CN105417774B - 2‑（4 aminomethyl phenyls）The recoverying and utilizing method of benzoxazole synthesis technique waste water - Google Patents
2‑（4 aminomethyl phenyls）The recoverying and utilizing method of benzoxazole synthesis technique waste water Download PDFInfo
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- CN105417774B CN105417774B CN201510828447.2A CN201510828447A CN105417774B CN 105417774 B CN105417774 B CN 105417774B CN 201510828447 A CN201510828447 A CN 201510828447A CN 105417774 B CN105417774 B CN 105417774B
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- aminophenol
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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
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- 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
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- 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
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- 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
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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
- 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
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
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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
- 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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Abstract
The present invention relates to one kind using p-methylbenzoic acid and o-aminophenol as Material synthesis 2（4 aminomethyl phenyls）The recovery and treatment method of p-methylbenzoic acid and o-aminophenol in benzoxazole technique waste water, it is characterised in that：First acidifying separates out p-methylbenzoic acid precipitation, and p-methylbenzoic acid is recovered by filtration；Filtrate is handled with reducing agent, is adjusted pH value to alkalescence, is then adsorbed with polymeric adsorbent, and eluent is adjusted to pH8.5 9, concentrated by elution parsing, and cooling separates out phenol, filter to obtain o-aminophenol.The present invention can cost-effectively in recovery process waste water p-methylbenzoic acid and o-aminophenol, its purity respectively reaches 94.5% and more than 95.8%, can in the condensation reaction feed intake and apply mechanically directly as raw material.Processing procedure is not directed to use with organic solvent, does not produce secondary environmental pollution, clean environment firendly.
Description
Technical field
The present invention relates to a kind of process for treating industrial waste water, and in particular in a kind of synthesis technique waste water to methylbenzene first
The recovery and treatment method of acid and o-aminophenol.
Background technology
2-（4- aminomethyl phenyls）- benzoxazoles are synthesis fluorescent whitening agent OBs -1（2,2 '-（4,4 '-diphenylethyllene）It is double
Benzoxazole）A kind of important precursor.Existing synthetic method is in a kettle. by p-methylbenzoic acid and adjacent aminobenzene
Phenol is dissolved in solvent naphtha, using boric acid as catalyst, is passed through nitrogen, is warming up to 140-160 DEG C of dehydrating condensation, generates 2-（4- methyl
Phenyl）- benzoxazoles.Its composition principle is as follows：
Using above-mentioned production technology, it is dehydrated through intermolecular condensation dehydration and intramolecular condensation in the reaction of two steps, course of reaction
The water of generation is constantly separated by water knockout drum, so that reaction is further completed.In actual production process, 1Kg productions are often produced
Product, the technique waste water of generation is about 0.2Kg including material water.Before this, the water that synthetic reaction is produced typically is immediately discharged to sewage
Stand and handled, have no the report cost-effectively recycled to it.
The present inventor is found surprisingly that by the analysis to condensation waste water composition, and about 0.4-0.5% is contained in condensation waste water
P-methylbenzoic acid, 2-4% o-aminophenols and adjacent amino quinones and micro solvent naphtha, product, so as to develop a kind of warp
The effective recoverying and utilizing method that helps is comprehensively utilized to it.
The content of the invention
2- is produced using p-methylbenzoic acid and o-aminophenol as raw material（4- aminomethyl phenyls）The waste water that-benzoxazoles are produced
Character be usually：Just when separating for achromaticity and clarification liquid, show alkalescence, pH value places color after a period of time about in 9-10
Gradually turn yellow, it is green, dark green, black, it is cold after have a small amount of black precipitate.Waste component through analysis be mainly raw material p-methylbenzoic acid,
O-aminophenol, adjacent amino quinones, micro solvent naphtha and product 2-（4- aminomethyl phenyls）- benzoxazoles, wherein to methylbenzene first
Acid is containing about 0.4-0.5%, and o-aminophenol is containing about 2-4%.Before this, sewage plant is typically immediately discharged to, through activated sludge, good
Gas, aeration, sedimentation, filtration treatment, though COD is up to standard in institute's effluent, water quality still has certain color.
The characteristics of the present inventor is directed to this technique waste water, develops a kind of cost-effective method recycled to it：
P-methylbenzoic acid precipitation is separated out using first acidifying, p-methylbenzoic acid is recovered by filtration；Quinone in filtrate water is reduced to phenol simultaneously again
Adjust pH value to neutrality, through CD101 resin adsorptions, waste water is to become colorless or faint yellow, drain into sewage plant processing；Resin diluted acid again
Desorb, be neutralized to neutrality, concentration cooling separates out and reclaims o-aminophenol.This project is creatively reclaimed from condensation waste water
To the p-methylbenzoic acid and o-aminophenol of high-purity, 94.5% and more than 95.8% are respectively reached, can be existed directly as raw material
Feed intake and apply mechanically in condensation reaction, and realize the up to standard in line of waste water, with certain economy and environmental benefit.
