CN102976511A - Coking wastewater membrane filtration concentrate recycle method - Google Patents
Coking wastewater membrane filtration concentrate recycle method Download PDFInfo
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- CN102976511A CN102976511A CN2012104354966A CN201210435496A CN102976511A CN 102976511 A CN102976511 A CN 102976511A CN 2012104354966 A CN2012104354966 A CN 2012104354966A CN 201210435496 A CN201210435496 A CN 201210435496A CN 102976511 A CN102976511 A CN 102976511A
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Abstract
The invention discloses a coking wastewater membrane filtration concentrate recycle method. The method comprises the following steps: 1, adjusting the pH value of a membrane filtration concentrate to 2.0-5.0, adding a ferrous salt and H2O2, and carrying out an oxidation reaction under air stirring; 2, adding an alkali to the obtained reaction solution after ending the reaction, precipitating, and carrying out solid-liquid separation to obtain a clear liquid; 3, removing impurities in the clear liquid through ultra-filtration and nano-filtration, and recycling nano-filtration outlet water; and 4, returning concentrated water generated after the ultra-filtration and the nano-filtration to step 1 as dilution water to dilute the concentrate. The method allows the coking wastewater membrane filtration concentrate to be processed through adopting a Fenton method in order to remove a plurality of toxic and refractory organic compounds in the membrane filtration concentrate, and COD, chloride ions and sulfate radicals to be removed through utilizing an ultra-filtration and nano-filtration system, so most impurities in the membrane filtration concentrate can be removed, and the finally obtained water reaches standards of industrial water or domestic water.
Description
Technical field
The present invention relates to a kind of sewage water treatment method, especially a kind of recoverying and utilizing method of coking chemical waste water film-filter concentration liquid.
Background technology
China is global coke production and consumption big country, Coke Industry is when satisfying the every profession and trade development needs such as iron and steel, chemical industry, machinery, and the three industrial wastes that it brings are processed problem, also become increasingly conspicuous, especially the processing of coking chemical waste water, especially focus and the difficult point of research in the industry.Contain the organic pollutants such as a large amount of phenols, alcohols, aromatic hydrocarbons, biphenyl, pyridine, indoles and quinoline in the coking chemical waste water, also contain the hazardous and noxious substances such as cyanogen, inorganic fluorion, chlorion and ammonia nitrogen, pollutent colourity is high, this waste water is after ultrafiltration, nanofiltration, reverse osmosis technology are processed, contain undegradable organic constituent and other hazardous and noxious substances in the upper water in the film-filter concentration liquid that produces, this concentrated solution belongs to the high-concentration organic industrial waste water than bio-refractory.
The treatment process of the film-filter concentration liquid of pertinent literature report mainly concentrates on evaporation, coagulation, absorption and advanced oxidation processes etc. at present.Wherein method of evaporation is mainly used in desalination, and the boiling vaporizer that it adopts and flash distillation type vaporizer treatment capacity are all little, and very easily fouling of container, are only applicable to small-sized waste water treatment plant; Coagulant sedimentation need to drop into coagulating agent in waste water, the micelle that it produces and the colloidalmaterial generation charge neutrality in the waste water, form particles settling, though have the advantages such as the nutritive substances such as the colourity of removing, oil content, microorganism, nitrogen and phosphorus, heavy metal and organism, but can produce a large amount of mud, also need mud is processed again; The absorption rule is to utilize the porousness solid matter to make sorbent material, and with certain pollutent in its surface adsorption waste water, pollutant load is high in the film-filter concentration liquid, when processing with absorption method, need to add a large amount of sorbent materials, the regenerative process more complicated of sorbent material, processing costs is also higher.
Comprehensive above-mentioned situation, it is strong that advanced oxidation processes has oxidation capacity, and speed of reaction is fast, the processing efficiency advantages of higher, and also most of reaction can carry out at normal temperatures and pressures, so at home and abroad progressively applied.The Fenton method is a kind of in the high-level oxidation technology, namely utilizes Fe
2+And H
2O
2Between chain reaction catalysis generate the OH free radical, and the OH free radical has strong oxidizing property, the organic compound of can oxidation various poisonous and difficult degradations is to reach the purpose of removing pollutent.
