CN106430801A - Method for treating coking wastewater - Google Patents

Method for treating coking wastewater Download PDF

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Publication number
CN106430801A
CN106430801A CN201510493001.9A CN201510493001A CN106430801A CN 106430801 A CN106430801 A CN 106430801A CN 201510493001 A CN201510493001 A CN 201510493001A CN 106430801 A CN106430801 A CN 106430801A
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coking
wastewater
treatment
enzyme
water
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CN106430801B (en
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陶军
王君婷
刘畅
沈振华
周超
裘慕贤
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Baowu Carbon Technology Co ltd
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Shanghai Baosteel Chemical Co Ltd
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Abstract

The invention provides a method for treating coking wastewater, which comprises the following steps: the coking wastewater enters an anoxic tank for denitrification reaction, the coking wastewater is stirred uniformly to mix water quality and prevent activated sludge from depositing, the pH value of the coking wastewater is adjusted to be 7.5-8.5, and compound common biological enzyme is added into the anoxic tank; the effluent of the anoxic tank enters an aerobic tank for nitration reaction, and the aerobic tank is added with compound common biological enzyme and special enzyme; the effluent of the aerobic tank is delivered by 2 paths through a sludge reflux pump: one path returns to the anoxic section to further remove T-N, and the other path is led into a membrane separation tank; the mixed liquid is subjected to solid-liquid separation by a water producing pump in a suction filtration mode, activated sludge is retained in a biochemical system, and the subsequent process of filtered effluent enables the effluent to reach the standard and be discharged outside. The invention can degrade the COD of the effluent to below 70mg/l, degrade the T-CN to below 0.5mg/l, reduce the turbidity to below 1NTU, and achieve the direct discharge standard of the discharge Standard of pollutants for coking chemical industry (GB16171-2012) through subsequent simple materialization.

Description

A kind of method of Treatment of Wastewater in Coking
Technical field
The invention belongs to water-treatment technology field, more particularly to new, the efficient Treatment of Wastewater in Coking method of one kind.
Background technology
Coking chemical waste water is the waste water that coal is formed in high temperature and medium temperature carbonization, gas purification and chemical productss subtractive process, wherein Inorganic containing the organic pollutions such as phenols, benzene homologues, polycyclic aromatic hydrocarbon, nitrogen-containing heterocycle compound and ammonia, cyanogen, rhodanides etc. Pollutant, complicated component, constituent species are various, and organic pollution concentration and Colority of Sewage Water height, toxicity are big, and property is highly stable, It is a kind of typical difficult degradation complexity toxic industrial organic wastewater.Intractability for meeting qualified discharge is big, relatively costly, such as Deal with improperly, National Water Environmental will be caused with great harm.
Most domestic enterprise execution steel industry discharge standard GB13456-92 (containing coking industry) at present.In October, 2012 1, country promulgated《Coking chemistry emission of industrial pollutants standard》(GB16171-2012), hereinafter referred to as new standard.Newly Standard is more strict on Pollutant emission concentration and monitoring range, to float, COD, ammonia nitrogen, petroleum-type and cyanide Emission request is obviously improved, and increased the emission request of BOD5, T-N, benzene and polycyclic aromatic hydrocarbon;Meanwhile, new standard also accordingly carries Rise ton product water consume to require.For the water process present situation of domestic coking industry, the strict law enforcement of this standard will be to coking industry Huge challenge.Substantially domestic all apparatus for treating carbonized waste waters all must carry out upgrading, is only possible to meet emission request; The management level for the treatment of facility also must be lifted further simultaneously.
And Technologies of Coke Plant Wastewater Treatment ripe at present needs to pay the fortune of costliness to stably reach the up-to-date discharge standard of country Row cost, most domestic coal chemical enterprise cannot bear, and therefore development life cycle cost is lower, the less coking of environmental risk Waste Water Treatment and the research of specific technique, significant to realize Sustainable Development of Enterprises and raising synthesized competitiveness.
