CN104609641B - Sebacic acid wastewater evaporative desalination pretreatment method - Google Patents
Sebacic acid wastewater evaporative desalination pretreatment method Download PDFInfo
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- CN104609641B CN104609641B CN201310540214.3A CN201310540214A CN104609641B CN 104609641 B CN104609641 B CN 104609641B CN 201310540214 A CN201310540214 A CN 201310540214A CN 104609641 B CN104609641 B CN 104609641B
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- waste water
- decanedioic acid
- evaporative desalination
- flocculation
- sebacic acid
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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
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 decanedioic acid containing high concentration sodium sulfate is useless
Water evaporation desalination preprocess method.
Background technology
Decanedioic acid be a kind of important have valency industrial chemicals, be widely used in production engineering plastics, fire-resistant lubricants, epoxy
Resin curing agent, sebacic anhydride, synthetic lubricant fluid, alcohol phenol resin, polyester resin, Glass Fiber Reinforcement, cosmetics etc..China
It is the country of decanedioic acid yield maximum in the world, mainly adopt the cracking process production technology with Oleum Ricini as raw material at present, per ton
Product need to consume 150～250kg phenol, produces 25～40 tons of waste water, wherein phenol content is 2 for 2000～5000mg/L, pH
～3, sodium sulphate content be 6～10%, COD content be 10000～20000mg/L.Decanedioic acid waste water belongs to high salt, high phenol, high COD
Waste water；According to estimates, the decanedioic acid enterprise of a 40000t/a produces 1,500,000 tons/a of waste water, if this waste water does not carry out improving process,
Severe contamination can be caused to environment.
Decanedioic acid is produced waste water and is mainly processed using " extraction → evaporation → biochemical " technique at present, and water outlet can reach dirt
Water comprehensive discharge standard one-level A, also can be back to production after further advanced treating.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 is daily to produce a large amount of high salt high COD circulating mother liquor, if discharge, lacks economically feasible disposal side
Method；If not discharging, being easily caused vapo(u)rization system and blocking or not crystalline polamer occur, cause regular shut-down (breakdown) mainteance, impact enterprise
The continuous prodution of industry and the raising of overall production efficiency.
（2）Circulating mother liquor is high salt high COD waste liquid, and in evaporative crystallization sodium sulfate, content of organics is more than 1%, all belongs to solid
Waste, if can not properly be disposed, by serious environment pollution；If strictly relevant regulation is processed, enterprise's waste water control is comprehensive
Synthesizing this will increase by tens times.
Also lack one kind at present and can solve the problem that the problems referred to above and economically viable method.
Content of the invention
The purpose of the present invention is the deficiency for existing decanedioic acid method of wastewater treatment, provides a kind of Technological Economy feasible
Decanedioic acid waste water evaporative desalination preprocess method, fundamentally solves the operation shakiness that decanedioic acid waste water direct evaporation desalination leads to
Determine and a solidification disposal of waste difficult problem.
The thinking of the present invention is to carry out purified treatment before decanedioic acid waste water enters evaporative desalination system, goes organic in eliminating water
Thing, sulfide, float and other impurity are so that directly obtain clean condensed water and technical grade sulfuric acid after waste water evaporative desalination
Sodium.
The technical problem to be solved is to be realized by following technical scheme.The present invention is a kind of last of the ten Heavenly stems two
Sour waste water evaporative desalination preprocess method, is characterized in：First purified treatment is carried out to decanedioic acid waste water before waste water evaporative desalination, its
Step includes：
（1）Do not dilute biochemical treatment, organics removal；
（2）Flocculation sediment is processed, and removes colourity, float, colloid and foreign ion；
（3）Filtration treatment, removes oil removal, colloid and other impurity further.
In a kind of decanedioic acid waste water evaporative desalination preprocess method technical scheme of the present invention, further preferred skill
Art scheme or technical characteristic are：
1. carrying out step（1）Front first use castor oil acid, sec-octyl alcohol, QH type extractant or other solvent to decanedioic acid waste water
Carry out extraction to process except phenol, make the COD ＜ 5000mg/L of decanedioic acid waste water, volatile phenol ＜ 200mg/L, total salt 5～15%.
2. step（1）Using biochemical processing process be " hydrolysis acidification+aerobic ", its technological parameter is respectively：
Hydrolysis acidification：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. step（2）The method of flocculation is chemical flocculation or electric flocculation；According to chemical flocculation, from iron-based flocculating agent；
According to electric flocculation, from iron plate electrode.
