CN101544421B - Method for treating coking wastewater - Google Patents
Method for treating coking wastewater Download PDFInfo
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- CN101544421B CN101544421B CN200810035057XA CN200810035057A CN101544421B CN 101544421 B CN101544421 B CN 101544421B CN 200810035057X A CN200810035057X A CN 200810035057XA CN 200810035057 A CN200810035057 A CN 200810035057A CN 101544421 B CN101544421 B CN 101544421B
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- slag
- blast furnace
- furnace slag
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- bio
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The invention provides a method for treating coking wastewater, which comprises the following steps: (1) sieving blast furnace slag and steel slag; (2) filling the sieved blast furnace slag and steel slag into a bioreactor, with the blast furnace slag accounting for 0 to 100 percent by mass; (3) starting the acclimatization of the bioreactor; and (4) introducing the coking wastewater into a bioreactor. The method achieves the aim of resourcefully utilizing the blast furnace slag and the steel slag when treating the coking wastewater and reducing wastewater treating cost.
Description
Technical field
The invention belongs to environment protection and resource utilization field, specifically, the present invention relates to the processing of coking chemical waste water and the second stage employ of blast furnace slag and slag.
Background technology
The complicated component of coking chemical waste water is changeable, COD, NH
3-N concentration is higher, and organic components is complicated, contains organic pollutants such as a large amount of phenols, biphenyl, pyridine, indoles and quinoline; Also contain hazardous and noxious substances such as cyanogen, inorganic fluorion and ammonia nitrogen; Pollutent colourity is high, and in water, has stable in properties with true solution and accurate colloidal form.COD in the waste water and colourity are difficult to be removed, so the processing of coking chemical waste water is a great problem of domestic and international field of waste water treatment always.
At present, adopt biological process to handle to coking chemical waste water, technology commonly used mainly contains A/O and A/A/O and various modified form thereof more.Because of the difference of production technique, raw material etc., NH in the different enterprises coking chemical waste water
3The content difference of-N is very big, and is general all more than 100mg/L, have up to more than the 300mg/L.1mg/L NH
3-N is nitrated to be NO
3 --N need consume the basicity of 7.14mg (with CaCO
3Meter), is in the suitable growing environment, must extraly adds alkaline matter such as Na for guaranteeing mikrobe
2CO
3, NaHCO
3Or NaOH etc., with the basicity that consumes in the additional nitration process.
Generally more than 50mg/L, conventional biological treatment does not almost have removal effect to fluorion to the content of fluorion in the coking chemical waste water, for satisfying emission standard, needs to adopt the materialization measure to do further processing.For fluoride waste, its treatment process mainly contains: absorption method, electrocoagulation, reverse osmosis method, ion exchange method, chemical precipitation method and coagulant sedimentation etc.Wherein, absorption method is mainly used in the processing to tap water; The ion exchange method expense is high, and strict to waste water quality; Electrocoagulation and reverse osmosis method device are complicated, and current consumption is big, the few employing.Therefore, for the higher trade effluent of fluorinion concentration, often adopt chemical precipitation method and coagulant sedimentation.
Chemical precipitation method generally adopts calcium salt (like calcium sulfate and calcium chloride) or lime, but the CaF that forms
2Particle is less, is not easy deposition, and can be wrapped in Ca (OH)
2Or CaSO
4The surface, makes it and can not make full use of, so amount ratio is bigger.Even use solvability CaCl preferably
2, its consumption generally also need maintain 2～5 times of theoretical consumption, and this mainly is because Ca
2+And F
-Generate CaF
2Speed slower, be fast reaction speed, need to add excessive Ca
2+The new CaF that forms
2Fine-grain itself has certain solubleness (18 ℃ time be 16.3mg/L).In addition, owing to some component such as CO in the waste water
3 2-, SO
4 2-, SiO
4 4-Be adsorbed on the CaF of new formation Deng negatively charged ion
2CaF can be slowed down in the fine-grain surface
2The further growth of crystal grain causes CaF
2Deposition is difficult for from water, separating out.Therefore, the fluorine mass concentration generally between 20～50mg/L, still is higher than the primary standard (10mg/L) of " national sewage comprehensive emission standard " GB8978-1996 in the water outlet after the processing, still needs and further handles.
