CN102344223A - Treatment or recycling method and purpose for coal gasification and coal carbonization waste water - Google Patents
Treatment or recycling method and purpose for coal gasification and coal carbonization waste water Download PDFInfo
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Abstract
The invention provides a treatment or recycling method and purpose for coal gasification and coal carbonization waste water. The method employs a combined technology of '' pretreatment + efficient + anoxic / aerobic treatment + efficient aeration biofilter + advanced treatment '' with details seen in a specification. The invention has advantages that efficient anoxic treatment not only eliminates organic pollutants in the waste water to reduce post treatment process load but also enhances waste water biodegradability; the efficient aeration biofilter efficiently gathers microbes growing slow, so as to improve processing effect on difficultly degraded organic matters and ammonia nitrogen in the waste water, guarantee stable operation of the integral combined technology and effectively mitigate process operating difficulty of the subsequent advanced treatment. The invention is suitable for standard reached discharging or recycling and present engineering reconstruction and upgrade of gasification and coal carbonization waste water, as well as standard reached discharging or recycling and present engineering reconstruction and upgrade of similar coal chemical industry waste water and waste water containing high density difficultly degraded organic matter.
Description
Technical field
The present invention relates to wastewater treatment and reuse field; More particularly; Relate to the method and the purposes of gasification and Treatment of Coking Effluent or reuse and existing engineering upgrading, and similar Coal Chemical Industry and contain higher concentration hardly degraded organic substance wastewater treatment qualified discharge or reuse and existing engineering upgrading.
Background technology
Coking chemical waste water and coal gasification waste water are coking charcoal and the high density poisonous organic wastewater of making the difficult for biological degradation that produces in the course of gas, are mainly derived from the coke-oven plant of ferrous metallurgy and coking industry and the producer gas plant of system coal gas.Mainly contain ammonia nitrogen (NH in coking chemical waste water and the coal gasification waste water
3-N), pollution substances such as the heterogeneous ring compound of prussiate, phenolic cpd, polycyclc aromatic compound and nitrogenous, oxygen, sulphur and fatty compounds, have " three cause " effect, huge to HUMAN HEALTH with the ecotope threat.Except that forming complicacy, coking and coal gasification waste water also have characteristics such as the change of water quality amplitude is big, biodegradability is poor, toxicity is big.
The seventies in 20th century, coking of domestic main employing Wastewater Treated by Activated Sludge Process and coal gasification waste water after the processing, have only phenol and BOD can reach discharging standards; Generally adopt two sections biochemistry, extended aeration the eighties or strengthen methods such as biochemical (like biological iron, biological carbon, add growth hormone etc.) and handle coking and coal gasification waste water; The clearance of phenol in the processed waste water, thiocyanide, BOD is more than 90%; Reached national discharging whom has marked; But COD and ammonia nitrogen do not reach discharging standards (Tang Lizhen, 1994).Ministry of Metallurgical Industry's investigation in 1997, the COD after the coke-oven plant more than 90% and producer gas plant are handled, ammonia nitrogen can't (Wang Yeyao etc., 2002) up to standard.
Since the seventies, mainly carried out the research that biological method is handled coking and coal gasification waste water abroad, like gac one activated sludge process, two sections biological fluidized bed anoxic aerobic methods, suspended sludge anoxic aerobic method, media filtration method and pure-oxygen aeration method etc.
Got into since the nineties; Fast development along with biotechnology; What various biological reinforcing technologies were a large amount of uses in domestic and international coking and the coal gasification waste water processing; Parallel with it is the development of various physics, chemistry, materialization technology, materialization-bio combined innovation technology, and the approach of coking and coal gasification waste water processing has been opened up in the development of various emerging technologies greatly.
