CN104803542A - Integrated treatment and reuse technology of esterification wastewater - Google Patents
Integrated treatment and reuse technology of esterification wastewater Download PDFInfo
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- CN104803542A CN104803542A CN201410038333.3A CN201410038333A CN104803542A CN 104803542 A CN104803542 A CN 104803542A CN 201410038333 A CN201410038333 A CN 201410038333A CN 104803542 A CN104803542 A CN 104803542A
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Abstract
The invention relates to the field of esterification wastewater treatment technologies, and concretely relates to an integrated treatment and reuse technology of esterification wastewater. The technology comprises the following steps: 1, pretreating: adjusting the pH value of the esterification wastewater through an adjusting tank, and allowing the esterification wastewater to enter a coagulative precipitation tank in order to remove tiny suspension particles and flocs in the esterification wastewater; 2, carrying out biochemical treatment: allowing the treated esterification wastewater to sequentially go through a first-stage ABR reactor, a second-stage ABR reactor and a bio-contact oxidation tank in order to greatly reduce COD in the wastewater; 3, carrying out advanced oxidation: carrying out UV/O3 oxidation on the treated esterification wastewater obtained in step 2 in order to remove difficultly degraded organic matters; and 4, carrying out membrane treatment: carrying out multi-medium filtration, active carbon filtration and reverse osmosis membrane treatment on the treated esterification wastewater obtained in step 3 in order to obtain reusable purified water. The technology solves a problem that esterification wastewater treated through present technologies cannot be discharged in a standard reaching manner or reused, and can be widely used to solve integrated treatment and reuse of the esterification wastewater.
Description
Technical field
The present invention relates to environmental science field, particularly, the present invention relates to a kind of integrated treatment and reuse technology of esterification waste water.The present invention is applicable to the wastewater treatment of chemical industry, especially the efficient process of high density esterification waste water.
Background technology
In recent years, foster with under the condition of social economy's rapid advances in national policy, the chemical industry of China is fast-developing, and the esterification waste water discharged in production process is on the increase, environmentally safe formation great threat.Esterification class waste water, the waste water namely produced in esterification, generally comes from polyester production process.Because esterification reaction process is reversible, and reaction is extremely slow, usually selects the vitriol oil as catalyzer, the pH value of waste water is very low, acid strong, contains glycol ether in waste water simultaneously, acetaldehyde, ethylene glycol, 2-methyl isophthalic acid, the organism such as 3-dioxolanes, cause esterification waste water complicated component, pollution substance relative molecular mass is large, and containing benzene ring structure, be difficult to biological degradation, COD value is high, and intractability is large.Data presentation, by the end of the year 2012, Polyester production capacity will reach 7,000 ten thousand tons, and China's polyester production capacity reaches 3,800 ten thousand tons, accounts for 54% of world's aggregated capacity, become that global PET Industry Chain is the longest, the most influential big producing country.And often produce 1 ton of polyester product, the waste water directly generated in the esterification stage reaches 0.187 ton, calculates with China's 3,800 ten thousand tons of polyester annual capacities, and the esterification waste water of discharge reaches 710.6 ten thousand tons, accounts for more than 10% of whole polyester chemical fibre industry sewage total emission volumn.
At present, " integrated wastewater discharge standard " (GB8978-1996) specifies the enterprise that on January 1st, 1998 builds afterwards, its COD first discharge standard generally answers≤100mg/L, but for wastewater regenerating and recycling, " recirculated cooling water Standard of reclaimed water " (HG/T3923-2007) specifies, CODcr answers≤80mg/L." urban sewage reutilization industry water standard " (GB/T19923-2005) specifies, the COD of Open recirling cooling water system make up water, boiler feedwater, technique and product water answers≤60mg/L.Along with country is to the attention of field of Environment Protection, industrial wastewater discharge standard and industrial regeneration water water quality standard all will improve, and it is also proposed higher requirement to esterification waste water treatment process.Current esterification waste water treatment process mainly contains three major types: the first kind is biochemical treatment, comprises biological catalytic oxidation, upflow anaerobic sludge blanket reactor (UASB), A/O technique, A
2/ O technique etc.; Equations of The Second Kind is advanced oxidation processes, comprises Fenton oxidation method, supercritical Water Oxidation Technology etc.; 3rd class is materializing strategy, comprises distillation, rectifying, charcoal absorption etc.
