CN1176026C - Method of treating phenol-containing effluent and recovering resource in 2-methyl-4-chlorophenoxyacetic acid producing process - Google Patents
Method of treating phenol-containing effluent and recovering resource in 2-methyl-4-chlorophenoxyacetic acid producing process Download PDFInfo
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- CN1176026C CN1176026C CNB021384665A CN02138466A CN1176026C CN 1176026 C CN1176026 C CN 1176026C CN B021384665 A CNB021384665 A CN B021384665A CN 02138466 A CN02138466 A CN 02138466A CN 1176026 C CN1176026 C CN 1176026C
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- China
- Prior art keywords
- methyl
- tower
- production process
- chlorophenoxyacetic acid
- desorption
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000005574 MCPA Substances 0.000 title claims abstract description 24
- WHKUVVPPKQRRBV-UHFFFAOYSA-N Trasan Chemical compound CC1=CC(Cl)=CC=C1OCC(O)=O WHKUVVPPKQRRBV-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000002351 wastewater Substances 0.000 claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 25
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000010521 absorption reaction Methods 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000001179 sorption measurement Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000003795 desorption Methods 0.000 claims description 32
- 239000003463 adsorbent Substances 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 238000004064 recycling Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 238000004132 cross linking Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000004065 wastewater treatment Methods 0.000 claims description 5
- 230000008929 regeneration Effects 0.000 claims description 4
- 238000011069 regeneration method Methods 0.000 claims description 4
- 229920001429 chelating resin Polymers 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 6
- 239000004009 herbicide Substances 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract 1
- YZHUMGUJCQRKBT-UHFFFAOYSA-M sodium chlorate Chemical compound [Na+].[O-]Cl(=O)=O YZHUMGUJCQRKBT-UHFFFAOYSA-M 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000008399 tap water Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Landscapes
- Water Treatment By Sorption (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a weed killer as agricultural chemicals, particularly a method for treating wastewater containing phenol in the production process of 2-methyl-4-chlorophenoxyacetic acid and for recovering resources. The method comprises the steps that A), waste water containing phenol in the production process of 2-methyl-4-chlorophenoxyacetic acid is filtered, the filtered liquid passes through an adsorption tower filled with macroporous resin under the conditions of the temperature of 0 to 40 DEG C. and the flow rate of 0.5 to 5 BV/h, and the water after absorption can reach the discharge standard through biochemical advanced treatment; B), the macroporous resin adsorbing orthocresol is desorbed and regenerated by a desorbing agent; C), the pH value of the desorbed high-concentration desorbing liquid is adjusted to 0.5 to 1.5, and the separated orthocresol as organic raw materials returns to the production process; water phase returns to the wastewater treating process for adsorption again, and low-concentration desorbing liquid is used for preparing the next batch for circular use. After wastewater is treated by the method, the phenol concentration is reduced to less than 5 mg/L, the removal rate of phenol is more than 99%, and the recovery rate of phenol is more than 80%. Thereby, the treatment of wastewater and the reutilization of resources are realized.
Description
One, technical field
The present invention relates to the improvement and its recovery method as resource of phenolic wastewater in a kind of pesticide herbicide production process, specifically, be the improvement and its recovery method as resource of the phenolic wastewater that produces in weedicide 2-methyl-4-chlorophenoxyacetic acid (being called for short 2 first, 4 chlorine or the MCPA) production process.
Two, background technology
2-methyl-4-chlorophenoxyacetic acid is a hormone-type selective herbicide behind a kind of bud.Domestic main employing at present is traditional with the ortho-cresol be raw material through condensation, acidifying, chlorating synthetic route, produce one ton of 2-methyl-4-chlorophenoxyacetic acid and discharge 15 tons of strongly acid wastewaters, COD approximately
CrUp to 20000～30000mg/L, wherein phenol content 1500～3000mg/L also contains the sodium-chlor about 10% in addition.
Before the present invention finishes, the existing domestic and foreign literature of recent two decades is retrieved, do not find about the improvement of phenolic wastewater in the 2-methyl-4-chlorophenoxyacetic acid production process and the report of resource recycling.
