CN1994936B - Method for processing and resuing carbinol waste water for circulated cooling water - Google Patents
Method for processing and resuing carbinol waste water for circulated cooling water Download PDFInfo
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- CN1994936B CN1994936B CN2006101298545A CN200610129854A CN1994936B CN 1994936 B CN1994936 B CN 1994936B CN 2006101298545 A CN2006101298545 A CN 2006101298545A CN 200610129854 A CN200610129854 A CN 200610129854A CN 1994936 B CN1994936 B CN 1994936B
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Abstract
The invention discloses a method for recycling industrial wastewater with carbinol from methanol plant for circulating cooling water, which adoptings a treatment process integration system including hydrolytic adjusting pond, microaerobic biological contact oxidization; aerobic biological contact oxidization, concreting sedimentation, active charcoal filtering and UV disinfection. In the biological contact oxidization, elastic cubic packing and microporous aeration system are used as packing. In the microaerobic biological contact oxidization process, organism is decomposed with 0.5-1. 0mg/L DO and and biodegradability of wastwater is greatly improved; in the aerobic biological contact oxidization, CODcr is effectively removed with 2-4mg/L DO; the suspension matter in output water of aerobic biochemical pond is removed via concreting sedimentation; suspension matter and organic matter is further removed by active charcoal filtering and finally the output water is repatedly used as supply water of circulating cooling waterafter UV disinfection. The method has the advantage of simple operation, low running cost, little equipment investment, repeatedly used wastewater and no secondary pollution.
Description
Technical field
The present invention relates to methanol industrial wastewater and handle and reuse, specifically a kind of Methanol Plant is produced the wastewater containing methanol of methyl alcohol discharging and is handled the method that is back to recirculated cooling water.
Background technology
Methyl alcohol is a kind of important material in pharmacy, chemical industry and pesticide producing.In methanol production process, the vinasse by discharging at the bottom of the rectifying tower is commonly referred to methanol waste water.Methanol waste water has the strong impulse smell, and its main component is methyl alcohol, ethanol, higher alcohols and aldehydes; Also contain some long-chain compounds.
The treatment process of at present common methanol waste water has physico-chemical process, chemical method and biochemical process, and these methods can be carried out in various degree processing to methanol waste water.Physico-chemical process and chemical method are halfway treatment processs, the bioremediation effect is better, comprising anaerobic biological treatment and aerobic biological treatment, and the processing of the methanol waste water of lower concentration during aerobe is handled and is used for more, its capacity of resisting impact load a little less than, move the improper sludge bulking that causes easily; Anaerobic treatment is used for the processing of the waste water of high density more, and the water outlet effect is better.
It is according to the low-boiling physical property of alcohols in the waste water that gasification is handled methanol waste water, utilize the waste heat boiler that generally has in the chemical fertilizers production as thermal source, the vaporization low-boiling-point organic compound advances Gas-making Furnace then and is used to make unstripped gas, reaches to administer waste water and the dual purpose that reclaims raw material.During actual motion, can continuously or be interrupted and in waste heat boiler, advance waste water.One switching valve can be set, so that control or soft water advance waste heat boiler separately, or waste water mixes laggard waste heat boiler with soft water.This method flow process is simple, need not to acquire main equipment, is easy to control and management, can realize the purpose that waste water does not give up, turns harm into good.
