CN1168671C - Treatment of washing waste water produced in the course of sorbic acid production and its recovery method as resource - Google Patents
Treatment of washing waste water produced in the course of sorbic acid production and its recovery method as resource Download PDFInfo
- Publication number
- CN1168671C CN1168671C CNB02138195XA CN02138195A CN1168671C CN 1168671 C CN1168671 C CN 1168671C CN B02138195X A CNB02138195X A CN B02138195XA CN 02138195 A CN02138195 A CN 02138195A CN 1168671 C CN1168671 C CN 1168671C
- Authority
- CN
- China
- Prior art keywords
- resin
- sorbic acid
- macroporous adsorbent
- desorption
- xad
- 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.)
- Expired - Lifetime
Links
- 239000004334 sorbic acid Substances 0.000 title claims abstract description 57
- 229940075582 sorbic acid Drugs 0.000 title claims abstract description 57
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 235000010199 sorbic acid Nutrition 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000011084 recovery Methods 0.000 title claims description 9
- 239000002351 wastewater Substances 0.000 title abstract description 14
- 238000005406 washing Methods 0.000 title abstract description 5
- 229920005989 resin Polymers 0.000 claims abstract description 62
- 239000011347 resin Substances 0.000 claims abstract description 62
- 238000003795 desorption Methods 0.000 claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001179 sorption measurement Methods 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000008399 tap water Substances 0.000 claims abstract description 8
- 235000020679 tap water Nutrition 0.000 claims abstract description 7
- 239000003463 adsorbent Substances 0.000 claims description 18
- 230000008929 regeneration Effects 0.000 claims description 11
- 238000011069 regeneration method Methods 0.000 claims description 11
- 238000010828 elution Methods 0.000 claims description 8
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 229920001429 chelating resin Polymers 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000002699 waste material Substances 0.000 abstract 3
- 229920001577 copolymer Polymers 0.000 abstract 1
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000000274 adsorptive effect Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The present invention discloses a method for treating waste washing water from sorbic acid production and recovering resources. Waste washing water from sorbic acid production passes through a macroporous adsorption resin column of styrene-divinylbenzene copolymers, so that sorbic acid in the waste water absorbs on macroporous resin. After that the resin is eluted and regenerated by industrial alcohol and tap water, and the regenerated resin can be used repeatedly. High-concentration desorption liquid containing sorbic acid returns to the production process to recover industrial alcohol and sorbic acid through rectification, and low-concentration desorption liquid is used as a desorption agent of the next batch for circular use. The adsorbed resin can also be desorbed and regenerated by aqueous sodium hydroxide and tap water. Sorbic acid can be separated and recovered by adding aid in the high-concentration desorption liquid, and the low-concentration desorption liquid and waste washing liquid can prepare the desorption agent of the next batch for circular use. The method has the advantage of convenient operation and can reduce CODcr of wastewater and can recover the sorbic acid in wastewater. The method treats wastewater, creates conditions for the standard discharge after further biochemical treatment and changes pollutant into resources.
Description
One, technical field
The present invention relates to the improvement of the washes that discharges in the sanitas Sorbic Acid production process, particularly, is the recovery method to Sorbic Acid in the washes.
Two, background technology
Sorbic Acid, chemical name are 2, the 4-Sorbic Acid, are the minimum sanitass of toxicity of generally acknowledging in the world at present.Washes in the Sorbic Acid production produces in Sorbic Acid crude product making beating treating process, and one ton of Sorbic Acid of every production discharges 1.5 tons of washess approximately.Waste water is near water white transparency, and the pH value is about 3.5, and the about 32000mg/L of CODcr value mainly contains organism such as Sorbic Acid (about the about 2000mg/L of content) and a spot of ethanol in the waste water.
The domestic and foreign literature retrieval shows that the technology of the present invention had not been seen bibliographical information.
Three, summary of the invention
1, goal of the invention
The purpose of this invention is to provide and a kind ofly can effectively administer the washes of Sorbic Acid in producing, make the significantly reduced while of its CODcr can also reclaim Sorbic Acid in the waste water, realize the method for the cleaner production of resource recycling.