Membrane bioreactor (MBR) is the novel state Waste Water Treatment of membrane separation technique and biologic treating technique combination. Traditional biological treatment technology end second pond is replaced with membrane module, in bioreactor, keeps high activity sludge concentration, improve life Thing processes organic loading, thus reducing sewage treatment facility floor space, and reduces surplus sludge volume by keeping low sludge loading, Thus reducing the investment of waste water disposal facility and the purpose of operation cost.But it is applied to Treatment of Coking Effluent field and still deposits Water outlet COD higher it is impossible to directly discharge;Membrane module is easily dirty stifled, increases the problem of operation cost.
Enzyme is a kind of protein with catalysiss.It has specificity, efficiency compared with general chemical catalyst High gentle with reaction condition the advantages of.There is number with the enzyme of hundred million note species in nature, different enzymes can be catalyzed single substrate and occur Specified chemical is reacted.The water quality characteristic of coking chemical waste water determines the flora species sum that coking chemical waste water biochemical system can be enriched with Amount, a part of flora therein is had the advantage status, and diazine of can degrading, pyridine, quinoline, indole, naphthalene, uh, Phenanthrene etc. is multi-ring and microorganism of heteroaromatic organic compound is then in the status of weak tendency relatively.We are by coking chemical waste water Component and property are analyzed, and search out these multi-ring and heteroaromatic material enzyme of can specifically degrading, are added To in biochemical treatment system, develop this part weak tendency flora, to improve the activity of this part flora and to be enriched with more quantity, make It progressively becomes dominant bacteria.The increase of the raising of bacterial activity and quantity means that process load, the raising for the treatment of effeciency, Originally it was difficult to biodegradable part Organic substance and also obtained different degrees of degraded because of the raising of bacterial activity, made water outlet COD is greatly reduced.Simultaneously by adding the enzyme of salt resistance, anti-cyaniding species, strengthen biochemical system microorganism Poison resistance and impact resistance, improve system stability.
Content of the invention
In order to solve the above problems, the invention provides a kind of method of Treatment of Wastewater in Coking.
Technical scheme is as follows:
A kind of method of Treatment of Wastewater in Coking is it is characterised in that comprise the steps:
(1) coking chemical waste water entrance anoxia groove carries out anti-nitration reaction, is uniformly mixed merely by stirring water quality and prevents activated sludge from sinking Long-pending, add compound common enzyme into described anoxia groove, adjust coking chemical waste water pH 7.5~8.5, temperature control 25~ 35 DEG C, DO controls in below 0.5mg/l, and reaction time is 16~25 hours;
(2) described anoxia groove water outlet carries out nitration reaction by overflow entrance aerobic slot, adds compound ordinary student in aerobic slot Thing enzyme and specific enzymes, adjust nitrification pH 6.5~7.5, at 25~35 DEG C, return current ratio of the mixed liquid controls 1 temperature control: 1~5 times of raw water amount, DO controls in 3~5mg/l, and MLSS controls in 4000~6000mg/l, and reaction time is 40~55 Hour;
(3) aerobic slot water outlet divides 2 tunnel conveyings by sludge reflux pump:Anoxia section is returned to remove further to T-N in one tunnel, separately One tunnel imports membrance separation groove;
(4) wastewater pH in membrance separation groove is maintained at 6.5~7.5, temperature control at 25~35 DEG C, DO controls 3~ 5mg/l, MLSS control in 6000~10000mg/l, and reaction time is 10~25 hours;
(5) by producing water pump to make mixed liquor solid-liquid separation by way of being filtered by suction, activated sludge is trapped in biochemical system, After filtration, water outlet subsequently can connect materialization or Advanced Oxidation Technics in Dealing makes water outlet standard discharge or enters depth reclaiming system further deeply Change is processed.
According to a kind of method of Treatment of Wastewater in Coking of the present invention it is preferred that institute in anoxia groove in described step (1) State compound common enzyme and include Digestive Enzyme, cellulase, hemicellulase, amylase and cyanogen hydrase.
Further, in described step (1), the dosage of compound common enzyme is 0.1g~0.2g/ ton water.
According to a kind of method of Treatment of Wastewater in Coking of the present invention it is preferred that compound common described in step (2) Enzyme includes Digestive Enzyme, cellulase, hemicellulase, amylase and cyanogen hydrase, and described specific enzymes are naphthaline dioxygenase.
