CN101786767A - Advanced treatment process of coking waste water by combining ozone oxidation method and membrane separation technology - Google Patents

Advanced treatment process of coking waste water by combining ozone oxidation method and membrane separation technology Download PDF

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Publication number
CN101786767A
CN101786767A CN 201010117965 CN201010117965A CN101786767A CN 101786767 A CN101786767 A CN 101786767A CN 201010117965 CN201010117965 CN 201010117965 CN 201010117965 A CN201010117965 A CN 201010117965A CN 101786767 A CN101786767 A CN 101786767A
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China
Prior art keywords
water
waste water
treatment
coking
advanced treatment
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CN 201010117965
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Chinese (zh)
Inventor
张一红
尹君贤
杜连喜
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中冶焦耐(大连)工程技术有限公司
中冶焦耐工程技术有限公司
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Priority to CN 201010117965 priority Critical patent/CN101786767A/en
Publication of CN101786767A publication Critical patent/CN101786767A/en

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Abstract

The invention relates to an advanced treatment process of coking waste water, which is characterized in that MBR (Membrane Bio-Reactor) treatment, ozone contact oxidation treatment, activated carbon adsorption treatment and reverse osmosis membrane treatment of the coking waste water after pretreatment and A/O biochemical treatment are sequentially carried out to satisfy the water quality requirement of makeup water for producing clean circulating water, and a small amount of concentrated solution can be sprayed to a coal yard for dust fall and dust prevention and also can be used as the makeup water for wet quenching. The invention has the advantages that the biochemical sludge concentration and the volume load of a biochemical reaction pond are improved, coagulation treatment is cancelled, and occupied land is saved; outlet water can be directly recycled as the makeup water for a system for producing the clean circulating water, and the reutilization of a water resource and the zero emission of the coking waste water are realized.