Physico-chemical processes is used in the pre-treatment and the advanced treatment stage of coking and coal gasification waste water processing usually, is used for reducing coking and coal gasification waste water toxicity, auxiliary biological treatment, alleviates biological treatment load or assurance final outflow water water quality.The physico-chemical processes method mainly contains burning method, ammonia still process method, extraction process, air supporting method, absorption method, coagulant sedimentation, membrane separation process, electrochemical process, oxygenant oxidation method.Physico-chemical process is mainly as the auxiliary process of biological treatment; Guarantee biological treatment system steady running or guarantee the wastewater treatment qualified discharge that it specifically adopts methods to carry out reasonable combination and selection according to concrete water quality and quantity situation, enterprise present situation and emission request.Wherein pretreatment technology adopts technologies such as oil removal, air supporting usually, to remove most of oils in the waste water, guarantees the steady running of biological treatment; Advanced treatment process mainly solves hardly degraded organic substance problem in the waste water, and concrete grammar adopts methods such as coagulating sedimentation, oxidizing, flocculating and electrochemistry usually.
Biological process all is the of paramount importance method of wastewater treatment all the time, utilizes the metabolic processes of mikrobe that pollutants in waste water is removed, and compares with physics, chemical process to have efficient advantage.Biological process is the main process in the wastewater treatment, and therefore the directly success or failure of decision sewage treatment project of its operation quality are waste water treatment process key for design links.Mainly comprise two ends aerating activated sludge process, aerobic/anaerobic biomembrance process, A/O method (comprising AAO, AAOO method etc.), natural biology facture, SBR method etc. at present; More than various conventional bioremediations can solve coking and the coal gasification waste water problem in a certain respect in handling to a certain extent at certain; But in general; It is difficult to guarantee the comprehensive up to standard and steady running of wastewater treatment, and the existence investment is big, working cost is high, floor space reaches the secondary pollution problems of being correlated with greatly.
In recent years; Water quality characteristics and difficulty in treatment according to coking and coal gasification waste water; New Development has been put on display wet oxidation process, flue gas facture, supercritical water oxidation method, plasma technique facture, ultrasonication method, irradiation method and photocatalytic oxidation etc.; More than various new technologies or because the investment working cost is high; Perhaps owing to still be in the laboratory study stage, perhaps have certain feasibility to a certain enterprise Special Circumstances, it is still having a large amount of work to do aspect practical engineering application of ubiquity and the popularization.
At present, domestic majority coking and coal gasification plant waste water are main with biological treatment still, generally adopt activated sludge process and A
2O (anaerobism+anoxic+aerobic) technology.A
2The treatment effect of O technology is superior to activated sludge process, still, and through A
2Water outlet after the O art breading is difficult to reach secondary discharge standard, particularly COD and the NH in the discharging standards (GB8978-1996)
3These two indexs of-N are difficult to reach emission request simultaneously, firsts and seconds standard-required water outlet COD and NH among the GB8978-1996
3-N is lower than 100mg/L, 150mg/L and 15mg/L, 25mg/L respectively.It is to contain a certain amount of hardly degraded organic substance in coking and the coal gasification waste water that COD is difficult to major cause up to standard, enters into final outflow water thereby these hardly degraded organic substances are difficult to obtain degraded in bio-reactor; Because COD is higher in the aerobic reactor; All be to be dominant bacteria in the conventional reactors with heterotrophic bacterium (mainly being nutrition) with the organic carbon source; Suppressed the growth of nitrifier; In addition, the hardly degraded organic substance with bio-toxicity also will suppress the growth of nitrifier in higher concentration range, so water outlet NH
3-N also is difficult to up to standard.
Summary of the invention
The objective of the invention is to fill up the vacancy of present domestic and international similar gasification and Technologies of Coke Plant Wastewater Treatment, a kind of novel gasification and Treatment of Coking Effluent or recycling method are provided.