Application for a patent for invention CN 102249475A discloses a kind for the treatment of process of film-filter concentration liquid, relates to Fenton reagent, and the former water of film-filter concentration liquid enters reaction vessel, minute 1～8 adding H
2O
2And Fe
2+, control pH value is 2.0～4.0; Time 30～360min, regulating the pH value is 4.0～6.0, stirs flocculation, time 10～60min; Regulating the pH value is 6.0～9.0, staticly settles 15～45min; Supernatant liquor enters the biochemical treatment unit, and sedimentation mud enters sludge treating system; Total dosage of Fenton reagent is H in mass ratio
2O
2/ COD is 0.5～4.5; Fe
2+/ COD is 0.1～4.5; Administration timing of drug is spaced apart 10～150min; Add quality at every turn and be 33～100% of the last time.The method only is to utilize the Fenton oxidation technology to improve the biodegradability of film-filter concentration liquid.Patent CN 101786753A discloses a kind of advanced waste treatment method, relates to the reaction of Fenton reagent, has added catalyzer before reaction, and the Fenton reagent add-on is optimized.The waste water that the method is processed also can only reach the standard of effluxing.The sewage that above-mentioned two patent applications are processed all can not reach process water or domestic water standard, can not direct reuse.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of recoverying and utilizing method of coking chemical waste water film-filter concentration liquid, with direct reuse as process water or domestic water.
For solving the problems of the technologies described above, the present invention's take steps into:
(1) film-filter concentration liquid is 2.0～5.0 through being adjusted to the pH value, then adds ferrous salt and H
2O
2, under pneumatic blending, carry out oxidizing reaction;
(2) after above-mentioned reaction finishes, add alkali in reaction solution, after the precipitin reaction fully, solid-liquid separation obtains clear liquid;
(3) utilize ultrafiltration and nanofiltration to remove impurity in the clear liquid, the nanofiltration water outlet is recoverable;
(4) the dense water of described ultrafiltration and nanofiltration generation is got back to step (1) as dilution water, is used for the dilution concentrated solution.
Ultrafiltration in the step of the present invention (3) and nanofiltration are followed successively by sand filtration, ultrafiltration, security personnel's filtration and nanofiltration.The top filling quartz sand of the used sand-bed filter of described sand filtration, the thin burnt grain of bottom filling, flyash or activated carbon.
The add-on of ferrous salt is counted in every liter of film-filter concentration liquid with ferrous ion and is added 0.02～0.07g in the step of the present invention (1), and the add-on of hydrogen peroxide is to add 10～20mL in every liter of film-filter concentration liquid; The air flow quantity of pneumatic blending is 0.1～0.5L/h, and oxidation time is 0.5～7h.
Alkali in the step of the present invention (2) is solid or the solution of sodium hydroxide, potassium hydroxide, yellow soda ash or salt of wormwood, or the salkali waste concentrated solution.
Adopt successively settling tank and mechanical accelerating purifying pool to carry out solid-liquid separation in the step of the present invention (2).
The beneficial effect that adopts technique scheme to produce is: the present invention adopts first the film-filter concentration liquid of Fenton method Treatment of Wastewater in Coking, removes the organic compound of the various poisonous and difficult degradation in the film-filter concentration liquid; Recycling ultrafiltration and nanofiltration system are removed COD, chlorion, sulfate ion, thereby with most Impurity removals in the film-filter concentration liquid, reach the standard of process water or domestic water.Adopt the present invention to process concentrated solution, the final outflow water suspension content is 0mg/L, colourity (platinum-cobalt look number)＜5, COD＜10mg/L, Cl
-＜5mg/L, SO
4 2-＜0.3mg/L can be used as process water or domestic water, thus realize film-filter concentration liquid entirely be recovered utilization.
The present invention makes it the impurity of more effective removal film-filter concentration liquid by improving the technique of oxidizing reaction, has the better characteristics for the treatment of effect.
Description of drawings
The present invention is further detailed explanation below in conjunction with the drawings and specific embodiments.
Fig. 1 is the process flow sheet of present device system.