4. step（3）Filter depth handling process is multimedium mechanical filter or sand filtration or microfiltration, ultrafiltration technology.
In the inventive method, using biochemical method, decanedioic acid waste water is processed, because its operating cost is minimum, hold most
Easily accepted by enterprise.Described biochemical treatment is to carry out biochemical treatment under the conditions of decanedioic acid waste water does not dilute desalination, goes eliminating water
In Organic substance, phenols, sulfide and other impurity.Decanedioic acid waste water directly can carry out aerobic treatment, but optimal work
Skill is " hydrolysis acidification+aerobic ".Hydrolysis acidification can improve the biochemical of waste water, and after first hydrolysis acidification, aerobic treatment can be more
The thoroughly Organic substance in degradation water, and improve stability and the impact resistance of technique.
After biochemical treatment, COD, phenol and sulfide content are all greatly reduced waste water, are processed further using flocculation process,
The impurity contents such as float in eliminating water, colloid can be removed.For coagulating sedimentation, can be selected for aluminum system and ferrum system wadding under normal circumstances
One of solidifying agent, but for high sodium sulfate wastewater, AlSnSi alloy effect on driving birds is not good, the pharmaceutical quantities of needs are big, and flco
Sedimentation velocity is slower, therefore preferably selects iron-based flocculating agent.For avoiding introducing foreign ion, therefore iron-based flocculating agent is preferably with polymerization
Ferrous sulfate and do not select iron chloride or poly-ferric chloride.According to electric flocculation technique, available battery lead plate include iron plate and
Aluminium sheet, its principle is that on battery lead plate, Ion release produces flocculating effect, should select iron plate as electrode the reason same.Chemistry
The construction of flocculation and operating cost are low compared with electric flocculation, but effect is slightly poor, need to carry out combined selection according to practical situation.
After waste water flocculating precipitation, still contain the impurity such as a small amount of float, colloid.For improving the pure of sodium sulfate crystal
Degree.Carry out filter depth process after waste water flocculating.Can be selected for multiple filtration side such as multi-medium filtering, microfiltration or ultrafiltration membrance filter
Method, to reach the purpose removing a small amount of float of water outlet and colloid after flocculation sediment.
In technical solution of the present invention, decanedioic acid waste water refers to that decanedioic acid produces waste water through except the pretreated waste water of phenol.
Decanedioic acid produces waste water raw water COD ＞ 10000mg/L, phenol ＞ 2000mg/L, is removed by methods such as extraction, macroporous resin adsorption
Phenol is simultaneously back to production by phenol.Extractant used can be castor oil acid, sec-octyl alcohol, QH type complexing extractant or other non-aqueous
Phase solvent.
The inventive method, can also be by following that evaporative desalination produces used as the preprocess method of decanedioic acid waste water evaporative desalination
Ring mother solution is processed as biochemical treatment water inlet, solves a process difficult problem for evaporation mother solution, thus reduce decanedioic acid further giving up
The yield of water evaporation system circulation mother solution.
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, decanedioic acid waste water evaporates
Desalination system influent COD ＜ 200mg/L, in addition can ＜ 100mg/L, make vapo(u)rization system run stability be improved.
（2）In existing method, vapo(u)rization system produces a large amount of circulating mother liquors daily, there is presently no a kind of economically viable place
Reason method.Application the inventive method, the yield of circulating mother liquor can reduce more than 90%, and the circulating mother liquor producing still may be used
Processed with returning in the pretreatment system of application the inventive method, be that circulating mother liquor safe disposal and recycling provides
Solution route.
（3）Evaporation condensed water COD ＞ 500mg/L after decanedioic acid waste water evaporative desalination in existing method, also needs to locate further
Reason could be discharged or reuse.Application the inventive method, the evaporation condensed water COD ＜ 40mg/L that evaporative desalination system produces, can be straight
Take back use.
（4）The COD that the sodium sulfate crystal that in existing method, decanedioic acid waste water evaporative desalination produces contains, impurity are more, product
Xiang Bujia.After application the inventive method, the solid sodium sulfate purity of evaporative crystallization greatly improves it might even be possible to reach industrial sulphuric acid
Sodium purity requirement.
Specific embodiment
Below in conjunction with specific embodiment, present invention is illustrated, in order to those skilled in the art, the present invention is entered
One step understands.
Embodiment 1, a kind of decanedioic acid waste water evaporative desalination preprocess method, first to decanedioic acid waste water before waste water evaporative desalination
Carry out purified treatment, its step includes：
（1）Do not dilute biochemical treatment, organics removal；
（2）Flocculation sediment is processed, and removes colourity, float, colloid and foreign ion；
（3）Filtration treatment, removes oil removal, colloid and other impurity further.
