CN104609641A - Sebacic acid wastewater evaporative desalination pretreatment method - Google Patents
Sebacic acid wastewater evaporative desalination pretreatment method Download PDFInfo
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- CN104609641A CN104609641A CN201310540214.3A CN201310540214A CN104609641A CN 104609641 A CN104609641 A CN 104609641A CN 201310540214 A CN201310540214 A CN 201310540214A CN 104609641 A CN104609641 A CN 104609641A
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- sebacic acid
- waste water
- evaporative desalination
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
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Abstract
The invention relates to a sebacic acid wastewater evaporative desalination pretreatment method. The method is characterized in that sebacic acid wastewater is purified before evaporative desalination of the wastewater, and comprises the following steps: carrying out biochemical treatment without dilution to remove organic matters; carrying out flocculating settlement treatment to remove chroma, suspensions, colloids and impurity ions; and filtering to further remove suspensions, colloids and other impurities. The amount of a high-salinity high-COD cycle mother liquor generated in the evaporation process during the evaporative desalination of the sebacic acid wastewater through the method reduces 90% or more, so the running stability of an evaporation system is improved, and obtained evaporation condensed water and solid sodium sulfate can directly reach sebacic acid production reuse water standards and national industrial sodium sulfate II level standards respectively.
Description
Technical field
The invention belongs to wastewater treatment and resource technology field, specifically a kind of containing high concentration sodium sulfate sebacic acid waste water evaporative desalination pretreatment process.
Background technology
Sebacic acid a kind ofly important has valency industrial chemicals, is widely used in production engineering plastics, fire-resistant lubricants, epoxy curing agent, sebacic anhydride, ucon oil, alcohol phenol resins, vibrin, Glass Fiber Reinforcement, makeup etc.China is the country that sebacic acid output is maximum in the world, mainly adopting with Viscotrol C is at present the cracking process production technique of raw material, product per ton need consume 150 ~ 250kg phenol, produce 25 ~ 40 tons of waste water, wherein phenol content is 2000 ~ 5000mg/L, pH is 2 ~ 3, sodium sulphate content is 6 ~ 10%, COD content is 10000 ~ 20000mg/L.Sebacic acid waste water belongs to high salt, high phenol, high-COD waste water; According to estimates, the sebacic acid enterprise of a 40000t/a produces waste water 1,500,000 tons/a, if this waste water does not carry out improving process, can cause severe contamination to environment.
Current sebacic acid factory effluent mainly adopts " extraction → evaporation → biochemical ", and technique processes, and water outlet can reach integrated wastewater discharge standard one-level A, also can be back to production after further advanced treatment.But because vapo(u)rization system influent COD is up to 2000 ~ 20000mg/L, there are the following problems for this technique:
(1) vapo(u)rization system produces a large amount of high salt height COD circulating mother liquor every day, if discharge, lacks economically feasible method of disposal; If do not discharge, easily cause vapo(u)rization system to occur blocking or non-crystallizable phenomenon, cause regular break-down maintenance, affect the continuous prodution of enterprise and the raising of integral production efficiency.
(2) circulating mother liquor is high salt height COD waste liquid, and in evaporative crystallization sodium sulfate, organic content is greater than 1%, all belongs to solid waste, if can not properly be disposed, by serious environment pollution; If strict regulations processes, enterprise's waste water control comprehensive cost is by increase by tens times.
Also lack one at present can solve the problem and economically viable method.
Summary of the invention
The object of the invention is the deficiency for existing sebacic acid method of wastewater treatment, the sebacic acid waste water evaporative desalination pretreatment process providing a kind of Technological Economy feasible, fundamentally solves fluctuation of service and a solidification disposal of waste difficult problem that sebacic acid waste water direct evaporative desalination causes.
Thinking of the present invention carries out purifying treatment before sebacic acid waste water enters evaporative desalination system, removes organism, sulfide, suspended substance and other impurity in water, directly obtains clean water of condensation and technical grade sodium sulfate after making waste water evaporative desalination.
Technical problem to be solved by this invention is realized by following technical scheme.The present invention is a kind of sebacic acid waste water evaporative desalination pretreatment process, and be characterized in: first carry out purifying treatment to sebacic acid waste water before waste water evaporative desalination, its step comprises:
(1) biochemical treatment is not diluted, organics removal;
(2) flocculation sediment process, removes colourity, suspended substance, colloid and foreign ion;
(3) filtration treatment, removes suspended substance, colloid and other impurity further.
