CN104926030A - Semi coke sewage disposal and regeneration recycle method - Google Patents

Semi coke sewage disposal and regeneration recycle method Download PDF

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Publication number
CN104926030A
CN104926030A CN201510277196.3A CN201510277196A CN104926030A CN 104926030 A CN104926030 A CN 104926030A CN 201510277196 A CN201510277196 A CN 201510277196A CN 104926030 A CN104926030 A CN 104926030A
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China
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waste water
blue charcoal
membrane
treatment
cod
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CN201510277196.3A
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Chinese (zh)
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张世文
王峰
殷明彩
林菁
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波鹰(厦门)科技有限公司
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Priority to CN201510277196.3A priority Critical patent/CN104926030A/en
Publication of CN104926030A publication Critical patent/CN104926030A/en

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Abstract

A semi coke sewage disposal and regeneration recycle method comprises the following steps: (1) coarse filtering; (2) membrane filtering; (3) detarring; (4) dephenolizing; (5) deaminizing and denitriding; (6) desulfurizing; (7) anaerobic treatment; (8) aerobic treatment; (9) electrolyzing; (10) secondary anaerobic treatment; (11) membrane disposal or biological aerated filter biochemistry; (12) desalting. Deep disposal of semi coke sewage is performed by a combined disposal process of processes of membrane filtering, detarring, dephenolizing, deaminizing and denitriding, anaerobic treatment, aerobic treatment, electrolyzing, desalting and the like, recycle of resources of coal coke, phenol and ammonia is realized, and disposal cost of the semi coke sewage is greatly reduced.

Description

Blue charcoal wastewater treatment and cyclic utilization method
Technical field
The invention belongs to the field for the treatment of of water pollution of environmental engineering, more specifically refer to a kind of blue charcoal wastewater treatment and cyclic utilization method.
Background technology
Blue charcoal is also known as semicoke, and the important source material that coke powder is iron alloy, gas maked coal, Coal Chemical Industry are produced is that raw coal obtains through low-temperature pyrolysis (about 650 DEG C).Blue charcoal is produced, gas purification process can produce waste water, is referred to as blue charcoal waste water, is a kind of complicated component, Pollutant levels are high, stable in properties, biodegradability are poor, the great trade effluent of intractability.Inorganic pollutant in blue charcoal waste water mainly contains sulfide, prussiate, ammonia nitrogen and thiocyanide etc.; Organic pollutant is based on coal tar oily substance, and the content of phenolic compound is very high, in addition, and the aromatics also containing many rings and nitrogenous, sulphur, oxygen heterogeneous ring compound etc.Blue charcoal waste water is completely different from coking chemical waste water, contrasts in the blue charcoal waste water of table 1 and coking chemical waste water principal pollutant index.Contrast from table 1 and table 2, blue charcoal waste water principal pollutant index is ten times of coking chemical waste water.Therefore, although the treatment process of coking chemical waste water is many, its treatment process is not suitable for blue charcoal waste water.At present, the process of blue charcoal waste water does not also have ripe method, and its treatment process and its main component fully utilize very urgent.He Bin, Wang Yae " Guangxi Chemical Industry " the 36th volume the 12nd phase report the research that ammonia still process-dephenolize-SBR processes blue charcoal waste water; Yang Yipu etc. " environmental engineering journal " the 8th volume the tenth second phase describe the effect of blue charcoal Phenol for Waste Water class extracting substances and recovery, but all just solve the problem of blue certain angle of charcoal waste water.Although the current method about blue charcoal wastewater treatment is reported for work much, also improve at present and the ripe and blue charcoal method of wastewater treatment of practicality.
The blue charcoal waste water of table 1 and coking chemical waste water principal pollutant index
Sequence number Principal pollutant Blue charcoal waste water Coking chemical waste water
1 COD (mg/L) 10000~75000 3500~5000
2 BOD (mg/L) 3000~5000 1170~2000
3 pH 8~10 8~9
4 Tar (mg/L) 5000~40000 100~200
5 Ammonia nitrogen (mg/L) 500~5000 200~400
6 Total phenol (mg/L) 1000~6000 600~800
7 Colourity (doubly) 10000~30000 1000~1500
The water quality characteristics of blue charcoal waste water determines the hazardness of its complexity.Such as, wherein there is grave danger to ecotope in contained ammonia nitrogen, phenolic compound and aromatics.In addition, the industry byproduct such as coal tar, ammonia, phenol in blue charcoal waste water also has the value of recycling.
Summary of the invention
The invention provides a kind of blue charcoal wastewater treatment and cyclic utilization method, its main purpose is to overcome the shortcomings such as the inadequate technical deficiency of the existing blue charcoal wastewater treatment degree of depth.
The present invention adopts following technical scheme:
A kind of blue charcoal wastewater treatment recycling utilization device and method, comprises the following steps:
(1) coarse filtration: be 10000 ~ 75000mg/L by COD, ammonia nitrogen be 500 ~ 5000mg/L, total phenol is 1000 ~ 6000mg/L, colourity is 10000 ~ 30000 times, pH value be 8 ~ 10 blue charcoal waste water carry out coarse filtration through grid or screen cloth, removing macrobead foreign material;
(2) membrane filtration: the blue charcoal waste water of the removing macrobead thing through coarse filtration is added acid for adjusting pH to 2 ~ 6, then the concentrated solution of coal tar and the dialyzate of removing coal tar must be rich in through membrane filtration, cycles of concentration is 3 ~ 10;
(3) detar: the concentrated solution that step (2) must be rich in coal tar through membrane filtration obtains the blue charcoal waste water of detar through gravity settling separation or centrifugation, and the clearance of its COD is 30 ~ 55%;
(4) dephenolize: the blue charcoal waste water after the dialyzate of step (2) membrane filtration gained and the de-coal tar of step (3) is mixed, add extraction agent extracting and separating and obtain the blue charcoal waste water of dephenolize, the clearance of its COD is 35 ~ 70%;
(5) ammonia nitrogen removal: the blue charcoal waste water of step (4) dephenolize gained is added alkaline solution and regulates its pH to 9 ~ 11, heating evaporation removing ammonia, ammonia absorbs through persulfate solution to be produced ammonium sulfate or obtains liquefied ammonia and the blue charcoal waste water of deamination through cooling liquid;
(6) desulfurization: add sweetening agent toward the blue charcoal waste water of the deamination after step (5) ammonia nitrogen removal, as ferrous sulfate, generate iron sulfide precipitates and the blue charcoal waste water of desulfurization, the clearance of its COD is 10 ~ 20%, prevents sulfide to the murder by poisoning of biochemistry, improves its biochemical effects;
(7) anaerobic treatment: blue for the desulfurization of step (6) desulfurization gained charcoal waste water is added alkaline solution and regulates its pH to 6 ~ 9, anaerobic pond is entered through lift pump, anerobe, the absorption of oxygen bacterium of holding concurrently, fermentation, methane phase acting in conjunction in anaerobic pond, organic acid is resolved into methane and carbon dioxide, improved B/C value and the removing most COD of waste water by anaerobic treatment, improve the biodegradability of waste water;
(8) aerobic treatment: charcoal waste water blue after step (7) anaerobic treatment is entered Aerobic Pond and intermediate sedimentation pond through lift pump, and the partial sludge in intermediate sedimentation pond is back to Aerobic Pond by reflux pump, by the organism in the blue charcoal waste water of the further oxygenolysis of aerobic treatment, the degree of depth removes COD and BOD; Evenly fill up a large amount of biological suspended packings in Aerobic Pond, perch for aerobic microbiological provides, the place of growth and breeding so that microorganism forms microbial film at filling surface; Aeration aerating stirring system is provided with bottom Aerobic Pond, oxygenation is carried out to sewage, the dissolved oxygen in water is made to maintain 2 ~ 4 mg/L, utilize the effect that gas rises simultaneously, suspended substance in pond is more fully contacted with water, additionally by the agitaion of gas and clear water back flushing, can effectively wash away the aging microbial film of filling surface growth, impel biomembranous update, make the activity that microbial film remains higher;
(9) electrolysis: charcoal waste water blue after step (8) aerobic treatment is entered electrolysis machine and carries out electrolysis, to remove colourity, smelly, make the difficulty biochemical macromolecular cpd open loop chain rupture in waste water simultaneously, become can be biochemical small molecules, further raising B/C value, improves the condition of subsequent biochemical process; The adjacent two interelectrode voltages of electrolysis machine are 2 ~ 12V, and current density is 10 ~ 320mA/cm 2;
(10) secondary anaerobic treatment: the blue charcoal waste water of step (9) electrolysis gained is entered secondary anaerobic pond through lift pump, anerobe, the absorption of oxygen bacterium of holding concurrently, fermentation, methane phase acting in conjunction in anaerobic pond, organic acid is resolved into methane and carbon dioxide, improve the B/C value of waste water by anaerobic treatment and remove most COD further, improving the biodegradability of waste water;
(11) MBR process or BAF biochemistry (BAF is biochemical)
Blue charcoal waste water after step (10) secondary anaerobic treatment enters MBR treatment unit or BAF, is purified, remove COD, SS and ammonia nitrogen further, be purified waste water by the filtering separation of membrane treatment appts or oxidation degradation effect to waste water;
(12) desalination: the waste water after step (11) MBR process or BAF biochemistry (BAF is biochemical) enters desalting plant, be separated to obtain water-dialyzing and condensed water, water-dialyzing enters reuse water basin, and condensed water then enters evaporative crystallization pond through discharge channel discharge and carries out crystallization treatment; Described desalting plant can be the one of reverse osmosis system, nanofiltration system.