Therefore, the invention provides one kind using p-methylbenzoic acid and o-aminophenol as Material synthesis 2-（4- methylbenzenes
Base）The recovery and treatment method of p-methylbenzoic acid and o-aminophenol in-benzoxazole technique waste waters, it is characterised in that should
Method comprises the following steps：
a）First acidifying separates out p-methylbenzoic acid precipitation, and p-methylbenzoic acid is recovered by filtration：Taking technique waste water, uses inorganic acid
Acidifying, solution becomes red by bottle green, and has yellow mercury oxide, filters, and reclaims yellow solid, as p-methylbenzoic acid；
b）Filtrate is handled with reducing agent, and solution colour is by red change buff；With
c）Continued to adjust pH value to alkalescence with alkali lye, post is crossed with 30-40ml/h speed with polymeric adsorbent and adsorbed, it is complete
Finish, cross liquid after post neutralized to the neutral laggard sewage plants of pH；Resin is parsed with elution in post, then adjusts eluent
To pH8.5-9, the 1/3-1/2 of original volume is concentrated under reduced pressure into, is cooled, that is, separates out phenol, filtering produces o-aminophenol.
Wherein step a）Described in inorganic acid be selected from sulfuric acid or hydrochloric acid, preferably watery hydrochloric acid.
PH value has crystallization to separate out when being adjusted to 3, but precipitation is more complete in pH1-2, and p-methylbenzoic acid is remained in filtrate
Seldom.
Step b）Described in reducing agent be selected from NaHS or Na2SO3, preferably Na2SO3。
Step c）In alkali can be inorganic base, the hydroxide of preferred as alkali, such as sodium hydroxide, potassium hydroxide
Deng more preferably using 20% sodium hydroxide solution.
The preferred CD101 macroporous absorbent resins of resin described in step c).
Absorption and desorption temperature：Temperature is preferably low during absorption, can be slightly below room temperature；Room temperature is can be slightly higher than during desorption.
The eluant, eluent is selected from acid or aqueous slkali, preferably hydrochloric acid.
In summary, by adopting the above-described technical solution, the present invention compared with prior art, acquired technological progress
It is：
1）Cost-effectively material useful in recovery process waste water：P-methylbenzoic acid and o-aminophenol.Often handle
The recyclable p-methylbenzoic acid 4-5Kg of one ton of condensation waste water, o-aminophenol 18-20Kg, purity respectively reach 94.5% He
More than 95.8%, it can in the condensation reaction feed intake and apply mechanically directly as raw material.One ton of condensation waste water is handled, two material conjunctions can be obtained
Valuation value 600-665 members, and processing cost is about 77.2 yuan, extra earning 480-540 members.
2）Processing procedure is not directed to use with organic solvent, does not produce secondary environmental pollution, clean environment firendly.
3）The direct qualified discharge of technique waste water.The COD value of before processing technique waste water is 480, and after handling, COD value is
80, COD clearances reach 83.3%.
4）The more conventional processing of processed waste water color has larger change.Due to employing reducing agent processing in processing procedure,
Quinones substance therein is transformed into phenol and reclaimed, therefore quinones substance content is greatly lowered in processed waste water, waste water color have compared with
Take on a new look to big degree.
The present invention is described in further detail below in conjunction with specific embodiment.
Embodiment
Following examples are used to illustrate the present invention, are not limitation of the invention.
Embodiment 1-3 is 2-（4- aminomethyl phenyls）P-methylbenzoic acid and neighbour in-benzoxazole synthesis technique waste water
The recovery and treatment method of amino-phenol
Specifically：
Embodiment 1
The condensation process reaction integrated water 500ml collected between pick-up（About 20-30 times of resin volume）, with watery hydrochloric acid acid
Change to pH1.5, stirring, solution becomes red by bottle green, and has yellow mercury oxide, filters, and reclaims the p-methylbenzoic acid of yellow
Crude product 2.35g（Purity 94.52%, HPLC）；Adjust pH value to 6 with 20% sodium sulfite solution this filtrate, solution colour is by red change
Buff, then continue tune pH value to 8.5-9 with 20% sodium hydroxide solution, use polymeric adsorbent（CD101 resins）With 30-40ml/h
Speed cross post and adsorbed, finish, cross liquid after post neutralized to the neutral laggard sewage plants of pH；About 15% salt of resin in post
Acid solution 50ml elution parsings, elution speed is identical with crossing post speed, and eluent neutralizes through 40% sodium hydroxide and adjusts pH value to 8.5-
9, the 1/3-1/2 of original volume is concentrated under reduced pressure into, cools, that is, separates out phenol, filters, obtains o-aminophenol crude product 9.9g（Purity
95.92%, HPLC）.