In a kind of sebacic acid waste water evaporative desalination pretreatment process technical scheme of the present invention, preferred technical scheme or technical characteristic are further:
1. step (1) is front first carries out extraction except phenol process with ricinolic acid, sec-octyl alcohol, QH type extraction agent or other solvent to sebacic acid waste water carrying out, and makes the COD < 5000mg/L of sebacic acid waste water, volatile phenol < 200mg/L, total salt 5 ~ 15%.
2. the biochemical processing process that step (1) adopts is " acidication+aerobic ", and its processing parameter is respectively:
Acidication: HRT=8 ~ 48h, MLSS=4000 ~ 20000mg/L, F/M=0.1 ~ 0.4;
Aerobic: HRT=12 ~ 72h, MLSS=2000 ~ 5000mg/L, dissolved oxygen 2.0 ~ 4.0mg/L, F/M=0.2 ~ 1.0.
3. the method that step (2) is flocculated is chemical flocculation or electricity flocculation; According to chemical flocculation, select iron-based flocculating agent; According to electricity flocculation, select iron plate electrode.
4. step (3) filter depth treatment process is multimedium mechanical filter or sand filtration or micro-filtration, ultrafiltration technology.
In the inventive method, adopt biochemical method sebacic acid waste water is processed because its running cost is minimum, the most easily accept by enterprise.Described biochemical treatment carries out biochemical treatment under sebacic acid waste water does not dilute desalination condition, removes organism, phenols, sulfide and other impurity in water.Sebacic acid waste water directly can carry out aerobic treatment, but optimised process is " acidication+aerobic ".Acidication can improve the biochemical of waste water, and after first acidication, aerobic treatment can organism in more thorough degradation water, and improves stability and the impact resistance of technique.
Waste water is after biochemical treatment, and COD, phenol and sulfide content all significantly reduce, and adopts flocculation process to process further, can remove the foreign matter contents such as the suspended substance in water, colloid.For coagulating sedimentation, under normal circumstances can one in aluminium system and iron-based flocculating agent, but for high sodium sulfate wastewater, AlSnSi alloy poor effect, the pharmaceutical quantities of needs is large, and floc settling velocity is comparatively slow, therefore preferably selects iron-based flocculating agent.For avoiding introducing foreign ion, therefore iron-based flocculating agent preferably adopts polymerization ferrous sulfate and does not select iron(ic) chloride or poly-ferric chloride.According to electric flocculation process, available battery lead plate comprises iron plate and aluminium sheet, and its principle is that on battery lead plate, Ion release produces flocculating effect, and same reason should select iron plate as electrode.The construction of chemical flocculation and the more electric flocculation of running cost low, but effect is slightly poor, needs to carry out comprehensive selection according to practical situation.
After waste water flocculating precipitation, still containing a small amount of impurity such as suspended substance, colloid.For improving the purity of sodium sulfate crystal.Filter depth process is carried out after waste water flocculating.The multiple filter methods such as multi-medium filtering, micro-filtration or ultrafiltration membrance filter can be selected, to reach the object removing a small amount of suspended substance of water outlet and colloid after flocculation sediment.
In technical solution of the present invention, sebacic acid waste water refers to that sebacic acid factory effluent is through removing the pretreated waste water of phenol.Sebacic acid factory effluent former water COD > 10000mg/L, phenol > 2000mg/L, remove phenol by methods such as extraction, macroporous resin adsorption and phenol be back to production.Extraction agent used can be ricinolic acid, sec-octyl alcohol, QH type complexing extractant or other Examples of non-aqueous solvents.
The inventive method is as the pretreatment process of sebacic acid waste water evaporative desalination, the circulating mother liquor that evaporative desalination can also be produced processes as biochemical treatment water inlet, solve a process difficult problem for mother liquid evaporation, thus reduce the generation of sebacic acid waste water vapo(u)rization system circulating mother liquor further.
Compared with prior art, the advantage of the inventive method is as follows:
(1) in existing method, vapo(u)rization system influent COD > 2000mg/L; Application the inventive method, sebacic acid waste water evaporative desalination system influent COD < 200mg/L, even can < 100mg/L, and the stability that vapo(u)rization system is run is improved.
(2) in existing method, vapo(u)rization system produces a large amount of circulating mother liquor every day, does not also have a kind of economically viable treatment process at present.Application the inventive method, the generation of circulating mother liquor can reduce more than 90%, and produce circulating mother liquor still can get back to application the inventive method pretreatment system in process, for circulating mother liquor safe disposal and recycle provide solution route.