The object of the invention can realize through following measure: adopt " pre-treatment+efficient anaerobic+anoxic/aerobic+high efficient aeration biological filter+advanced treatment " combination process (hereinafter to be referred as the PAOD combination process) to handle gasification and coking chemical waste water.Gasification and coking chemical waste water through overregulate, after oil removal, deposition and the air supporting; Remove most suspended substances SS and oily substance in the waste water at this; To guarantee the steady running of follow-up anaerobic treatment process, pretreated water outlet gets into the anaerobic biological treatment technique unit, removes the portion C OD in the waste water at this; Reduce the subsequent treatment process load, improve wastewater biodegradability; The anaerobism water outlet enters into anoxic/the aerobic and high efficient aeration biological filtering tank process of back segment, further removes COD, ammonia nitrogen, volatile phenol, prussiate, sulfide and petroleum substance in the waste water; The water outlet of high efficient aeration biological filter after advanced oxidation is handled qualified discharge or through technology desalinations such as r-o-s after reuse.
Wherein:
In the A section; Adopt the efficient anaerobic treatment process; Pool-type structure adopts UASB, EGSB, IC, ABR and modified version, and the pond body adopts steel reinforced concrete anticorrosion structure or steelwork, and three separators and water distributor are set in the pond; Add special-purpose granule sludge during commissioning test to accelerate toggle speed, design loading is 5-8kg COD/m
3.d, the COD removal effect is about 25-40%, and B/C is to improving about 0.04-0.12.
In the O section; Adopt anoxic/aerobic and high efficient aeration biological filtering tank process; Anoxic/aerobic employing conventional activated sludge method; The pond type can adopt A/O, oxidation ditch etc., and the high efficient aeration biological filtering tank process adopts the filter tank structure among the patent publication No. CN101746884A, and the anoxic pond design loading is 1.5-3.0kg COD/m
3.d, dissolved oxygen is controlled at about 0.3-0.8mg/L; The Aerobic Pond design loading is 0.8-1.5kg COD/m
3.d, dissolved oxygen is controlled at about 2-4mg/L; High efficient aeration biological filtering tank process design loading is 0.3-0.5kg COD/m
3.d, dissolved oxygen is controlled at about 3-5mg/L; Anoxic/aerobic and high efficient aeration biological filtering tank process are to the COD in coking and the coal gasification waste water, BOD
5, ammonia nitrogen, volatile phenol, sulfide, prussiate and petroleum-type clearance reach 88-93%, 92-97%, 96-99%, 99.9%, 98.5-99.5% and 98.0-99.5%.
When containing the not biodegradable organism of higher concentration in the higher or waste water when the standard of efflux wastewater; Can behind the high efficient aeration biological filtering tank process, put one section advanced oxidation treatment process by tail; Through regulating wastewater pH, replenish proper amount of oxidant, ferrous sulfate or gac, through effects such as oxidation, absorption and depositions; Effectively remove colourity and hardly degraded organic substance in the waste water, guarantee discharged wastewater met the national standard.For example, when water outlet COD in high efficient aeration biological filter is 263mg/L, pH is 8.0; When colourity was 800 times, through adding the sulfur waste acid for adjusting pH to 3-5, the iron vitriol dosage was 500mg/L; 30% ydrogen peroxide 50 dosage is 0.5ml/L; Aerated reaction 2-3h adds lime or caustic soda and regulates about pH to 7.8-8.2 that water outlet COD is 36.4mg/L behind the deposition 1-2h, and colourity is 2 times.
The high efficient aeration biological filtering tank process can be realized efficient coupling with wastewater recycling treatment process such as reverse osmosis desalination; The pretreatment technology that is fit to membrane technique in the waste water recycling processing; Increase the cycles of concentration of membrane process, realize recycle and enterprise's sewage " zero release " of water resources.
This technology not only is applicable to gasification and Treatment of Coking Effluent or reuse and existing engineering upgrading, also is applicable to similar Coal Chemical Industry and contains higher concentration hardly degraded organic substance wastewater treatment qualified discharge or reuse and existing engineering upgrading.