Three, summary of the invention
1, goal of the invention
The improvement and its recovery method as resource that the purpose of this invention is to provide phenolic wastewater in a kind of 2-methyl-4-chlorophenoxyacetic acid production process, utilize the inventive method can from this waste water, remove and separate, reclaim the organic raw material ortho-cresol that runs off therein, realize the combination of waste water treatment and resource recycling.
2, technical scheme
The improvement of phenolic wastewater and resource recycling method in a kind of 2-methyl-4-chlorophenoxyacetic acid production process, key step is as follows:
A) the strongly-acid phenolic wastewater that gives off in the 2-methyl-4-chlorophenoxyacetic acid production process after filtration, is the condition of 0.5～5BV/h under at 0～40 ℃ with flow with filtrate, by being filled with the adsorption tower of macroporous adsorbent resin, absorption effluent realizes qualified discharge through biochemical treatment again;
B) will adsorb the macroporous adsorbent resin desorption and regeneration of ortho-cresol with the desorbing agent NaOH aqueous solution;
C) high concentration desorption liquid that gets off of desorption returns the organic raw material ortho-cresol of separating out to production process after regulating pH and being 0.5～1.5, and water returns the waste water treatment flow process and adsorbs again, and light concentration desorption liquid is used to prepare next batch desorbing agent recycled.
Described desorbing agent is the NaOH aqueous solution.The NaOH concentration of aqueous solution is 1～3mol/L, and desorption temperature is 40～80 ℃, and the flow of desorbing agent is 0.2～3.5BV/h.
Described macroporous adsorbent resin can be home-made NDA-99, NDA-88, NDA-150, CHA-101, CHA-111, NKA, H-103 etc. have the superhigh cross-linking macroporous adsorbent resin of high-specific surface area, or U.S. Amberlite XAD-2, XAD-4, XAD-7, XAD-8 series polymeric adsorbent, or Japanese Diaion HP series macroporous adsorbent resin.Preferred superhigh cross-linking macroporous adsorbent resin NDA-99.
The improvement of phenolic wastewater and resource recycling method can adopt double-column in series absorption in the 2-methyl-4-chlorophenoxyacetic acid production process of the present invention, the operation scheme of single tower desorption, I, II, three adsorption towers of III promptly are set, earlier with I, II tower series connection following current absorption, the I tower is as first post, the II tower is as stern post, after the absorption of I tower is saturated, switch to II, III tower series connection following current absorption, the II tower is as first post, and the III tower is as stern post, the I tower carries out the following current desorption and regeneration simultaneously, so cyclical operation, thus guarantee the operation continuously all the time of whole device, increase work efficiency.
3, beneficial effect
The present invention compared with prior art, its remarkable advantage is: can to make phenol content be that the strongly acid wastewater of 1500～3000mg/L is through after the above-mentioned processing for the improvement of phenolic wastewater and resource recycling method in the 2-methyl-4-chlorophenoxyacetic acid production process of the present invention, the water outlet water white transparency, phenol content is reduced to below the 5mg/L, phenol clearance＞99%, the phenol rate of recovery＞80%, but and water outlet qualified discharge after biochemical treatment.
Four, embodiment
Below further specify the present invention by specific embodiment:
Embodiment 1
10mL (about 7.5 gram) NDA-99 superhigh cross-linking macroporous adsorbent resin packed in the glass adsorption column of strap clamp cover, and (φ 12 * 160mm).(20～25 ℃) pass through resin bed with the flow of 40mL/h after filtering with the light yellow strongly-acid phenolic wastewater (pH=0.86) that emits in the 2-methyl-4-chlorophenoxyacetic acid production process under the room temperature, and wastewater treatment capacity is that 220mL/ criticizes.Raw wastewater phenol content is 2333mg/L, and absorption effluent water white transparency, phenol content are 2.88mg/L, phenol clearance＞99%.
Use the NaOH aqueous solution of 20mL2mol/L, the NaOH aqueous solution and the 20mL tap water flow with 15mL/h under 60 ± 5 ℃ temperature of 10mL1mol/L to carry out desorption by resin bed, phenol desorption rate＞99% successively.Just begun effusive 10mL desorption liquid and be red-brown, be high concentration desorption liquid, phenol content is 38574mg/L.Hydrochloric acid soln with 37% transfers to 1.05 with its pH, separates out the scarlet oil reservoir, it can be returned production process through separating, the water after the acid adjustment with carry out adsorption treatment again after waste water mixes.The back is effusive to be light concentration desorption liquid (about 40mL), is used to prepare the next batch desorbing agent.
