CN105417774A - Recycling method of 2-(4-methyl phenyl)-benzoxazole synthetic process wastewater - Google Patents

Recycling method of 2-(4-methyl phenyl)-benzoxazole synthetic process wastewater Download PDF

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CN105417774A
CN105417774A CN201510828447.2A CN201510828447A CN105417774A CN 105417774 A CN105417774 A CN 105417774A CN 201510828447 A CN201510828447 A CN 201510828447A CN 105417774 A CN105417774 A CN 105417774A
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aminophenol
ortho
recovery
treatment method
acid
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CN105417774B (en
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王斌
李德宝
杨玉忠
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HUBEI HONGXIN CHEMICAL CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/10—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a recycling and treating method of p-toluic acid and ortho-aminophenol in wastewater of a process for synthesizing 2-(4-methyl phenyl)-benzoxazole by taking the p-toluic acid and the ortho-aminophenol as raw materials. The method is characterized by comprising the steps that p-toluic acid precipitates are firstly precipitated out through acidification, and the p-toluic acid is recycled through filtration; filtrate is treated with a reducing agent, the pH value of the filtrate is regulated to be alkali, adsorption is performed with adsorbent resin, elution and analysis are performed, the pH of eluant is regulated to 8.5-9, concentrating and temperature lowering are performed to precipitate phenol out, and filtration is performed to obtain the ortho-aminophenol. According to the method, the p-toluic acid and the ortho-aminophenol in the process wastewater can be economically and effectively recycled, the purity of the p-toluic acid and the purity of the ortho-aminophenol can reach 94.5% or above and 95.8% or above respectively, and the p-toluic acid and the ortho-aminophenol can directly serve as the raw materials to be put and used over and over again in a condensation reaction; organic solvent is not related and used in the treatment process, secondary environmental pollution is not generated, cleanliness and environmental protection are achieved.