Description

The advanced treatment process of coking waste water that the ozone oxidation method combines with membrane separation technique
Technical field
The present invention relates to a kind of treatment process of coking chemical waste water, be particularly related to a kind of method that adopts advanced oxidation processes to combine coking chemical waste water is carried out advanced treatment process, aim to provide a kind of coking wastewater deep treatment new technology that can reduce all kinds of pollutant loads in the coking chemical waste water significantly with membrane separation technique.
Background technology
At present, Treatment of Coking Effluent generally adopts A/O biological denitrificaion treatment technology, handles the back water-quality guideline and can reach national specified discharge standard, and part is back to wet quenching, dedusting, coal gas water seal equal turbidity circulating water system and makes make up water.And the advanced treatment of coking chemical waste water is generally adopted means such as sand filtration, biological filter, coagulating treatment, although water outlet COD is controlled at about 100mg/L, suspension content can not satisfy and produce water purification water water quality requirement about 30mg/L; The employing activated carbon filtration that has, can remove COD and suspended substance in the water effectively, COD is dropped to below the 60mg/L, suspension content but does not almost have effect to deliquescent solid saltiness below 5mg/L, in addition, the saturated back of charcoal absorption is just ineffective, the regenerative process more complicated, cost is higher, and therefore only depending on single activated carbon filtration unit not reach the reuse purpose does not have promotional value yet.
Summary of the invention
The present invention has overcome deficiency of the prior art, and a kind of advanced treatment process of coking waste water that can reduce all kinds of pollutant loads such as COD and suspended substance in the waste water significantly is provided.
For achieving the above object, the present invention is achieved through the following technical solutions:
A kind of advanced treatment process of coking waste water, coking chemical waste water after pre-treatment, the A/O biochemical treatment enters MBR, and MBR produces water and handles through O3 contacted oxidation, after the coking chemical waste water after charcoal absorption and the reverse-osmosis treated can satisfy and produce clean circulating water system water quality requirement and reuse.
The water-quality guideline of coking chemical waste water after biochemical treatment and MBR Membrane Bioreactor for Wastewater Treatment: CODcr≤120mg/L, NH 3-N≤5mg/L, ss suspended solid<5mg/L, phenol<0.5mg/L, prussiate<0.5mg/L, PH:6.5-7.5.
O3 contacted oxidation treating processes technical parameter: ozone dosage 50~70mg/L; 30~60 minutes duration of contact; PH value 6.5~7.5; Percent of decolourization 〉=70%; Coking chemical waste water is water-quality guideline: CODcr≤100mg/L, ss suspended solid<5mg/L, phenol<0.3mg/L, prussiate<0.3mg/L, percent of decolourization 〉=70% after O3 contacted oxidation is handled.
Activated carbon adsorber technical parameter: granulated active carbon particle diameter 1~3mm, length 2~6mm; Iodine number 800~1200mg/g; Charcoal layer height 3~4.5m; 10~20 minutes duration of contact; Hydraulic load 10~20m/h; Back washing strength 8~12L/sm 2Backwashing time 5~10 minutes; Coking chemical waste water is water-quality guideline: CODcr≤80mg/L, ss suspended solid<5mg/L, phenol<0.3mg/L, prussiate<0.3mg/L, percent of decolourization 〉=50% after charcoal absorption is handled.
Reverse osmosis membrane processing technical parameter: filtering accuracy 0.001 μ m; Operating pressure is 2~3.5MPa; 15 minutes pollution index≤4; Add Scale inhibitors 20~30mg/L; Add sterilant 5~10mg/L; Reductive agent 20~30mg/L; Be 65~75% under 25 ℃ of water production rate temperature, the operating pressure 2.5MPa condition; Ratio of desalinization 95~97%; The water-quality guideline of coking chemical waste water water outlet after reverse osmosis membrane separation is handled: CODcr≤30mg/L, phenol≤0.2mg/L, prussiate≤0.2mg/L, NH 3-N≤5mg/L, SS<0.1mg/L, oil<0.1mg/L, PH6.5~7.5, saltiness≤200mg/L, hardness≤15mg/L are (with CaCO 3Meter).