Biological iron processes is in bio-reactor or water inlet, to add a certain amount of molysite, tames into biological iron mud through cultivating, and handles the usefulness of waste water to improve common biological process, strengthens and enlarge the method for purification function.The article of retrieving domestic and international related patent U.S. Patent No. and delivering is learnt: present biological iron materials mainly are several kinds of molysite, cast iron, iron filings etc.Be used for the biological treatment of waste water difficult for biological degradation such as leather-making waste water, dyeing waste water, pharmacy waste water more, strengthen treatment effect COD, SS etc.Research shows: compare COD in the sewage when adding iron ion and not adding iron ion
CrClearance will improve 15-20%.
In iron and steel enterprise, blast furnace slag and slag are first, second big solid by-products.According to estimates, China will have more than one hundred million tons blast furnace slag to produce in 2007, and the year quantum of output of slag is at least 5,000 ten thousand tons.Up to the present, blast furnace slag is mainly used in the Additive of building material industry such as concrete, cement and makes slag wool etc., is used to develop fields such as siliceous fertilizer on a small quantity; The best approach of slag second stage employ is as blast furnace, converter raw material, in Iron And Steel Plant, recycle voluntarily, but utilization is limited, in addition, also can be used for road engineering, building materials raw material and fill out the hole make ground etc.Valuable elements a large amount of in blast furnace slag and the slag are not fully utilized, and on the whole, the added value of its utilization is lower.
The own toxicological harmless effect of blast furnace slag and slag, and surface irregularity have certain porosity, help attached growth of microorganisms, can be used as the filler of wastewater treatment; The slow release of alkaline matters such as the CaO in blast furnace slag and the slag, MgO can be played the effect that replenishes basicity, and the aluminium salt that is discharged into simultaneously in the water also has throwing out, can improve aging biomembranous settling property, and the calcium that is dissolved in the water also has the defluorination function; Iron in blast furnace slag and the slag can discharge under the acting in conjunction of physics, chemistry and mikrobe lentamente, forms stable biological source of iron, brings into play the effect of biological iron.Therefore, if can blast furnace slag and slag be applied in the WWT, both can realize the treatment of wastes with processes of wastes against one another, reduce the processing cost of sewage, can open up blast furnace slag, Application Areas that slag is new again, reduce its stacking amount.
Therefore, the object of the present invention is to provide a kind of novel method of utilizing blast furnace slag and slag Treatment of Wastewater in Coking.
Summary of the invention
The present invention provides a kind of method of Treatment of Wastewater in Coking, may further comprise the steps:
(1) blast furnace slag and slag are sieved;
(2) blast furnace slag and the slag after will sieving is filled in the bio-reactor, and the shared ratio of said blast furnace slag is 0～100%;
(3) domestication of bio-reactor starts; And
(4) coking chemical waste water is introduced aerobe reactor.
Said screening can adopt sieve apparatus to carry out.
Said step (1) comprises sieves into several groups of granular fillers that particle diameter is 3～5mm, 5～10mm, 10～20mm and 20～50mm with said blast furnace slag and slag.
The filling of said filler can be adopted a kind of particle size range or adopt the combination of different-grain diameter scope to load.Adopt two or more mechanical fraction, can adapt to different wastewater treatment requirements.Concentration of suspension is higher when intaking, and is blocked for preventing filler when water quality is relatively poor, makes the bigger bigger ratio of filler accounting of particle diameter; The concentration of suspended substance is lower in water inlet, when water quality is better, makes the less filler of particle diameter account for bigger ratio, to increase media area, improves microorganism concn, strengthens filteration, improves the removal effect to pollutent.
