CN1304882A - Treatment and rediaimation of waste water in production of 4,4'-dinitrobistyrene-2,2'-bisulfonic acid - Google Patents
Treatment and rediaimation of waste water in production of 4,4'-dinitrobistyrene-2,2'-bisulfonic acid Download PDFInfo
- Publication number
- CN1304882A CN1304882A CN01108020.5A CN01108020A CN1304882A CN 1304882 A CN1304882 A CN 1304882A CN 01108020 A CN01108020 A CN 01108020A CN 1304882 A CN1304882 A CN 1304882A
- Authority
- CN
- China
- Prior art keywords
- resin
- acid
- sodium hydroxide
- waste water
- disulfonic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002253 acid Substances 0.000 title claims abstract description 49
- 239000002351 wastewater Substances 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000011347 resin Substances 0.000 claims abstract description 31
- 229920005989 resin Polymers 0.000 claims abstract description 31
- 238000003795 desorption Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 238000010521 absorption reaction Methods 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000001179 sorption measurement Methods 0.000 claims description 10
- 239000003957 anion exchange resin Substances 0.000 claims description 9
- 238000004064 recycling Methods 0.000 claims description 5
- 229920001429 chelating resin Polymers 0.000 claims description 3
- 230000008929 regeneration Effects 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 13
- 238000011084 recovery Methods 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- REJHVSOVQBJEBF-UHFFFAOYSA-N DSD-acid Natural products OS(=O)(=O)C1=CC(N)=CC=C1C=CC1=CC=C(N)C=C1S(O)(=O)=O REJHVSOVQBJEBF-UHFFFAOYSA-N 0.000 abstract 2
- UETHPMGVZHBAFB-OWOJBTEDSA-N 4,4'-dinitro-trans-stilbene-2,2'-disulfonic acid Chemical compound OS(=O)(=O)C1=CC([N+]([O-])=O)=CC=C1\C=C\C1=CC=C([N+]([O-])=O)C=C1S(O)(=O)=O UETHPMGVZHBAFB-OWOJBTEDSA-N 0.000 abstract 1
- REJHVSOVQBJEBF-OWOJBTEDSA-N 5-azaniumyl-2-[(e)-2-(4-azaniumyl-2-sulfonatophenyl)ethenyl]benzenesulfonate Chemical compound OS(=O)(=O)C1=CC(N)=CC=C1\C=C\C1=CC=C(N)C=C1S(O)(=O)=O REJHVSOVQBJEBF-OWOJBTEDSA-N 0.000 abstract 1
- 125000000129 anionic group Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 5
- 238000002306 biochemical method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 1
- 241000406668 Loxodonta cyclotis Species 0.000 description 1
- 102000004316 Oxidoreductases Human genes 0.000 description 1
- 108090000854 Oxidoreductases Proteins 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Water Treatment By Sorption (AREA)
Abstract
A process for treating and reclaiming the waste liquid of 4,4'-dinitrostilbene-2,2'-disulfonic acid (DNS acid) generated in the oxidizing step in preparing 4,4'-diamino stilbene-2,2'-disulfonic acid (DSD acid) features that said waste liquid passes through weak-alkaline anionic macroreticular resin fixed-bed. Its advantages are nearly colouless treated water, reducing CODer from 13000-18000 mg/L to 1000 mg/L, increasing BOD5/CODer from 0.05 to 0.36, reuse of resin after desorption, and high recovery of DNS acid (up to 65% or more).
Description
The present invention relates to dyestuff intermediate 4,4 '-diaminobenzil-2, the improvement of 2 '-disulfonic acid (DSD acid) oxidation operation factory effluent.Particularly, be in the DSD acid oxidase operation factory effluent 4,4 '-dinitrobenzene toluylene-2,2 '-disulfonic acid (DNS acid) Separation and Recovery and comprehensive utilization.
DSD acid is a kind of important dyestuff intermediate, be to make raw material with para-nitrotoluene, under certain temperature condition, produce through chemical reaction processes such as sulfonation, oxidation, condensation and reduction, give off a large amount of filtration waste liquids in the oxidative condensation stage, i.e. our waste water to be processed (hereinafter to be referred as the DNS acid producing waste water).This method is produced one ton of DNS acid will discharge about 20 tons of aterrimus waste water, COD
CrUp to 13000-18000mg/L, colourity wherein contains DNS acid 3500-7000mg/L greater than 24000 times, also contains the inorganic salt about 20% in addition.
The purpose of this invention is to provide and a kind ofly can effectively administer the DNS acid producing waste water, can reclaim the method for the DNS acid in the waste water simultaneously, realize the unification of waste water treatment and resource recycling.