Embodiment
Embodiment 1: the recoverying and utilizing method of this coking chemical waste water film-filter concentration liquid adopts following processing step.
Adopt device systems shown in Figure 1, get the concentrated solution of domestic certain chemical industrial park coking chemical waste water after nanofiltration is processed, at first in equalizing tank 1, regulate concentrated solution pH value to 4.0; Then the concentrated solution that will regulate after the pH value is squeezed in the aerated reaction pond 2, adds ferrous sulfate and count 0.05g with ferrous ion in every liter of concentrated solution, adds H in every liter of concentrated solution
2O
2Be 15mL, under the air speed of 0.2L/h stirs, react 5h; After reaction finishes, after the adding solid sodium hydroxide extremely precipitates fully in reaction solution, after settling tank 3, mechanical accelerating purifying pool 4 carry out precipitate and separate, supernatant liquor filters through sand-bed filter 5, ultra-fine filter 6, cartridge filter 7, nanofiltration device 8 respectively, wherein, the top filling quartz sand of sand-bed filter, the thin burnt grain of bottom filling.Each stage effluent quality is as shown in table 1, and the nanofiltration water outlet namely can be used as make up water or the domestic water of process water; The dense water that ultra-fine filter 6, nanofiltration device 8 produce is as being used for the dilution concentrated solution in the dilution water equalizing tank.
Embodiment 2: the recoverying and utilizing method of this coking chemical waste water film-filter concentration liquid adopts following processing step.
Adopt device systems shown in Figure 1, get the concentrated solution of domestic certain chemical industrial park coking chemical waste water after nanofiltration is processed, at first in equalizing tank 1, regulate concentrated solution pH value to 5.0; Then the concentrated solution that will regulate after the pH value is squeezed in the aerated reaction pond 2, adds iron protoxide and count 0.04g with ferrous ion in every liter of concentrated solution, adds H in every liter of concentrated solution
2O
2Be 10mL, under the air speed of 0.3L/h stirs, react 2h; After reaction finishes, in reaction solution, add the potassium hydroxide saturated solution, after settling tank 3, mechanical accelerating purifying pool 4 precipitate, supernatant liquor filters through sand-bed filter 5, ultra-fine filter 6, cartridge filter 7, nanofiltration device 8 respectively, wherein, the top filling quartz sand of sand-bed filter, bottom filling activated carbon.Each stage effluent quality is as shown in table 2, and the nanofiltration water outlet namely can be used as make up water or the domestic water of process water, and the dense water that ultra-fine filter 6, nanofiltration device 8 produce is as being used for the dilution concentrated solution in the dilution water equalizing tank.
Embodiment 3: the recoverying and utilizing method of this coking chemical waste water film-filter concentration liquid adopts following processing step.
Adopt device systems shown in Figure 1, get the concentrated solution of domestic certain chemical industrial park coking chemical waste water after nanofiltration is processed, at first in equalizing tank 1, regulate concentrated solution pH value to 2.0; Then the concentrated solution that will regulate after the pH value is squeezed in the aerated reaction pond 2, adds ferrous hydroxide and count 0.02g with ferrous ion in every liter of concentrated solution, adds H in every liter of concentrated solution
2O
2Be 18mL, under the air speed of 0.5L/h stirs, react 0.5h; After reaction finishes, the concentrated solution that in reaction solution, adds useless yellow soda ash, after settling tank 3, mechanical accelerating purifying pool 4 precipitate, supernatant liquor filters through sand-bed filter 5, ultra-fine filter 6, cartridge filter 7, nanofiltration device 8 respectively, wherein, the top filling quartz sand of sand-bed filter, bottom filling flyash.Each stage effluent quality is as shown in table 3, and the nanofiltration water outlet namely can be used as make up water or the domestic water of process water, and the dense water that ultra-fine filter 6, nanofiltration device 8 produce is as being used for the dilution concentrated solution in the dilution water equalizing tank.
Embodiment 4: the recoverying and utilizing method of this coking chemical waste water film-filter concentration liquid adopts following processing step.