Further, the dosage of the compound common enzyme in described step (2) is 0.2g~0.4g/ ton water, specific enzymes Dosage be 0.1g~0.3g/ ton water.
According to a kind of method of Treatment of Wastewater in Coking of the present invention it is preferred that throwing in aerobic slot in described step (2) Plus fluidized bed type floating stuffing as carrier to adhere to aerobic enzyme and activated sludge.
According to a kind of method of Treatment of Wastewater in Coking of the present invention it is preferred that described fluidized bed type floating stuffing material is poly- Ethylene, specific surface area is 300~1000/m3, the ratio that adds is for the 10%~20% of aerobic slot volume.
According to a kind of method of Treatment of Wastewater in Coking of the present invention it is preferred that the regulation of described pH is by adding NaOH One of solution, KOH solution or ammonia spirit.
Further, the regulation of described pH is by adding NaOH solution.
According to a kind of method of Treatment of Wastewater in Coking of the present invention it is preferred that membrance separation groove in described step (4) In the form of built-in organic Flat Membrane, PVDF material, membrane aperture is 0.04~0.1 μm,.
According to a kind of method of Treatment of Wastewater in Coking of the present invention it is preferred that in membrance separation groove in described step (4) Membranous system adopt intermittent filtration drive manner:Produce water pump setting and often take out 1~2min out of service after every suction 8~10min, with this Continuously run as a cycle circulation.
Further, produce water pump setting and often take out 1min out of service after every suction 9min, continuously run in this, as a cycle circulation.
Detailed Description Of The Invention:
The present invention is directed to ingredient properties and the difficulty in treatment of coking chemical waste water, creatively by related the answering of difficult for coking chemical waste water component Close enzyme interpolation membrane separation technique to replace in the AO+MBR system of conventional biochemical sedimentation tank, increased the efficiency of biochemical reaction, Enhancement microbiological effect and impact resistance are persistently reduced so that reducing water outlet COD with total cyanogen index;When enzyme Establishing Afterwards, micelle bacterium takes advantage, and deliquescent oil is effectively degraded, and activated sludge viscosity reduces, and reduces the dirty stifled possibility of film Property, remain the advantage that membrane separation technique system sludge output is low, operating cost is low, effluent quality good, floor space is little simultaneously, But also reduce the loss of enzyme using the characteristic that film has crown_interception to larger molecular organicses, improve making of enzyme With efficiency, reduce it and run use cost.The present invention has farthest played the complementary action of MBR and biological enzyme technology, is Inexpensive comprehensive treatment technique for Treatment of Coking Effluent exploitation.
The device that the present invention adopts includes anoxia groove, aerobic slot, sludge reflux pump, membrance separation groove, membrane module, produces water pump.Should Processing system carrying out practically step is as follows:
(1) adjustment tank waste water is pumped into anoxia groove by water delivery and carries out anti-nitration reaction.Played by stirrer paddle in anoxia groove Uniformly mixing water quality and the effect preventing activated sludge deposition, PH is maintained at 7.5~8.5, temperature control at 25~35 DEG C, DO controls in below 0.5mg/l, and reaction time is 16~25 hours.
(2) water outlet of anoxia groove carries out nitration reaction by overflow entrance aerobic slot.Adjust nitrification PH to 6.5~7.5, At 25~35 DEG C, return current ratio of the mixed liquid controls 1 temperature control:1~5 times of raw water amount, DO (dissolved oxygen) controls in 3~5mg/l, MLSS (sludge concentration) controls in 4000~6000mg/l, and reaction time is 40~55 hours.
(3) aerobic slot water outlet divides 2 tunnel conveyings by sludge reflux pump:Anoxia section is returned to remove further to T-N in one tunnel, separately One tunnel imports membrance separation groove.
(4) membrance separation groove PH is maintained at 6.5~7.5, and at 25~35 DEG C, DO controls in 3~5mg/l temperature control, MLSS Control in 6000~10000mg/l, reaction time is 10~25 hours.
