment and reuse technology to solve the matter of great urgency.The reuse of coking chemical waste water at present both at home and abroad still is not reported and industrialized developing, and along with useless Water reuse more and more is subjected to the attention of each side, the processing of research coking chemical waste water and reuse will become a development trend from now on.
The objective of the invention is to change the thinking of traditional biochemical process Treatment of Wastewater in Coking, propose " adopt the physico-chemical process Treatment of Wastewater in Coking; and with coking waste water reuse; realize that water is not gone to river, wastewater zero discharge " novel method, reduce the processing cost of coking chemical waste water, save the mass production water simultaneously,, and adapted to the development trend of nation-building a water-saving society for the wastewater treatment and the reuse of the iron and steel coal chemical enterprise in the whole nation provides most economical, the most practical, a most feasible approach.
The present technique invention realizes by following measure:
1. coking chemical waste water is removed most ammonia-nitrogen by ammonia still process earlier, and the fertilizer of reclaim(ed) sulfuric acid ammonium class.
2. the ammonia still process water outlet enters chemical reaction pond, adopts the ammonia nitrogen in chemical precipitation method (MAP method) the removal coking chemical waste water, and the throw out to ammonia is reclaimed simultaneously, obtains the high fertilizer of a kind of fertilizer efficiency.
3. add highly basic and make the phenol in the coking chemical waste water be converted into phenates in chemical reaction pond, phenates is present in the waste water and is back to use sintering, steel-making and coking washes links such as ammonia, and under the high temperature action of these links, phenates can resolve into CO
2And water.
4. in chemical reaction pond, add decyanation agent such as soda ash, molysite, make that cyanogen class material is converted into Na in the coking chemical waste water
4Fe (CN)
6The precipitation and remove.
5. the chemical reaction pond water outlet enters coagulative precipitation tank, wherein adds aluminium salt or molysite class inorganic flocculating agent and organic polymer coargulator (as polyacrylamide), and the consumption and the ratio of regulating both, effectively removes the suspended substance in the waste water.
6. the settling tank water outlet is back to use converter dust-removing through after filtering, systems such as ammonia and sintering are washed in coking.
The processing and the reuse of the coking chemical waste water to the effect that of present technique invention, at first adopt physico-chemical process to remove pollutents such as ammonia nitrogen in the coking chemical waste water, phenol, cyanogen, suspended substance, make its reach can reuse standard, coking chemical waste water after will handling then is back to use other water-using sectors of enterprises as water of productive use, washes ammonia, converter dust-removing and sintering etc. as coking.
The present technique invention has following characteristics:
1. adopt the physico-chemical process Treatment of Wastewater in Coking, overcome biochemical process handle need add 2-10 doubly dilute with fresh water, initial stage have high input, defective such as running cost height, fluctuation of service, floor space are big, reduce the processing cost of coking chemical waste water, saved a large amount of water of productive use for enterprise simultaneously.
2. the coking waste water reuse after will handling is to the enterprises other system, realizes that substantially water do not go to river, and wastewater zero discharge can be saved a large amount of process waters for enterprise.
3. " the MAP method " that adopt ammonia still process and grow up recently removes ammonia nitrogen, promptly by preliminary ammonia still process, adds Mg then in coking chemical waste water
2+(magnesium salts), PO
4 3-(phosphoric acid salt), reacting with ammonia nitrogen in the waste water generates MgNH
4PO
46H
2O (ammonium magnesium phosphate, Magnesium Ammonium Phosphate, i.e. MAP) precipitation removes by filter then, and ammonia nitrogen content can be reduced to below the 100mg/L by the 4000mg/L before handling.In addition, the precipitation that reaction generates is the high fertilizer of a kind of fertilizer efficiency, thereby waste reclaimation can be become useless be " treasured ".
4. add highly basic in coking chemical waste water, reduce toxicity thereby allow phenol be transformed into phenates, phenates is present in and is back to use sintering, steel-making and coking in the waste water and washes links such as ammonia, and under the high temperature action of these links, phenates can resolve into CO
2And water, phenol content can be dropped to below the 2.0mg/L by the 1500-2000mg/L before handling.