Adopt device systems shown in Figure 1, get the concentrated solution of domestic certain chemical industrial park coking chemical waste water after nanofiltration is processed, at first in equalizing tank 1, regulate concentrated solution pH value to 3.0; Then the concentrated solution that will regulate after the pH value is squeezed in the aerated reaction pond 2, adds iron protochloride and count 0.07g with ferrous ion in every liter of concentrated solution, adds H in every liter of concentrated solution
2O
2Be 20mL, under the air speed of 0.1L/h stirs, react 7h; Reaction adds salt of wormwood, after settling tank 3, mechanical accelerating purifying pool 4 precipitate after finishing in reaction solution, supernatant liquor filters through sand-bed filter 5, ultra-fine filter 6, cartridge filter 7, nanofiltration device 8 respectively, wherein, the top of sand-bed filter filling quartz sand, bottom filling gac.Each stage effluent quality is as shown in table 4, and the nanofiltration water outlet namely can be used as make up water or the domestic water of process water, and the dense water that ultra-fine filter 6, nanofiltration device 8 produce is as being used for the dilution concentrated solution in the dilution water equalizing tank.
Claims (6)
1. the recoverying and utilizing method of a coking chemical waste water film-filter concentration liquid is characterized in that, the method step is:
(1) film-filter concentration liquid is 2.0～5.0 through being adjusted to the pH value, then adds ferrous salt and H
2O
2, under pneumatic blending, carry out oxidizing reaction;
(2) after above-mentioned reaction finishes, add alkali in reaction solution, after the precipitin reaction fully, solid-liquid separation obtains clear liquid;
(3) utilize ultrafiltration and nanofiltration to remove impurity in the clear liquid, the nanofiltration water outlet is recoverable;
(4) the dense water of described ultrafiltration and nanofiltration generation is got back to step (1) as dilution water, is used for the dilution concentrated solution.
2. the recoverying and utilizing method of coking chemical waste water film-filter concentration liquid according to claim 1 is characterized in that: the ultrafiltration in the described step (3) and nanofiltration are followed successively by sand filtration, ultrafiltration, security personnel and filter and nanofiltration.
3. the recoverying and utilizing method of coking chemical waste water film-filter concentration liquid according to claim 2 is characterized in that: the top filling quartz sand of the used sand-bed filter of described sand filtration, the thin burnt grain of bottom filling, flyash or activated carbon.
4. according to claim 1, the recoverying and utilizing method of 2 or 3 described coking chemical waste water film-filter concentration liquids, it is characterized in that: the add-on of ferrous salt is counted in every liter of film-filter concentration liquid with ferrous ion and is added 0.02～0.07g in the described step (1), and the add-on of hydrogen peroxide is to add 10～20mL in every liter of film-filter concentration liquid; The air flow quantity of pneumatic blending is 0.1～0.5L/h, and oxidation time is 0.5～7h.
5. according to claim 1, the recoverying and utilizing method of 2 or 3 described coking chemical waste water film-filter concentration liquids, it is characterized in that: the alkali in the described step (2) is solid or the solution of sodium hydroxide, potassium hydroxide, yellow soda ash or salt of wormwood, or the salkali waste concentrated solution.