Step (2) described membrane filtration is the one of ceramic membrane filter or metal membrane filter; The ceramic membrane element aperture of ceramic membrane filter system is 20 ~ 100nm; The metallic membrane element aperture of metal membrane filter system is 30 ~ 100nm; Operating pressure is 3 ~ 6bar, and temperature is 15 ~ 55 DEG C.By the membrane concentration tar of step (2) all in concentrated solution, the clearance of the COD of dialyzate about 5000 ~ 34000mg/L, COD reaches 30 ~ 55%.
The concentrated solution being rich in coal tar through membrane filtration described in step (2) membrane filtration pumps in whizzer, is the blue charcoal waste water of coal tar and decoking through centrifugation; The centrifugal force of centrifugation is 2200 ~ 4000.
Gravity settling separation described in step (3) detar is that the concentrated solution being rich in coal tar through membrane filtration is put into gravity settling basin, is the blue charcoal waste water of coal tar and decoking through gravity settling separation.
Step (3) detar process not only achieves the recycling of coal tar in blue charcoal waste water, and the COD of waste water is reduced by 30 ~ 55%, significantly reduces colourity, ensures the carrying out of subsequent production technique.
Detar described in step (3) adds acid to regulate its pH to 2 ~ 5, and its acid used is the one of sulfuric acid, hydrochloric acid or nitric acid; The best is sulfuric acid, and consumption is 5 ~ 7kg/m 3.
Extraction described in step (4) dephenolize extraction agent used is kerosene, N, N ,-dimethyl-g yl acetamide (N, N ,-503), the one of tributyl phosphate or crude benzol or its mixture;
Extraction described in step (4) dephenolize optimum extractant used is the N of 20-30%, N ,-dimethyl-g yl acetamide (N, N ,-503) with the mixture of kerosene.
Extraction described in step (4) dephenolize optimum extractant used is the tributyl phosphate of 20-33% and the mixture of kerosene.
Extraction described in step (4) dephenolize extraction agent used is 1:5 with ratio the best of blue charcoal waste water, i.e. every cube of Milan charcoal waste water extraction agent 200L.
The electrolysis machine of step (9) electrolysis is provided with power supply and electrolyzer, and the electrode materials in described electrolyzer is the one in graphite, titanium, iron, aluminium, zinc, copper, lead, nickel, molybdenum, chromium, alloy and nano-catalytic inert material.
The membrane module of the described MBR device described in step (11) is selected from the one in Pvdf Microporous Hollow Fiber Membrane, polypropylene hollow fiber membrane, ps hollow fiber uf membrane, polyethersulfone, polyacrylonitrile and PVC hollow fiber membrane, membrane pore size is 0.10 ~ 0.2 μm, operating pressure is-1 ~-50kPa, and working temperature is 5 ~ 45 DEG C;
The reverse osmosis membrane assembly of the reverse osmosis system described in step (12) desalination is rolled membrane module, mould material is cellulose acetate film or composite membrane in organic membrane, the molecular weight cut-off of mould material is 50 ~ 200MWCO, and entrance pressure can be 6.0 ~ 45.0bar, goes out pressure and can be 4.5 ~ 33.5 bar.
Nanofiltration membrane component in nanofiltration system described in step (12) desalination is the one of tubular membrane component, rolled membrane module or plate film assembly, and operating pressure is 6 ~ 45bar, and working temperature is 20 ~ 45 DEG C, and optimum temps is 35 ~ 40 DEG C.
As mentioned above, each step to the principal pollutant removal effect of blue charcoal waste water as table 2.
The each step of table 2 is to the removal effect table of main contamination index
Compared to the prior art, tool has the following advantages in the present invention:
(1), after blue charcoal waste water being regulated pH2 ~ 6, through membrane filtration, the tar in blue charcoal waste water is concentrated in concentrated solution, the volume of blue charcoal waste water can be reduced more than 3 times, both save facility investment, and reduced energy consumption again, and significantly reduced production cost.
(2) by gravity settling separation or centrifugation, the coal tar of 5 ~ 40 kilograms can be reclaimed from every cube of waste water, not only achieve the recycling of coal tar in blue charcoal waste water, and the COD of waste water is reduced by 30 ~ 55%, significantly reduce colourity, ensure the carrying out of subsequent production technique.
(3) after the dialyzate of membrane filtration gained and the detar waste water of coal tar oil recovery gained mix, through toning extracting and separating, the crude phenols of 1 ~ 6 kilogram can be reclaimed from every cube of waste water, realize the recycling of blue charcoal Phenol for Waste Water, eradicated again the harm of phenol to rear end wastewater biochemical process, the COD of blue charcoal waste water declines 35 ~ 75% simultaneously.
(4) the blue charcoal waste water after the dephenolize of deamination gained can remove ammonia after overregulating pH, heating evaporation, can reclaim the ammonia of 0.5 ~ 5 kilogram, realize the recycling of ammonia from every cube of waste water.
(5) by the combined treatment process of the processes such as membrane filtration, coal tar recovering, dephenolize, deamination, anaerobic treatment, aerobic treatment, electrolysis reverse osmosis desalination, carry out the advanced treatment of blue charcoal waste water, finally realize waste water reclamation water circulation use, realize abatement of pollution and resources conservation.
(6) by the recycling of the resources such as coal tar, phenol, ammonia, not only achieve the recycling of resource, and considerably reduce the processing cost of blue charcoal waste water.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Referring to Fig. 1, the specific embodiment of the present invention is described.
The present invention is based on the composition of blue charcoal waste water, character and existing processing scheme, devise a kind of blue charcoal wastewater treatment and cyclic utilization method, it relates to the combined treatment process of the processes such as membrane filtration, detar, dephenolize, ammonia nitrogen removal, anaerobic treatment, aerobic treatment, electrolysis, desalination, thus forms a kind of method that effectively can realize blue charcoal Sewage advanced treatment recycling utilization.
embodiment 1
certain blue charcoal wastewater treatment and cyclic utilization method
(1) coarse filtration: be 10000mg/L by COD, ammonia nitrogen be 500mg/L, total phenol is 1000mg/L, colourity is 10000 times, pH value be 8 blue charcoal waste water carry out coarse filtration through grid or screen cloth, removing macrobead foreign material;
(2) membrane filtration: the blue charcoal waste water of the removing macrobead thing through coarse filtration is added sulphur acid for adjusting pH to 6 breakdown of emulsion, must be rich in the concentrated solution of coal tar and the dialyzate of removing coal tar through membrane filtration, cycles of concentration is 8 ~ 10;
Described membrane filtration is ceramic membrane filter, and the ceramic membrane element aperture of ceramic membrane filter system is 30nm; Operating pressure is 3 ~ 6bar, and temperature is 15 ~ 55 DEG C.
(3) detar: the concentrated solution that step (2) must be rich in coal tar through membrane filtration, through gravity settling 24 hours, is separated to obtain the coal tar that reclaims and detar waste water.
Described gravity settling the blue charcoal concentrated through step (2) described membrane filtration is concentrated waste water put into gravity settling basin, be the coal tar on upper strata and the decoking waste water of lower floor through gravity settling separation, the coal tar on upper strata reclaims to obtain coal tar 3kg/m through recovery tube 3.
After described detar, the COD of waste water is 7213mg/L, and ammonia nitrogen is 521mg/L, total phenol is 1103mg/L, colourity is 500 times.
(4) dephenolize: by the dialyzate of step (2) ceramic membrane filter gained and and the blue charcoal waste water of step (3) coal tar oil recovery gained add extraction agent extracting and separating and obtain crude phenols 1 kg/m 3charcoal waste water blue with dephenolize.
Described extraction extraction agent used is N, N ,-dimethyl-g yl acetamide (N, N ,-503) with the mixture of kerosene.
After described dephenolize, the COD of waste water is 2932mg/L, and ammonia nitrogen is 532mg/L, total phenol is 103mg/L, colourity is 500 times.
(5) ammonia nitrogen removal: the blue charcoal waste water of step (4) dephenolize gained is added alkaline solution and regulates its pH to 11, heating evaporation removing ammonia, ammonia absorbs through persulfate solution to be produced ammonium sulfate or obtains liquefied ammonia and the blue charcoal waste water of deamination through cooling liquid.
After described deamination, the pollutent index of blue charcoal waste water is: COD is 1913mg/L, and ammonia nitrogen is 65.1mg/L, total phenol is 213.4mg/L, colourity is 500 times.