The methanol waste water anaerobic biological treatment is that methyl alcohol is converted into methane by dual mode in the anaerobic treatment process: (1) directly transforms: 4CH
3OH → 3CH
4+ CO
2+ 2H
2O; (2) be converted into acetate earlier and change into methane: 4CH again
3OH+CO
2→ 3CH
3COOH+2H
2O, CH
3COOH+H
2O → CH
4+ CO
2+ H
2O.Anaerobism is to handle the method preferably that contains high concentration methanol waste water, and its advantage is that working cost is low, and recyclable methane, and surplus sludge volume is few, save energy.Up-flow anaerobic sludge blanket method (UASB) is compared with conventional treatment technology art, and this technology has higher operating load and reaches treatment effect preferably.In addition, the anaerobic-aerobic activated sludge process is a kind of a kind of method of handling high concentration methanol waste water preferably,
The processing of methanol waste water aerobe has multiple, and abundant as the oxidation ditch design capacity, the waste water hydraulic detention time is longer, can guarantee the water outlet qualified discharge.Aerobic biological fluid-bed treatment process selects for use a kind of type material as bio-carrier, makes it to form three-phase fluidization with liquid and air in bed.Compare with conventional aerobe treatment technology (as surface aeration method, contact oxidation method etc.), it is high that it handles load, and treatment effect is good.The shortcoming of aerobic biological fluid-bed treatment process is that power consumption is bigger, biomass content height in the water outlet.
The immobilized biological activated carbon technology is to handle a kind of method preferably of lower concentration methanol waste water, lower concentration methanol waste water for fertilizer industry, can adopt the fixed cell technology to handle, can keep higher biomass in the reactor, having operation starts fast, the processing efficiency height, the advantage of stable operation.Utilize granulated active carbon to fix engineering bacteria, reached the collaborative purpose of removing methyl alcohol of gac and engineering bacteria as carrier.But this method investment is big, the operational administrative complexity.
Summary of the invention
The object of the present invention is to provide a kind of methanol industrial wastewater to handle the method that is back to recirculated cooling water, make methanol waste water reach the recirculated cooling water processing requirements.
To achieve these goals, the present invention has adopted hydrolyzing regulation pond, and---------coagulating sedimentation---activated carbon filtration---UV disinfects technology integrated system technology to aerobic bio-contact oxidation to little oxygen bio-contact oxidation.
Ultimate principle of the present invention:
1. agitator and interpolation active sludge under water are housed in the hydrolyzing regulation pond.Existing regulatory function has the biological hydrolysis acidification again.Hydrolyzing regulation pond is equipped with the tubing system that mud refluxes, regularly from biochemistry pool and coagulative precipitation tank returnedactivatedsludge.
2. the ultimate principle of little oxygen biochemistry pool is to be oxygen source with the air, with the elastic solid filler is bio-carrier, cover one deck microbial film above the carrier, in carrier and process that waste water fully contacts, organism enters microbial film, biological metabolism Degradation by double oxygen on the microbial film and aerobic microbiological group is removed organism, reduces COD.The present invention adopts the synergy degradation of organic substances of holding concurrently oxygen animalcule group and multiple aerobic microbiological group, the oxygen animalcule of holding concurrently is degraded to organism earlier, forms easily organic intermediate product of degraded of low molecule, improves the biodegradability of waste water, by the degraded fully of aerobic microbiological, generate CO at last
2+ H
2O.Because certain roughness is arranged above the filler, add a small amount of aeration of filler, current are more slow, and certain dissolved oxygen and organism are arranged, and perch breeding for the microorganism on the filler, and the cultivation domestication through has after a while formed sophisticated microbial film at filling surface.
3. the ultimate principle in aerobic biochemical pond and little oxygen biochemistry pool are similar, and different is that little oxygen pond aeration rate is few, and the Aerobic Pond aeration rate is big.Aerobic biochemical pond DO is 2～4mg/L, on the microbial film mainly be aerobic microbiological in action.
4. coagulative precipitation tank is by dosing coagulant before line mixer such as PAC, make biofloculation and chemical flocculation form synergy, remove suspended substance and organism, for follow-up charcoal absorption filtration creates conditions, prolong the work period of gac, reduce the back flushing frequency.The coagulating sedimentation sludge part is back to hydrolyzing regulation pond.Part mud decomposes at hydrolytic tank self carries out decrement.
5. gac pond: filter and remove tiny suspended substance, reduce turbidity, remove remaining organism by absorption simultaneously.The general one day air-water backwashing in gac pond once, backwash water is back to hydrolyzing regulation pond.