Description

2-(4-aminomethyl phenyl) recoverying and utilizing method of-benzoxazole synthesis technique waste water
Technical field
The present invention relates to a kind of process for treating industrial waste water, be specifically related to the recovery and treatment method of p-methylbenzoic acid in a kind of synthesis technique waste water and Ortho-Aminophenol.
Background technology
2-(4-aminomethyl phenyl)-benzoxazoles are synthesis fluorescent whitening agent OB-1(2,2 '-(4,4 '-diphenylethyllene) dibenzoxazine) a kind of important precursor.Existing synthetic method in a kettle. p-methylbenzoic acid and Ortho-Aminophenol is dissolved in solvent oil, using boric acid as catalyzer, passes into nitrogen, is warming up to 140-160 DEG C of dehydrating condensation, generates 2-(4-aminomethyl phenyl)-benzoxazoles.Its composition principle is as follows:
Adopt above-mentioned production technique, through intermolecular condensation dehydration and intramolecular condensation dewater two steps reaction, the water generated in reaction process is constantly separated by water trap, be beneficial to react complete further.In actual production process, often produce 1Kg product, the processing wastewater of generation comprises material water and is about 0.2Kg.Before this, generally the water that building-up reactions is produced directly is drained into sewage plant and process, have no the report that it is recycled cost-effectively.
The present inventor is by the analysis to condensation waste water composition, unexpected discovery, containing solvent oil, the product of the p-methylbenzoic acid of the 0.4-0.5% that has an appointment, 2-4% Ortho-Aminophenol and adjacent amino quinones and trace in condensation waste water, thus develop a kind of cost-effective recoverying and utilizing method it is fully utilized.
Summary of the invention
With p-methylbenzoic acid and Ortho-Aminophenol for raw material production 2-(4-aminomethyl phenyl) proterties of waste water that produces of-benzoxazoles is generally: liquid when just separating being achromaticity and clarification, aobvious alkalescence, pH value is about 9-10, place color after for some time turn yellow gradually, green, dark green, black, have a small amount of black precipitate after cold.Waste component is mainly raw material p-methylbenzoic acid, Ortho-Aminophenol, adjacent amino quinones by analysis, the solvent oil of trace and product 2-(4-aminomethyl phenyl)-benzoxazoles, wherein p-methylbenzoic acid is about containing 0.4-0.5%, and Ortho-Aminophenol is about containing 2-4%.Before this, generally it is directly drained into sewage plant, through active sludge, aerobic, aeration, sedimentation, filtration treatment, though COD is up to standard in institute's effluent, water quality still has certain color.
The present inventor, for the feature of this processing wastewater, develops a kind of cost-effective method recycled it: adopt first acidifying to separate out p-methylbenzoic acid precipitation, filtered and recycled p-methylbenzoic acid; Again quinone in filtrate water is reduced to phenol and adjust pH to neutral, through CD101 resin absorption, namely waste water become colorless or faint yellow, drains into sewage plant process; Resin diluted acid desorb again, be neutralized to neutrality, concentrated cooling is separated out and reclaims Ortho-Aminophenol.This project creatively reclaims and obtains highly purified p-methylbenzoic acid and Ortho-Aminophenol from condensation waste water, reach more than 94.5% and 95.8% respectively, directly can feed intake in the condensation reaction as raw material and apply mechanically, and realize the up to standard in line of waste water, there is certain economy and environment benefit.
Therefore, the invention provides a kind of with p-methylbenzoic acid and Ortho-Aminophenol for Material synthesis 2-(4-aminomethyl phenyl) recovery and treatment method of p-methylbenzoic acid in-benzoxazole processing wastewaters and Ortho-Aminophenol, it is characterized in that, the method comprises the following steps:
A) first acidifying separates out p-methylbenzoic acid precipitation, filtered and recycled p-methylbenzoic acid: taking technique waste water, and with mineral acid acidified, solution becomes red by deep green, and has yellow mercury oxide, filters, and reclaims yellow solid, is p-methylbenzoic acid;
B) filtrate uses reductive agent process, and solution colour is by red stain deep yellow; With
C) continue adjust pH to alkalescence with alkali lye, cross post adsorb with polymeric adsorbent with the speed of 30-40ml/h, complete, after crossing post, liquid is through being neutralized to the neutral laggard sewage plant of pH; In post, resin elution is resolved, and then elutriant is adjusted to pH8.5-9, is evaporated to the 1/3-1/2 of original volume, and cooling, namely separates out phenol, filter and obtain Ortho-Aminophenol.
Wherein mineral acid described in step a) is selected from sulfuric acid or hydrochloric acid, preferred dilute hydrochloric acid.
PH value has crystallization when being adjusted to 3, but separates out comparatively complete when pH1-2, and in filtrate, p-methylbenzoic acid is seldom residual.
Described in step b), reductive agent is selected from NaHS or Na 2sO 3, preferred Na 2sO 3.
Alkali in step c) can be the oxyhydroxide of mineral alkali, preferred as alkali, such as sodium hydroxide, potassium hydroxide etc., more preferably uses 20% sodium hydroxide solution.