Embodiment 2, in a kind of decanedioic acid waste water evaporative desalination preprocess method described in embodiment 1：Carrying out step（1）
Front first with castor oil acid, sec-octyl alcohol, QH type extractant or other solvent, decanedioic acid waste water is carried out with extraction and processes except phenol, make the last of the ten Heavenly stems two
The COD ＜ 5000mg/L of sour waste water, volatile phenol ＜ 200mg/L, total salt 5～15%.
Embodiment 3, in a kind of decanedioic acid waste water evaporative desalination preprocess method described in embodiment 1 or 2：Step（1）Adopt
Biochemical processing process is " hydrolysis acidification+aerobic ", and its technological parameter is respectively：
Hydrolysis acidification：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 decanedioic acid waste water evaporative desalination preprocess method described in embodiment 1-3 any one：Step
Suddenly（2）The method of flocculation is chemical flocculation or electric flocculation；According to chemical flocculation, from iron-based flocculating agent；According to electric flocculation,
From iron plate electrode.
Embodiment 5, in a kind of decanedioic acid waste water evaporative desalination preprocess method described in embodiment 1-4 any one：Step
Suddenly（3）Filter depth handling process is multimedium mechanical filter or sand filtration or microfiltration, ultrafiltration technology.
Embodiment 6, a kind of decanedioic acid waste water evaporative desalination preprocess method experiment：
Hebei enterprise decanedioic acid produces waste water, and COD is 12000～15000mg/L, and phenol content is 3000～4000mg/
L, sodium sulphate content is 6～10%.Multitple extraction is carried out using castor oil acid to waste water and removes phenol, reclaim the phenol in waste water simultaneously.
After except phenol pretreatment, waste water COD is 3500～4200mg/L, and phenol content is 50～150mg/L, and pH is 5.0～6.0.
Using the inventive method, above-mentioned waste water is processed, the process water yield is 1～2m3/d.
（1）Inoculation salt tolerant activated sludge processes decanedioic acid waste water in " hydrolysis acidification+aerobic " biochemical test device.Hydrolysis
Acidification pool adopts UASB, 1.5 m3, the time of staying 18～36h, sludge seeding amount 1000～20000mg/L, F/M=0.1～0.4；
Aerobic Pond adopts conventional activated sludge process, 3m3, the time of staying 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 after biochemistry, SS ＜ 50mg/L, phenol ＜ 0.5mg/L.Described resistance to
Salt activated sludge is with decanedioic acid waste water as carbon source and the energy, and near decanedioic acid workshop, soil or irrigation canals and ditches bed mud are as salt tolerant
Microbe-derived, directly culture obtains under the conditions of 5～15% sodium sulfate.
（2）Bio-chemical effluent carries out chemical flocculation process, and flocculant and flocculation aid select polymerization ferrous sulfate and PAM respectively,
After flocculation, pH is controlled to 8.0～9.0.Flocculation water outlet COD ＜ 150mg/L, SS ＜ 10mg/L
（3）Flocculation sediment water outlet to be simulated at the ultrafilter membrane that aperture is 0.5 μm using the membrane filtration that aperture is 0.45 μm
The effect of reason waste water.Water outlet COD ＜ 100mg/L after filtration, SS ＜ 1mg/L,.
By above-mentioned final outflow water with being evaporated processing, evaporation condensed water COD ＜ 40mg/L；Gained solid sodium sulfate white
Powder.Prove to be evaporated desalination again using the inventive method, the evaporation condensed water of acquisition meets decanedioic acid and produces recycle-water
Requirement, the solid sodium sulfate of acquisition meets II grade of Grade A standard of industrial sulphuric acid sodium.
Embodiment 7, a kind of decanedioic acid waste water evaporative desalination preprocess method experiment：
Waste water is same as Example 6.
Pretreatment is carried out using the inventive method to waste water, the process water yield is 60m3/ d, arranges 2 sets of parallel systems, often covers
30m3/ d, for every set system：
（1）Seed sludge is same as Example 6, hydrolysis acidification pool dischargeable capacity 30m3, hydraulic detention time 24h, if outward
Circulate and outer circulation flow is 1～3 with the ratio of flow of inlet water:1；Aerobic Pond adopts MBBR pond, and floating stuffing adds ratio 30%,
Basin's effective volume 60m3.During stable operation, 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 7.5～8.5,20～35 DEG C of water temperature.