5. in coking chemical waste water, add decyanation agent such as soda ash, molysite, make cyanogen class material be converted into Na
4Fe (CN)
6Precipitation and removing, the content of prussiate can be reduced to below the 0.5mg/L by the 35-50mg/L before handling.
6. in coking chemical waste water, add aluminium salt or molysite class inorganic flocculating agent and organic polymer coargulator (as polyacrylamide), and the consumption and the ratio of regulating both, effectively remove the suspended substance in the waste water, the content of suspended substance can be reduced to below the 100mg/L by the 300-500mg/L before handling.
Accompanying drawing is Treatment of Coking Effluent and recovering process flow figure.
Below in conjunction with accompanying drawing and specific embodiment the present invention is further described:
Certain coke-oven plant 100m
3The Treatment of Coking Effluent of/h:
1. coking chemical waste water is removed most ammonia-nitrogen by ammonia still process earlier, adds ammonia still process auxiliary agent (as milk of lime) in the ammonia still process process, simultaneously reclaim(ed) sulfuric acid ammonium inorganic fertilizer.
2. the ammonia still process water outlet enters chemical reaction pond, wherein adds the MAP agent and carries out chemical precipitation except that ammonia nitrogen; Make phenol be transformed into phenates reduction toxicity thereby add highly basic, phenates is present in the waste water and is back to use sintering, steel-making and coking washes links such as ammonia, and under the high temperature action of these links, phenates can resolve into CO
2And water; Add decyanation agent such as soda ash, molysite, make cyanogen class material be converted into precipitation and remove.
3. the chemical reaction pond water outlet enters coagulative precipitation tank, by adding aluminium salt or molysite class inorganic flocculating agent (as polymeric ferric aluminum) and organic polymer coargulator (as polyacrylamide), and the consumption of regulating both is respectively 500mg/L and 125mg/L, effectively removes the suspended substance in the waste water.
4. the settling tank water outlet is back to use other system after further removing suspended substance through strainer, wherein 40m
3/ h is back to converter dedusting line, 45m
3/ h is back to coking and washes ammonia, 15m
3/ h is back to sintering.
5. the mud in the settling tank reclaims a certain amount of fertilizer then through the pressure filter filter-press dehydration from solid slag.
Claims (2)
1. Treatment of Coking Effluent and reuse method, adopt the physico-chemical process Treatment of Wastewater in Coking, remove ammonia nitrogen, phenol, cyanogen, suspended substance pollutent in the coking chemical waste water, make its reach can reuse standard, and the coking chemical waste water after will handling is back to use converter dust-removing, coking as water of productive use and washes ammonia, inner other system of sintering, the steps in sequence that it is characterized in that Treatment of Wastewater in Coking is for removing ammonia nitrogen, remove phenol, remove cyanogen, removing suspended substance, and the concrete grammar of each step is as follows
(1) remove ammonia nitrogen: after coking chemical waste water is carried out preliminary ammonia still process, add magnesium salts and phosphoric acid salt, reacting with ammonia nitrogen in the waste water generates MgNH
4PO
46H
2The O precipitation removes by filter then, and ammonia nitrogen content can be reduced to below the 100mg/L by the 4000mg/L before handling;
(2) remove phenol: add highly basic in coking chemical waste water, reduce toxicity thereby allow phenol be transformed into phenates, phenates is present in the coking chemical waste water and is back to use sintering, steel-making and coking washes the ammonia link, and under the high temperature action of these links, phenates can resolve into CO
2And water, the content of aldehydes matter can be reduced to below the 2.0mg/L by the 1500-2000mg/L before handling;
(3) remove cyanogen: in coking chemical waste water, add soda ash, molysite decyanation agent, make cyanogen class material be converted into Na
4Fe (CN)
6Precipitation and removing, the content of prussiate can be reduced to below the 0.5mg/L by the 35-50mg/L before handling;
(4) remove suspended substance: in coking chemical waste water, add aluminium salt or molysite class inorganic flocculating agent and organic polymer coargulator, and the consumption and the ratio of regulating both, effectively remove the suspended substance in the waste water, the content of suspended substance can be reduced to below the 100mg/L by the 300-500mg/L before handling.