2, technical scheme
For achieving the above object, the improvement and its recovery method as resource of the washes during Sorbic Acid of the present invention is produced is characterized in that this method may further comprise the steps:
A) under 0～40 ℃ temperature, washes during Sorbic Acid is produced is with the flow of 1-20BV/h, the adsorption column of the macroporous adsorbent resin by being filled with vinylbenzene-divinylbenzene copolymerization, the Sorbic Acid organism is adsorbed on the resin, the absorption effluent water white transparency, the about 15000mg/L of chemical oxygen demand (COD) (CODcr) value, Sorbic Acid content is less than 50mg/L;
B) under 40～70 ℃ temperature, flow with 0.5～4BV/h, with steps A) in adsorbed organic macroporous adsorbent resin industrial alcohol desorption and regenerations such as Sorbic Acid, dense desorption liquid returns production workshop section and reclaims industrial spirit and Sorbic Acid through rectifying, and rare desorption liquid is made the next batch desorbing agent and recycled;
C) with step B) in the resin washed with ethanol wash with water again, the water elution attached liquid is applied mechanically in the production technique, macroporous adsorbent resin can use behind desorption and regeneration repeatedly.
The improvement and its recovery method as resource of the washes in the above-mentioned Sorbic Acid production can also be realized by following steps:
A) under 0～40 ℃ temperature, the washes in the Sorbic Acid production is with the adsorption column of the flow of the 1-20BV/h macroporous adsorbent resin by being filled with vinylbenzene-divinylbenzene copolymerization;
B), successively use 2%～20% aqueous sodium hydroxide solution and tap water desorption and regeneration with having adsorbed the organic macroporous adsorbent resin of Sorbic Acid in the step a) with 0.5～4BV/h at 40～80 ℃;
C) the dense desorption liquid of the sodium hydroxide in the step b) is added acid out and go out and reclaim Sorbic Acid, rare desorption liquid and water elution attached liquid preparation next batch desorbing agent recycle.
Above-mentioned macroporous adsorbent resin is homemade CHA-111 resin, ND-100 resin, H-103 resin, JX-101 resin, NDA-99 resin and the NDA-150 resin with superhigh cross-linking polystyrene structure, or the XAD-2 of U.S. Amberlite, XAD-4 and XAD-7 resin, and Japanese Diaion HP series macroporous adsorbent resin.NDA-150 resin preferably.
3, effect
After adopting the washes in the method processing Sorbic Acid production process of the present invention, the CODcr value of waste water is reduced to about 15000mg/L from about 32000mg/L, and the CODcr clearance is about 50%; Sorbic Acid content is reduced to below the 50mg/L from about 2000mg/L, and eliminating rate of absorption is greater than 97.5%.Desorption liquid returns in the production workshop section and reclaims Sorbic Acid, about the crude product Sorbic Acid 1.6kg of recyclable purity more than 94%, has realized the improvement and the resource utilization of waste water from waste water per ton.
Four, embodiment
Further specify the present invention by the following examples:
Embodiment 1:
10mL (about 7.5g) NDA-150 resin is filled in (Φ 12 * 160mm) in the glass column of insulation jacket.
Get the washes in the production of 400mL Sorbic Acid, the about 32000mg/L of CODcr value of washes, the about 2000mg/L of Sorbic Acid content, at ambient temperature waste water is flow through resin column with the flow of 60ml/h, absorption is finished, adsorb the water CODcr value that and be reduced to about 15000mg/L, Sorbic Acid content is reduced to below the 50mg/L.
NDA-150 resin after absorption is that ethanol and the 30mL tap water of 50 ℃ 30mL carries out desorption and regeneration with temperature, and flow is 10mL/h, and resin can recover adsorptive power behind desorption and regeneration, and the desorption rate of Sorbic Acid is near 100%.High concentration desorption liquid (15mL) returns production workshop section and reclaims industrial spirit and Sorbic Acid through rectifying, and light concentration desorption liquid (15mL) is as the first desorbing agent of using of next batch, and water elution attached liquid (30mL) cover is used in the production technique.