Technical scheme of the present invention is as follows:
A kind of improvement of DNS acid producing waste water and resource recycling method, it is: A) the DNS acid producing waste water is after filtration after the pre-treatment, at 10-30 ℃ and flow is by being filled with the macropore weak basic anion exchange resin and having the adsorption tower of heating jacket under 0.5-2.0BV/h (BV the is the resin bed volume) condition, make that most of organism such as DNS acid is adsorbed on the resin in the waste water, absorption effluent approaches colourless, COD
CrReduce to about 1000mg/L BOD by 13000-18000mg/L
5/ COD
CrBring up to more than 0.36 from 0.05, available routine biochemistry method is carried out qualified discharge after the biochemical treatment to the absorption effluent liquid.B) with concentration be the aqueous sodium hydroxide solution of 1.0-2.0mol/L as desorbing agent, will adsorb organic macropore weak basic anion exchange resin desorption and regeneration such as DNS acid in the waste water, the temperature of wash-out is 30-48 ℃, the desorbing agent flow is 0.5-2.0BV/h.Desorbing agent is use earlier the high-concentration sodium hydroxide aqueous solution, afterwards with the low-concentration sodium hydroxide aqueous solution or even with the water that does not contain sodium hydroxide.C) the high density elutriant that elutes is by acid adjustment, the recovery DNS acid of saltouing; The lower concentration elutriant is used to prepare the next batch desorbing agent and recycles.
Above-mentioned macropore weak basic anion exchange resin can be homemade ND-804 resin, D301 resin, D396 resin, D370 resin, D354 resin or D311 resin, or the Amberlite series macropore weak basic anion exchange resin of U.S. Rohm-Haas company production, preferably ND-804 resin or D301 resin.
The improvement of DNS acid producing waste water of the present invention and resource recycling method can adopt double-column in series to adsorb single tower desorption operation method, I, II, three adsorption towers of III promptly are set, and with I, the series connection of II tower, the I tower is the one-level adsorption tower earlier, the II tower is the secondary absorption tower, after the absorption of I tower is saturated, switch to II, III tower series connection absorption, the II tower is the one-level adsorption tower, the III tower is the secondary absorption tower, the I tower carries out desorption and regeneration simultaneously, and so circulation can make entire treatment device continuous operation.
The improvement of DNS acid producing waste water of the present invention and resource recycling technology can make COD
CrBe 13000-18000mg/L, the strongly acid wastewater that contains DNS acid 3500-7000mg/L and other organic aterrimuss (colourity is greater than 24000 times) after treatment, COD
CrReduce to about 1000mg/L, clearance is greater than 92%, and colourity drops to below 80 times, and clearance is near 100%, BOD
5/ COD
CrBring up to more than 0.36 from 0.05, obviously improved the biodegradability of waste water, available routine biochemistry method is carried out qualified discharge after the advanced treatment to the absorption effluent liquid, DNS acid clearance is 100%, the rate of recovery reaches 65.5%, the DNS acid of reclaiming turns back to and is used for reduction reaction in the production and prepares DSD acid, to the not influence of purity of the finished product DSD acid.
Further specify the present invention by the following examples.
Embodiment 1:
80mL (about 60 gram) ND-804 resin (productions of Golden Elephant chemical plant, Danyang City) packed in the glass adsorption column that strap clamp overlaps, and (φ 30 * 250mm).(20 ℃) allow filtered DNS acid producing waste water pass through resin bed, the COD of waste water with the flow of 80mL/h under the room temperature
CrConcentration is 14790mg/L, pH=1-2, and the concentration of DNS acid is 3490mg/L, 24800 times of colourities.The treatment capacity of waste water is 800mL/ when criticizing, and absorption effluent colourity only is 80 times, the average COD of water outlet
CrBe 1080mg/L, clearance is 92.7%, and DNS acid does not detect, and clearance is 100%, the BOD of water outlet
5/ COD
CrRatio brings up to 0.36, and available common biochemical process carries out advanced treatment.
Water with 80mL2mol/L sodium hydroxide solution and 240mL is made desorbing agent, carries out desorption with the 120mL/h flow by resin bed at 35-40 ℃, and organic desorption rate is more than 95%.160mL high concentration desorption liquid before collecting reclaims DNS acid through the acid adjustment-operation of saltouing, and the rate of recovery reaches 68.5%, and light concentration desorption liquid is used to prepare the next batch desorbing agent.