Embodiment 2
100mL (about 75 gram) NDA-99 resin packed in the glass adsorption column of strap clamp cover, and (φ 32 * 360mm).(25～30 ℃) pass through resin bed with the flow of 350mL/h after filtering with the light yellow strongly-acid phenolic wastewater (pH=1.02) that emits in the 2-methyl-4-chlorophenoxyacetic acid production process under the room temperature, and wastewater treatment capacity is that 2250mL/ criticizes.Raw wastewater phenol content is 2387mg/L, and absorption effluent water white transparency, phenol content are 3.23mg/L, phenol clearance＞99%.
Use the NaOH aqueous solution of 200mL2mol/L, the NaOH aqueous solution and the 200mL tap water flow with 100mL/h under 60 ± 5 ℃ temperature of 100mL1mol/L to carry out desorption by resin bed, phenol desorption rate＞99% successively.Just begun effusive 100mL desorption liquid and be red-brown, be high concentration desorption liquid, phenol content is 42358mg/L.Hydrochloric acid soln with 37% transfers to 0.54 with its pH, separates out the scarlet oil reservoir, and the weight that obtains the crude product ortho-cresol through separation is about 3.3g, it can be returned production process, water with carry out adsorption treatment again after waste water mixes.The back is effusive to be light concentration desorption liquid (about 400mL), is used to prepare the next batch desorbing agent.
Embodiment 3
A) absorbing process
(φ 600 * 3500mm), every tower filling 600 kilograms of resins of NDA-99 (about 800L) to select 3 identical adsorption towers of specification for use.Under room temperature (25～30 ℃), with the light yellow strongly-acid phenolic wastewater (phenol content 2431mg/L) that gives off in the 2-methyl-4-chlorophenoxyacetic acid production process, squeeze into adsorption tower with pump after filtering, the method for I, II tower double-column in series following current absorption is adopted in absorption, and absorption flow is 3.2m
3/ h, every batch processed amount is controlled at 20m
3Waste water after treatment, water outlet phenol content is reduced to 3.16mg/L, but after biochemical treatment qualified discharge.
B) desorption and regeneration
With the first post I tower of absorption NaOH aqueous solution desorption.The concrete operations step is as follows: earlier raffinate in the I tower is drained, and inject adsorption tower with the hot water adverse current, make it be preheated to 60 ℃.Use 1.6m then successively
3The 2mol/LNaOH aqueous solution, 0.8m
3The 1mol/LNaOH aqueous solution and 1.6m
3Tap water is with 0.8m
3The flow of/h carries out the following current desorption.Preceding 0.8m
3Desorption liquid phenol content be 48976mg/L, transfer pH to 0.51 with 37% hydrochloric acid soln, the ortho-cresol crude product weight of separating out through separation is about 28.3kg, and it is returned production process, water after the acid adjustment and waste water carry out adsorption treatment after mixing again; Back 3.2m
3Desorption liquid put into storage tank, be used to prepare the next batch desorption liquid.
I tower after desorption finishes will be as the stern post of the 3rd batch of waste water adsorption operations (when handling second batch of waste water, post headed by the II tower, the III tower is a stern post).
Embodiment 4
Change the NDA-99 resin among the embodiment 1 into NDA-88, NDA-150, H-103, CHA-111, CHA-101, other has the macroporous adsorbent resin of high-specific surface area NKA etc., or AmberliteXAD-2, XAD-4, XAD-7, XAD-8 series polymeric adsorbent, or Diaion HP series macroporous adsorbent resin etc., handle this waste water under the identical operations condition, the result shows that they have in various degree decline to absorption, the desorption performance of phenol.
Claims (6)
1, the improvement and the resource recycling method of phenolic wastewater in a kind of 2-methyl-4-chlorophenoxyacetic acid production process is characterized in that this method may further comprise the steps:
A) the strongly-acid phenolic wastewater that gives off in the 2-methyl-4-chlorophenoxyacetic acid production process after filtration, is the condition of 0.5～5BV/h under at 0～40 ℃ with flow with filtrate, by being filled with the adsorption tower of macroporous adsorbent resin, absorption effluent gets final product qualified discharge through biochemical treatment again;
B) will adsorb the macroporous adsorbent resin desorption and regeneration of ortho-cresol with the desorbing agent NaOH aqueous solution;
C) high concentration desorption liquid that gets off of desorption returns the organic raw material ortho-cresol of separating out to production process after regulating pH to 0.5～1.5, and water is got back to the waste water treatment flow process and adsorbed again, and light concentration desorption liquid is used to prepare next batch desorbing agent recycled.