(6) desulfurization: add sweetening agent toward the deamination charcoal waste water after step (5) ammonia nitrogen removal, as ferrous sulfate, generate iron sulfide precipitates and the blue charcoal waste water of desulfurization, prevent sulfide to the murder by poisoning of biochemistry, improve its biochemical effects, the clearance of COD is 18.7%;
The pollutent index of the blue charcoal waste water of described desulfurization is: COD is 1554.92mg/L, and ammonia nitrogen is 49mg/L, total phenol is 210mg/L, colourity is 200 times.
(7) anaerobic treatment: blue for the desulfurization of step (6) desulfurization gained charcoal waste water is added alkaline solution and regulates its pH to 6 ~ 9, anaerobic pond is entered through lift pump, anerobe, the absorption of oxygen bacterium of holding concurrently, fermentation, methane phase acting in conjunction in anaerobic pond, organic acid is resolved into methane and carbon dioxide, improved B/C value and the removing most COD of waste water by anaerobic treatment, improve the biodegradability of waste water.
The pollutent index of the described blue charcoal waste water through anaerobic treatment is: COD is 403mg/L, and ammonia nitrogen is 51mg/L, total phenol is 11mg/L, colourity is 150 times.
(8 aerobic treatment: (after 7 anaerobic treatment, blue charcoal waste water enters Aerobic Pond and intermediate sedimentation pond through lift pump by step, and the partial sludge in intermediate sedimentation pond is back to Aerobic Pond by reflux pump, by the organism in the blue charcoal waste water of the further oxygenolysis of aerobic treatment, the degree of depth removes COD and BOD; Evenly fill up a large amount of biological suspended packings in Aerobic Pond, perch for aerobic microbiological provides, the place of growth and breeding so that microorganism forms microbial film at filling surface.Aeration aerating stirring system is provided with bottom Aerobic Pond, oxygenation is carried out to sewage, the dissolved oxygen in water is made to maintain 2 ~ 4 mg/L, utilize the effect that gas rises simultaneously, suspended substance in pond is more fully contacted with water, additionally by the agitaion of gas and clear water back flushing, can effectively wash away the aging microbial film of filling surface growth, impel biomembranous update, make the activity that microbial film remains higher.
The pollutent index of the described blue charcoal waste water through aerobic treatment is: COD is 320mg/L, and ammonia nitrogen is 11mg/L, total phenol is 1mg/L, colourity is 100 times.
(9 electrolysis: (after 8 aerobic treatment, blue charcoal waste water enters electrolysis machine and carries out electrolysis by step, to remove colourity, smelly, make the difficulty biochemical macromolecular cpd open loop chain rupture in waste water simultaneously, become can be biochemical small molecules, further raising B/C value, improves the condition of subsequent biochemical process; The adjacent two interelectrode voltages of electrolysis machine are 2 ~ 12V, and current density is 10 ~ 320mA/cm 2;
Described electrolysis machine is provided with power supply and electrolyzer, and the electrode materials in described electrolyzer is the one in graphite, titanium, iron, aluminium, zinc, copper, lead, nickel, molybdenum, chromium, alloy and nano-catalytic inert material.
(10 anaerobic treatment: (the blue charcoal waste water of 9 electrolysis gained enters secondary anaerobic pond through lift pump by step, anerobe, the absorption of oxygen bacterium of holding concurrently, fermentation, methane phase acting in conjunction in anaerobic pond, organic acid is resolved into methane and carbon dioxide, improve the B/C value of waste water by anaerobic treatment and remove most COD further, improving the biodegradability of waste water.
The pollutent index of the described blue charcoal waste water through secondary anaerobic treatment is: COD is 80.2mg/L, and ammonia nitrogen is 16mg/L, total phenol is 1mg/L, colourity is 150 times.
(11 BAF biochemistry (BAF is biochemical)
(the blue charcoal waste water after 10 anaerobic treatment enters BAF to step, by oxidation degradation effect, waste water is purified, further removing COD, SS and ammonia nitrogen, be purified waste water, and its COD is 50 mg/L, SS is 15 mg/L, ammonia nitrogen 5 mg/L, colourity 8 times.
(12 desalinations: (waste water after 11 BAF biochemistry (BAF is biochemical) enters desalting plant to step, be separated to obtain water-dialyzing (reuse water) and condensed water, it is stand-by that water-dialyzing enters reuse water basin, and condensed water then enters evaporative crystallization pond through discharge channel discharge and carries out crystallization treatment;
Described desalting plant is nanofiltration system.
Nanofiltration membrane component in described nanofiltration system is the one of tubular membrane component, rolled membrane module or plate film assembly, and operating pressure is 6 ~ 45bar, and working temperature is 20 ~ 45 DEG C, and optimum temps is 35 ~ 40 DEG C.
embodiment 2
certain blue charcoal wastewater treatment and cyclic utilization method
(1) coarse filtration: be 34967mg/L by COD, ammonia nitrogen be 1911mg/L, total phenol is 6231mg/L, colourity is 2000 times, pH value be 8.1 blue charcoal waste water carry out coarse filtration through grid or screen cloth, removing macrobead foreign material;
(2) membrane filtration: the blue charcoal waste water of the removing macrobead thing through coarse filtration is added sulphur acid for adjusting pH to 3 ~ 4, must be rich in the concentrated solution of coal tar and the dialyzate of removing coal tar through membrane filtration, cycles of concentration is 5 times;
Described membrane filtration is ceramic membrane filter, and the ceramic membrane element aperture of ceramic membrane filter system is 20 ~ 100nm, and operating pressure is 3 ~ 6bar, and temperature is 15 ~ 55 DEG C.
The COD of described membrane filtration gained dialyzate is 9800 ~ 11500 mg/L.
(3) detar: step (2) must be rich in the concentrated solution of coal tar through centrifugation through membrane filtration, the coal tar of lower floor and the decoking waste water on upper strata, the coal tar of lower floor is through reclaiming to obtain coal tar 17.6kg/m 3.The centrifugal force of centrifugation is 3219.
(4) dephenolize: the detar waste water of the dialyzate of step (2) membrane filtration gained and step (3) coal tar oil recovery gained is added extraction agent extracting and separating and obtain crude phenols and the blue charcoal waste water of dephenolize.
Described extraction extraction agent used is N, N ,-dimethyl-g yl acetamide (N, N ,-503) with the mixture of kerosene.
After described dephenolize, the pollutent index of blue charcoal waste water is: COD is 4905mg/L, and ammonia nitrogen is 2211mg/L, total phenol is 339mg/L, colourity is 500 times.
(5) deamination: the blue charcoal waste water after step (4) dephenolize is added potassium hydroxide solution and regulates its pH to 10, heating evaporation removing ammonia, ammonia absorbs through persulfate solution produces ammonium sulfate.
After described deamination, the pollutent index of blue charcoal waste water is: COD is 1745.36mg/L, and ammonia nitrogen is 46.4mg/L, total phenol is 207mg/L, colourity is 500 times.
(6) desulfurization: add sweetening agent toward the deamination charcoal waste water after step (5) ammonia nitrogen removal, as ferrous sulfate, generates iron sulfide precipitates and the blue charcoal waste water of desulfurization, prevents sulfide to the murder by poisoning of biochemistry, improve its biochemical effects.
After described desulfurization, the pollutent index of blue charcoal waste water is: COD is 1455.36mg/L, and ammonia nitrogen is 47.4mg/L, total phenol is 192mg/L, colourity is 200 times.
(7) anaerobic treatment: the desulfurization charcoal waste water that step (6) desulfurization obtains is added alkaline solution and regulates its pH to 6 ~ 9, anaerobic pond is entered through lift pump, anerobe, the absorption of oxygen bacterium of holding concurrently, fermentation, methane phase acting in conjunction in anaerobic pond, organic acid is resolved into methane and carbon dioxide, improved B/C value and the removing most COD of waste water by anaerobic treatment, improve the biodegradability of waste water.
After described anaerobic treatment, the pollutent index of blue charcoal waste water is: COD is 436.34mg/L, and ammonia nitrogen is 13.4mg/L, total phenol is 207mg/L, colourity is 500 times.
(8) aerobic treatment: charcoal waste water blue after step (7) anaerobic treatment is entered Aerobic Pond and intermediate sedimentation pond through lift pump, and the partial sludge in intermediate sedimentation pond is back to Aerobic Pond by reflux pump, by the organism in the blue charcoal waste water of the further oxygenolysis of aerobic treatment, the degree of depth removes COD and BOD; Evenly fill up a large amount of biological suspended packings in Aerobic Pond, perch for aerobic microbiological provides, the place of growth and breeding so that microorganism forms microbial film at filling surface.Aeration aerating stirring system is provided with bottom Aerobic Pond, oxygenation is carried out to sewage, the dissolved oxygen in water is made to maintain 2 ~ 4 mg/L, utilize the effect that gas rises simultaneously, suspended substance in pond is more fully contacted with water, additionally by the agitaion of gas and clear water back flushing, can effectively wash away the aging microbial film of filling surface growth, impel biomembranous update, make the activity that microbial film remains higher.