Said bio-reactor is optional from aeration biological filter, high-rate filter, tower biological filter or bio-trickling filter.
The domestication of said bio-reactor starts can adopt natural membrane method, inoculation method, circulation to hang embrane method or quick spoil disposal extension embrane method.
Said coking chemical waste water can pump into from the bio-reactor bottom, and flow out at the top.
When filler minimizing or water outlet pH were on the low side in the said reactor drum, blast furnace slag that can add or more renew and slag filler normally moved to keep system.
Say that from physical property the intensity of blast furnace slag and slag is bigger, many micropores are contained in inside, have higher specific surface area, and surface ratio is more coarse, are easy to the microbial film apposition growth.Say that from chemical ingredients the staple of blast furnace slag is CaO and SiO
2, also have Al
2O
3, MgO, Fe
2O
3, MnO, comprise elements (seeing table 1) such as little P in addition; The main chemical compositions of slag is for having CaO, MgO, Al
2O
3And TFe, also contain a spot of SiO
2, MnO, S and P
2O
5Deng (seeing table 2), these materials all are needed trace elements in the microorganism growth process.
The main chemical compositions of table 1 blast furnace slag (%)
Annotate: data are that the dried slag of blast furnace with Baosteel is an example.
The chemical ingredients of table 2 bessemer furnace slag (%)
Annotate: data are that the converter slag with Baosteel is an example.
Contain a large amount of ammonia nitrogens and organonitrogen in the coking chemical waste water, in the aerobic reaction process, can be converted into nitric nitrogen, need consume a large amount of basicity simultaneously,, need add alkaline matter such as yellow soda ash etc. for the pH that keeps in the system is neutral.Because the CaO in the blast furnace slag is a combined, release to birth ratio is slower, during separately as filler; When if ammonia-nitrogen content is higher in the handled water; Its basicity that discharges can not be offset the basicity of nitrated consumption fully, causes water outlet pH slant acidity, still need add alkali lye; And contain the free CaO of part in the slag, and and after contacting, water can be discharged into rapidly in the water, water outlet pH often is increased to more than 10 when using separately.Water quality situation according to handled coking chemical waste water; With blast furnace slag and slag combination treatment coking chemical waste water according to a certain percentage; The basicity that makes blast furnace slag and slag discharge just in time can be replenished the basicity that consumes in the coking chemical waste water nitrifying process; Thereby can cancel adding of alkali lye, practice thrift the working cost of system.
The calcium salt that discharges in CaO in blast furnace slag, the slag and the bioprocesses can be with the F in the coking chemical waste water
-Reaction generates CaF
2Deposition, thus reach the purpose of defluorination.Adopt chemical precipitation method to remove F
-The time, a very big problem is exactly the CaF that reaction generates
2Particle is less, causes CaF
2Deposition is difficult for from water, separating out, and causes F in the water outlet
-Higher; And with blast furnace slag and slag filler, the CaF of generation as bio-reactor
2Particle can be used as the nucleus of microbial film mud, and the outer slime layer of the born of the same parents of microorganism secretion can be with a plurality of CaF simultaneously
2Particle flocculation forms the bigger mud granule of settling property excellent particle size together, with washing away or discharge system such as back flushing of current, and through precipitate and separate, so F in the water outlet
-Concentration is lower.
In addition, the iron in blast furnace slag and the slag discharges Fe lentamente under the acting in conjunction of physics, chemistry and mikrobe etc.
2+, Fe
3+, play the effect of biological iron, therefore can improve the removal effect of biological treatment system to COD etc.