Compare with traditional technology, advantage of the present invention is: efficient anaerobic is not only effectively subdued organic pollutant in the waste water, reduces the back-end processing technical load, and can improve wastewater biodegradability; The high efficient aeration biological filter is fast to contaminant degradation speed in the waste water, and processing efficiency is high, strong shock resistance, and effectively the slow-paced mikrobe of enrichment and growth is improved treatment effect such as hardly degraded organic substance and ammonia nitrogen in the waste water, and is stable and the mud generation is few; With the pretreatment technology of high efficient aeration biological filter, can guarantee that integrally combined technology is stable, and effectively alleviate follow-up advanced treatment process operation difficulty, and then reduce working cost as the check on technology and the advanced treatment process of conventional activated sludge method.
Description of drawings
Fig. 1: process flow sheet of the present invention
------water route
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Embodiment
Enumerate 3 embodiment below,, the present invention is further specified, but the present invention is not only limited to this 3 embodiment in conjunction with accompanying drawing.
Embodiment 1
Water inlet COD and NH after utilizing aforesaid combination technology to the pre-treatment of process coagulating sedimentation
3The actual coal gasification waste water that-N is respectively about 2865mg/L and 127mg/L carries out lab scale experiment processing; The experiment flooding velocity is 100mL/h, and the effective volume of anoxic biological filter and secondary aerobic biological filter reactor drum is 6000mL, anoxic biological filter reactor drum waterpower residence time 20h; Secondary aerobic biological filter reactor drum waterpower residence time 40h; The carrier loadings is 60% in the reactor drum, and single carrier bulk is 20mm * 20mm * 20mm, and wet density is 0.9g/cm
3, water holding capacity is 2500%, dissolved oxygen concentration is controlled at 4～6mg/L in the aerobic reactor, and replenishes enough basicity, all inoculates Treatment of Coking Effluent factory active sludge in the reactor drum of biological filter, adds engineering bacteria B350M and carries out biological reinforced processing, water outlet COD and NH
3-N about 221.0-357.28mg/L and 5mg/L, is not having under backflow and the supplementary carbon source situation respectively, and the nitre nitrogen concentration is stabilized in the 4.67-33.24mg/L scope, and technology has reached about 70-75% the direct removal efficient of total nitrogen.The advanced oxidation advanced treatment is carried out in biological water outlet, and COD is 263mg/L, and pH is 8.0; When colourity was 800 times, through adding the full 3-5 of sulfur waste acid for adjusting pH, the iron vitriol dosage was 500mg/L; 30% ydrogen peroxide 50 dosage is 0.5ml/L; Aerated reaction 2-3h adds lime or caustic soda and regulates about pH to 7.8-8.2 that water outlet COD is 36.4mg/L behind the deposition 1-2h, and colourity is 2 times.
Embodiment 2
Certain coking branch office of iron and steel group produces comprehensive wastewater 10848m
3/ d (452m
3/ h), adopt above combination process that it is handled.Comprehensive wastewater is promoted to oil removal and air-float technology to remove most of oils and SS in the waste water through pump after equalizing tank is collected; Pretreated waste water gets into the anoxic pond and the Aerobic Pond of rear end and handles after anaerobic pond is handled; The Aerobic Pond water outlet gets into two film processing systems after getting into high efficient aeration biological filter advanced treatment; Film effluent reuse after desalination is in the technological cycle water coolant, and liquid concentrator is used for blast furnace slag flushing before the film.
Adopt above combination process to handle coal tar comprehensive discharge waste water, designed water is 10848m
3/ d (452m
3/ h), the carrier loadings is 60% in the high efficient aeration biological filter, and single carrier bulk is 30mm * 30mm * 30mm, and wet density is 1.1g/cm
3, water holding capacity is 2500%, all inoculates Treatment of Coking Effluent factory active sludge in the biological reaction tank, adds engineering bacteria B350M and carries out biological reinforced processing.Equalizing tank comes water COD after pre-treatment
Cr, BOD
5, ammonia nitrogen, volatile phenol, sulfide and prussiate be respectively 1600-2600mg/L, 700-1000mg/L, 260-350mg/L, 300-500mg/L, 10-20mg/L and 4-10mg/L, biology aerobic water outlet COD
Cr, BOD
5, ammonia nitrogen, volatile phenol, sulfide and prussiate be respectively 90-125mg/L, 8-13mg/L, 3-5mg/L, 0.3-0.5mg/L, 0.2-0.4mg/L and 0.1-0.3mg/L; Bio-chemical effluent reuse after two film systems advanced treatment is up to standard; Film system ratio of desalinization is more than 97%, and the water recovery reaches 66-72%.