After described aerobic treatment, the pollutent index of blue charcoal waste water is: COD is 174.54mg/L, and ammonia nitrogen is 9.4mg/L, total phenol is 7mg/L, colourity is 80 times.
(9) electrolysis: blue charcoal waste water after step (8) process is entered electrolysis machine and carries out electrolysis, to remove colourity, smelly, make the difficulty biochemical macromolecular cpd open loop chain rupture in waste water simultaneously, become can be biochemical small molecules, further raising B/C value, improves the condition of subsequent biochemical process; The adjacent two interelectrode voltages of electrolysis machine are 2 ~ 12V, and current density is 10 ~ 320mA/cm 2;
Described electrolysis machine is provided with power supply and electrolyzer, and the electrode materials in described electrolyzer is the one in graphite, titanium, iron, aluminium, zinc, copper, lead, nickel, molybdenum, chromium, alloy and nano-catalytic inert material.
(10) anaerobic treatment: the blue charcoal waste water of step (9) electrolysis gained is entered secondary anaerobic pond through lift pump, anerobe, the absorption of oxygen bacterium of holding concurrently, fermentation, methane phase acting in conjunction in anaerobic pond, organic acid is resolved into methane and carbon dioxide, improve the B/C value of waste water by anaerobic treatment and remove most COD further, improving the biodegradability of waste water.
After described anaerobic treatment, the pollutent index of blue charcoal waste water is: COD is 58.34mg/L, and ammonia nitrogen is 7.7mg/L, total phenol is 1mg/L, colourity is 20 times.
(11) MBR process
Blue charcoal waste water after step (10) secondary anaerobic treatment enters MBR treatment unit, is purified, remove COD, SS and ammonia nitrogen further, be purified waste water by the filtering separation of MBR treatment unit to waste water;
(12) desalination: the waste water after step (11) film process enters desalting plant, be separated to obtain water-dialyzing and condensed water, water-dialyzing enters reuse water basin, and condensed water then enters evaporative crystallization pond through discharge channel discharge and carries out crystallization treatment;
Described desalting plant can be reverse osmosis system, and the yield of reuse water is 75%.
The reverse osmosis membrane assembly of described reverse osmosis system is rolled membrane module, and mould material is cellulose acetate film or composite membrane in organic membrane, and the molecular weight cut-off of mould material is 50 ~ 200MWCO, and entrance pressure can be 6.0 ~ 45.0bar, goes out pressure and can be 4.5 ~ 33.5 bar.
embodiment 3
certain blue charcoal wastewater treatment and cyclic utilization method
(1) coarse filtration: be 29335mg/L by COD, ammonia nitrogen be 1500mg/L, total phenol is 4100mg/L, colourity is 19000 times, pH value be 8.1 blue charcoal waste water carry out coarse filtration through grid or screen cloth, removing macrobead foreign material;
(2) membrane filtration: the blue charcoal waste water of the removing macrobead thing through coarse filtration is added nitre acid for adjusting pH to 2 ~ 4, must be rich in the concentrated solution of coal tar and the dialyzate of removing coal tar through membrane filtration, cycles of concentration is 10;
Described membrane filtration is ceramic membrane filter, and the ceramic membrane element aperture of ceramic membrane filter system is 20 ~ 100nm, and operating pressure is 3 ~ 6bar, and temperature is 15 ~ 55 DEG C.
(3) coal tar oil recovery: concentrated solution centrifugation step (2) must being rich in coal tar through membrane filtration, obtains coal tar and the detar waste water of recovery;
Described centrifugation pumps in whizzer by the blue charcoal thickened waste water be separated through membrane concentration, and be the coal tar of lower floor and the decoking waste water on upper strata through centrifugation, the coal tar of lower floor reclaims through recovery tube; The centrifugal force of centrifugation is 3400.
Described coal tar is through reclaiming to obtain coal tar 15.2kg/m 3.
After described coal tar recovering, the pollutent index of blue charcoal waste water is: COD is 11494mg/L, and ammonia nitrogen is 1617mg/L, total phenol is 4239mg/L, colourity is 500 times.
(4) dephenolize: the detar waste water of the dialyzate of step (2) membrane filtration gained and step (3) coal tar oil recovery gained is added extraction agent extracting and separating and obtain crude phenols and the blue charcoal waste water of dephenolize.
Described extraction extraction agent used is kerosene.
After described dephenolize, the pollutent index of blue charcoal waste water is: COD is 5280.9mg/L, and ammonia nitrogen is 1701mg/L, total phenol is 309mg/L, colourity is 500 times.
(5) deamination: the blue charcoal waste water after step (4) dephenolize is added potassium hydroxide solution and regulates its pH to 10, heating evaporation removing ammonia, ammonia absorbs through persulfate solution produces ammonium sulfate.
After described deamination, the pollutent index of blue charcoal waste water is: COD is 2488.4mg/L, and ammonia nitrogen is 43.9mg/L, total phenol is 201mg/L, colourity is 500 times.
(6) desulfurization: add sweetening agent toward the deamination charcoal waste water after step (5) ammonia nitrogen removal, as ferrous sulfate, generates iron sulfide precipitates and the blue charcoal waste water of desulfurization, prevents sulfide to the murder by poisoning of biochemistry, improve its biochemical effects,
After described desulfurization, the pollutent index of blue charcoal waste water is: COD is 1959.00mg/L, and ammonia nitrogen is 39.8mg/L, total phenol is 170mg/L, colourity is 200 times.
(7) anaerobic treatment: blue for the desulfurization of step (6) desulfurization gained charcoal waste water is added alkaline solution and regulates its pH to 6 ~ 9, anaerobic pond is entered through lift pump, anerobe, the absorption of oxygen bacterium of holding concurrently, fermentation, methane phase acting in conjunction in anaerobic pond, organic acid is resolved into methane and carbon dioxide, improved B/C value and the removing most COD of waste water by anaerobic treatment, improve the biodegradability of waste water.
After described anaerobism, the pollutent index of blue charcoal waste water is: COD is 622.1mg/L, and ammonia nitrogen is 39.1mg/L, total phenol is 9mg/L, colourity is 500 times.
(8) aerobic treatment: charcoal waste water blue after step (7) anaerobic treatment is entered Aerobic Pond and intermediate sedimentation pond through lift pump, and the partial sludge in intermediate sedimentation pond is back to Aerobic Pond by reflux pump, by the organism in the blue charcoal waste water of the further oxygenolysis of aerobic treatment, the degree of depth removes COD and BOD; Evenly fill up a large amount of biological suspended packings in Aerobic Pond, perch for aerobic microbiological provides, the place of growth and breeding so that microorganism forms microbial film at filling surface.Aeration aerating stirring system is provided with bottom Aerobic Pond, oxygenation is carried out to sewage, the dissolved oxygen in water is made to maintain 2 ~ 4 mg/L, utilize the effect that gas rises simultaneously, suspended substance in pond is more fully contacted with water, additionally by the agitaion of gas and clear water back flushing, can effectively wash away the aging microbial film of filling surface growth, impel biomembranous update, make the activity that microbial film remains higher.
The pollutent index of described aerobic rear blue charcoal waste water is: COD is 241.6mg/L, and ammonia nitrogen is 9.1mg/L, total phenol is 1mg/L, colourity is 70 times.
(9) electrolysis: charcoal waste water blue after step (8) aerobic treatment is entered electrolysis machine and carries out electrolysis, to remove colourity, smelly, make the difficulty biochemical macromolecular cpd open loop chain rupture in waste water simultaneously, become can be biochemical small molecules, further raising B/C value, improves the condition of subsequent biochemical process; The adjacent two interelectrode voltages of electrolysis machine are 2 ~ 12V, and current density is 10 ~ 320mA/cm 2;
Described electrolysis machine is provided with power supply and electrolyzer, and the electrode materials in described electrolyzer is the one in graphite, titanium, iron, aluminium, zinc, copper, lead, nickel, molybdenum, chromium, alloy and nano-catalytic inert material.
(10) secondary anaerobic treatment: the blue charcoal waste water of step (9) electrolysis gained is entered secondary anaerobic pond through lift pump, anerobe, the absorption of oxygen bacterium of holding concurrently, fermentation, methane phase acting in conjunction in anaerobic pond, organic acid is resolved into methane and carbon dioxide, improve the B/C value of waste water by anaerobic treatment and remove most COD further, improving the biodegradability of waste water;
(11) BAF biochemistry (BAF is biochemical)
Blue charcoal waste water after step (10) secondary anaerobic treatment enters BAF, is purified, remove COD, SS and ammonia nitrogen further, be purified waste water by oxidation degradation effect to waste water.
(12) desalination: the waste water after step (11) BAF biochemistry (BAF is biochemical) enters desalting plant, be separated to obtain water-dialyzing and condensed water, water-dialyzing enters reuse water basin, and condensed water then enters evaporative crystallization pond through discharge channel discharge and carries out crystallization treatment;
Described desalting plant is nanofiltration system.