Therefore the mixed fillers Treatment of Wastewater in Coking that adopts blast furnace slag and slag to form; Not only can save the medicament expense usefulness that additional basicity, defluorination and molysite add; Can also practice thrift these medicaments add and the dissolution equipment expense (molysite has very strong corrodibility mostly; Like iron trichloride, it is erosion-resisting that medicament adds that equipment such as pump required in the process, pipeline and medicine storing pot all require, and cost is than higher).When realizing blast furnace slag, steel slag resource utilization, reduced the investment and the working cost of WWT.
Beneficial effect
The present invention deeply excavates adsorption precipitation performance and valuable constituent (Fe, CaO, the Al of blast furnace slag and slag
2O
3And MgO etc.); The multiple functions such as stable source of iron and efficient carrier that the mixed fillers that makes blast furnace slag and slag form has the basicity of providing, defluorination simultaneously and microorganism growth is provided; Reach the purpose that not only improves water treatment effect but also reduce cost for wastewater treatment; Realized the treatment of wastes with processes of wastes against one another, the purpose that blast furnace slag, steel slag resourceization are utilized has again been opened up the new application in the Treatment of Coking Effluent field of blast furnace slag and slag.
Embodiment
Below combine accompanying drawing that the present invention is made more detailed description with embodiment.These embodiment only are the descriptions to best mode for carrying out the invention, scope of the present invention are not had any restriction.
Embodiment 1
Filler all adopts blast furnace slag, particle size range 5～10mm.Adopt BAF, the hydraulic detention time 50h of system handles the coking chemical waste water of certain coke-oven plant.Coking chemical waste water influent quality pH8.44～8.67, COD1028～1560mg/L, NH
3-N145～202mg/L, F
-43～65mg/L.After the blast furnace slag reactor for treatment, effluent quality reaches: pH6.68～7.05, COD156～237mg/L, NH
3-N0～3.2mg/L, F
-9.5～16.7mg/L.Water outlet pH and NH
3-N can satisfy " integrated wastewater discharge standard " first discharge standard (GB8978-1996), the F in the water outlet
-Can satisfy the low geographic secondary discharge standard of fluorine.
Embodiment 2
The ratio of blast furnace slag and slag adopted 90%: 10%.Adopt BAF, reactor lower part loads the mixing slag of 50% particle diameter, 10～20mm, and the mixing slag of 50% particle diameter, 5～10mm is loaded on top, and the hydraulic detention time 60h of system handles the coking chemical waste water of certain coke-oven plant.Influent quality: pH8.08～9.26, COD1488～2570mg/L, NH
3-N137～375mg/L, F
-44～81mg/L.After blast furnace slag and slag mixed fillers reactor for treatment, effluent quality reaches: pH6.75～7.42, COD232～338mg/L, NH
3-N0～5.6mg/L, F
-12.5～18.3mg/L.Water outlet pH and NH
3-N can satisfy " integrated wastewater discharge standard " first discharge standard (GB8978-1996), the F in the water outlet
-Can satisfy the low geographic secondary discharge standard of fluorine.
Embodiment 3
The ratio of blast furnace slag and slag adopted 80%: 20%.Adopt BAF; Reactor lower part loads the mixing slag of 40% particle diameter, 10～20mm, and the mixing slag of 40% particle diameter, 5～10mm is loaded at the middle part, and the mixing slag of 20% particle diameter, 3～5mm is filled on top; The hydraulic detention time 65h of system handles certain synthetic coking chemical waste water.Influent quality: pH8.05～8.20, COD1480～1550mg/L, NH
3-N436～458mg/L, F
-75～83mg/L.After blast furnace slag and slag mixed fillers reactor for treatment, effluent quality reaches: pH7.05～7.48, COD105～139mg/L, NH
3-N0～6.2mg/L, F
-9.8～15.6mg/L.Water outlet pH and NH
3-N can satisfy " integrated wastewater discharge standard " first discharge standard (GB8978-1996), the F in the water outlet
-Can satisfy the low geographic secondary discharge standard of fluorine.