2, a kind of Treatment of Coking Effluent according to claim 1 and reuse method is characterized in that organic polymer coargulator is a polyacrylamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100402152A CN100526236C (en) | 2004-07-15 | 2004-07-15 | Process for treating and recovering wastewater of coking |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100402152A CN100526236C (en) | 2004-07-15 | 2004-07-15 | Process for treating and recovering wastewater of coking |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1721344A CN1721344A (en) | 2006-01-18 |
| CN100526236C true CN100526236C (en) | 2009-08-12 |
Family
ID=35912015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100402152A Expired - Fee Related CN100526236C (en) | 2004-07-15 | 2004-07-15 | Process for treating and recovering wastewater of coking |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100526236C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100465110C (en) * | 2006-12-30 | 2009-03-04 | 山东大隆实业有限公司 | Coking waste water reuse treatment method |
| CN101792224B (en) * | 2010-03-30 | 2012-06-27 | 上海华畅环保设备发展有限公司 | Method and device for processing emptied water of delayed coking |
| CN101898233A (en) * | 2010-08-20 | 2010-12-01 | 秦皇岛首秦金属材料有限公司 | Method for reducing fluorine content of continuous casting secondary cooling water |
| CN102774985A (en) * | 2012-07-18 | 2012-11-14 | 常州大学 | Method for treating high-concentration ammonia-nitrogen in coal chemical wastewater |
| CN104162449B (en) * | 2014-08-22 | 2016-03-30 | 陕西驭腾实业有限公司 | A kind of coking chemical waste water pyrolysis catalysts and preparation method thereof |
| CN105296748A (en) * | 2015-11-27 | 2016-02-03 | 山东石横特钢集团有限公司 | Harmless disposal method of distilled ammonia waste water |
| CN109399848B (en) * | 2018-10-19 | 2021-09-03 | 盐城迪赛诺制药有限公司 | High-salt high-ammonia nitrogen wastewater treatment method |
| CN112939358B (en) * | 2021-02-05 | 2021-11-26 | 内蒙古包钢集团环境工程研究院有限公司 | Phenol-cyanogen wastewater reduction method |
| CN112939359B (en) * | 2021-02-05 | 2022-04-05 | 内蒙古包钢集团环境工程研究院有限公司 | Phenol-cyanogen wastewater treatment system and phenol-cyanogen wastewater treatment method |
-
2004
- 2004-07-15 CN CNB2004100402152A patent/CN100526236C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 催化湿式氧化法处理焦化废水的分析. 方振炜，李光明，赵建夫.工业水处理，第23卷第1期. 2003 |
| 催化湿式氧化法处理焦化废水的分析. 方振炜，李光明，赵建夫.工业水处理，第23卷第1期. 2003 * |
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| Publication number | Publication date |
|---|---|
| CN1721344A (en) | 2006-01-18 |
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Address after: Hi tech building, East Road, hi tech Zone, Chengdu, Sichuan Patentee after: Chengdu Organic Chemicals Co., Ltd., Chinese Academy of Sciences Address before: Chengdu four people's South Road, Sichuan, China Academy of Sciences Chengdu Organic Chemical Co., Ltd. Patentee before: Chengdu Organic Chemicals Co., Ltd., Chinese Academy of Sciences |
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| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Chengdu Zhongke Purui Purifying Equipment Co., Ltd. Assignor: Chengdu Organic Chemicals Co., Ltd., Chinese Academy of Sciences Contract record no.: 2011510000172 Denomination of invention: Process for treating and recovering wastewater of coking Granted publication date: 20090812 License type: Exclusive License Open date: 20060118 Record date: 20110818 |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090812 Termination date: 20130715 |