UASB treatment technology.Catalana de Polimers company of Spain is at the UASB esterification waste water treatment facility of Barcelona, and its reactor volume is 600m
3, flow velocity is 0.5m/s, and esterification waste water and fiber waste water design discharge are respectively 108m
3/ d(COD is 30g/L) and 96m
3/ d(COD is 4.5g/L), reflux ratio R=5, organic loading is that every gram of VSS produces 0.6gCOD every day, and sludge output is little, and water outlet COD is lower than 3g/L.Can not qualified discharge.
Active sludge+biological contact oxidation process.Oil of SPC head factory, by polyester production waste water, enters aeration tank after pH regulator, enters settling tank subsequently, and afterwards, adopt conventional activated sludge process+biological contact oxidation process, the clearance of COD can reach 82% ~ 92%.But be less than 100mg/L to water outlet COD, then the COD value of intaking must control to be less than 1250mg/L, namely aerobic treatment unit volumetric loading can not be high.The weak point of this technique changes more responsive to water quality, the water yield, not resistance to Organic loading shock, and sludge output is large, and energy consumption is higher, produces shipwreck with up to standard.
Pre-treatment+anaerobism+aerobic.Esterification waste water, after equalizing tank pre-treatment, enters the anaerobic biofilter adopting soft-filler, enters biological contact oxidation pond subsequently, finally enter second pond.After process, COD value is down to 260mg/L by 20200mg/L, and BOD value is down to 80mg/L by 5000mg/L.
Stripping stripping+anaerobism+activated sludge process+oxygen of holding concurrently+aerobic.Esterification waste water pre-treatment can alleviate the toxic side effect of the organism such as formaldehyde, acetaldehyde to biochemical reaction greatly, by workshop stripping apparatus by Acetaldehyde in Was-te Water class material stripping, improves the efficiency of subsequent disposal.All waste water is pooled to mixing water equalizing tank and mixes the rear anaerobic reation pool that all enters and process, and reduces the concentration of waste water mesophytization inhibitory substance.Activated sludge process+oxygen+aerobic treatment process of holding concurrently has organic molecule and part larger molecular organics well removes Decomposition, and COD value is down to below 100mg/L from 5000mg/L.
Supercritical Water Oxidation Technology.The people such as Spain Cocero utilize the PET polyester production waste water of supercritical Water Oxidation Technology process Catalana de Polimers company, and total chemical oxygen demand (COD) (TOC) is 16g/L, the main ethylene glycol containing massfraction 4% in waste water.Select air velocity to be 30 ~ 34kg/h in experiment, under supercritical region pressure remains on 23MPa, carry out supercritical water oxidation.Result shows: when service temperature is 630 DEG C, only react 50s, and TOC clearance can reach 99.9%.But this method one-time investment is large, and running cost is higher.
Distillation method+activated sludge process+Fenton oxidation method.The polyester waste water COD value in Turkey chemical plant is 180 ~ 230g/L, and pH value is 2.3.First the said firm uses distil process that the COD of former water is reduced to 40g/L, then uses ordinary activated sludge and Fenton oxidation method to process.Research finds, uses the mixture of the distilled esterification waste water of conventional activated sludge process process and sanitary sewage, and after waiting for 10 days after dilution, sludge loading is 0.1gCOD/gVSS, removes about 70%COD, and water outlet COD is at about 12g/L; But adopt Fenton oxidation method, the time, COD clearance can reach 67%; Adopt activated sludge process+Fenton oxidation method, COD value can be down to 5.8g/L.
Stripping+hydrolysis+rectifying.Zhejiang University adopts " stripping+hydrolysis+rectifying " method, and from polyester waste water, reclaim ethylene glycol and acetaldehyde, this method is patented.By esterification waste water after stripping is concentrated, carry out evaporation concentration and rectification and purification.Because the treatment time is long, costly, limit the industrial application of this technology.
Cohesion distillation+bio-contact oxidation.Under certain pH value, utilize flocculation agent the part non-water soluble substance in esterification waste water to be flocculated, distill after filtration, after distillation, COD is 1000 ~ 1200mg/L, and after two stage biological catalytic oxidation, water outlet COD is 116mg/L.
Aeration+charcoal absorption.The waste water that Luoyang Petrochemical chemical fibre factory produces is PTA and PET composite waste mainly, and by " twice aeration+active carbon adsorption technology ", influent COD is between 7000 ~ 9500mg/L, and water outlet COD value is down to 280 ~ 950mg/L.