Step c) described in the preferred CD101 macroporous adsorbent resin of resin.
Sorption and desorption temperature: during absorption, temperature should be low, can a little less than room temperature; Can a little more than room temperature during desorb.
Described eluent is selected from acid or alkaline solution, preferred hydrochloric acid.
In sum, owing to have employed technique scheme, compared with prior art, acquired technical progress is in the present invention:
1) useful in recovery process waste water cost-effectively material: p-methylbenzoic acid and Ortho-Aminophenol.Often process one ton of recyclable p-methylbenzoic acid 4-5Kg of condensation waste water, Ortho-Aminophenol 18-20Kg, purity reaches more than 94.5% and 95.8% respectively, directly can feed intake in the condensation reaction as raw material and apply mechanically.Process one ton of condensation waste water, two material aggregate value 600-665 units can be obtained, and processing cost is about 77.2 yuan, extra earning 480-540 unit.
2) treating processes does not relate to an organic solvent, does not produce secondary environmental pollution, clean environment firendly.
3) the direct qualified discharge of processing wastewater.Before process, the COD value of processing wastewater is 480, and after process, COD value is that 80, COD clearances reach 83.3%.
4) processed waste water color comparatively conventional processing have larger change.Owing to have employed reductive agent process in treating processes, quinones substance is wherein transformed into phenol and reclaims, therefore in processed waste water, quinones substance content greatly reduces, and waste water color has takes on a new look largely.
The present invention is described in further detail below in conjunction with specific embodiment.
Embodiment
Following examples, for illustration of the present invention, are not limitation of the invention.
Embodiment 1-3 is 2-(4-aminomethyl phenyl) recovery and treatment method of p-methylbenzoic acid in-benzoxazole synthesis technique waste water and Ortho-Aminophenol
Particularly:
Embodiment 1
The condensation operation reaction integrated water 500ml(collected between picking up the car is about the 20-30 of resin volume doubly), be acidified to pH1.5 with dilute hydrochloric acid, stir, solution becomes red by deep green, and has yellow mercury oxide, filters, reclaim yellow p-methylbenzoic acid crude product 2.35g(purity 94.52%, HPLC); By this filtrate with 20% sodium sulfite solution adjust pH to 6, solution colour is by red stain deep yellow, adjust pH is continued to 8.5-9 again with 20% sodium hydroxide solution, cross post with polymeric adsorbent (CD101 resin) with the speed of 30-40ml/h to adsorb, complete, after crossing post, liquid is through being neutralized to the neutral laggard sewage plant of pH; In post, resin about 15% hydrochloric acid solution 50ml wash-out is resolved, elution speed is identical with crossing post speed, elutriant through 40% sodium hydroxide neutralization and adjust pH to 8.5-9, be evaporated to the 1/3-1/2 of original volume, cooling, namely separates out phenol, filters, obtain Ortho-Aminophenol crude product 9.9g(purity 95.92%, HPLC).
Embodiment 2
The condensation operation reaction integrated water 500ml(collected between picking up the car is about the 20-30 of resin volume doubly), be acidified to pH1.5 with dilute hydrochloric acid, stir, solution becomes red by deep green, and has yellow mercury oxide, filters, reclaim yellow p-methylbenzoic acid crude product 2.33g(purity 94.50%, HPLC); By this filtrate with 30% sodium hydrosulfide adjust pH to 6, solution colour is by red stain deep yellow, adjust pH is continued to 8.5-9 again with 20% sodium hydroxide solution, cross post with polymeric adsorbent (CD101 resin) with the speed of 30-40ml/h to adsorb, complete, after crossing post, liquid is through being neutralized to the neutral laggard sewage plant of pH; Resin about 15% hydrochloric acid solution 50ml wash-out in post, elution speed is identical with crossing post speed, elutriant through 40% sodium hydroxide neutralization and adjust pH to 8.5-9, be evaporated to the 1/3-1/2 of original volume, cooling, namely separates out phenol, filter, obtain Ortho-Aminophenol crude product 9.5g(purity 95.82%, HPLC).
Embodiment 3
The condensation operation reaction integrated water 500ml(collected between picking up the car is about the 20-30 of resin volume doubly), be acidified to pH1.5 with dilute hydrochloric acid, stir, solution becomes red by deep green, and has yellow mercury oxide, filters, reclaim yellow p-methylbenzoic acid crude product 2.30g(purity 94.55%, HPLC); By this filtrate with 30% sodium hydrosulfide adjust pH to 6, solution colour is by red stain deep yellow, adjust pH is continued to 8.5-9 again with 20% sodium hydroxide solution, cross post with polymeric adsorbent (CD101 resin) with the speed of 30-40ml/h to adsorb, complete, after crossing post, liquid is through being neutralized to the neutral laggard sewage plant of pH; Resin about 4% sodium hydroxide solution 50ml wash-out in post, elution speed is identical with crossing post speed, elutriant through 15% hydrochloric acid solution adjust pH to 8.5-9, be evaporated to the 1/3-1/2 of original volume, cooling, namely separates out phenol, filter, obtain Ortho-Aminophenol crude product 9.8g(purity 95.88%, HPLC).

