CN104609640B - Comprehensive treatment method of sebacic acid production wastewater - Google Patents
Comprehensive treatment method of sebacic acid production wastewater Download PDFInfo
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- CN104609640B CN104609640B CN201310540100.9A CN201310540100A CN104609640B CN 104609640 B CN104609640 B CN 104609640B CN 201310540100 A CN201310540100 A CN 201310540100A CN 104609640 B CN104609640 B CN 104609640B
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Abstract
The invention belongs to the technical field of wastewater treatment and recycling, and discloses a comprehensive treatment method of sebacic acid production wastewater. The sebacic acid production wastewater sequentially goes through an extraction device, a biochemical device, an advanced treatment device and an evaporative desalination device in order to realize treatment of the sebacic acid production wastewater, wherein a cycle mother liquor generated in the evaporation device returns to the biochemical device in order to carry treatment. The method allows phenol and sodium sulfate in the sebacic acid production wastewater to be recovered, and also allows treated wastewater to be directly reused. The method has the advantages of simple enforcement steps, maximal reduction of the sewage discharge capacity and pollutant transfer, and true realization of the zero discharge of sebacic acid wastewater treatment.
Description
Technical field
The invention belongs to wastewater treatment and resource technology field, specifically high concentration sodium sulfate decanedioic acid waste water is entered
The method of row integrated treatment, thus recycling the utility in waste water as far as possible, and at utmost reduces waste water and pollution
The discharge capacity of thing.
Background technology
Decanedioic acid is that a kind of important have valency industrial chemicals.China is decanedioic acid manufacturing country maximum in the world, leads at present
Oleum Ricini to be adopted is the cracking process production technology of raw material.Produce decanedioic acid per ton and need to consume 150～250kg phenol, produce 25
～40 tons of waste water, wherein phenol content be 2000～5000mg/L, pH be 2～3, sodium sulphate content be 5～15%, COD content
For 10000～20000mg/L.
Decanedioic acid produces waste water handling process the most ripe at present is " extraction → evaporation → biochemical ", water outlet COD ＜ 40mg/
L, also can be back to production after advanced treating.But, in this technique, vapo(u)rization system influent COD reaches 2000～20000mg/L, leads
There are the following problems for the operation of induced evaporation system：
(1) circulating mother liquor yield is big, there is presently no an economically viable processing method.If not discharging, easily lead
Blocking or not crystalline polamer in induced evaporation system, causes regular shut-down (breakdown) mainteance, the continuous prodution of impact enterprise and whole
The raising of body 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%, also contains it
Its impurity, belongs to slag salt, if can not properly be disposed it would be possible to serious environment pollution；If strictly relevant regulation is processed,
Enterprise's waste water control integrated cost 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 technical problem to be solved in the present invention is the evaporation mother solution disposal difficulties that decanedioic acid waste water direct evaporation desalination produces.
The purpose of the present invention is for the deficiencies in the prior art, provides a kind of method, and the method is capable of the up to standard of decanedioic acid waste water
Process with reuse, reclaim waste water in phenol and sodium sulfate, reduce evaporation process in circulating mother liquor yield, avoid slag salt
Produce, improve the stability that whole decanedioic acid Waste Water Treatment runs.
The thinking of the present invention：After decanedioic acid waste water removes phenol, carry out purified treatment before entering evaporative desalination system, remove in water
Organic substance, sulfide, float and other impurity, thus can reach of both effect：
1. clean condensed water and technical grade sulfuric acid sodium are directly obtained after waste water evaporative desalination, after need not processing further just
With direct reuse and can sell.
2. in vapo(u)rization system, the yield of circulating mother liquor reduces more than 90%, will greatly improve stablizing of vapo(u)rization system operation
Property and service life.
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
The integrated conduct method of acid producing waste water, is characterized in：Described decanedioic acid waste water is successively through extraction equipment, biochemical device, depth
Processing meanss and evaporative desalination device are processed in interior system, and wherein, the circulating mother liquor that evaporative desalination device produces returns to
Biochemical device is processed.
Decanedioic acid of the present invention produces in the integrated conduct method of waste water, further preferred technical scheme or skill
Art feature is：
1. extraction equipment using castor oil acid, sec-octyl alcohol, QH complexing extractant, dichloroethanes or other Examples of non-aqueous solvents as
Extractant.
2. the technique that biochemical device is taken is " hydrolysis acidification+aerobic " technique, water after extraction is processed, degradation of organic substances
With sulfur oxide compound.
3. its technological parameter is respectively preferably：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.
4. advanced treatment apparatus include flocculation plant and defecator, make bio-chemical effluent after treatment, colloid therein and
Concentration of suspension ＜ 1mg/L.
5. evaporative desalination device is MVR, the evaporation condensed water direct reuse obtaining.
In the inventive method, the purpose of extraction equipment is to remove decanedioic acid to produce the phenol in waste water and be back to production.