Embodiment 3
Certain coking group produces comprehensive wastewater 1680m
3/ d (70m
3/ h), adopt above combination process that it is handled.Comprehensive wastewater is promoted to oil removal and air-float technology to remove most of oils and SS in the waste water through pump after equalizing tank is collected; Pretreated waste water gets into the anoxic pond and the Aerobic Pond of rear end and handles after handle in the efficient anaerobic pond; The Aerobic Pond water outlet gets into two film processing systems after getting into high efficient aeration biological filter advanced treatment; Film effluent reuse after desalination is in the technological cycle water coolant, and liquid concentrator is used for the coal yard coal washing or further handles the back qualified discharge before the film.
Adopt above combination process to handle coal tar comprehensive discharge waste water, designed water is 1680m
3/ d (70m
3/ h), the carrier loadings is 60% in the high efficient aeration biological filter, and single carrier bulk is 30mm * 30mm * 30mm, and wet density is 1.1g/cm
3, water holding capacity is 2500%, all inoculates Treatment of Coking Effluent factory active sludge in the biological reaction tank, adds engineering bacteria B350M and carries out biological reinforced processing.Equalizing tank comes water COD after pre-treatment (oil removal, deposition and air supporting)
Cr, BOD
5, ammonia nitrogen, volatile phenol, sulfide and prussiate be respectively 4000-5000mg/L, 1400-1600mg/L, 320-360mg/L, 600-640mg/L, 15-30mg/L and 8-15mg/L, biology aerobic water outlet COD
Cr, BOD
5, ammonia nitrogen, volatile phenol, sulfide and prussiate be respectively 180-260mg/L, 11-23mg/L, 4-7mg/L, 0.3-0.4mg/L, 0.2-0.3mg/L and 0.2-0.4mg/L; Bio-chemical effluent reuse after two film systems advanced treatment is up to standard; Film system ratio of desalinization is more than 97%, and the water recovery reaches 64-68%.
Can see by above-mentioned instance; No matter be lab scale experiment or practical applications; The present invention all has good treatment effect for coking chemical waste water and gasification, and final outflow water can reach the first discharge standard (GB8978-1996) in the integrated wastewater discharge standard after advanced oxidation is handled, and biological water outlet can reach the recirculated cooling water water supply standard fully after two film desalinations; Film system ratio of desalinization is more than 97%, and the water recovery reaches about 65%.
Claims (7)
1. a gasification and Treatment of Coking Effluent or recycling method is characterized in that: adopt the PAOD combination process to handle gasification and coking chemical waste water, wherein:
The P section is represented pre-treatment, adopts technologies such as adjusting, oil removal, deposition and air supporting;
The A section is represented anaerobic treatment, adopts the efficient anaerobe treatment process;
The O section is represented aerobic treatment, and adopting anoxic/aerobic and high efficient aeration biological filter is the HABF treatment process;
D section representing depth is handled, and adopts treatment process such as advanced oxidation or reverse osmosis membrane;
Gasification and coking chemical waste water through overregulate, after oil removal, deposition and the air supporting; Remove most suspended substances SS and oily substance in the waste water at this; To guarantee the steady running of follow-up anaerobic treatment process, pretreated water outlet gets into the anaerobic biological treatment technique unit, removes the portion C OD in the waste water at this; Reduce the subsequent treatment process load, improve wastewater biodegradability; The anaerobism water outlet enters into anoxic/the aerobic and high efficient aeration biological filtering tank process of back segment, further removes COD, ammonia nitrogen, volatile phenol, prussiate, sulfide and petroleum substance in the waste water; The water outlet of high efficient aeration biological filter after advanced oxidation is handled qualified discharge or through technology desalinations such as r-o-s after reuse.