Other waste water relatively, the domestic and international research to esterification waste water is less at present, and treatment effect is different, but produces the requirement that water almost all can not reach industrial reuse water quality.For the market predicament solving esterification waste water complicated component, acidity is strong, COD high (>18000mg/L), biodegradability are poor, conventional treatment technology can not reach ideal process effect, need a kind of efficient and rational integrated treatment and reuse technology.
Summary of the invention
The object of this invention is to provide a kind of integrated treatment and reuse technology of esterification waste water.
The present invention comprises following technological step:
1) pre-treatment: first esterification waste water regulates pH through equalizing tank, then enters coagulative precipitation tank, utilizes flocculation agent to remove Ester in esterification waste water and small suspended substance etc.
2) biochemical treatment: the esterification waste water after step 1) process, successively through two-stage ABR reactor and biological contact oxidation pond, makes the COD of waste water significantly reduce, improves biodegradability.
3) precipitate: by the suspended particulate of the esterification waste water after step 3) process in second pond removing waste water, precipitating sludge drains into sludge sump.
4) advanced oxidation: the esterification waste water after step 3) process is by UV/ozone (UV/O
3) oxidation stage, removing hardly degraded organic substance.
5) film process: the esterification waste water after step 4) process, by multi-medium filtering, activated carbon filtration and reverse osmosis, obtaining can the water purification of reuse, and the water purification of acquisition imports industrial water system, and dense water is directed at step 2) circular treatment further.
Wherein,
Described step 1), before waste water enters flocculation sedimentation tank, by alkaline purification, controls the pH of waste water between 7 ~ 9.
The working pressure of described step 5) reverse osmosis is between 0.6 ~ 1.4MPa.
According to technology of the present invention, wherein said step 1) uses the conventional preconditioning technique in this area, dosing coagulation, precipitation, but due to flocculation agent, flocculating effect is undesirable in acid condition, so technology of the present invention is before flocculation sediment, esterification waste water pH is adjusted between 7 ~ 9, in addition owing to containing film treating processes in technology of the present invention, in order to reduce fouling membrane, flocculation agent adopts inorganic flocculating agent.
According to technology of the present invention, wherein said biological treatment step comprises two-stage ABR reactor and biological contact oxidation pond.One, ABR has that biological interception capacity is strong, waterpower mixing condition is good, structure is simple, hydraulic performance is good, dead band is few, stable, capacity of resisting impact load is strong, processing efficiency is high, the series of advantages such as sludge output is few, ideally achieve heterogeneous anaerobic technique stage by stage.The clearance of single-stage ABR to esterification waste water COD is greater than 80%, and two-stage ABR reactor can improve the clearance of COD, guarantees that the influent COD of subsequent bio contact-oxidation pool is less than 1000mg/L; Its two, biological contact oxidation pond method is a kind of novel biochemical procss for treating waste water developing out on the basis of activated sludge process and biomembrance process.In aeration tank, filler is housed, active sludge is attached to filling surface, pass through aeration, microbial film is directly subject to the strong agitation of upstream, constantly update, thus improve decontamination effect improving, have that the treatment time is short, volume is little, good purification, effluent quality are good and stablize, mud do not need the advantages such as backflow is not also expanded, power consumption is little.
According to technology of the present invention, wherein said advanced oxidation step comprises UV/O
3coupling technique.Owing to being used alone UV or O
3the ability removing hardly degraded organic substance is poor, adopts UV and O
3the high-level oxidation technology of coupling, can efficiently except the hardly degraded organic substance in waste water.