Embodiment 2:
Adsorption column and operational condition are with embodiment 1, but filling D301 resin, the COD of water outlet
CrBe 1120mg/L, clearance is 92.4%, does not detect DNS acid in the water outlet.
The flow with 80mL/h under 48 ℃ carries out desorption by resin bed with 80mL1.5mol/L and 160mL1mol/L sodium hydroxide solution, and organic desorption rate is more than 95%.160mL high concentration desorption liquid before collecting reclaims DNS acid through the acid adjustment-operation of saltouing, and the rate of recovery reaches 65.5%, and light concentration desorption liquid is used to prepare the next batch desorbing agent.
Embodiment 3:
A. absorption: select three adsorption towers for use, every tower internal diameter 600mm, tower height 5500mm, every tower is loaded ND-804 resin 600kg (about 800L), pH ≈ 1.5, COD
CrBe 15000-18000mg/L, the DNS acid content is that 3500-7000mg/L, temperature are that 20 ℃ of left and right sides DNS acid producing waste waters are squeezed into adsorption tower after filtering, the way of I, II double-column in series following current absorption is adopted in absorption, and absorption flow is 800L/h, and every batch processing amount is 10m
3Waste water after treatment, average water outlet COD
CrLess than 1000mg/L, wherein DNS acid does not detect, and absorption effluent can be handled the back qualified discharge with general biochemical method.
B. desorption: having adsorbed 10m
3The I adsorption tower aqueous sodium hydroxide solution desorption of waste water.Earlier I tower raffinate is drained, in chuck, inject hot water and make resin be preheated to 40 ℃, add 0.8m then successively
32mol/L aqueous sodium hydroxide solution and 2.4m
3Water is with 1.2m
3/ h flow adverse current is carried out desorption by resin bed, and desorption temperature is 40 ± 5 ℃, with preceding 1.2m
3High concentration desorption liquid and back 2.0m
3Light concentration desorption liquid enters two storage tanks respectively, and is stand-by.
High concentration desorption liquid in the storage tank transfers to pH=1 with sulfuric acid earlier, adds 15%NaCl then, has crystal to separate out, and filters and collects, dries, and gets 35kgDNS acid, can turn back in the DNS acid reduction reaction production technique.Light concentration desorption liquid is used to prepare the next batch desorbing agent.
Embodiment 4:
Change the resin among the embodiment 1 into Amberlite series macropore weak basic anion exchange resin, homemade D311, D396, D370, D354 resin, except that the batch processing wastewater flow rate changed to some extent, other result substantially roughly the same.
Claims (7)
1. one kind 4,4 '-dinitrobenzene toluylene-2, the improvement of 2 '-disulfonic acid factory effluent and resource recycling method is characterized in that:
A) will be through pretreated 4,4 '-dinitrobenzene toluylene-2, the waste water that discharges in the production of 2 '-disulfonic acid is by being filled with the macropore weak basic anion exchange resin and having the adsorption tower of heating jacket, make in the waste water 4,4 '-dinitrobenzene toluylene-2, most of organism such as 2 '-disulfonic acid is adsorbed on the resin
B) with aqueous sodium hydroxide solution as desorbing agent, will adsorb in the waste water 4,4 '-dinitrobenzene toluylene-2, organic macropore weak basic anion exchange resin such as 2 '-disulfonic acid desorption and regeneration,
C) the high density elutriant that elutes by acid adjustment, saltout, filtered and recycled 4,4 '-dinitrobenzene toluylene-2,2 '-disulfonic acid, the lower concentration elutriant is used to prepare the next batch desorbing agent, recycles.
2. method according to claim 1, it is characterized in that the macropore weak basic anion exchange resin is ND-804 resin, D301 resin, D396 resin, D370 resin, D354 resin or D311 resin, or Amberlite series macropore weak basic anion exchange resin.
3. method according to claim 2 is characterized in that preferably ND-804 resin or D301 resin.
4. method according to claim 1 is characterized in that steps A is to carry out under 10-30 ℃ of temperature, flow is 1.0-3.0BV/h.
5. method according to claim 1, the concentration that it is characterized in that aqueous sodium hydroxide solution in step B is 1.0-2.0mol/L.
6. method according to claim 5 is characterized in that the desorbing agent aqueous sodium hydroxide solution is earlier with the aqueous sodium hydroxide solution of high density, the back with the aqueous sodium hydroxide solution of lower concentration or the water that do not contain sodium hydroxide as desorbing agent.