Nanofiltration membrane component in described nanofiltration system is the one of tubular membrane component, rolled membrane module or plate film assembly, and operating pressure is 6 ~ 45bar, and working temperature is 20 ~ 45 DEG C, and optimum temps is 35 ~ 40 DEG C.
embodiment 4
certain blue charcoal wastewater treatment and cyclic utilization method
(1) coarse filtration: be 34967mg/L by COD, ammonia nitrogen be 1911mg/L, total phenol is 6231mg/L, colourity is 2000 times, pH value be 8.1 blue charcoal waste water carry out coarse filtration through grid or screen cloth, removing macrobead foreign material;
(2) membrane filtration: the blue charcoal waste water of the removing macrobead thing through coarse filtration must be rich in the concentrated solution of coal tar and the dialyzate of removing coal tar through membrane filtration, and cycles of concentration is 5;
Described membrane filtration is ceramic membrane, and the ceramic membrane element aperture of ceramic membrane filter system is 20 ~ 100nm, and operating pressure is 3 ~ 6bar, and temperature is 15 ~ 55 DEG C.
(3) detar: the concentrated solution that step (2) must be rich in coal tar through membrane filtration is added sulphur acid for adjusting pH to 4, through centrifugation, the coal tar of lower floor and the decoking waste water on upper strata, the coal tar of lower floor is through reclaiming to obtain coal tar 17.8kg/m 3.The centrifugal force of centrifugation is 3219.
(4) dephenolize: the detar waste water of the dialyzate of step (2) membrane filtration gained and step (3) coal tar oil recovery gained is added sulphuric acid soln and regulates its pH to 3.5, adds extraction agent extracting and separating and obtains crude phenols and the blue charcoal waste water of dephenolize.
Described extraction extraction agent used is the mixture of tributyl phosphate and kerosene is extraction agent.
After described dephenolize, the pollutent index of blue charcoal waste water is: COD is 4116mg/L, and ammonia nitrogen is 2200mg/L, total phenol is 357mg/L, colourity is 500 times.
(5) deamination: the blue charcoal waste water after step (4) dephenolize is added sodium hydroxide solution and regulates its pH to 10, heating evaporation removing ammonia, ammonia absorbs through persulfate solution produces ammonium sulfate.
After described deamination, the pollutent index of blue charcoal waste water is: COD is 1642.31mg/L, and ammonia nitrogen is 36.5mg/L, total phenol is 226mg/L, colourity is 500 times.
(6) desulfurization: add sweetening agent toward the deamination charcoal waste water after step (5) ammonia nitrogen removal, as ferrous sulfate, generates iron sulfide precipitates and the blue charcoal waste water of desulfurization, prevents sulfide to the murder by poisoning of biochemistry, improve its biochemical effects.
(7) anaerobic treatment: blue for the desulfurization of step (6) desulfurization gained charcoal waste water is added alkaline solution and regulates its pH to 6 ~ 9, anaerobic pond is entered through lift pump, anerobe, the absorption of oxygen bacterium of holding concurrently, fermentation, methane phase acting in conjunction in anaerobic pond, organic acid is resolved into methane and carbon dioxide, improved B/C value and the removing most COD of waste water by anaerobic treatment, improve the biodegradability of waste water.
After described anaerobic treatment, the pollutent index of blue charcoal waste water is: COD is 314.31mg/L, and ammonia nitrogen is 11.5mg/L, total phenol is 197mg/L, colourity is 500 times.
(8) aerobic treatment: charcoal waste water blue after step (7) anaerobic treatment is entered Aerobic Pond and intermediate sedimentation pond through lift pump, and the partial sludge in intermediate sedimentation pond is back to Aerobic Pond by reflux pump, by the organism in the blue charcoal waste water of the further oxygenolysis of aerobic treatment, the degree of depth removes COD and BOD; Evenly fill up a large amount of biological suspended packings in Aerobic Pond, perch for aerobic microbiological provides, the place of growth and breeding so that microorganism forms microbial film at filling surface.Aeration aerating stirring system is provided with bottom Aerobic Pond, oxygenation is carried out to sewage, the dissolved oxygen in water is made to maintain 2 ~ 4 mg/L, utilize the effect that gas rises simultaneously, suspended substance in pond is more fully contacted with water, additionally by the agitaion of gas and clear water back flushing, can effectively wash away the aging microbial film of filling surface growth, impel biomembranous update, make the activity that microbial film remains higher.
After described aerobic treatment, the pollutent index of blue charcoal waste water is: COD is 97.80mg/L, and ammonia nitrogen is 10.7mg/L, total phenol is 1mg/L, colourity is 80 times.
(9) electrolysis: charcoal waste water blue after step (8) aerobic treatment is entered electrolysis machine and carries out electrolysis, to remove colourity, smelly, make the difficulty biochemical macromolecular cpd open loop chain rupture in waste water simultaneously, become can be biochemical small molecules, further raising B/C value, improves the condition of subsequent biochemical process; The adjacent two interelectrode voltages of electrolysis machine are 2 ~ 12V, and current density is 10 ~ 320mA/cm 2;
Described electrolysis machine is provided with power supply and electrolyzer, and the electrode materials in described electrolyzer is the one in graphite, titanium, iron, aluminium, zinc, copper, lead, nickel, molybdenum, chromium, alloy and nano-catalytic inert material.
(10) secondary anaerobic treatment: the blue charcoal waste water of step (9) electrolysis gained is entered secondary anaerobic pond through lift pump, anerobe, the absorption of oxygen bacterium of holding concurrently, fermentation, methane phase acting in conjunction in anaerobic pond, organic acid is resolved into methane and carbon dioxide, improve the B/C value of waste water by anaerobic treatment and remove most COD further, improving the biodegradability of waste water.
After described anaerobic treatment, the pollutent index of blue charcoal waste water is: COD is 48.34mg/L, and ammonia nitrogen is 7.5mg/L, colourity is 10 times.
(11) MBR process
Blue charcoal waste water after step (10) secondary anaerobic treatment enters MBR treatment unit, is purified waste water by the filtering separation of membrane treatment appts, and removing COD and ammonia nitrogen, be purified waste water further;
(12) desalination: the waste water after step (11) MBR process enters desalting plant, be separated to obtain water-dialyzing and condensed water, water-dialyzing enters reuse water basin, and condensed water then enters evaporative crystallization pond through discharge channel discharge and carries out crystallization treatment;
Described desalting plant can be reverse osmosis system, and the yield of reuse water is 75%.
The reverse osmosis membrane assembly of described reverse osmosis system is rolled membrane module, and mould material is cellulose acetate film or composite membrane in organic membrane, and the molecular weight cut-off of mould material is 50 ~ 200MWCO, and entrance pressure can be 6.0 ~ 45.0bar, goes out pressure and can be 4.5 ~ 33.5 bar.
embodiment 5
certain blue charcoal wastewater treatment and cyclic utilization method
(1) coarse filtration: be 14393mg/L by COD, ammonia nitrogen be 1772mg/L, total phenol is 1900mg/L, colourity is 19000 times, pH value be 8.3 blue charcoal waste water carry out coarse filtration through grid or screen cloth, removing macrobead foreign material;
(2) membrane filtration: the blue charcoal waste water of the removing macrobead thing through coarse filtration is added nitre acid for adjusting pH to 2 ~ 4, must be rich in the concentrated solution of coal tar and the dialyzate of removing coal tar through membrane filtration, cycles of concentration is 10;
Described membrane filtration is ceramic membrane filter, and the ceramic membrane element aperture of ceramic membrane filter system is 20 ~ 100nm, and operating pressure is 3 ~ 6bar, and temperature is 15 ~ 55 DEG C.
(3) detar: concentrated solution centrifugation step (2) must being rich in coal tar through membrane filtration, obtains coal tar and the detar waste water of recovery;
Described centrifugation pumps in whizzer by the blue charcoal thickened waste water be separated through membrane concentration, and be the coal tar of lower floor and the decoking waste water on upper strata through centrifugation, the coal tar of lower floor reclaims through recovery tube; The centrifugal force of centrifugation is 3400.
Described coal tar is through reclaiming to obtain coal tar 3.2kg/m 3.
After described coal tar recovering, the pollutent index of blue charcoal waste water is: COD is 11196mg/L, and ammonia nitrogen is 1817mg/L, total phenol is 5039mg/L, colourity is 500 times.
(4) dephenolize: the detar waste water of the dialyzate of step (2) membrane filtration gained and step (3) coal tar oil recovery gained is added sulphuric acid soln and regulates its pH value to 6, adds extraction agent extracting and separating and obtains crude phenols and the blue charcoal waste water of dephenolize.
Described extraction extraction agent used is crude benzol.
After described dephenolize, the pollutent index of blue charcoal waste water is: COD is 2447.9mg/L, and ammonia nitrogen is 1701mg/L, total phenol is 309mg/L, colourity is 500 times.
(5) deamination: the blue charcoal waste water after step (4) dephenolize is added potassium hydroxide solution and regulates its pH to 10, heating evaporation removing ammonia, ammonia absorbs through persulfate solution produces ammonium sulfate.