Decanedioic acid waste water COD ＜ 200mg/L, SS ＜ 100mg/L after biochemical treatment.
（2）Using electric flocculation, bio-chemical effluent is flocculated, 12 sets of iron plate electrodes, battery lead plate a size of 600mm ×
1400mm × 3mm, arranges perpendicular stream Sedimentation tank after electric flocculation.Warp simultaneously reduces COD, water outlet COD ＜ 120mg/L, SS ＜ 10mg/L.
（3）Flocculation water outlet is filtered through more medium filter and active carbon filter, water outlet COD ＜ 100mg/L, SS ＜ 1mg/
L.
Claims (4)
1. a kind of decanedioic acid waste water evaporative desalination preprocess method it is characterised in that：First decanedioic acid is given up before waste water evaporative desalination
Water carries out purified treatment, and decanedioic acid waste water refers to that decanedioic acid produces waste water through except the pretreated waste water of phenol；Its step includes：
(1) biochemical treatment, organics removal are not diluted；Using biochemical processing process be " hydrolysis acidification+aerobic ", its technique join
Number is respectively：
Hydrolysis acidification：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；
(2) flocculation sediment is processed, and removes colourity, float, colloid and foreign ion；
(3) filtration treatment, removes oil removal, colloid and other impurity further.
2. a kind of decanedioic acid waste water evaporative desalination preprocess method according to claim 1 it is characterised in that：Walked
Suddenly first with castor oil acid, sec-octyl alcohol or QH type extractant, decanedioic acid waste water is carried out before (1) with extraction process except phenol, make decanedioic acid
The COD ＜ 5000mg/L of waste water, volatile phenol ＜ 200mg/L, total salt 5～15%.
3. a kind of decanedioic acid waste water evaporative desalination preprocess method according to claim 1 it is characterised in that：Step (2)
The method of flocculation is chemical flocculation or electric flocculation；According to chemical flocculation, from iron-based flocculating agent；According to electric flocculation, select
Iron plate electrode.
4. a kind of decanedioic acid waste water evaporative desalination preprocess method according to claim 1 it is characterised in that：Step (3)
Filter depth handling process is multimedium mechanical filter or sand filtration or microfiltration, ultrafiltration technology.
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| CN105084529B (en) * | 2015-09-11 | 2018-08-21 | 中蓝连海设计研究院有限公司 | A method of handling decanedioic acid waste water using halophile |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1450006A (en) * | 2002-04-05 | 2003-10-22 | 山东海化天合有机化工有限公司 | Treatment of phenol containing decanedioic acid waste water by extractive distillation |
| CN101654305A (en) * | 2009-09-18 | 2010-02-24 | 清华大学 | Process for changing phenolic nitrate effluent into useful material by extracting, evaporating, crystallizing and coupling |
| CN102503034A (en) * | 2011-11-08 | 2012-06-20 | 中蓝连海设计研究院 | Treatment method of phenol-containing liquid waste in sebacic acid production |
| EP2479149A1 (en) * | 2009-09-17 | 2012-07-25 | Ningbo Wanhua Polyurethanes Co., Ltd. | Method for treating waste saline water produced in production process of diphenylmethane diisocyanate (mdi) |
| CN102874958A (en) * | 2011-07-11 | 2013-01-16 | 凯膜过滤技术(上海)有限公司 | Method for treating and reusing sodium sulfate containing organic waste water |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101575152B (en) * | 2008-05-05 | 2011-06-01 | 上海芝东商务咨询有限公司 | Reusable method of decanedioic acid phenol-containing wastewater |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1450006A (en) * | 2002-04-05 | 2003-10-22 | 山东海化天合有机化工有限公司 | Treatment of phenol containing decanedioic acid waste water by extractive distillation |
| EP2479149A1 (en) * | 2009-09-17 | 2012-07-25 | Ningbo Wanhua Polyurethanes Co., Ltd. | Method for treating waste saline water produced in production process of diphenylmethane diisocyanate (mdi) |
| CN101654305A (en) * | 2009-09-18 | 2010-02-24 | 清华大学 | Process for changing phenolic nitrate effluent into useful material by extracting, evaporating, crystallizing and coupling |
| CN102874958A (en) * | 2011-07-11 | 2013-01-16 | 凯膜过滤技术(上海)有限公司 | Method for treating and reusing sodium sulfate containing organic waste water |
| CN102503034A (en) * | 2011-11-08 | 2012-06-20 | 中蓝连海设计研究院 | Treatment method of phenol-containing liquid waste in sebacic acid production |
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