According to technology of the present invention, in wherein said film treatment step, comprise multi-medium filtering, activated carbon filtration and reverse osmosis process.(1) pre-treatment of reverse osmosis comprises use more medium filter, activated carbon filtration, disc filter, ultrafiltration, micro-filtration.Method of the present invention preferably uses more medium filter and activated charcoal filter, more medium filter can remove macrobead suspended substance in water, thus reduce the SDI value of water, meet the water quality requirement of deep layer purification, this equipment has cheap, and working cost is low, simple to operate, the features such as filtrate can repeatedly use through backwash, filtrate long service life.Activated charcoal filter can remove peculiar smell in water, organism, colloid, iron and chlorine residue, for the turbidity, the colourity that reduce water body, purify water, reduce and also have good effect to the pollution etc. of follow-up system (reverse osmosis), this equipment has the features such as investment is low, efficiency is high, operation and maintenance expense is low, influent quality requirement is loose, stable effluent quality.More medium filter and activated charcoal filter series connection, as the pre-treatment of reverse osmosis, can guarantee the influent quality stably reaching standard of reverse osmosis further.When strainer is after use some cycles, because filtrate top layer retains or the outside surface absorption foreign material of some amount or spot, make water degradation after filter, flow reduces, water inlet and the increase of outlet conduit pressure difference.Now, tackle strainer and carry out back flushing.Back flushing utilizes flow reversal by filter material layer, filtering layer expanded, suspends, and by means of flow shear and particle collision frictional force cleaning filter material layer, and discharged by dirt in filtering layer.(2) reverse osmosis (RO) is the sepn process utilizing permeable membrane (semi-permeable membranes) optionally to retain solute through solvent (normally water).RO is pressure-driven membrane separation technique, is filtration medium with reverse osmosis membrane, the various mineral ions in trap water, colloidalmaterial, bacterium and macromole solute, thus obtains the water of clean system.The concentrated water discharge of reverse osmosis, to one-level ABR water-in, on the one hand can dilute the COD concentration of esterification waste water after flocculation sediment, and hardly degraded organic substance can be made in esterification waste water on the other hand through UV/O
3advanced oxidation is processed into labile organic compound, after reverse osmosis concentration, then enters biochemical system circular treatment, is finally decomposed.
The present invention discloses a kind of integrated treatment and reuse technology of esterification waste water.First esterification waste water is removed suspended substance in water and colloid macromolecules by pre-treatment by the present invention, is then reduced the COD in former water by two-stage ABR reactor and biological contact oxidation pond further, then utilizes UV/O
3the high-level oxidation technology degree of depth removes the organism in former water, and treatment solution, by after more medium filter, activated charcoal filter and reverse osmosis, in further reduction water after COD, is directly recycled.After technology of the present invention solves prior art process esterification waste water, its final outflow water COD concentration is difficult to qualified discharge and can not meets the problem of standards for industrial water usage.The technology of the present invention extensively can solve comprehensive treating process and the utilization of esterification waste water.
Accompanying drawing explanation
The schema of Fig. 1 integrated treatment and reuse technology of esterification waste water according to an embodiment of the invention.
Embodiment
Below in conjunction with accompanying drawing 1 and embodiment, the present invention will be further described:
Embodiment 1
Utilize the concrete steps that esterification class waste water comprehensive treating process involved in the present invention and reuse technology are purified liquid waste:
1) pre-treatment: initial esterification waste water COD is 50000mg/L, BOD be 12000mg/L, SS is 750mg/L.After the pH that equalizing tank regulates esterification waste water, enter coagulative precipitation tank, flocculation agent is added by chemical feed pipe, utilizes to stir to make the Ester in waste water and the abundant flocculation sediment of suspended substance.Waste water leading indicator after flocculation sediment is: COD is 27000mg/L, BOD be 6500mg/L, SS is 220mg/L.
2) biochemical treatment: by the esterification waste water after step 1) process by two-stage ABR reactor, reduces the COD of waste water, improves biodegradability.Waste water leading indicator after anaerobic baffled process is: COD is 1100mg/L, BOD be 300mg/L, SS is 155mg/L.Subsequently by biological contact oxidation pond, reduce the COD of waste water further.Waste water leading indicator after biological contact oxidization treatment is: COD is 170mg/L, BOD be 80mg/L, SS is 95mg/L.
3) precipitate: by step 2) process after esterification waste water through second pond removing waste water in suspended particulate, precipitating sludge drains into sludge sump.The leading indicator of secondary clarifier effluent is: COD is 145mg/L, BOD be 70mg/L, SS is 40mg/L.
4) advanced oxidation: the esterification waste water after step 3) process is passed through UV/O
3oxidation, effectively removes hardly degraded organic substance.Through UV/O
3waste water leading indicator after oxidation is: COD is 83mg/L, BOD be 55mg/L, SS is 30mg/L.
5) by the esterification waste water after step 4) process through quartz sand filtration, activated carbon filtration and reverse osmosis, the water purification of acquisition imports water of productive use system, and dense water is directed at step 1) circularly purifying.Water purification leading indicator after above-mentioned steps process is: COD is 45mg/L, BOD be 10mg/L, SS is 15mg/L, meets industrial reuse water quality standard.
Embodiment 2
Utilize the concrete steps that esterification class waste water comprehensive treating process involved in the present invention and reuse technology are purified liquid waste:
1) pre-treatment: initial esterification waste water COD is 70000mg/L, after the pH that equalizing tank regulates esterification waste water, enter coagulative precipitation tank, flocculation agent is added by chemical feed pipe, utilizes to stir to make the Ester in waste water and the abundant flocculation sediment of suspended substance.Waste water leading indicator after flocculation sediment is: COD is 39000mg/L.