Described reverse osmosis membrane adopts cross flow filter, and operating pressure 2~3.5MPa, filtering accuracy 0.001 μ m, concentrated solution account for and handle 35~25% of the water yield, concentrated solution water quality: CODcr≤310mg/L, saltiness≤44000mg/L.
Described MBR film is the thread film of tubular fibre, and the work period is 2-4 minute, 20-40 second intermittently, and required suction force be-0.01~-0.04MPa, filtering accuracy 0.5 μ m, the mistake water flux is 10~15L/m under 25 ℃, operating pressure 0.15MPa condition 2.hr.
Described medium working temperature is 18~30 ℃.
Compared with prior art, advantage of the present invention is: improved the biochemical sludge concentration and the volumetric loading of biochemical reaction tank, the cancellation coagulating treatment has been saved occupation of land; But the water outlet direct reuse is realized the utilization again of water resources and the zero release of coking chemical waste water in producing clean circulating water system water as a supplement.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
See Fig. 1, coking waste water treatment process, coking chemical waste water priority after pre-treatment and the A/O biochemical treatment coking chemical waste water after MBR Membrane Bioreactor for Wastewater Treatment, O3 contacted oxidation processing, charcoal absorption processing, reverse osmosis membrane processing successively can satisfy the clean circulating water system water quality requirement of production, it is dustproof that a spot of concentrated solution can be sprayed onto the coal yard depositing dust, also can be used as the make up water of wet quenching.
The Aerobic Pond mixed solution of A/O technology enters MBR, and it is the raw water of advanced treatment process that MBR produces the water outlet of water after as biochemical treatment, and the MBR of this technology is the preprocessing means as advanced treatment; MBR belongs to hollow fiber ultrafiltration membrane, the immersion structure, and its efficient crown_interception can all kinds of bacterial classifications of effectively catching, and it is trapped in the bio-reactor fully, make biochemical reaction smooth, effectively remove corresponding pollutent, avoid the loss of mud.The MBR film is the thread film of tubular fibre, and the work period is 2-4 minute, 20-40 second intermittently, and required suction force be-0.01~-0.04MPa, filtering accuracy 0.5 μ m, crossing water flux and be under 25 ℃, operating pressure 0.15MPa condition is 10~15L/m 2.hr.The medium working temperature is 18~30 ℃.The MBR membrane bioreactor produces the water water-quality guideline: CODcr≤120mg/L, NH 3-N≤5mg/L, ss suspended solid<5mg/L, phenol<0.5mg/L, prussiate<0.5mg/L, PH:6.5-7.5.
O3 contacted oxidation is very strong, and the organism in the water is had the intensive oxidative degradation, reduces the COD in the waste water, and decolouring is had certain effect.The effect of ozonize is exactly to protect reverse osmosis membrane assembly, makes its pollution level that reduces the film surface as much as possible, improves the work period and the producing water ratio of film.Waste water is water-quality guideline: CODcr≤100mg/L, ss suspended solid<5mg/L, phenol<0.3mg/L, prussiate<0.3mg/L, percent of decolourization 〉=70% after O3 contacted oxidation is handled.
Activated carbon adsorber is removed and is not consumed or redundant ozone, the COD of being partly dissolved property and certain colourity.Charcoal absorption is played the effect of security personnel's strainer to reverse osmosis membrane assembly.
Coking chemical waste water is water-quality guideline after activated carbon treatment: CODcr≤80mg/L, ss suspended solid<5mg/L, phenol<0.3mg/L, prussiate<0.3mg/L, percent of decolourization 〉=50%.