Claims (9)
1. the method for a Treatment of Wastewater in Coking is characterized in that may further comprise the steps:
(1) blast furnace slag and slag are sieved;
(2) blast furnace slag and the slag after will sieving is filled in the aerobe reactor, and the shared ratio of said blast furnace slag is 0～100%;
(3) domestication of bio-reactor starts; And
(4) coking chemical waste water is introduced aerobe reactor.
2. the method for claim 1 is characterized in that, said screening adopts sieve apparatus to carry out.
3. the method for claim 1 is characterized in that, said step (1) comprises sieves into several groups of granular fillers that particle diameter is 3～5mm, 5～10mm, 10～20mm and 20～50mm with said blast furnace slag and slag.
4. method as claimed in claim 3 is characterized in that a kind of particle size range is adopted in the filling of said filler.
5. method as claimed in claim 3 is characterized in that, the filling of said filler adopts the combination of different-grain diameter scope to load.
6. the method for claim 1 is characterized in that, said bio-reactor is selected from BAF, high-rate filter or bio-trickling filter.
7. the method for claim 1 is characterized in that, the domestication of said bio-reactor starts adopts natural membrane method, inoculation method, circulation to hang embrane method or quick spoil disposal extension embrane method.
8. the method for claim 1 is characterized in that, said coking chemical waste water pumps into from the bio-reactor bottom, and flow out at the top.
9. the method for claim 1 is characterized in that, said method also comprises when filler minimizing or water outlet pH are on the low side in the said reactor drum, the blast furnace slag and the slag filler that add or more renew.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810035057XA CN101544421B (en) | 2008-03-25 | 2008-03-25 | Method for treating coking wastewater |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810035057XA CN101544421B (en) | 2008-03-25 | 2008-03-25 | Method for treating coking wastewater |
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|---|---|
| CN101544421A CN101544421A (en) | 2009-09-30 |
| CN101544421B true CN101544421B (en) | 2012-01-11 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106865740B (en) * | 2017-02-24 | 2020-04-24 | 上海宝汇环境科技有限公司 | Biological carrier for coking wastewater biochemical system treatment and application |
| CN106830303B (en) * | 2017-02-28 | 2020-11-27 | 同济大学 | Method for treating sewage by utilizing waste incineration slag |
| CN108408881A (en) * | 2018-03-19 | 2018-08-17 | 包头钢铁（集团）有限责任公司 | It is a kind of using metallurgical solid waste as the biological aerated filter of filtrate |
| CN110624498B (en) * | 2018-06-21 | 2022-08-16 | 宝山钢铁股份有限公司 | Composite steel slag-based heavy metal adsorbent |
| CN109928492A (en) * | 2019-04-18 | 2019-06-25 | 南京清元景和环境科技有限公司 | The preparation method of modified activated carbon biologic packing material for biofilter |
| CN112028257A (en) * | 2020-07-27 | 2020-12-04 | 江苏若焱环境设计有限公司 | Preliminary sewage purification facility of drain |
| CN114057331B (en) * | 2021-11-08 | 2023-10-03 | 上海天汉环境资源有限公司 | Method and treatment system for removing fluorine pollution in incineration waste gas washing water |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1792895A (en) * | 2005-11-08 | 2006-06-28 | 重庆工学院 | Tech. for biochemical treating sulphur-containing chark waste water of high concentrating high ammonia nitrogen |
| CN1958486A (en) * | 2006-11-10 | 2007-05-09 | 哈尔滨工业大学 | Advanced treatment method for carbonization wastewater |
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2008
- 2008-03-25 CN CN200810035057XA patent/CN101544421B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1792895A (en) * | 2005-11-08 | 2006-06-28 | 重庆工学院 | Tech. for biochemical treating sulphur-containing chark waste water of high concentrating high ammonia nitrogen |
| CN1958486A (en) * | 2006-11-10 | 2007-05-09 | 哈尔滨工业大学 | Advanced treatment method for carbonization wastewater |
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