6.UV sterilizer is to utilize the destruction kill bacteria of the UV-light of predominant wavelength 253.7nm to bacterium.
Characteristics of the present invention:
(1) hydrolyzing regulation pond has dual-use function, both had powerful water quality and quantity regulatory function, had certain biological hydrolysis acidifying function again, difficult biochemical organism had been had good degradation function, can increase substantially the biodegradability of waste water, for the generate subsequent metallization processes creates conditions.This technology has stronger economy, safe and reliable, practical, anti-shock loading, and mud is realized refluxing, and has reduced mud handling capacity, greatly reduces investment and working cost.
(2) little oxygen biological treatment is compared with the anaerobic technique of routine, has eliminated H
2The generation of peculiar smell such as S is compared with aerobic process simultaneously, has reduced aeration rate, has saved power consumption, is the biological treatment of an energy-conservation odorless.
(3) little oxygen biochemical process and routine biochemistry process optimization combination, reliable, be easy to control, simple to operate, stable water outlet, especially anti impulsion load.
(4) system process advanced person, combination is reasonable, and activated carbon filtration technology need not frequent backwash, and filtration cycle is long, and treatment effect is good, and water outlet is very stable, anti impulsion load.
Description of drawings
Fig. 1 is a process flow diagram of the present invention
Embodiment
In hydrolyzing regulation pond, add a certain amount of active sludge, mix by agitator under water.The equalizing tank water outlet is promoted by water pump 2 and enters little oxygen biochemistry pool 3 from top, and filler is installed biochemistry pool 3 internal upper parts and micro-pore aeration system is arranged at the bottom, and DO is normally operation under the condition of 0.5～1.0mg/L in the pond.The water outlet of little oxygen biochemistry pool is promoted by water pump 4 and enters aerobic biochemical pond 5 from the bottom, and aerating system is arranged at 5 bottoms, aerobic biochemical pond, and the aerator top is equipped with filler, is normally operation under the condition of 2～4mg/L at DO.The aerobic biochemical pond enters line mixer 6 from the top water outlet, and dosing coagulant PAC enters inclined-plate clarifying basin 8 by water pump 7 lifting pressurizations.The settling tank water outlet enters activated carbon filtration 9, and filter back water enters the recirculated cooling water pond through uv sterilizer 10 and recycles.The normal operating parameter of each technology of methanol waste water treatment system is: (1) hydrolyzing regulation pond: 35～37 ℃ of pond water temperatures, pH value 6～9, DO 0～1mg/l, HRT 16h, MLSS 1～4g/L; (2) little oxygen biological treatment: 32 ℃ of controlling reactor front end water temperatures, pH value 7～8, DO 0.5～1mg/l, HRT 4h, MLSS 3～5g/L; (3) aeration aerobe contact process: 30 ℃ of control water temperature, pH value 8～9, DO=2～4mg/l, MLSS 2～3g/L, HRT 6h; (4) coagulation-settlement process: 20～30 ℃ of water temperatures, pH value 7～8, HRT 40min adds PAC 5～10mg/l; (5) BAC filters: 10～30 ℃ of control water temperature, pH value 8, DO＞4mg/l, 30 ℃ of backwash water temperatures, backwash cycle 24h, backwash time 7min, backwash water yield 2m
3, backwash tolerance 2m
3, filtering velocity 18m/h; (6) sterilization process: control water temperature is not less than 10 ℃ winter, about 30 ℃ of summers, pH value 7～8, DO＞4mg/l, CODcr＜10mg/l..
Under each technology normal running (operation) conditions of Waste Water Treatment, it is as shown in table 1 to handle each waste water treatment process operation treatment effect of back.