Embodiment 2
The condensation process reaction integrated water 500ml collected between pick-up（About 20-30 times of resin volume）, with watery hydrochloric acid acid
Change to pH1.5, stirring, solution becomes red by bottle green, and has yellow mercury oxide, filters, and reclaims the p-methylbenzoic acid of yellow
Crude product 2.33g（Purity 94.50%, HPLC）；Adjust pH value to 6 with 30% sodium hydrosulfide this filtrate, solution colour is by red change
Buff, then continue tune pH value to 8.5-9 with 20% sodium hydroxide solution, use polymeric adsorbent（CD101 resins）With 30-40ml/h
Speed cross post and adsorbed, finish, cross liquid after post neutralized to the neutral laggard sewage plants of pH；About 15% salt of resin in post
Acid solution 50ml is eluted, and elution speed is identical with crossing post speed, and eluent neutralizes through 40% sodium hydroxide and adjusts pH value to 8.5-9, subtracts
Pressure is concentrated into the 1/3-1/2 of original volume, and cooling separates out phenol, filter, obtain o-aminophenol crude product 9.5g（Purity 95.82%,
HPLC）.
Embodiment 3
The condensation process reaction integrated water 500ml collected between pick-up（About 20-30 times of resin volume）, with watery hydrochloric acid acid
Change to pH1.5, stirring, solution becomes red by bottle green, and has yellow mercury oxide, filters, and reclaims the p-methylbenzoic acid of yellow
Crude product 2.30g（Purity 94.55%, HPLC）；Adjust pH value to 6 with 30% sodium hydrosulfide this filtrate, solution colour is by red change
Buff, then continue tune pH value to 8.5-9 with 20% sodium hydroxide solution, use polymeric adsorbent（CD101 resins）With 30-40ml/h
Speed cross post and adsorbed, finish, cross liquid after post neutralized to the neutral laggard sewage plants of pH；About 4% hydrogen-oxygen of resin in post
Change sodium solution 50ml elutions, elution speed is identical with crossing post speed, and eluent adjusts pH value to 8.5-9 through 15% hydrochloric acid solution, depressurizes dense
The 1/3-1/2 of original volume is reduced to, cools, that is, separates out phenol, filters, obtains o-aminophenol crude product 9.8g（Purity 95.88%, HPLC）.
Claims (7)
1. one kind is using p-methylbenzoic acid and o-aminophenol as Material synthesis 2-（4- aminomethyl phenyls）- benzoxazole technique waste waters
In p-methylbenzoic acid and o-aminophenol recovery and treatment method, it is characterised in that this method comprises the following steps：
a）Taking technique waste water, with mineral acid acidified, solution becomes red by bottle green, and has yellow mercury oxide, filters, and reclaims yellow
Solid, as p-methylbenzoic acid；
b）Filtrate is handled with reducing agent, and solution colour is by red change buff；With
c）Continued to adjust pH value to alkalescence with sodium hydroxide solution, post crossed with 30-40ml/h speed with polymeric adsorbent and adsorbed,
Finish, cross liquid after post neutralized to the neutral laggard sewage plants of pH；Eluent, is then adjusted to by resin elution in post
PH 8.5-9, are concentrated under reduced pressure into the 1/3-1/2 of original volume, cooling, that is, separate out phenol, and filtering produces o-aminophenol.
2. recovery and treatment method according to claim 1, wherein step a）Described in inorganic acid be selected from sulfuric acid or hydrochloric acid.
3. recovery and treatment method according to claim 2, wherein the acid is selected from watery hydrochloric acid.
4. recovery and treatment method according to claim 1, wherein step b）Described in reducing agent be selected from NaHS or Na2SO3。
5. recovery and treatment method according to claim 4, the wherein reducing agent described in step b) are Na2SO3。
6. the recovery and treatment method according to claim 1 or 2 or 3 any one, wherein sodium hydroxide solution are 20% hydrogen-oxygen
Change sodium water solution.
7. recovery and treatment method according to claim 1, wherein step c）Described in the preferred CD101 macroporous absorptions tree of resin
Fat.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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- |
| 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 |
Citations (4)
| 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 |
| 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 |
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- 2015-11-24 CN CN201510828447.2A patent/CN105417774B/en active Active
Patent Citations (4)
| 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 |
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