After described deamination, the pollutent index of blue charcoal waste water is: COD is 1527.4mg/L, and ammonia nitrogen is 65.3mg/L, total phenol is 201mg/L, colourity is 500 times.
(6) desulfurization: add sweetening agent toward the deamination charcoal waste water after step (5) ammonia nitrogen removal, as ferrous sulfate, generates iron sulfide precipitates and the blue charcoal waste water of desulfurization, prevents sulfide to the murder by poisoning of biochemistry, improve its biochemical effects.
(7) anaerobic treatment: blue for the desulfurization of step (6) desulfurization gained charcoal waste water is added alkaline solution and regulates its pH to 6 ~ 9, anaerobic pond is entered through lift pump, anerobe, the absorption of oxygen bacterium of holding concurrently, fermentation, methane phase acting in conjunction in anaerobic pond, organic acid is resolved into methane and carbon dioxide, improved B/C value and the removing most COD of waste water by anaerobic treatment, improve the biodegradability of waste water.
After described anaerobism, the pollutent index of blue charcoal waste water is: COD is 332.6mg/L, and ammonia nitrogen is 39.1mg/L, total phenol is 9mg/L, colourity is 500 times.
(8) aerobic treatment: charcoal waste water blue after step (7) anaerobic treatment is entered Aerobic Pond and intermediate sedimentation pond through lift pump, and the partial sludge in intermediate sedimentation pond is back to Aerobic Pond by reflux pump, by the organism in the blue charcoal waste water of the further oxygenolysis of aerobic treatment, the degree of depth removes COD and BOD; Evenly fill up a large amount of biological suspended packings in Aerobic Pond, perch for aerobic microbiological provides, the place of growth and breeding so that microorganism forms microbial film at filling surface.Aeration aerating stirring system is provided with bottom Aerobic Pond, oxygenation is carried out to sewage, the dissolved oxygen in water is made to maintain 2 ~ 4 mg/L, utilize the effect that gas rises simultaneously, suspended substance in pond is more fully contacted with water, additionally by the agitaion of gas and clear water back flushing, can effectively wash away the aging microbial film of filling surface growth, impel biomembranous update, make the activity that microbial film remains higher.
The pollutent index of described aerobic rear blue charcoal waste water is: COD is 152.6mg/L, and ammonia nitrogen is 9.1mg/L, total phenol is 1mg/L, colourity is 70 times.
(9) electrolysis: charcoal waste water blue after step (8) aerobic treatment is entered electrolysis machine and carries out electrolysis, to remove colourity, smelly, make the difficulty biochemical macromolecular cpd open loop chain rupture in waste water simultaneously, become can be biochemical small molecules, further raising B/C value, improves the condition of subsequent biochemical process; The adjacent two interelectrode voltages of electrolysis machine are 2 ~ 12V, and current density is 10 ~ 320mA/cm 2;
Described electrolysis machine is provided with power supply and electrolyzer, and the electrode materials in described electrolyzer is the one in graphite, titanium, iron, aluminium, zinc, copper, lead, nickel, molybdenum, chromium, alloy and nano-catalytic inert material.
(10) secondary anaerobic treatment: the blue charcoal waste water of step (9) electrolysis gained is entered secondary anaerobic pond through lift pump, anerobe, the absorption of oxygen bacterium of holding concurrently, fermentation, methane phase acting in conjunction in anaerobic pond, organic acid is resolved into methane and carbon dioxide, improve the B/C value of waste water by anaerobic treatment and remove most COD further, improving the biodegradability of waste water;
(11) BAF biochemistry (BAF is biochemical)
Blue charcoal waste water after step (10) secondary anaerobic treatment enters BAF, is purified, remove COD, SS and ammonia nitrogen further, be purified waste water by oxidation degradation effect to waste water.
(12) desalination: the waste water after step (11) BAF biochemistry (BAF is biochemical) enters desalting plant, be separated to obtain water-dialyzing and condensed water, water-dialyzing enters reuse water basin, and condensed water then enters evaporative crystallization pond through discharge channel discharge and carries out crystallization treatment;
Described desalting plant can be reverse osmosis system, and the yield of reuse water is 75%.
The reverse osmosis membrane assembly of described reverse osmosis system is rolled membrane module, and mould material is cellulose acetate film or composite membrane in organic membrane, and the molecular weight cut-off of mould material is 50 ~ 200MWCO, and entrance pressure can be 6.0 ~ 45.0bar, goes out pressure and can be 4.5 ~ 33.5 bar.
embodiment 6
certain blue charcoal waste water (cool circulation water) process and cyclic utilization method
(1) coarse filtration: be 14679mg/L by COD, ammonia nitrogen be 1740mg/L, total phenol is 4900mg/L, colourity is 18000 times, pH value be 8.3 blue charcoal waste water carry out coarse filtration through grid or screen cloth, removing macrobead foreign material;
(2) membrane filtration: the blue charcoal waste water of the removing macrobead thing through coarse filtration is added nitre acid for adjusting pH to 2 ~ 4, must be rich in the concentrated solution of coal tar and the dialyzate of removing coal tar through membrane filtration, cycles of concentration is 10;
Described membrane filtration is ceramic membrane filter, and the ceramic membrane element aperture of ceramic membrane filter system is 20 ~ 100nm, and operating pressure is 3 ~ 6bar, and temperature is 15 ~ 55 DEG C.
The dialyzate COD of described ceramic membrane filter gained is 9679mg/L, and membrane filtration is 34% to the clearance of COD.
(3) detar: concentrated solution centrifugation step (2) must being rich in coal tar through membrane filtration, obtains coal tar and the detar waste water of recovery;
Described centrifugation pumps in whizzer by the blue charcoal thickened waste water be separated through membrane concentration, and be the coal tar of lower floor and the decoking waste water on upper strata through centrifugation, the coal tar of lower floor reclaims through recovery tube; The centrifugal force of centrifugation is 3400.
Described coal tar is through reclaiming to obtain coal tar 5.2kg/m 3.
After described detar, the pollutent index of blue charcoal waste water is: COD is 9891mg/L, and ammonia nitrogen is 1817mg/L, total phenol is 5039mg/L, colourity is 500 times.
(4) dephenolize: the detar waste water of the dialyzate of step (2) membrane filtration gained and step (3) coal tar oil recovery gained is added extraction agent extracting and separating and obtain crude phenols and the blue charcoal waste water of dephenolize.
Described extraction extraction agent used is crude benzol.
The organic phase of described extraction obtains crude phenols 4.753 kg/m through fractionation by distillation 3, organic phase is that crude benzol recycles.
After described dephenolize, the pollutent index of blue charcoal waste water is: COD is 3580.9mg/L, and ammonia nitrogen is 1771mg/L, total phenol is 309mg/L, colourity is 500 times.
(5) deamination: the blue charcoal waste water after step (4) dephenolize is added potassium hydroxide solution and regulates its pH to 11, heating evaporation removing ammonia, ammonia absorbs through persulfate solution produces ammonium sulfate.
After described deamination, the pollutent index of blue charcoal waste water is: COD is 2088.4mg/L, and ammonia nitrogen is 43.9mg/L, total phenol is 201mg/L, colourity is 500 times.
(6) desulfurization: add sweetening agent toward the deamination charcoal waste water after step (5) ammonia nitrogen removal, as ferrous sulfate, generates iron sulfide precipitates and the blue charcoal waste water of desulfurization, prevents sulfide to the murder by poisoning of biochemistry, improve its biochemical effects.
After described desulfurization, the pollutent index of blue charcoal waste water is: COD is 1655.9mg/L, and ammonia nitrogen is 46.9mg/L, total phenol is 160mg/L, colourity is 200 times.
(7) anaerobic treatment: blue for the desulfurization of step (6) desulfurization gained charcoal waste water is added alkaline solution and regulates its pH to 6 ~ 9, anaerobic pond is entered through lift pump, anerobe, the absorption of oxygen bacterium of holding concurrently, fermentation, methane phase acting in conjunction in anaerobic pond, organic acid is resolved into methane and carbon dioxide, improved B/C value and the removing most COD of waste water by anaerobic treatment, improve the biodegradability of waste water.
After described anaerobism, the pollutent index of blue charcoal waste water is: COD is 411.6mg/L, and ammonia nitrogen is 39.1mg/L, total phenol is 9mg/L, colourity is 500 times.
(8) aerobic treatment: charcoal waste water blue after step (7) anaerobic treatment is entered Aerobic Pond and intermediate sedimentation pond through lift pump, and the partial sludge in intermediate sedimentation pond is back to Aerobic Pond by reflux pump, by the organism in the blue charcoal waste water of the further oxygenolysis of aerobic treatment, the degree of depth removes COD and BOD; Evenly fill up a large amount of biological suspended packings in Aerobic Pond, perch for aerobic microbiological provides, the place of growth and breeding so that microorganism forms microbial film at filling surface.Aeration aerating stirring system is provided with bottom Aerobic Pond, oxygenation is carried out to sewage, the dissolved oxygen in water is made to maintain 2 ~ 4 mg/L, utilize the effect that gas rises simultaneously, suspended substance in pond is more fully contacted with water, additionally by the agitaion of gas and clear water back flushing, can effectively wash away the aging microbial film of filling surface growth, impel biomembranous update, make the activity that microbial film remains higher.