(5) by producing water pump to make mixed liquor solid-liquid separation by way of being filtered by suction, activated sludge is trapped in biochemical system, After filtration, water outlet subsequently can connect materialization or Advanced Oxidation Technics in Dealing makes water outlet standard discharge or enters depth reclaiming system further deeply Change is processed.
Compound common enzyme is added (including Digestive Enzyme, cellulase, half fibre in anoxia groove in described step (1) The plain enzyme of dimension, amylase, cyanogen hydrase), wherein dosage is 0.1g~0.2g/ ton water.
Compound common enzyme is added (including Digestive Enzyme, cellulase, half fibre in aerobic slot in described step (2) The plain enzyme of dimension, amylase, cyanogen hydrase) with specific enzymes-naphthaline dioxygenase, wherein compound common enzyme dosage be 0.2g~ 0.4g/ ton water, specific enzymes dosage is 0.1g~0.3g/ ton water.
Fluidized bed type floating stuffing is added dirty to adhere to aerobic enzyme and activity as carrier in described step (2) aerobic slot Mud, material is polyethylene, and specific surface area is 300~1000m2/m3, the ratio that adds is for the 10%~20% of aerobic slot volume.
Described step (4) membrance separation groove in the form of built-in organic Flat Membrane, PVDF material, membrane aperture be 0.04~0.1 μm.Membranous system adopts intermittent filtration drive manner:Produce water pump setting and often take out 1min out of service after every suction 9min, made with this Continuously run for a cycle circulation.Aeration when not aspirating can realize effective face cleaning effect.
The diaphragm of described Flat Membrane is attached to the both sides of ABS gripper shoe, and diaphragm is filter layer and the PET having polrvinyl chloride material The composite construction that the supporting layer of non-woven fabrics material is formed.Diaphragm has (0.8 μm) of the small-bore distribution of concentration.Monolithic membrane element The area of part is 1.4, membrane component quantity totally 50, and total filter area is 70.(structural representation Fig. 2) flat membrane component Structure includes film, gripper shoe, water producing pipe ozzle etc..
Described biochemical system refers to the waste water treatment process being formed by anoxia+aerobic combination, and in anoxia groove, heterotrophic bacteria is by waste water In suspended contaminant and dissolved organic matter be hydrolyzed to organic acid, make larger molecular organicses be decomposed into small organic molecule, insoluble Property Organic substance change into dissolved organic matter, when these through anaerobic hydrolysis products enter aerobic slots carry out Aerobic Process for Treatment when, can Improve the biodegradability of sewage and the efficiency of oxygen;In anoxia section, the pollutant such as protein, fat are carried out ammonification by heterotrophic bacteria (to be had N on chain or the amino in aminoacid) ammonia that dissociates (NH3, NH4+), under sufficient oxygen supply condition, autotrophic bacteria NH3-N (NH4+) is oxidized to NO3- by Nitrification, and the control by flowing back is back to anoxic pond, under anoxic conditions, NO3- is reduced to molecular nitrogen (N2) and completes C, N, O circulation in ecology by the Denitrification of heterotrophic bacteria, realizes Sewage harmless treatment.
The Advantageous Effects of a kind of method of Treatment of Wastewater in Coking that the present invention provides:
(1) original biochemical system floor space is big, biochemical treatment needed for structures can be greatly decreased with treatment technology of the present invention Use floor space and cost of investment to reduce.
(2) original AO PROCESS FOR TREATMENT water outlet COD is in 250~350mg/l, T-CN in 4~5mg/l, this Bright technology can be by water outlet COD degradation to below 80mg/l, and T-CN is degraded to below 0.5mg/l, turbidity drop to 1NTU with Under, subsequently simple materialization just can reach《Coking chemistry emission of industrial pollutants standard》(GB16171-2012) direct discharge standard.
(3) present invention membrane module is greatly reduced simultaneously, enzyme add and follow-up materializing strategy operating cost, technical office Managing operating cost is<7 yuan/ton of water, more original AO technique has higher economic benefit.
Brief description
A kind of flow chart of efficient process coking chemical waste water method that Fig. 1 provides for the present invention.
The structure chart of the flat membrane component that Fig. 2 applies for the present invention.