Reverse osmosis (Reveser Osmosis, be called for short RO) is to be motivating force with pressure, and utilizes the reverse osmosis membrane can only permeate water and can not see through the selectivity of solute and make the technology of solute and water sepn in the aqueous solution.Reverse osmosis membrane assembly produces water can satisfy the clean circulating water system water quality requirement of production, and a spot of concentrated solution can be sprayed onto coal yard, also can be used as the make up water of wet quenching.
The water-quality guideline of coking chemical waste water water outlet after reverse osmosis membrane processing: CODcr≤30mg/L, phenol≤0.2mg/L, prussiate≤0.2mg/L, NH 3-N≤5mg/L, SS<0.1mg/L, oil<0.1mg/L, PH6.5~7.5, saltiness≤200mg/L, hardness≤15mg/L are (with CaCO 3Meter).
The advanced treatment technical parameter is as follows:
(1) the MBR membrane bioreactor has related parameter
1. the working hour is 2~4 minutes, 20~40 seconds intermittent times;
2. operating pressure (suction force)-0.01~-0.04MPa;
3. filtering accuracy 0.5 μ m;
4. cross water flux 10~15L/m 2.hr (25 ℃, operating pressure-0.01MPa condition under).
5. medium temperature is 25~30 ℃
(2) O3 contacted oxidation is handled related parameter
1. every liter of coking chemical waste water of ozone dosage 50~70mg/;
2. 30~60 minutes duration of contact;
3. the pH value 6.5~7.5;
4. percent of decolourization 〉=70%.
(3) activated carbon adsorber has related parameter
1. granulated active carbon particle diameter 1~3mm, length 2~6mm;
2. iodine number 800~1200mg/g;
3. charcoal layer height 3~4.5m;
4. 10~20 minutes duration of contact;
5. hydraulic load 10~20m/h;
6. back washing strength 8~12L/sm 2
7. backwashing time is 5~10 minutes.
(4) the RO reverse osmosis membrane processing has related parameter
1. filtering accuracy 0.001 μ m
2. operating pressure is 2~3.5MPa
3. 15 minutes pollution index≤4
4. add every liter of coking chemical waste water of Scale inhibitors 20~30mg/;
5. add every liter of coking chemical waste water of sterilant 5~10mg/;
6. every liter of coking chemical waste water of reductive agent 20~30mg/;
7. water production rate 65~75% (25 ℃, operating pressure 2.5MPa condition under)
8. ratio of desalinization 95~97%.
In the above-mentioned treating processes, employed Scale inhibitors, sterilant, reductive agent are the medicaments that uses in the coking chemical waste water conventional treatment process.
Example 1:, produce coking chemical waste water 76m for producing 1500000 tons of scale coke-oven plants of coke per year 3/ h, recirculated water sewer 52m 3/ h, it is 128m that accumulative total is handled the water yield 3/ h.Biochemical system adopts A/O internal recycle biological denitrificaion treatment technology, and the MBR water production rate is 128m 3/ h, water quality: CODCr≤120mg/L, NH 3-N≤5mg/L, SS≤5mg/L, phenol≤0.5mg/L, prussiate≤0.5mg/L reach national comprehensive discharge secondary standard.Deliver to O3 contacted oxidation tower and the O that produces from ozonizer through force (forcing) pump then 3Fully contact is finished the oxygenolysis that is difficult to pollutents such as biological degradation COD is handled, and removes through activated carbon adsorber more not to be consumed or redundant ozone, the COD of being partly dissolved property and certain colourity.The activated carbon adsorber water outlet is after reverse osmosis feedwater pump and high-pressure pump series connection pressurization, enter reverse-osmosis membrane element, macromolecule contaminant in the water and being partly dissolved property solids content are separated in the concentrated solution, and reverse osmosis membrane assembly produces the water water-quality guideline and reaches CODCr≤30mg/L, phenol≤0.2mg/L, prussiate≤0.2mg/L, NH 3-N≤5mg/L, oil<0.1mg/L, SS<0.1mg/L, PH6.5~7.5, saltiness≤200mg/L, hardness≤15mg/L (in CaCO3) satisfy " urban sewage reutilization-process water water quality " requirement (GB/T19923-2005) simultaneously.The reverse osmosis unit water production rate (account for handle the water yield~75%) 96m 3/ h is back to and produces clean circulating water system water as a supplement.Isolating concentrated solution (account for handle the water yield~25%) about 32m 3/ h is sprayed onto the coal yard depositing dust or as the make up water of wet quenching.