The pollutent index of described aerobic rear blue charcoal waste water is: COD is 156.1mg/L, and ammonia nitrogen is 9.1mg/L, total phenol is 1mg/L, colourity is 70 times.
(9) electrolysis: charcoal waste water blue after step (8) aerobic treatment is entered electrolysis machine and carries out electrolysis, to remove colourity, smelly, make the difficulty biochemical macromolecular cpd open loop chain rupture in waste water simultaneously, become can be biochemical small molecules, further raising B/C value, improves the condition of subsequent biochemical process; The adjacent two interelectrode voltages of electrolysis machine are 2 ~ 12V, and current density is 10 ~ 320mA/cm 2;
Described electrolysis machine is provided with power supply and electrolyzer, and the electrode materials in described electrolyzer is the one in graphite, titanium, iron, aluminium, zinc, copper, lead, nickel, molybdenum, chromium, alloy and nano-catalytic inert material.
(10) secondary anaerobic treatment: the blue charcoal waste water of step (9) electrolysis gained is entered secondary anaerobic pond through lift pump, anerobe, the absorption of oxygen bacterium of holding concurrently, fermentation, methane phase acting in conjunction in anaerobic pond, organic acid is resolved into methane and carbon dioxide, improve the B/C value of waste water by anaerobic treatment and remove most COD further, improving the biodegradability of waste water;
(11) BAF biochemistry (BAF is biochemical)
Blue charcoal waste water after step (10) secondary anaerobic treatment enters BAF, is purified, remove COD, SS and ammonia nitrogen further, be purified waste water by oxidation degradation effect to waste water.
(12) desalination: the waste water after step (11) BAF biochemistry (BAF is biochemical) enters desalting plant, be separated to obtain water-dialyzing and condensed water, water-dialyzing enters reuse water basin, and condensed water then enters evaporative crystallization pond through discharge channel discharge and carries out crystallization treatment;
Described desalting plant is nanofiltration system.
Nanofiltration membrane component in described nanofiltration system is the one of tubular membrane component, rolled membrane module or plate film assembly, and operating pressure is 6 ~ 45bar, and working temperature is 20 ~ 45 DEG C, and optimum temps is 35 ~ 40 DEG C.
embodiment 7
Certain blue charcoal wastewater treatment recycling utilization and Resource comprehensive utilization method.
(1) coarse filtration: be 75000mg/L by COD, ammonia nitrogen be 5000mg/L, total phenol is 6000mg/L, colourity is 30000 times, pH value be 10 blue charcoal waste water carry out coarse filtration through grid or screen cloth, removing macrobead foreign material;
(2) membrane filtration: the blue charcoal waste water of the removing macrobead thing through coarse filtration is added acid for adjusting pH to 3 ~ 4, must be rich in the concentrated solution of coal tar and the dialyzate of removing coal tar through membrane filtration, cycles of concentration is 3;
Described membrane filtration is metal membrane filter; The metallic membrane element aperture of metal membrane filter system is 30 ~ 100nm; Operating pressure is 3 ~ 6bar, and temperature is 15 ~ 55 DEG C.
(3) detar: the concentrated solution that step (2) must be rich in coal tar through membrane filtration, centrifugation, obtains coal tar and the detar waste water of recovery.
Described centrifugation pumps in whizzer by the blue charcoal thickened waste water be separated through membrane concentration, is the coal tar of lower floor and the decoking waste water on upper strata through centrifugation, and the coal tar of lower floor is through reclaiming to obtain tar 40kg/m 3.
The pollutent index of the blue charcoal waste water after described detar is: COD is 23841mg/L, and ammonia nitrogen is 6383mg/L, total phenol is 6305.9mg/L, colourity is 500 times.
(4) dephenolize: add hydrochloric acid soln after the dialyzate of step (2) metal membrane filter gained and the blue charcoal waste water of step (3) detar gained being mixed and regulate its pH to 2, adds extraction agent extracting and separating and obtains crude phenols and the blue charcoal waste water of dephenolize.
Described extraction extraction agent used is kerosene, and the ratio of kerosene and waste water is 1:5, and extract three times, phenol is extracted in kerosene organic phase, and liquid-liquid separation must containing the kerosene organic phase of phenol and blue charcoal waste water phase.Be separated to obtain crude phenols 5.9 kg/m 3.
After described phenol removal, the pollutent index of waste water is: COD is 9928mg/L, and ammonia nitrogen is 6383mg/L, total phenol is 305.3mg/L, colourity is 500.
(4) deamination: the detar waste water of the dialyzate of step (2) membrane filtration gained and step (3) coal tar oil recovery gained is added alkaline solution and regulates its pH to 9, heating evaporation removing ammonia, ammonia obtains liquefied ammonia and the blue charcoal waste water of deamination through overcooling.
The pollutent index of described deamination processed waste water is: COD is 2587.5mg/L, and ammonia nitrogen is 81mg/L, total phenol is 301.5mg/L, colourity is 500 times.
(6) desulfurization: add sweetening agent toward the deamination charcoal waste water after step (5) ammonia nitrogen removal, as ferrous sulfate, generates iron sulfide precipitates and the blue charcoal waste water of desulfurization, prevents sulfide to the murder by poisoning of biochemistry, improve its biochemical effects.
(7) anaerobic treatment: blue for the desulfurization of step (6) desulfurization gained charcoal waste water is added alkaline solution and regulates its pH to 6 ~ 9, anaerobic pond is entered through lift pump, anerobe, the absorption of oxygen bacterium of holding concurrently, fermentation, methane phase acting in conjunction in anaerobic pond, organic acid is resolved into methane and carbon dioxide, improved B/C value and the removing most COD of waste water by anaerobic treatment, improve the biodegradability of waste water.
After described anaerobic treatment, the pollutent index of waste water is: COD is 595.2mg/L, and ammonia nitrogen is 51mg/L, total phenol is 433mg/L, colourity is 500 times.
(8) aerobic treatment: charcoal waste water blue after step (7) anaerobic treatment is entered Aerobic Pond and intermediate sedimentation pond through lift pump, and the partial sludge in intermediate sedimentation pond is back to Aerobic Pond by reflux pump, by the organism in the blue charcoal waste water of the further oxygenolysis of aerobic treatment, the degree of depth removes COD and BOD; Evenly fill up a large amount of biological suspended packings in Aerobic Pond, perch for aerobic microbiological provides, the place of growth and breeding so that microorganism forms microbial film at filling surface.Aeration aerating stirring system is provided with bottom Aerobic Pond, oxygenation is carried out to sewage, the dissolved oxygen in water is made to maintain 2 ~ 4 mg/L, utilize the effect that gas rises simultaneously, suspended substance in pond is more fully contacted with water, additionally by the agitaion of gas and clear water back flushing, can effectively wash away the aging microbial film of filling surface growth, impel biomembranous update, make the activity that microbial film remains higher.
After described aerobic treatment, the pollutent index of waste water is: COD is 232.1mg/L, and ammonia nitrogen is 11mg/L, total phenol is 0.3mg/L, colourity is 200 times.
(9) electrolysis: charcoal waste water blue after step (8) aerobic treatment is entered electrolysis machine and carries out electrolysis, to remove colourity, smelly, make the difficulty biochemical macromolecular cpd open loop chain rupture in waste water simultaneously, become can be biochemical small molecules, further raising B/C value, improves the condition of subsequent biochemical process; The adjacent two interelectrode voltages of electrolysis machine are 2 ~ 12V, and current density is 10 ~ 320mA/cm 2.
Described electrolysis machine is provided with power supply and electrolyzer, and the electrode materials in described electrolyzer is the one in graphite, titanium, iron, aluminium, zinc, copper, lead, nickel, molybdenum, chromium, alloy and nano-catalytic inert material.
(10) secondary anaerobic treatment: the blue charcoal waste water of step (9) electrolysis gained is entered secondary anaerobic pond through lift pump, anerobe, the absorption of oxygen bacterium of holding concurrently, fermentation, methane phase acting in conjunction in anaerobic pond, organic acid is resolved into methane and carbon dioxide, improve the B/C value of waste water by anaerobic treatment and remove most COD further, improving the biodegradability of waste water.
After described anaerobic treatment, the pollutent index of waste water is: COD is 116.08mg/L, and ammonia nitrogen is 9mg/L, colourity is 200 times.
(11) MBR process
Blue charcoal waste water after step (10) secondary anaerobic treatment enters MBR treatment unit, is purified, remove COD, ammonia nitrogen further, be purified waste water by the filtering separation of MBR treatment unit or oxidation degradation effect to waste water.