6. according to claim 1, the recoverying and utilizing method of 2 or 3 described coking chemical waste water film-filter concentration liquids, it is characterized in that: adopt successively settling tank and mechanical accelerating purifying pool to carry out solid-liquid separation in the described step (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104354966A CN102976511A (en) | 2012-11-05 | 2012-11-05 | Coking wastewater membrane filtration concentrate recycle method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104354966A CN102976511A (en) | 2012-11-05 | 2012-11-05 | Coking wastewater membrane filtration concentrate recycle method |
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| CN2012104354966A Pending CN102976511A (en) | 2012-11-05 | 2012-11-05 | Coking wastewater membrane filtration concentrate recycle method |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420450A (en) * | 2013-08-27 | 2013-12-04 | 广州悦活环保科技有限公司 | Double membrane mutual flushing type double water outlet reverse osmosis water purifier |
| CN104386855A (en) * | 2014-11-13 | 2015-03-04 | 福建恒嘉环保设备有限公司 | Method for preventing membrane filtration concentrated liquid from being scaled |
| CN105439310A (en) * | 2014-06-27 | 2016-03-30 | 中国石油化工股份有限公司 | Sulfate organic wastewater treatment method |
| CN105712539A (en) * | 2016-04-11 | 2016-06-29 | 浙江碧源环保科技有限公司 | Deep treatment system and process for coked phenol and cyanide wastewater |
| CN107226554A (en) * | 2017-07-20 | 2017-10-03 | 同济大学 | A kind of method of ferrous salt activation persulfate pretreatment Ghana filter point salt treatment RO/NF concentrated waters |
| CN109956593A (en) * | 2019-04-29 | 2019-07-02 | 苏州无为环境科技有限公司 | A kind of emergency wastewater treatment method |
| CN110104845A (en) * | 2019-06-11 | 2019-08-09 | 武汉深能环保新沟垃圾发电有限公司 | A kind of percolation liquid membrane processing method reducing concentration output of fluid |
| US10703660B2 (en) | 2017-08-04 | 2020-07-07 | Citic Envirotech Ltd | Method and system for treatment of organic contaminants by coupling Fenton reaction with membrane filtration |
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| JPS5520666A (en) * | 1978-07-31 | 1980-02-14 | Gunze Ltd | Sludge recovery method |
| WO2002004359A1 (en) * | 2000-07-07 | 2002-01-17 | Microbar, Inc. | Method of treating industrial waste waters |
| CN101560045A (en) * | 2009-06-04 | 2009-10-21 | 北京美华博大环境工程有限公司 | Coal chemical wastewater treating technique |
| CN102139979A (en) * | 2011-05-05 | 2011-08-03 | 中国科学院生态环境研究中心 | Method for treating coking waste water by electro-Fenton-coagulation combination process |
-
2012
- 2012-11-05 CN CN2012104354966A patent/CN102976511A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5520666A (en) * | 1978-07-31 | 1980-02-14 | Gunze Ltd | Sludge recovery method |
| WO2002004359A1 (en) * | 2000-07-07 | 2002-01-17 | Microbar, Inc. | Method of treating industrial waste waters |
| CN101560045A (en) * | 2009-06-04 | 2009-10-21 | 北京美华博大环境工程有限公司 | Coal chemical wastewater treating technique |
| CN102139979A (en) * | 2011-05-05 | 2011-08-03 | 中国科学院生态环境研究中心 | Method for treating coking waste water by electro-Fenton-coagulation combination process |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420450A (en) * | 2013-08-27 | 2013-12-04 | 广州悦活环保科技有限公司 | Double membrane mutual flushing type double water outlet reverse osmosis water purifier |
| CN105439310A (en) * | 2014-06-27 | 2016-03-30 | 中国石油化工股份有限公司 | Sulfate organic wastewater treatment method |
| CN104386855A (en) * | 2014-11-13 | 2015-03-04 | 福建恒嘉环保设备有限公司 | Method for preventing membrane filtration concentrated liquid from being scaled |
| CN104386855B (en) * | 2014-11-13 | 2016-05-18 | 福建恒嘉环保设备有限公司 | A kind of antiscaling method of film-filter concentration liquid |
| CN105712539A (en) * | 2016-04-11 | 2016-06-29 | 浙江碧源环保科技有限公司 | Deep treatment system and process for coked phenol and cyanide wastewater |
| CN107226554A (en) * | 2017-07-20 | 2017-10-03 | 同济大学 | A kind of method of ferrous salt activation persulfate pretreatment Ghana filter point salt treatment RO/NF concentrated waters |
| US10703660B2 (en) | 2017-08-04 | 2020-07-07 | Citic Envirotech Ltd | Method and system for treatment of organic contaminants by coupling Fenton reaction with membrane filtration |
| CN109956593A (en) * | 2019-04-29 | 2019-07-02 | 苏州无为环境科技有限公司 | A kind of emergency wastewater treatment method |
| CN110104845A (en) * | 2019-06-11 | 2019-08-09 | 武汉深能环保新沟垃圾发电有限公司 | A kind of percolation liquid membrane processing method reducing concentration output of fluid |
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Application publication date: 20130320 |