Embodiment 2:
100mL (about 75g) NDA-150 resin is filled in (Φ 30 * 250mm) in the glass column of insulation jacket.Get the washes in the production of 4500mL Sorbic Acid, the about 32000mg/L of CODcr value of washes, the about 2000mg/L of Sorbic Acid content, at ambient temperature waste water is flow through resin column with the flow of 400ml/h, absorption is finished, the CODcr value of absorption effluent is reduced to about 15000mg/L, and Sorbic Acid content is reduced to below the 50mg/L.
NDA-150 resin temperature after absorption is that 4% aqueous sodium hydroxide solution and the 300mL tap water of 8% aqueous sodium hydroxide solution, the 200mL of 60 ℃ 200mL carries out desorption and regeneration, and flow is 100mL/h.Resin can recover adsorptive power behind desorption and regeneration.The desorption rate of Sorbic Acid is near 100%.High concentration desorption liquid (200mL) adds acid out and goes out and reclaim Sorbic Acid, and light concentration desorption liquid (200mL) preparation next batch desorbing agent recycles.Water elution attached liquid (300mL) preparation next batch desorbing agent recycles.
Embodiment 3:
A) absorbing process
The adsorption tower internal diameter 420mm that selects for use, 0.27 ton of (about 0.35m of filling NDA-150 resin in the tower height 2880mm, tower
3).
Washes (the about 32000mg/L of CODcr value, the about 2000mg/L of Sorbic Acid content) in will producing through filtering Sorbic Acid is at normal temperatures squeezed into adsorption tower with pump, and absorption flow is 2.1m
3/ h, every batch processed amount is 14.0m
3, waste water is reduced to about 15000mg/L through CODcr value after the adsorption treatment, and Sorbic Acid content is reduced to below the 50mg/L.
B) desorption and regeneration
Adopt 1.05m
3Industrial alcohol and 1.05m
3Tap water carries out desorption and regeneration to the polymeric adsorbent tower of finishing absorption process.Earlier raffinate in the tower is drained, use 0.18m then
3, 50 ℃ the reverse injection adsorption tower of industrial alcohol and soaked 30 minutes, use 0.87m afterwards
3, 50 ℃ industrial alcohol following current wash-out resin, the desorption flow is 0.35m
3/ h, high concentration ethanol desorption liquid (0.525m
3) return production workshop section and reclaim industrial alcohol and Sorbic Acid, light concentration desorption liquid (0.525m
3) as next batch head desorbing agent.Treat that ethanol flows to end from adsorption tower after, use 0.18m again
3Room temperature the reverse injection adsorption tower of water and soaked 10 minutes, then, fast the water elution attached liquid following current in the tower is drained, so with 1.05m
3Water be divided into washing resin six times.Water elution attached liquid (1.05m
3) overlap and use in the production technique.
Embodiment 4:
NDA-150 resin among the embodiment 1 is changed into superhigh cross-linking polystyrene macroporous adsorbent resins such as JX-101 resin, H-103 resin and NDA-99 resin, or the XAD-2 of Amberlite, XAD-4 and XAD-7 resin, or Diaion HP series macroporous adsorbent resin, other operational conditions remain unchanged, except that every batch processing amount, adsorption effect and desorption effect changed, other results substantially roughly the same.
Claims (4)
- The improvement and its recovery method as resource of the washes during 1, a kind of Sorbic Acid is produced is characterized in that this method may further comprise the steps:A) under 0～40 ℃ temperature, the washes in the Sorbic Acid production is with the adsorption column of the flow of the 1-20BV/h macroporous adsorbent resin by being filled with vinylbenzene-divinylbenzene copolymerization;B) under 40～70 ℃ temperature, successively use industrial alcohol and tap water desorption and regeneration with having adsorbed the organic macroporous adsorbent resin of Sorbic Acid in the step a) with the flow of 0.5～4BV/h;C) the dense desorption liquid of the ethanol in the step b) is returned production workshop section to reclaim industrial spirit and Sorbic Acid, rare desorption liquid is made the next batch desorbing agent and is recycled; The water elution attached liquid is applied mechanically in the production technique.