Claims (9)

1. with p-methylbenzoic acid and Ortho-Aminophenol for Material synthesis 2-(4-aminomethyl phenyl) recovery and treatment method of p-methylbenzoic acid in-benzoxazole processing wastewater and Ortho-Aminophenol, it is characterized in that, the method comprises the following steps:
A) taking technique waste water, with mineral acid acidified, solution becomes red by deep green, and has yellow mercury oxide, filters, and reclaims yellow solid, is p-methylbenzoic acid;
B) filtrate uses reductive agent process, and solution colour is by red stain deep yellow; With
C) continue adjust pH to alkalescence with sodium hydroxide solution, cross post adsorb with polymeric adsorbent with the speed of 30-40ml/h, complete, after crossing post, liquid is through being neutralized to the neutral laggard sewage plant of pH; In post, resin elution, is then adjusted to pH8.5-9 by elutriant, is evaporated to the 1/3-1/2 of original volume, and cooling, namely separates out phenol, filter and obtain Ortho-Aminophenol.
2. the recovery and treatment method according to claim 1, wherein mineral acid described in step a) is selected from sulfuric acid or hydrochloric acid.
3. recovery and treatment method according to claim 2, wherein said acid is selected from dilute hydrochloric acid.
4. the recovery and treatment method according to claim 1, wherein described in step b), reductive agent is selected from NaHS or Na 2sO 3.
5. recovery and treatment method according to claim 4, wherein step b) described in reductive agent be Na 2sO 3.
6. the recovery and treatment method according to claim 1 or 2 or 3, wherein sodium hydroxide solution is the aqueous sodium hydroxide solution of 20%.
7. the p-methylbenzoic acid in the processing wastewater according to claim 1 and the recovery and treatment method of Ortho-Aminophenol, the wherein preferred CD101 macroporous adsorbent resin of resin described in step c).
8. the p-methylbenzoic acid in the processing wastewater according to claim 2 and the recovery and treatment method of Ortho-Aminophenol, pH value is adjusted to 1-3.
9. recovery and treatment method according to claim 8, wherein said pH value is adjusted to 1-2.
CN201510828447.2A 2015-11-24 2015-11-24 2‑（4 aminomethyl phenyls）The recoverying and utilizing method of benzoxazole synthesis technique waste water Active CN105417774B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108129271A (en) * 2018-01-09 2018-06-08 江苏振方生物化学有限公司 A kind of method of the chloro- 3,5- dinitro-p-trifluorotoluenes waste water acidification recycling phenol of 4-
CN109438381A (en) * 2018-12-26 2019-03-08 湖北鸿鑫化工有限公司 A kind of 2-(4- aminomethyl phenyl)-benzoxazoles bottoms method of comprehensive utilization
CN111003904A (en) * 2019-12-31 2020-04-14 天津大学 Resourceful treatment method of high-concentration phenol-containing wastewater
CN114291916A (en) * 2021-12-31 2022-04-08 天富凯业(辽宁)新材料有限公司 System and method for recycling o-aminophenol from o-aminophenol acidification wastewater

Citations (4)

* Cited by examiner, † Cited by third party
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CN1712365A (en) * 2005-05-18 2005-12-28 南京大学 Treatment of wastewater from production of para-aminophenol and making it be resource
CN103265502A (en) * 2013-06-09 2013-08-28 湖北鸿鑫化工有限公司 Preparation method of 2,2'-(4,4'-distylyl) dibenzoxazole by adopting new sulphur method
CN104355455A (en) * 2014-11-20 2015-02-18 郑州航空工业管理学院 Ortho-aminophenol wastewater treatment method
WO2015157009A1 (en) * 2014-04-08 2015-10-15 Invista North America S.A.R.L. Pure plant waste water purification and recycle

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1712365A (en) * 2005-05-18 2005-12-28 南京大学 Treatment of wastewater from production of para-aminophenol and making it be resource
CN103265502A (en) * 2013-06-09 2013-08-28 湖北鸿鑫化工有限公司 Preparation method of 2,2'-(4,4'-distylyl) dibenzoxazole by adopting new sulphur method
WO2015157009A1 (en) * 2014-04-08 2015-10-15 Invista North America S.A.R.L. Pure plant waste water purification and recycle
CN104355455A (en) * 2014-11-20 2015-02-18 郑州航空工业管理学院 Ortho-aminophenol wastewater treatment method

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108129271A (en) * 2018-01-09 2018-06-08 江苏振方生物化学有限公司 A kind of method of the chloro- 3,5- dinitro-p-trifluorotoluenes waste water acidification recycling phenol of 4-
CN109438381A (en) * 2018-12-26 2019-03-08 湖北鸿鑫化工有限公司 A kind of 2-(4- aminomethyl phenyl)-benzoxazoles bottoms method of comprehensive utilization
CN109438381B (en) * 2018-12-26 2023-01-06 湖北鸿鑫化工有限公司 Comprehensive utilization method of 2- (4-methylphenyl) -benzoxazole distillation residues
CN111003904A (en) * 2019-12-31 2020-04-14 天津大学 Resourceful treatment method of high-concentration phenol-containing wastewater
CN114291916A (en) * 2021-12-31 2022-04-08 天富凯业(辽宁)新材料有限公司 System and method for recycling o-aminophenol from o-aminophenol acidification wastewater

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