Decanedioic acid is produced waste water and can be extracted from multi-solvents, including castor oil acid, sec-octyl alcohol, QH complexing extractant, dichloro
Ethane or other Examples of non-aqueous solvents.The extraction efficiency of different extractants, extraction process difference it should be entered according to practical situation
Row selects.For example, castor oil acid is the raw material in decanedioic acid production process, the extract direct reuse containing phenol, without carrying out
Back extraction；Its extraction process is simpler, but extraction efficiency relative mistake, the COD ＞ 4000mg/L of water after extraction, to the follow-up place of waste water
Reason brings larger burden.Sec-octyl alcohol is the intermediate product in decanedioic acid production process, relatively low as extractant expense with it；Secondary
Capryl alcohol extraction efficiency is higher than castor oil acid, but needs to be extracted and back extraction simultaneously, after its extraction water COD be 2000～
3000mg/L, complexing extractant produces the extraction efficiency highest of waste water to decanedioic acid, after the extraction of QH complexing extractant
Cost of water treatment after waste water COD is 1000～1500mg/L, and extraction is less than castor oil acid and sec-octyl alcohol as extractant.
After the extraction of decanedioic acid waste water is except phenol, does not dilute and process through biochemical device, biochemical process is " hydrolysis acidification+aerobic ".
Biochemical treatment can be relatively low operating cost degradation water in Organic substance and sulfide.
Decanedioic acid wastewater biochemical process after, bio-chemical effluent COD is relatively low, but also contain in waste water float, colloid and
Other impurity.If being now directly evaporated processing it is impossible to ensure that the sodium sulfate that evaporative desalination obtains has preferable quality,
Therefore decanedioic acid wastewater biochemical needs further advanced treating after processing, and uses water-borne glue body and TSM ＜ 1mg/L.The present invention
Advanced treatment apparatus include flocculation, absorption and defecator.Flocculation plant can adopt chemical flocculation and electric flocculation；Adsorbent equipment is adopted
With activated carbon as absorption filtering material；Defecator adopts more medium filter, microfiltration or ultrafiltration.
Enter evaporative desalination system through the decanedioic acid waste water of above-mentioned process to be processed.Evaporative desalination process selection energy consumption is relatively
Low multiple-effect evaporation, wherein optimal evaporative desalination system is four-effect evaporation and MVR, and wherein MVR cost of investment is higher, but runs
Cost is minimum.
Beneficial effects of the present invention：
(1) vapo(u)rization system influent COD ＜ 100mg/L, vapo(u)rization system circulating mother liquor yield reduces 90% compared with prior art
More than, thus greatly improve the stability of vapo(u)rization system operation, thus improving the efficiency of whole Waste Water Treatment.
(2) the evaporation condensed water COD ＜ 40mg/L that vapo(u)rization system obtains, the index such as its colourity, SS, turbidity is satisfied by producing
Quality of reused water standard, can be directly as production recycle-water.
(3) the sodium sulfate crystal purity that vapo(u)rization system obtains at least can reach II grade of standard of industrial sulphuric acid sodium.
(4) circulating mother liquor that vapo(u)rization system produces may return to biochemical device and processed, and thoroughly avoids circulating mother liquor
Outer row.
(5) at utmost reduce the discharge of decanedioic acid waste water and waste, the phenol of recovery and sodium sulfate can compensate for one
Office reason wastewater treatment expense is it is achieved that the integrated treatment of waste water and resource.
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 produces the integrated conduct method of waste water, and described decanedioic acid waste water is successively through extraction dress
Put, biochemical device, advanced treatment apparatus and evaporative desalination device are processed in interior system, wherein, evaporative desalination device produces
Raw circulating mother liquor returns to biochemical device and is processed.
Embodiment 2, in the method described in embodiment 1：Extraction equipment with castor oil acid, sec-octyl alcohol, QH complexing extractant, two
Ethyl chloride or other Examples of non-aqueous solvents are as extractant.
Embodiment 3, in the method described in embodiment 1 or 2：The technique that biochemical device is taken is " hydrolysis acidification+aerobic " work
Skill, is processed to water after extraction, degradation of organic substances and sulfur oxide compound.
Embodiment 4, in the method described in embodiment 1 or 2 or 3：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 5, in the method described in embodiment 1-4 any one：Advanced treatment apparatus include flocculation plant and filtration
Device, makes bio-chemical effluent after treatment, colloid therein and concentration of suspension ＜ 1mg/L.
Embodiment 6, in the method described in embodiment 1-5 any one：Evaporative desalination device is MVR, and the evaporation obtaining is cold
Solidifying water direct reuse.
Embodiment 7, a kind of decanedioic acid produces the integrated conduct method experiment of waste water：
Hebei decanedioic acid manufacturing enterprise, it is 12000～15000mg/L that decanedioic acid produces waste water COD, and phenol content is 3000
～4000mg/L, sodium sulphate content is 6～10%.
Pilot scale is carried out using the inventive method to above-mentioned waste water and processes test, the process water yield is 1～2m3/d.
(1) multitple extraction is carried out using castor oil acid to waste water and remove phenol, phenol reuse.After extraction water COD be 3500～
4200mg/L, phenol content is 50～150mg/L, and pH is 5.0～6.0.