7. method according to claim 1 is characterized in that adopting two series connection absorption, single tower desorption operation scheme of taking off.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011080205A CN1156407C (en) | 2001-01-05 | 2001-01-05 | Treatment and rediaimation of waste water in production of 4,4'-dinitrobistyrene-2,2'-bisulfonic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011080205A CN1156407C (en) | 2001-01-05 | 2001-01-05 | Treatment and rediaimation of waste water in production of 4,4'-dinitrobistyrene-2,2'-bisulfonic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1304882A true CN1304882A (en) | 2001-07-25 |
| CN1156407C CN1156407C (en) | 2004-07-07 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011080205A Expired - Fee Related CN1156407C (en) | 2001-01-05 | 2001-01-05 | Treatment and rediaimation of waste water in production of 4,4'-dinitrobistyrene-2,2'-bisulfonic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1156407C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295393A (en) * | 2011-08-22 | 2011-12-28 | 山西阳煤丰喜肥业(集团)有限责任公司 | Treatment process for production wastewater of DSD acid |
| CN102351748A (en) * | 2011-08-22 | 2012-02-15 | 山西阳煤丰喜肥业(集团)有限责任公司 | Preparation method for DNS (4,4'-dinitrostilbene-2,2'-disulphonic acid) sodium salt in DSD (4,4'-diaminodiphenylethylene-2,2'-disulfonic acid) acid production process |
| CN102863053A (en) * | 2012-09-14 | 2013-01-09 | 东南大学 | Treatment and resource recovery method for treating rinsing wastewater in production process of 2-naphthylamine-3,6,8-trisulfonic acid |
| CN103910454A (en) * | 2014-04-24 | 2014-07-09 | 山西阳煤丰喜肥业(集团)有限责任公司 | Device and method for decreasing temperature of DSD (4,4'-diamido diphenylethylene-disulfonic acid) wastewater |
| CN105110537A (en) * | 2015-08-21 | 2015-12-02 | 山西青山化工有限公司 | DSD acid oxidation waste water treatment and resource recycling method |
| CN113603264A (en) * | 2021-08-24 | 2021-11-05 | 北京盖雅环境科技有限公司 | Method for treating wastewater in DNS acid reduction section |
| CN113880184A (en) * | 2021-10-12 | 2022-01-04 | 南京理工大学 | Method for recycling NTO in wastewater |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100451000C (en) * | 2007-06-14 | 2009-01-14 | 天津大学 | Process of preparing high quality sodium salt of DSD acid with industrial DSD acid |
-
2001
- 2001-01-05 CN CNB011080205A patent/CN1156407C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295393A (en) * | 2011-08-22 | 2011-12-28 | 山西阳煤丰喜肥业(集团)有限责任公司 | Treatment process for production wastewater of DSD acid |
| CN102351748A (en) * | 2011-08-22 | 2012-02-15 | 山西阳煤丰喜肥业(集团)有限责任公司 | Preparation method for DNS (4,4'-dinitrostilbene-2,2'-disulphonic acid) sodium salt in DSD (4,4'-diaminodiphenylethylene-2,2'-disulfonic acid) acid production process |
| CN102295393B (en) * | 2011-08-22 | 2012-09-05 | 山西阳煤丰喜肥业(集团)有限责任公司 | Treatment process for production wastewater of DSD acid |
| CN102351748B (en) * | 2011-08-22 | 2013-08-21 | 山西阳煤丰喜肥业(集团)有限责任公司 | Preparation method for DNS (4,4'-dinitrostilbene-2,2'-disulphonic acid) sodium salt in DSD (4,4'-diaminodiphenylethylene-2,2'-disulfonic acid) acid production process |
| CN102863053A (en) * | 2012-09-14 | 2013-01-09 | 东南大学 | Treatment and resource recovery method for treating rinsing wastewater in production process of 2-naphthylamine-3,6,8-trisulfonic acid |
| CN103910454A (en) * | 2014-04-24 | 2014-07-09 | 山西阳煤丰喜肥业(集团)有限责任公司 | Device and method for decreasing temperature of DSD (4,4'-diamido diphenylethylene-disulfonic acid) wastewater |
| CN105110537A (en) * | 2015-08-21 | 2015-12-02 | 山西青山化工有限公司 | DSD acid oxidation waste water treatment and resource recycling method |
| CN113603264A (en) * | 2021-08-24 | 2021-11-05 | 北京盖雅环境科技有限公司 | Method for treating wastewater in DNS acid reduction section |
| CN113880184A (en) * | 2021-10-12 | 2022-01-04 | 南京理工大学 | Method for recycling NTO in wastewater |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1156407C (en) | 2004-07-07 |
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