Wherein:1- anoxia groove, 2- aeration tank (aerobic slot), 3- membrance separation groove, 4- agitator, 5- film, 6- gripper shoe, 7- Water producing pipe ozzle.
Specific embodiment
For a better understanding of the present invention, it is further elucidated with present disclosure with reference to embodiment, but present disclosure is not It is limited only to the following examples.Compound common enzyme that the present invention is applied and specific enzymes are commercial.
Embodiment 1
A kind of method of Treatment of Wastewater in Coking that the present invention provides:
Certain coking wastewater of iron and steel plant is taken to be processed:
Anoxia groove pH is maintained at 7.5~8.5, and at 25~35 DEG C, DO controls in below 0.5mg/l temperature control, and reaction stops Time is 18 hours;Wherein enzyme adds total amount is 0.1g/ ton water,
Aerobic slot pH controls 6.5~7.5, and at 25~35 DEG C, return current ratio of the mixed liquid is 1 to temperature control:3 times of raw water amounts, DO controls in 3~5mg/l, and MLSS controls in 6000mg/l, and floating stuffing adds 20% that ratio is aerobic slot volume; Reaction time is 46 hours;It is that (described common enzyme dosage is 0.2g/ to 0.3g/ ton water that described enzyme adds total amount Ton water, specific enzymes dosage is 0.1g/ ton water .),
The membranous system of described membrance separation groove adopts organic Flat Membrane PVDF material, and membrane aperture is 0.04~0.1 μm, and pH keeps 6.5~7.5, at 25~35 DEG C, DO controls in 3~5mg/l temperature control, and reaction time is 16 hours;
Before and after wastewater treatment, water quality data sees below form, and after process, the important indicator such as CODcr, total nitrogen, ammonia nitrogen all reaches coking The direct discharge standard of chemical industrial pollution thing discharge standard (GB16171-2012) table 2.
Project Before processing After process
CODcr ≤2000mg/l ≤70mg/l
Cyanide ≤30mg/l ≤0.5mg/l
Total nitrogen ≤500mg/l ≤20mg/l
Ammonia nitrogen ≤300mg/l ≤10mg/l
pH 6~9 6~9
Embodiment 2
A kind of method of Treatment of Wastewater in Coking that the present invention provides:
Certain coke-oven plant's coking chemical waste water is taken to be processed:
Anoxia groove pH is maintained at 7.5~8.5, and at 25~35 DEG C, DO controls in below 0.5mg/l temperature control, and reaction stops Time is 21 hours;Wherein enzyme adds total amount is 0.2g/ ton water,
Aerobic slot pH controls 6.5~7.5, and at 25~35 DEG C, return current ratio of the mixed liquid is 1 to temperature control:4 times of raw water amounts, DO controls in 3~5mg/l, and MLSS controls in 7000mg/l, and floating stuffing adds 20% that ratio is aerobic slot volume; Reaction time is 52 hours;It is that (described common enzyme dosage is 0.3g/ to 0.5g/ ton water that described enzyme adds total amount Ton water, specific enzymes dosage is 0.2g/ ton water .),
The membranous system of described membrance separation groove adopts organic Flat Membrane PVDF material, and membrane aperture is 0.04~0.1 μm, and pH keeps 6.5~7.5, at 25~35 DEG C, DO controls in 3~5mg/l temperature control, and reaction time is 21 hours;
Before and after wastewater treatment, water quality data sees below form, and after process, the important indicator such as CODcr, total nitrogen, ammonia nitrogen all reaches coking The direct discharge standard of chemical industrial pollution thing discharge standard (GB16171-2012) table 2.
Project Before processing After process
CODcr ≤5000mg/l ≤70mg/l
Cyanide ≤50mg/l ≤0.5mg/l
Total nitrogen ≤800mg/l ≤20mg/l
Ammonia nitrogen ≤500mg/l ≤10mg/l
pH 6~9 6~9
Certainly, those skilled in the art in the art it should be appreciated that above-described embodiment be intended merely to illustrate the present invention, and Non- as limitation of the invention, as long as in the spirit of the present invention, to the conversion of above-described embodiment, deformation all incite somebody to action Fall within the scope of the claims.