2) biochemical treatment: by the esterification waste water after step 1) process by two-stage ABR reactor, reduces the COD of waste water, improves biodegradability.Waste water COD after anaerobic baffled process is 1500mg/L, subsequently by biological contact oxidation pond, reduces the COD of waste water further.Waste water COD after biological contact oxidization treatment is 240mg/L.
3) precipitate: by step 2) process after esterification waste water through second pond removing waste water in suspended particulate, precipitating sludge drains into sludge sump.The leading indicator of secondary clarifier effluent is: COD is 200mg/L.
4) advanced oxidation: the esterification waste water after step 3) process is passed through UV/O
3oxidation, effectively removes hardly degraded organic substance.Through UV/O
3waste water leading indicator after oxidation is: COD is 80mg/L.
5) by the esterification waste water after step 4) process through quartz sand filtration, activated carbon filtration and reverse osmosis, the water purification of acquisition imports water of productive use system, and dense water is directed at step 1) circularly purifying.Water purification leading indicator after above-mentioned steps process is: COD is 40mg/L, meets industrial reuse water quality standard.
Claims (7)
1. an integrated treatment and reuse technology for esterification waste water, is characterized in that: the method comprises the steps:
1) pre-treatment: first esterification waste water regulates pH through equalizing tank, then enters coagulative precipitation tank, utilizes flocculation agent to remove Ester in esterification waste water and small suspended substance etc.
2) biochemical treatment: the esterification waste water after step 1) process, successively through two-stage anaerobic baffled reactor (ABR) and biological contact oxidation pond, makes the COD of waste water significantly reduce, improves biodegradability.
3) precipitate: by the suspended particulate of the esterification waste water after step 3) process in second pond removing waste water, precipitating sludge drains into sludge sump.
4) advanced oxidation: the esterification waste water after step 3) process passes through UV/O
3oxidation stage, removing hardly degraded organic substance.
5) film process: the esterification waste water after step 4) process, by multi-medium filtering, activated carbon filtration and reverse osmosis, obtaining can the water purification of reuse, and the water purification of acquisition imports industrial water system, and dense water is directed at step 2) circular treatment.
Wherein,
Described step 1) pH controls between 6 ~ 9;
Described step 2) temperature controls between 25 ~ 35 DEG C;
The working pressure of described step 5) reverse osmosis is 0.6 ~ 1.4MPa.
2. the integrated treatment and reuse technology of a kind of esterification waste water as claimed in claim 1, is characterized in that: the flocculation agent used in step 1) effectively can reduce the COD in former water.
3. the integrated treatment and reuse technology of a kind of esterification waste water as claimed in claim 1, is characterized in that: step 2) in anaerobic treatment adopt two-stage ABR reactor, processing efficiency is high, and sludge output is few.
4. the integrated treatment and reuse technology of a kind of esterification waste water as claimed in claim 1, is characterized in that: step 2) in adopt biological contact oxidation pond volumetric loading high, mud production rate is low.
5. the integrated treatment and reuse technology of a kind of esterification waste water as described in claim 2 and 3, is characterized in that: be optimized the sludge structure of anaerobism section, aerobic section and biophase.
6. the integrated treatment and reuse technology of a kind of esterification waste water as claimed in claim 1, is characterized in that: adopt UV and O in step 4)
3the high-level oxidation technology of coupling.
7. the integrated treatment and reuse technology of a kind of esterification waste water as claimed in claim 1, is characterized in that: in step 5), reverse osmosis concentrated water is back to first step ABR.
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| CN112479491A (en) * | 2020-11-18 | 2021-03-12 | 三桶油环保科技(宜兴)有限公司 | Advanced treatment and discharge method for fracturing flow-back fluid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111747601A (en) * | 2019-03-26 | 2020-10-09 | 中蓝连海设计研究院有限公司 | Treatment method of PTA-containing wastewater RO concentrated water |
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| CN112169243A (en) * | 2020-10-09 | 2021-01-05 | 石家庄新奥环保科技有限公司 | Treatment method of organic hazardous waste |
| CN112479491A (en) * | 2020-11-18 | 2021-03-12 | 三桶油环保科技(宜兴)有限公司 | Advanced treatment and discharge method for fracturing flow-back fluid |
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Application publication date: 20150729 |