(3) evaporation condensed water COD > 500mg/L after sebacic acid waste water evaporative desalination in existing method, also needs process further could discharge or reuse.Application the inventive method, the evaporation condensed water COD < 40mg/L that evaporative desalination system produces, can direct reuse.
(4) COD that the sodium sulfate crystal that in existing method, sebacic acid waste water evaporative desalination produces contains, impurity are more, not good.After application the inventive method, the solid sodium sulfate purity of evaporative crystallization improves greatly, even can reach the purity requirement of industrial sulphuric acid sodium.
Embodiment
Below in conjunction with specific embodiment, content of the present invention is described, so that those skilled in the art understand further to the present invention.
Embodiment 1, a kind of sebacic acid waste water evaporative desalination pretreatment process, first carry out purifying treatment to sebacic acid waste water before waste water evaporative desalination, its step comprises:
(1) biochemical treatment is not diluted, organics removal;
(2) flocculation sediment process, removes colourity, suspended substance, colloid and foreign ion;
(3) filtration treatment, removes suspended substance, colloid and other impurity further.
Embodiment 2, in a kind of sebacic acid waste water evaporative desalination pretreatment process described in embodiment 1: step (1) is front first carries out extraction except phenol process with ricinolic acid, sec-octyl alcohol, QH type extraction agent or other solvent to sebacic acid waste water carrying out, and makes the COD < 5000mg/L of sebacic acid waste water, volatile phenol < 200mg/L, total salt 5 ~ 15%.
Embodiment 3, in a kind of sebacic acid waste water evaporative desalination pretreatment process described in embodiment 1 or 2: the biochemical processing process that step (1) adopts is " acidication+aerobic ", and its processing parameter is respectively:
Acidication: HRT=8 ~ 48h, MLSS=4000 ~ 20000mg/L, F/M=0.1 ~ 0.4;
Aerobic: HRT=12 ~ 72h, MLSS=2000 ~ 5000mg/L, dissolved oxygen 2.0 ~ 4.0mg/L, F/M=0.2 ~ 1.0.
Embodiment 4, in a kind of sebacic acid waste water evaporative desalination pretreatment process of embodiment 1-3 described in any one: the method that step (2) is flocculated is chemical flocculation or electricity flocculation; According to chemical flocculation, select iron-based flocculating agent; According to electricity flocculation, select iron plate electrode.
Embodiment 5, in a kind of sebacic acid waste water evaporative desalination pretreatment process of embodiment 1-4 described in any one: step (3) filter depth treatment process is multimedium mechanical filter or sand filtration or micro-filtration, ultrafiltration technology.
Embodiment 6, a kind of sebacic acid waste water evaporative desalination pretreatment process experiment:
Hebei enterprise sebacic acid factory effluent, COD is 12000 ~ 15000mg/L, and phenol content is 3000 ~ 4000mg/L, and sodium sulphate content is 6 ~ 10%.Adopt ricinolic acid to carry out multi-stage solvent extraction except phenol to waste water, reclaim the phenol in waste water simultaneously.After removing phenol pre-treatment, waste water COD is 3500 ~ 4200mg/L, and phenol content is 50 ~ 150mg/L, pH is 5.0 ~ 6.0.
Adopt the inventive method to process above-mentioned waste water, the process water yield is 1 ~ 2m3/d.
(1) inoculate salt tolerant active sludge and process sebacic acid waste water in " acidication+aerobic " biochemical test device.Hydrolysis acidification pool adopts UASB, 1.5 m
3, the residence time 18 ~ 36h, sludge seeding amount 1000 ~ 20000mg/L, F/M=0.1 ~ 0.4; Aerobic Pond adopts conventional activated sludge process, 3m
3, the residence time 36 ~ 72h, sludge seeding amount 500 ~ 2000mg/L, F/M=0.4 ~ 0.6, dissolved oxygen 2.0 ~ 4.0mg/L.Water outlet COD < 200mg/L, SS < 50mg/L, phenol < 0.5mg/L after biochemical.Described salt tolerant active sludge is with sebacic acid waste water for carbon source and the energy, with soil near sebacic acid production plant or irrigation canals and ditches bed mud for salt-durable microbe is originated, directly to cultivate under 5 ~ 15% sodium sulfate conditions and obtains.