(2) after extracting, water enters the regulating reservoir of biochemical device, adopts " hydrolysis acidification+aerobic " PROCESS FOR TREATMENT.Hydrolysis acidification pool
Dischargeable capacity 1.5m3, retention time of sewage 18～36h, sludge concentration 10000～20000mg/L, sludge loading 0.1～
0.4kgCOD/(kgMLSS·d)；Aerobic Pond adopts conventional activated sludge process dischargeable capacity 3m3, retention time of sewage 36～72h,
Sludge concentration 2000～4000mg/L, sludge loading 0.4～0.6kgCOD/ (kgMLSS d), dissolved oxygen 2.0～4.0mg/L.
Through the Start-up and Adjustment of 3 months, bio-chemical effluent COD ＜ 200mg/L, SS ＜ 50mg/L, phenol ＜ 0.5mg/L.
(3) bio-chemical effluent adds polymerization ferrous sulfate and PAM carries out flocculation treatment, and pH is controlled to 8.0～9.0.Flocculate
Water COD ＜ 120mg/L, SS ＜ 10mg/L
(4) flocculation water outlet carries out activated carbon filtration and multi-medium filtering, water outlet COD ＜ 100mg/L, SS ＜ 1mg/L successively.
(5) filter water outlet and carry out multiple-effect evaporation, be evaporated completely, sodium sulfate ＞ 98% in gained solid salt, moisture, ferrum magnesium,
The indexs such as calcium, chlorine, whiteness all meet the II grade of Grade A requirement of industrial sulphuric acid sodium；Gained evaporation condensed water COD ＜ 30mg/L.
Embodiment 8, a kind of decanedioic acid produces the integrated conduct method experiment of waste water：
Hebei decanedioic acid manufacturing enterprise, it is 12000～15000mg/L that decanedioic acid produces waste water COD, and phenol content is 3000
～4000mg/L, sodium sulphate content is 6～10%.
Pilot scale is carried out using the inventive method to above-mentioned waste water and processes test, the process water yield is 1～2m3/d.
(1) one-level extraction is carried out using QH-1 type extractant to waste water and two-stage back extraction removes phenol, phenol reuse.Water after extraction
COD is 1000～1200mg/L, and phenol content is 30～50mg/L, and pH is 5.0～6.0.
(2) after extracting, water enters the regulating reservoir of biochemical device, adopts " hydrolysis acidification+aerobic " PROCESS FOR TREATMENT.Hydrolysis acidification pool
Dischargeable capacity 1m3, retention time of sewage 12～24h, sludge concentration 10000～20000mg/L, sludge loading 0.1～
0.4kgCOD/(kgMLSS·d)；Aerobic Pond adopts conventional activated sludge process dischargeable capacity 1m3, retention time of sewage 8～20h,
Sludge concentration 3000～4000mg/L, sludge loading 0.3～0.5kgCOD/ (kgMLSS d), dissolved oxygen 2.0～4.0mg/L.
Through the Start-up and Adjustment stable operation of 2 months, bio-chemical effluent COD ＜ 150mg/L, SS ＜ 20mg/L, phenol ＜ 0.5mg/L.
(3) bio-chemical effluent adds polymerization ferrous sulfate and PAM carries out flocculation treatment, and pH is controlled to 8.0～9.0.Flocculate
Water COD ＜ 120mg/L, SS ＜ 10mg/L
(4) flocculation water outlet carries out activated carbon filtration and multi-medium filtering, water outlet COD ＜ 100mg/L, SS ＜ 1mg/L successively
(5) filter water outlet and carry out multiple-effect evaporation, be evaporated completely, the index such as sodium sulfate ＞ 98%, whiteness in gained solid salt
All meet the II grade of Grade A requirement of industrial sulphuric acid sodium；Gained evaporation condensed water COD ＜ 30mg/L.
Claims (6)
1. a kind of decanedioic acid produce waste water integrated conduct method it is characterised in that：Described decanedioic acid waste water is successively through extraction dress
Put, biochemical device, advanced treatment apparatus and evaporative desalination device are processed, wherein, the circulation that evaporative desalination device produces is female
Liquid returns to biochemical device and is processed.
2. method according to claim 1 it is characterised in that：Extraction equipment is with castor oil acid, sec-octyl alcohol, QH complexometric extraction
Agent, dichloroethanes or other Examples of non-aqueous solvents are as extractant.
3. method according to claim 1 it is characterised in that：The technique that biochemical device is taken is " hydrolysis acidification+aerobic "
Technique, is processed to water after extraction, degradation of organic substances and sulfur oxide compound.
4. method according to claim 3 it is characterised in that：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.
5. method according to claim 1 it is characterised in that：Advanced treatment apparatus include flocculation plant and defecator,
Make bio-chemical effluent after treatment, colloid therein and concentration of suspension ＜ 1mg/L.
6. method according to claim 1 it is characterised in that：Evaporative desalination device is MVR, and the evaporation condensed water obtaining is straight
Take back use.
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