Claims (10)

1. a kind of method of Treatment of Wastewater in Coking is it is characterised in that comprise the steps:
(1) coking chemical waste water entrance anoxia groove carries out anti-nitration reaction, is uniformly mixed merely by stirring water quality and prevents activated sludge from sinking Long-pending, add compound common enzyme into described anoxia groove, adjust coking chemical waste water pH 7.5~8.5, temperature control 25~ 35 DEG C, DO controls in below 0.5mg/l, and reaction time is 16~25 hours;
(2) described anoxia groove water outlet carries out nitration reaction by overflow entrance aerobic slot, adds compound ordinary student in aerobic slot Thing enzyme and specific enzymes, adjust nitrification pH 6.5~7.5, at 25~35 DEG C, return current ratio of the mixed liquid controls 1 temperature control: 1~5 times of raw water amount, DO controls in 3~5mg/l, and MLSS controls in 4000~6000mg/l, and reaction time is 40~55 Hour;
(3) aerobic slot water outlet divides 2 tunnel conveyings by sludge reflux pump:Anoxia section is returned to remove further to T-N in one tunnel, separately One tunnel imports membrance separation groove;
(4) wastewater pH in membrance separation groove is maintained at 6.5~7.5, temperature control at 25~35 DEG C, DO controls 3~ 5mg/l, MLSS control in 6000~10000mg/l, and reaction time is 10~25 hours;
(5) by producing water pump to make mixed liquor solid-liquid separation by way of being filtered by suction, activated sludge is trapped in biochemical system, After filtration, water outlet subsequently can connect materialization or Advanced Oxidation Technics in Dealing makes water outlet standard discharge or enters depth reclaiming system further deeply Change is processed.
2. according to claim 1 a kind of method of Treatment of Wastewater in Coking it is characterised in that in described step (1) lack In oxygen groove, described compound common enzyme includes Digestive Enzyme, cellulase, hemicellulase, amylase and cyanogen hydrase.
3. a kind of method of Treatment of Wastewater in Coking according to claim 1 or claim 2 is it is characterised in that in described step (1) In compound common enzyme dosage be 0.1g~0.2g/ ton water.
4. according to claim 1 a kind of method of Treatment of Wastewater in Coking it is characterised in that multiple described in step (2) The common enzyme of mould assembly includes Digestive Enzyme, cellulase, hemicellulase, amylase and cyanogen hydrase, and described specific enzymes are naphthalene Dioxygenase.
5. according to claim 1 or 4 a kind of method of Treatment of Wastewater in Coking it is characterised in that in described step (2) In the dosage of compound common enzyme be 0.2g~0.4g/ ton water, the dosage of specific enzymes is 0.1g~0.3g/ ton water.
6. according to claim 1 a kind of method of Treatment of Wastewater in Coking it is characterised in that good in described step (2) Fluidized bed type floating stuffing is added as carrier to adhere to aerobic enzyme and activated sludge in oxygen groove.
7. according to claim 6 a kind of method of Treatment of Wastewater in Coking it is characterised in that described fluidized bed type suspend fill out Material material is polyethylene, and specific surface area is 300~1000/m3, the ratio that adds is for the 10%~20% of aerobic slot volume.
8. according to claim 1 a kind of method of Treatment of Wastewater in Coking it is characterised in that described pH regulation lead to Cross and add one of NaOH solution, KOH solution or ammonia spirit.
9. according to claim 1 a kind of method of Treatment of Wastewater in Coking it is characterised in that in described step (4) Membrance separation groove in the form of built-in organic Flat Membrane, PVDF material, membrane aperture be 0.04~0.1 μm,.
10. according to claim 1 a kind of method of Treatment of Wastewater in Coking it is characterised in that in described step (4) Adopt intermittent filtration drive manner in the membranous system of membrance separation groove:Produce water pump set often take out out of service after every suction 8~10min 1~2min, continuously runs in this, as a cycle circulation.
CN201510493001.9A 2015-08-12 2015-08-12 Method for treating coking wastewater Active CN106430801B (en)

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Patentee before: BAOWU CARBON MATERIAL TECHNOLOGY Co.,Ltd.

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