2, the improvement of phenolic wastewater and the method for resource recycling in the 2-methyl-4-chlorophenoxyacetic acid production process according to claim 1 is characterized in that described desorbing agent is the NaOH aqueous solution.
3, the improvement of phenolic wastewater and the method for resource recycling in the 2-methyl-4-chlorophenoxyacetic acid production process according to claim 1 and 2, when it is characterized in that using the NaOH aqueous solution as desorbing agent, the NaOH concentration of aqueous solution is 1～3mol/L, desorption temperature is 40～80 ℃, and the flow of desorbing agent is 0.2～3.5BV/h.
4, the improvement of phenolic wastewater and the method for resource recycling in the 2-methyl-4-chlorophenoxyacetic acid production process according to claim 1, it is characterized in that described macroporous adsorbent resin, be home-made NDA-99, NDA-88, NDA-150, CHA-101, CHA-111, NKA, H-103 have the superhigh cross-linking macroporous adsorbent resin of high-specific surface area, or U.S. Amberlite XAD-2, XAD-4, XAD-7, XAD-8 series polymeric adsorbent, or Japanese Diaion HP series macroporous adsorbent resin.
5, according to the improvement of phenolic wastewater and the method for resource recycling in claim 1 or the 4 described 2-methyl-4-chlorophenoxyacetic acid production processes, it is characterized in that the preferred superhigh cross-linking macroporous adsorbent resin of described macroporous adsorbent resin NDA-99.
6, the improvement and the resource recycling method of phenolic wastewater in the 2-methyl-4-chlorophenoxyacetic acid production process according to claim 1, it is characterized in that adopting double-column in series absorption, single tower desorption operation scheme, I, II, three adsorption towers of III promptly are set, earlier with I, II tower series connection following current absorption, the I tower is as first post, the II tower is as stern post, after the absorption of I tower is saturated, switch to II, III tower series connection following current absorption, the II tower is as first post, and the III tower is as stern post, the I tower carries out the following current desorption simultaneously, so cyclical operation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021384665A CN1176026C (en) | 2002-10-21 | 2002-10-21 | Method of treating phenol-containing effluent and recovering resource in 2-methyl-4-chlorophenoxyacetic acid producing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021384665A CN1176026C (en) | 2002-10-21 | 2002-10-21 | Method of treating phenol-containing effluent and recovering resource in 2-methyl-4-chlorophenoxyacetic acid producing process |
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| CN1403382A CN1403382A (en) | 2003-03-19 |
| CN1176026C true CN1176026C (en) | 2004-11-17 |
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| CNB021384665A Expired - Fee Related CN1176026C (en) | 2002-10-21 | 2002-10-21 | Method of treating phenol-containing effluent and recovering resource in 2-methyl-4-chlorophenoxyacetic acid producing process |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973660B (en) * | 2010-09-21 | 2012-02-29 | 浙江大学 | Recycling and pretreatment methods of raw materials containing benzene thiazole alcohol pesticide industrial wastewater |
| CN102381806A (en) * | 2011-08-11 | 2012-03-21 | 南京师范大学 | Method for treating nonylphenol polyoxyethylene ether industrial wastewater |
| CN102674607A (en) * | 2012-05-03 | 2012-09-19 | 江苏健谷化工有限公司 | Method for treating acid wastewater of 2-methyl-4-chlorophenoxyacetic acid through extraction, neutralization and distillation integration |
| CN104844416B (en) * | 2015-03-26 | 2016-08-10 | 南京师范大学 | Multitple extraction absorbs dichloromethane and the method for monochloroacetone in MCPA,MCP,methoxone synthesis tail gas |
| CN111995185A (en) * | 2020-08-20 | 2020-11-27 | 京博农化科技有限公司 | Treatment method of deep-color high-concentration and high-toxicity mixed pesticide industrial wastewater |
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