- The improvement and its recovery method as resource of the washes during 2, Sorbic Acid according to claim 1 is produced, it is characterized in that macroporous adsorbent resin used in the step a) is homemade CHA-111 resin, ND-100 resin, H-103 resin, JX-101 resin, NDA-99 resin and the NDA-150 resin with superhigh cross-linking polystyrene structure, or the XAD-2 of U.S. Amberlite, XAD-4 and XAD-7 resin, and Japanese Diaion HP series macroporous adsorbent resin.
- The improvement and its recovery method as resource of the washes during 3, a kind of Sorbic Acid is produced is characterized in that this method may further comprise the steps:A) under 0～40 ℃ temperature, the washes in the Sorbic Acid production is with the adsorption column of the flow of the 1-20BV/h macroporous adsorbent resin by being filled with vinylbenzene-divinylbenzene copolymerization;B), successively use 2%～20% aqueous sodium hydroxide solution and tap water desorption and regeneration with having adsorbed the organic macroporous adsorbent resin of Sorbic Acid in the step a) with 0.5～4BV/h at 40～80 ℃;C) the dense desorption liquid of the sodium hydroxide in the step b) is added acid out and go out and reclaim Sorbic Acid, rare desorption liquid and water elution attached liquid preparation next batch desorbing agent recycle.
- The improvement and its recovery method as resource of the washes during 4, Sorbic Acid according to claim 3 is produced, it is characterized in that macroporous adsorbent resin used in the step a) is homemade CHA-111 resin, ND-100 resin, H-103 resin, JX-101 resin, NDA-99 resin and the NDA-150 resin with superhigh cross-linking polystyrene structure, or the XAD-2 of U.S. Amberlite, XAD-4 and XAD-7 resin, and Japanese Diaion HP series macroporous adsorbent resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB02138195XA CN1168671C (en) | 2002-09-02 | 2002-09-02 | Treatment of washing waste water produced in the course of sorbic acid production and its recovery method as resource |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB02138195XA CN1168671C (en) | 2002-09-02 | 2002-09-02 | Treatment of washing waste water produced in the course of sorbic acid production and its recovery method as resource |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1400171A CN1400171A (en) | 2003-03-05 |
| CN1168671C true CN1168671C (en) | 2004-09-29 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB02138195XA Expired - Lifetime CN1168671C (en) | 2002-09-02 | 2002-09-02 | Treatment of washing waste water produced in the course of sorbic acid production and its recovery method as resource |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1168671C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101838025B (en) * | 2010-04-07 | 2013-03-27 | 南京大学 | Method for removing organic pollutants from underground water by using resin based permeable reactive barrier (PRB) technology |
| CN105175244B (en) * | 2015-11-06 | 2017-03-29 | 南通醋酸化工股份有限公司 | A kind of recovery and treatment method of sorbic acid spent acid |
| CN109956607A (en) * | 2019-04-01 | 2019-07-02 | 南京简迪环境工程有限公司 | A kind of technique of processing and taste removal containing organic acid wastewater |
| CN112978845A (en) * | 2021-04-14 | 2021-06-18 | 南京简迪环境工程有限公司 | Recycling treatment process for 1, 3-cyclohexanedione wastewater |
-
2002
- 2002-09-02 CN CNB02138195XA patent/CN1168671C/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| CN1400171A (en) | 2003-03-05 |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: NANTONG ACETIC ACID CHEMICAL Co.,Ltd. Assignor: Nanjing University Contract fulfillment period: 2009.3.12 to 2014.3.12 Contract record no.: 2009320000972 Denomination of invention: Treatment of washing waste water produced in the course of sorbic acid production and its recovery method as resource Granted publication date: 20040929 License type: Exclusive license Record date: 20090604 |
|
| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.3.12 TO 2014.3.12; CHANGE OF CONTRACT Name of requester: NANTONG ACETIC ACID CO., LTD. Effective date: 20090604 |
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| CX01 | Expiry of patent term |
Granted publication date: 20040929 |
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| CX01 | Expiry of patent term |