(hardness is with CaCO for each technology operation result of table 1
3Meter)
| The water quality project | Water inlet | Hydrolyzing regulation pond | Little oxygen biological treatment | Aerobe is handled | Coagulating sedimentation is handled | The BAC reaction tower | The UV sterilization process |
| CODcr (mg/l) methyl alcohol (%) pH turbidity (degree) specific conductivity total hardness total alkalinity Ca 2+(mg/L) CI -(mg/L) T-P(mg/L) NH 3-N (mg/L) total plate count (individual/mL) | 456 3.7 9.1 24.3 198 177 135 31 70 1.94 0.7 |
403 2.2 7.7 26 187 169 124 29 67 1.7 0.7 / / | 64/85％ 0.001/95％ 8 22 212 164 126 27 67 0.44 0.18 / / | 30/15％ 0.0002/9％ 8.3 18 209 146 115 21 53 0.33 0.04 / / | 19/10％ ＜0.0002 8 9 133 143 101 17 50 0.19 0.03 / / | 11/5%＜0.0001 7.7 1.6 127 142 108 16 39 0.16＜0.01 |
9/2％ ＜0.0001 7 1.9 142 131 87 13 42 0.12 ＜0.01 2×10 2 4×10 2 |
As can be seen from Table 1, methanol industrial wastewater principal pollutant water-quality guideline methyl alcohol and COD
CrMainly be that the biochemical process combined system is removed, wherein methyl alcohol can remove 95%, and CODcr can remove 95%.The removal of turbidity mainly is that coagulation-settlement process is removed, and follow-up BAC filters and the biological contact process of aeration internal recycle also can be removed a part.Each technology of other index all has certain removal effect.The treatment system water outlet reaches the industrial circulating cooling water water quality standard.
Since this engineering put into operation 1 year, treatment effect was stable always, and effluent quality is good.Main technique operation treatment effect scope of statistics is shown in Table 2.
(hardness is with CaCO for table 2 result statistical value scope
3Meter)
| The water quality project | Water inlet | The water outlet of life assemblage system | The BAC water outlet |
| CODcr (mg/l) methyl alcohol (%) pH turbidity (degree) specific conductivity total hardness total alkalinity Ca 2+(mg/L) CI -(mg/L) T-P(mg/L) NH 3-N (mg/L) total plate count (individual/mL) | 288～494 0.33～4.9 6.8～9.2 23.5～34.7 130～357 167～211 110～178 16～34 40～90 1.74～2.2 0.48～1.1 winters 8.9 * 10
6 |
14～30 0.0002 7.2～8.3 17.0～23.0 101～289 134～177 106～125 12～21 36～53 0.34～0.37 0.03～0.04 / / | 5～10＜0.0001 7.5～8.2 1.5～2.7 97～203 129～164 98～117 10～20 42～39 0.16～0.21＜0.01 |
From table 1 or 2 as can be seen,---------coagulating sedimentation---activated carbon filtration---UV disinfects the processing of technology integrated system and contains methanol industrial wastewater aerobic bio-contact oxidation little oxygen bio-contact oxidation to adopt hydrolyzing regulation pond, at raw water quality for containing methyl alcohol 0.03%～5%, pH6～10, turbidity is 23.5～34.7 degree, COD
CrBe under 200～500mg/l condition, every water-quality guideline such as the water outlet CODcr of system, methyl alcohol, specific conductivity, hardness (CaO), pH, turbidity and colourity all reach the requirement of industrial circulating cooling water water quality standard.
This treatment process system is rationally advanced, and is stable, reliable, have simple to operate, stable effluent quality, reduced investment, many advantages such as working cost is low.
Claims (3)
1. a Methanol Plant contains methanol industrial wastewater and handles the method that is back to recirculated cooling water, waste water enter that equilibrium that hydrolyzing regulation pond carries out water quality and quantity is regulated and organic anaerobic hydrolysis-acidification after, the biodegradability of raising waste water; By oxygen animalcule and the part aerobic degradation organism of holding concurrently; The water outlet of little oxygen biological reaction tank rises to the aerobe reaction tank by pump, carries out further bio-oxidation, and organism thoroughly is decomposed into CO
2+ H
2O removes COD
CrThe water outlet of aerobe reaction tank is carried out coagulating sedimentation by the line mixer dosing coagulant, removes suspended substance; Activated carbon filtration is carried out in the inclined-plate clarifying basin water outlet, further reduces suspended substance and removes not biochemical residual organic substances, and filter back water enters the recirculated cooling water pond by the UV sterilization and disinfection as supplementary feed and recycles.