Claims (8)

1. an advanced treatment process of coking waste water is characterized in that, comprises membrane bioreactor (MBR), O3 contacted oxidation processing, charcoal absorption processing, reverse-osmosis treated.Coking chemical waste water after pre-treatment, the A/O biochemical treatment enters MBR, and MBR produces water and handles through O3 contacted oxidation, after the coking chemical waste water after charcoal absorption and the reverse-osmosis treated can satisfy the clean circulating water system water quality requirement of production.
2. advanced treatment process of coking waste water according to claim 1 is characterized in that, the water-quality guideline of coking chemical waste water after A/O biochemical treatment and MBR Membrane Bioreactor for Wastewater Treatment: CODcr≤120mg/L, NH 3-N≤5mg/L, ss suspended solid<5mg/L, phenol<0.5mg/L, prussiate<0.5mg/L, PH:6.5-7.5.
3. advanced treatment process of coking waste water according to claim 1 is characterized in that, O3 contacted oxidation treating processes technical parameter: ozone dosage 50~70mg/L; 30~60 minutes duration of contact; PH value 6.5~7.5; Percent of decolourization 〉=70%; Coking chemical waste water water-quality guideline after O3 contacted oxidation is handled is CODcr≤100mg/L, ss suspended solid<5mg/L, phenol<0.3mg/L, prussiate<0.3mg/L, percent of decolourization 〉=70%.
4. advanced treatment process of coking waste water according to claim 1 is characterized in that, the activated carbon adsorber technical parameter: granulated active carbon particle diameter 1~3mm, length 2~6mm; Iodine number 800~1200mg/g; Charcoal layer height 3~4.5m; 10~20 minutes duration of contact; Hydraulic load 10~20m/h; Back washing strength 8~12L/sm 2Backwashing time 5~10 minutes; Coking chemical waste water water-quality guideline after charcoal absorption is handled is: CODcr≤80mg/L,, ss suspended solid<5mg/L, phenol<0.3mg/L, prussiate<0.3mg/L, percent of decolourization 〉=50%.
5. advanced treatment process of coking waste water according to claim 1 is characterized in that, the reverse osmosis membrane processing technical parameter: filtering accuracy 0.001 μ m; Operating pressure is 2~3.5MPa; 15 minutes pollution index≤4; Add Scale inhibitors 20~30mg/L; Add sterilant 5~10mg/L; Reductive agent 20~30mg/L; Be 65~75% under 25 ℃ of water production rate temperature, the operating pressure 2.5MPa condition; Ratio of desalinization 95~97%; The water-quality guideline of coking chemical waste water water outlet after reverse osmosis membrane separation is handled: CODcr≤30mg/L, phenol≤0.2mg/L, prussiate≤0.2mg/L, NH 3-N≤5mg/L, SS<0.1mg/L, oil<0.1mg/L, PH6.5~7.5, saltiness≤200mg/L, hardness≤15mg/L are (with CaCO 3Meter).
6. according to claim 1 or 6 described advanced treatment process of coking waste water, it is characterized in that, described reverse osmosis membrane filtration adopts cross flow filter, operating pressure 2~3.5MPa, filtering accuracy 0.001 μ m, concentrated solution accounts for handles 35~25% of the water yield, concentrated solution water quality: CODcr≤310mg/L, saltiness≤44000mg/L.
7. advanced treatment process of coking waste water according to claim 1, it is characterized in that, described MBR film is the thread film of tubular fibre, work period is 2-4 minute, 20-40 second intermittently, required suction force is-0.01~-0.04MPa, filtering accuracy 0.5 μ m, crossing water flux is 10~15L/m under 25 ℃, operating pressure 0.15MPa condition 2.hr.
8. advanced treatment process of coking waste water according to claim 1 is characterized in that: described medium working temperature is 18~30 ℃.
CN 201010117965 2010-03-05 2010-03-05 Advanced treatment process of coking waste water by combining ozone oxidation method and membrane separation technology CN101786767A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102659269A (en) * 2012-04-19 2012-09-12 北京美通科技发展有限公司 Efficient and stable coking wastewater advanced treatment process and treatment system
CN102775010A (en) * 2012-07-19 2012-11-14 太仓东能环保设备有限公司 Domestic sewage treatment device
CN103319048A (en) * 2013-06-29 2013-09-25 惠州市众惠环保工程有限公司 Method for recycling moisture from high-concentration organic sewage
CN103922549A (en) * 2014-05-06 2014-07-16 天脊煤化工集团股份有限公司 Coal gasification wastewater treating and recycling method and device
CN104098202A (en) * 2013-04-03 2014-10-15 中国石油化工股份有限公司 Treatment method for caprolactam biochemical wastewater
CN108928997A (en) * 2018-08-03 2018-12-04 北京赛科康仑环保科技有限公司 A kind of Treatment of Coking Effluent and reuse method

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102659269A (en) * 2012-04-19 2012-09-12 北京美通科技发展有限公司 Efficient and stable coking wastewater advanced treatment process and treatment system
CN102775010A (en) * 2012-07-19 2012-11-14 太仓东能环保设备有限公司 Domestic sewage treatment device
CN104098202A (en) * 2013-04-03 2014-10-15 中国石油化工股份有限公司 Treatment method for caprolactam biochemical wastewater
CN103319048A (en) * 2013-06-29 2013-09-25 惠州市众惠环保工程有限公司 Method for recycling moisture from high-concentration organic sewage
CN103922549A (en) * 2014-05-06 2014-07-16 天脊煤化工集团股份有限公司 Coal gasification wastewater treating and recycling method and device
CN103922549B (en) * 2014-05-06 2015-12-02 天脊煤化工集团股份有限公司 A kind of coal gasification waste water treatment and reuse method and device thereof
CN108928997A (en) * 2018-08-03 2018-12-04 北京赛科康仑环保科技有限公司 A kind of Treatment of Coking Effluent and reuse method

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Application publication date: 20100728