2. according to the novel combination technology of the described gasification of claim 1 and Treatment of Coking Effluent or reuse; It is characterized in that: in the A section, adopt the efficient anaerobic treatment process, pool-type structure adopts UASB, EGSB, IC, ABR and modified version; The pond body adopts steel reinforced concrete anticorrosion structure or steelwork; Three separators and water distributor are set in the pond, add special-purpose granule sludge during commissioning test to accelerate toggle speed, design loading is 5-8kgCOD/m
3.d, the COD removal effect is about 25-40%, and B/C is to improving about 0.04-0.12.
3. according to the novel combination technology of the described gasification of claim 1 and Treatment of Coking Effluent or reuse; It is characterized in that: in the O section; Adopt anoxic/aerobic and high efficient aeration biological filtering tank process, anoxic/aerobic employing conventional activated sludge method, the pond type can adopt A/O, oxidation ditch etc.; The high efficient aeration biological filtering tank process adopts the filter tank structure among the patent publication No. CN101746884A, and the anoxic pond design loading is 1.5-3.0kg COD/m
3.d, dissolved oxygen is controlled at about 0.3-0.8mg/L; The Aerobic Pond design loading is 0.8-1.5kg COD/m
3.d, dissolved oxygen is controlled at about 2-4mg/L; High efficient aeration biological filtering tank process design loading is 0.3-0.5kgCOD/m
3.d, dissolved oxygen is controlled at about 3-5mg/L; Anoxic/aerobic and high efficient aeration biological filtering tank process are to the COD in coking and the coal gasification waste water, BOD
5, ammonia nitrogen, volatile phenol, sulfide, prussiate and petroleum-type clearance reach 88-93%, 92-97%, 96-99%, 99.9%, 98.5-99.5% and 98.0-99.5%.
4. according to the novel combination technology of the described gasification of claim 1 and Treatment of Coking Effluent or reuse; When containing the not biodegradable organism of higher concentration in the higher or waste water when the standard of efflux wastewater; Can behind the high efficient aeration biological filtering tank process, put one section advanced oxidation treatment process by tail; Through regulating wastewater pH, replenish proper amount of oxidant, ferrous sulfate and gac, through effects such as oxidation, absorption and depositions; Effectively remove colourity and hardly degraded organic substance in the waste water, guarantee discharged wastewater met the national standard.
5. according to the novel combination technology of the described gasification of claim 1 and Treatment of Coking Effluent or reuse; The high efficient aeration biological filtering tank process can be realized efficient coupling with wastewater recycling treatment process such as reverse osmosis desalination; The pretreatment technology that is fit to membrane technique in the waste water recycling processing; Increase the cycles of concentration of membrane process, realize recycle and enterprise's sewage " zero release " of water resources.
6. according to the novel combination technology of the described gasification of claim 4 and Treatment of Coking Effluent or reuse, it is characterized in that: when water outlet COD in high efficient aeration biological filter is 263mg/L, pH is 8.0; When colourity was 800 times, through adding the sulfur waste acid for adjusting pH to 3-5, the iron vitriol dosage was 500mg/L; 30% ydrogen peroxide 50 dosage is 0.5ml/L; Aerated reaction 2-3h adds lime or caustic soda and regulates about pH to 7.8-8.2 that water outlet COD is 36.4mg/L behind the deposition 1-2h, and colourity is 2 times.
7. the novel combination technology of a gasification as claimed in claim 1 and Treatment of Coking Effluent or reuse; Not only be applicable to gasification and Treatment of Coking Effluent or reuse and existing engineering upgrading, also be applicable to similar Coal Chemical Industry and contain higher concentration hardly degraded organic substance wastewater treatment qualified discharge or reuse and existing engineering upgrading.
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Application publication date: 20120208 |