(2) bio-chemical effluent carries out chemical flocculation process, and flocculation agent and coagulant aids select polymerization ferrous sulfate and PAM respectively, and after flocculation, pH controls is 8.0 ~ 9.0.Flocculation water outlet COD < 150mg/L, SS < 10mg/L
(3) flocculation sediment water outlet adopts aperture to be that the membrane filtration of 0.45 μm is to simulate the effect that aperture is the ultrafiltration membrane treatment waste water of 0.5 μm.Filtration rear water outlet COD < 100mg/L, SS < 1mg/L.
By above-mentioned final outflow water with carrying out evaporation process, evaporation condensed water COD < 40mg/L; Gained solid sodium sulfate white powder.Prove to adopt the inventive method to carry out evaporative desalination again, the evaporation condensed water of acquisition meets the requirement that reuse water produced by sebacic acid, and the solid sodium sulfate of acquisition meets industrial sulphuric acid sodium II grade of acceptable end product standard.
Embodiment 7, a kind of sebacic acid waste water evaporative desalination pretreatment process experiment:
Waste water is identical with embodiment 6.
Adopt the inventive method to carry out pre-treatment to waste water, the process water yield is 60m
3/ d, arranges 2 cover parallel systems, often overlaps 30m
3/ d, for every cover system:
(1) seed sludge is identical with embodiment 6, hydrolysis acidification pool useful volume 30m
3, hydraulic detention time 24h, if outer circulation and outer circulation flow is 1 ~ 3:1 with the ratio of flooding velocity; Aerobic Pond adopts MBBR pond, and floating stuffing adds ratio 30%, basin's effective volume 60m
3.During steady running, hydrolysis acidification pool MLSS is 15000 ~ 25000mg/L, sludge loading F/M=0.1 ~ 0.2; Aerobic Pond MLSS is 3000 ~ 4000mg/L, F/M=0.2 ~ 0.4.Biochemical system pH is 7.5 ~ 8.5, water temperature 20 ~ 35 DEG C.
Sebacic acid waste water is COD < 200mg/L, SS < 100mg/L after biochemical treatment.
(2) adopt electricity flocculation to flocculate to bio-chemical effluent, 12 cover iron plate electrodes, battery lead plate is of a size of 600mm × 1400mm × 3mm, arranges perpendicular stream settling bowl after electricity flocculation.Warp also reduces COD, water outlet COD < 120mg/L, SS < 10mg/L.
(3) water outlet of flocculating is filtered through more medium filter and activated charcoal filter, water outlet COD < 100mg/L, SS < 1mg/L.
Claims (5)
1. a sebacic acid waste water evaporative desalination pretreatment process, it is characterized in that: first carry out purifying treatment to sebacic acid waste water before waste water evaporative desalination, its step comprises:
(1) biochemical treatment is not diluted, organics removal;
(2) flocculation sediment process, removes colourity, suspended substance, colloid and foreign ion;
(3) filtration treatment, removes suspended substance, colloid and other impurity further.
2. a kind of sebacic acid waste water evaporative desalination pretreatment process according to claim 1, it is characterized in that: step (1) is front first carries out extraction except phenol process with ricinolic acid, sec-octyl alcohol, QH type extraction agent or other solvent to sebacic acid waste water carrying out, and makes the COD < 5000mg/L of sebacic acid waste water, volatile phenol < 200mg/L, total salt 5 ~ 15%.
3. a kind of sebacic acid waste water evaporative desalination pretreatment process according to claim 1, is characterized in that: the biochemical processing process that step (1) adopts is " acidication+aerobic ", and its processing parameter is respectively:
Acidication: HRT=8 ~ 48h, MLSS=4000 ~ 20000mg/L, F/M=0.1 ~ 0.4;
Aerobic: HRT=12 ~ 72h, MLSS=2000 ~ 5000mg/L, dissolved oxygen 2.0 ~ 4.0mg/L, F/M=0.2 ~ 1.0.
4. a kind of sebacic acid waste water evaporative desalination pretreatment process according to claim 1, is characterized in that: the method that step (2) is flocculated is chemical flocculation or electricity flocculation; According to chemical flocculation, select iron-based flocculating agent; According to electricity flocculation, select iron plate electrode.
5. a kind of sebacic acid waste water evaporative desalination pretreatment process according to claim 1, is characterized in that: step (3) filter depth treatment process is multimedium mechanical filter or sand filtration or micro-filtration, ultrafiltration technology.
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Cited By (1)
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| CN105084529A (en) * | 2015-09-11 | 2015-11-25 | 中蓝连海设计研究院 | Method for treating sebacic acid wastewater by utilizing halophilic microorganisms |
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