The membrane module of described MBR device is selected from the one in Pvdf Microporous Hollow Fiber Membrane, polypropylene hollow fiber membrane, ps hollow fiber uf membrane, polyethersulfone, polyacrylonitrile and PVC hollow fiber membrane, membrane pore size is 0.10 ~ 0.2 μm, operating pressure is-1 ~-50kPa, and working temperature is 5 ~ 45 DEG C.
The pollutent index of described MBR processed waste water is 71.11mg/L, and ammonia nitrogen is 8mg/L, colourity is 12.
(12) desalination: the waste water after step (11) film process enters desalting plant, be separated to obtain water-dialyzing and condensed water, water-dialyzing enters reuse water basin, and condensed water then enters evaporative crystallization pond through discharge channel discharge and carries out crystallization treatment;
Described desalting plant is nanofiltration system.
Nanofiltration membrane component in described nanofiltration system is the one of tubular membrane component, rolled membrane module or plate film assembly, and operating pressure is 6 ~ 45bar, and working temperature is 20 ~ 45 DEG C, and optimum temps is 35 ~ 40 DEG C.
Above are only the specific embodiment of the present invention, but design concept of the present invention is not limited thereto, all changes utilizing this design the present invention to be carried out to unsubstantiality, all should belong to the behavior of invading scope.

Claims (9)

1. blue charcoal wastewater treatment and a cyclic utilization method, is characterized in that, comprise the steps:
(1) coarse filtration: be 10000 ~ 75000mg/L by COD, ammonia nitrogen be 500 ~ 5000mg/L, total phenol is 1000 ~ 6000mg/L, colourity is 10000 ~ 30000 times, pH value be 8 ~ 10 blue charcoal waste water carry out coarse filtration through grid or screen cloth, removing macrobead foreign material;
(2) membrane filtration: the blue charcoal waste water of the removing macrobead thing through coarse filtration is added acid for adjusting pH to 2 ~ 6, then the concentrated solution of coal tar and the dialyzate of removing coal tar must be rich in through membrane filtration, cycles of concentration is 3 ~ 10;
(3) detar: the concentrated solution that step (2) must be rich in coal tar through membrane filtration obtains the blue charcoal waste water of detar through gravity settling separation or centrifugation, and the clearance of its COD is 30 ~ 55%;
(4) dephenolize: the blue charcoal waste water after the dialyzate of step (2) membrane filtration gained and the de-coal tar of step (3) is mixed, add extraction agent extracting and separating and obtain the blue charcoal waste water of dephenolize, the clearance of COD is 35 ~ 70%;
(5) ammonia nitrogen removal: the blue charcoal waste water of step (4) dephenolize gained is added alkaline solution and regulates its pH to 9 ~ 11, heating evaporation removing ammonia, ammonia absorbs through persulfate solution to be produced ammonium sulfate or obtains liquefied ammonia and the blue charcoal waste water of deamination through cooling liquid;
(6) desulfurization: add sweetening agent toward the blue charcoal waste water of the deamination after step (5) ammonia nitrogen removal, as ferrous sulfate, generate iron sulfide precipitates and the blue charcoal waste water of desulfurization, prevent sulfide to the murder by poisoning of biochemistry, improve its biochemical effects, the clearance of COD is 10 ~ 20%;
(7) anaerobic treatment: blue for the desulfurization of step (6) desulfurization gained charcoal waste water is added alkaline solution and regulates its pH to 6 ~ 9, anaerobic pond is entered through lift pump, anerobe, the absorption of oxygen bacterium of holding concurrently, fermentation, methane phase acting in conjunction in anaerobic pond, organic acid is resolved into methane and carbon dioxide, improved B/C value and the removing most COD of waste water by anaerobic treatment, improve the biodegradability of waste water;
(8) aerobic treatment: charcoal waste water blue after step (7) anaerobic treatment is entered Aerobic Pond and intermediate sedimentation pond through lift pump, and the partial sludge in intermediate sedimentation pond is back to Aerobic Pond by reflux pump, by the organism in the blue charcoal waste water of the further oxygenolysis of aerobic treatment, the degree of depth removes COD and BOD; A large amount of biological suspended packings is evenly filled up in Aerobic Pond; Aeration aerating stirring system is provided with bottom Aerobic Pond, oxygenation is carried out to sewage, the dissolved oxygen in water is made to maintain 2 ~ 4 mg/L, utilize the effect that gas rises simultaneously, suspended substance in pond is more fully contacted with water, additionally by the agitaion of gas and clear water back flushing, can effectively wash away the aging microbial film of filling surface growth, impel biomembranous update, make the activity that microbial film remains higher;
(9) electrolysis: charcoal waste water blue after step (8) aerobic treatment is entered electrolysis machine and carries out electrolysis, to remove colourity, smelly, make the difficulty biochemical macromolecular cpd open loop chain rupture in waste water simultaneously, become can be biochemical small molecules, further raising B/C value, improves the condition of subsequent biochemical process; The adjacent two interelectrode voltages of electrolysis machine are 2 ~ 12V, and current density is 10 ~ 320mA/cm 2;
(10) secondary anaerobic treatment: the blue charcoal waste water of step (9) electrolysis gained is entered secondary anaerobic pond through lift pump, anerobe, the absorption of oxygen bacterium of holding concurrently, fermentation, methane phase acting in conjunction in anaerobic pond, organic acid is resolved into methane and carbon dioxide, improve the B/C value of waste water by anaerobic treatment and remove most COD further, improving the biodegradability of waste water;
(11) MBR process or BAF biochemistry: the blue charcoal waste water after step (10) secondary anaerobic treatment enters MBR treatment unit or BAF, by the filtering separation of membrane treatment appts or oxidation degradation effect, waste water is purified, further removing COD, SS and ammonia nitrogen, be purified waste water;
(12) desalination: the waste water after step (11) MBR process or BAF biochemistry enters desalting plant, and be separated to obtain water-dialyzing and condensed water, water-dialyzing enters reuse water basin, condensed water then enters evaporative crystallization pond through discharge channel discharge and carries out crystallization treatment; Described desalting plant is the one of reverse osmosis system or nanofiltration system.
2. blue charcoal use in waste water treatment cyclic utilization method as claimed in claim 1, is characterized in that: step (2) described membrane filtration is the one of ceramic membrane filter or metal membrane filter; The ceramic membrane element aperture of ceramic membrane filter system is 20 ~ 100nm; The metallic membrane element aperture of metal membrane filter system is 30 ~ 100nm; Operating pressure is 3 ~ 6bar, and temperature is 15 ~ 55 DEG C.
3. blue charcoal use in waste water treatment cyclic utilization method as claimed in claim 1, it is characterized in that: the gravity settling separation described in step (3) coal tar oil recovery is that the concentrated solution being rich in coal tar through membrane filtration is put into gravity settling basin, is the blue charcoal waste water of coal tar and decoking through gravity settling separation.
4. blue charcoal use in waste water treatment cyclic utilization method as claimed in claim 1, it is characterized in that: the concentrated solution being rich in coal tar through membrane filtration described in step (2) membrane filtration pumps in whizzer, is the blue charcoal waste water of coal tar and decoking through centrifugation; The centrifugal force of centrifugation is 2200 ~ 4000.
5. blue charcoal use in waste water treatment cyclic utilization method as claimed in claim 1, is characterized in that: the extraction agent used of the extraction described in step (4) dephenolize is kerosene, N, N ,-dimethyl-g yl acetamide (N, N ,-503), the one of tributyl phosphate or crude benzol or its mixture.
6. blue charcoal use in waste water treatment cyclic utilization method as claimed in claim 1, it is characterized in that: the electrolysis machine of step (9) electrolysis is provided with power supply and electrolyzer, the electrode materials in described electrolyzer is the one in graphite, titanium, iron, aluminium, zinc, copper, lead, nickel, molybdenum, chromium, alloy and nano-catalytic inert material.
7. blue charcoal use in waste water treatment cyclic utilization method as claimed in claim 1, it is characterized in that: the membrane module of the described MBR device described in step (11) is selected from the one in Pvdf Microporous Hollow Fiber Membrane, polypropylene hollow fiber membrane, ps hollow fiber uf membrane, polyethersulfone, polyacrylonitrile and PVC hollow fiber membrane, membrane pore size is 0.10 ~ 0.2 μm, operating pressure is-1 ~-50kPa, and working temperature is 5 ~ 45 DEG C.
8. blue charcoal use in waste water treatment cyclic utilization method as claimed in claim 1, it is characterized in that: the reverse osmosis membrane assembly of the reverse osmosis system described in step (12) desalination is rolled membrane module, mould material is cellulose acetate film or composite membrane in organic membrane, the molecular weight cut-off of mould material is 50 ~ 200MWCO, entrance pressure is 6.0 ~ 45.0bar, and going out pressure is 4.5 ~ 33.5 bar.
9. blue charcoal use in waste water treatment cyclic utilization method as claimed in claim 1, it is characterized in that: the nanofiltration membrane component in the nanofiltration system described in step (12) desalination is the one of tubular membrane component, rolled membrane module or plate film assembly, operating pressure is 6 ~ 45bar, and working temperature is 20 ~ 45 DEG C.
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