2. the method for claim 1 is characterized in that described waste water hydrolyzing regulation pond HRT is 8～24h; The DO of little oxygen biological reaction tank is controlled at 0.5～1.0mg/L, and HRT is 4～12h; The DO of aerobe reaction tank is controlled at 2～4mg/L, and HRT is 6～12h; Adopt inclined-plate clarifying basin behind the coagulation, coagulating agent adopts PAC, and dosage is 5～10mg/L; The activated carbon filtration adsorption time is 5～15 minutes; UV predominant wavelength is 253.7nm.
3. apparatus system of realizing the described method of claim 1, it mainly comprises:
---equalizing tank, rounded, in an agitator is under water arranged, active sludge is arranged in the pond;
---little oxygen biological reaction tank, be rectangle, micro-hole aerator is arranged at the bottom, and elastic solid filler is equipped with in the aerator top, and micro-pore aeration is connected with gas blower outside the pond;
---the aerobe reaction tank, cylindrical, micro-hole aerator is arranged at the bottom, the flexible 3-D filler in aerator top; The water inlet of aerobe reaction tank bottom, the top water outlet;
---coagulative precipitation tank, adopt the inclined-plate clarifying basin form; The PVC swash plate is arranged at top, and the bottom has sludge hopper to unify spoil disposal;
---activated charcoal filter, the top water inlet, the bottom water outlet, the cylindrical can shape, inside is granulated active carbon;
---the UV sterilizer, adopt duct type UV sterilizing unit;
---line mixer, be installed on the pipeline of aerobe reaction tank water outlet, aerobe reaction tank water outlet dosing coagulant carries out coagulating in line mixer, form mud and the thick suspended particle of volume and remove in settling tank.
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172744B (en) * | 2007-11-20 | 2011-06-15 | 中国科学院南京地理与湖泊研究所 | Process method and device for dimethyl ether production wastewater recycled for cooling water |
| CN101519267B (en) * | 2009-04-14 | 2011-08-24 | 北京师范大学 | Combined treatment process for high-concentration organic waste water |
| CN102050548B (en) * | 2009-10-29 | 2012-09-26 | 中国石油化工股份有限公司 | Treatment and reuse method of waste water in methanol-to-olefin process |
| CN102115293A (en) * | 2010-04-27 | 2011-07-06 | 北京新源国能科技有限公司 | Waste water biochemical treatment method |
| CN102060415B (en) * | 2010-11-22 | 2013-03-27 | 浙江省农业科学院 | Method for treating domestic waste leachate tail water in adsorption-coagulation way |
| CN102701457B (en) * | 2012-07-13 | 2014-05-21 | 中国水电顾问集团中南勘测设计研究院 | Device and method suitable for centralized wastewater treatment of towns and villages |
| CN102951775B (en) * | 2012-11-24 | 2014-07-02 | 青岛小川环保设备有限公司 | Integral sewage treatment method and device thereof |
| CN105236667A (en) * | 2014-07-07 | 2016-01-13 | 中石化洛阳工程有限公司 | Closed treatment method for wood-tar processing wastewater |
| CN105110442A (en) * | 2015-08-17 | 2015-12-02 | 李海兰 | Treatment agent for removing methanol, normal butanol and isobutanol in amino resin workshop waste water |
| CN109796105A (en) * | 2019-01-29 | 2019-05-24 | 上海伊克诺环境科技有限公司 | A kind of highly difficult organic wastewater treatment process |
| CN110066831B (en) * | 2019-03-13 | 2021-03-09 | 杭州电子科技大学 | Method for quickly preparing biogas from kitchen waste |
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