CN108329283B - Method for recovering chloropropene epoxidation water layer dissolved catalyst - Google Patents

Method for recovering chloropropene epoxidation water layer dissolved catalyst Download PDF

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CN108329283B
CN108329283B CN201810317354.7A CN201810317354A CN108329283B CN 108329283 B CN108329283 B CN 108329283B CN 201810317354 A CN201810317354 A CN 201810317354A CN 108329283 B CN108329283 B CN 108329283B
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water layer
chloropropene
catalyst
recovering
epoxidation
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CN108329283A (en
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孙诚
徐林
丁克鸿
黄杰军
王怡明
李明
马庆炎
吕丽
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Jiangsu Ruixiang Chemical Co Ltd
Jiangsu Yangnong Chemical Group Co Ltd
Jiangsu Ruisheng New Material Technology Co Ltd
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Jiangsu Ruixiang Chemical Co Ltd
Jiangsu Yangnong Chemical Group Co Ltd
Jiangsu Ruisheng New Material Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
    • 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
    • C02F1/26—Treatment of water, waste water, or sewage by extraction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/86—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/34—Halogenated alcohols
    • C07C31/42—Polyhydroxylic acyclic alcohols
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen

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  • Organic Chemistry (AREA)
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  • Environmental & Geological Engineering (AREA)
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Abstract

The invention relates to a method for recovering a dissolved catalyst in a chloropropene epoxidation water layer, in particular to a method for recovering a catalyst by removing organic matters in a water layer. The invention provides a method for recovering a chloropropene epoxidation water layer dissolved catalyst, which is characterized in that chloropropene, hydrogen peroxide and a heteropoly acid catalyst are subjected to oxidation reaction to obtain a water layer containing epichlorohydrin and 3-chloro-1, 2-propanediol, a certain amount of chloropropene is used for extracting the epichlorohydrin in the water layer, a certain amount of ether organic solvents such as ether and the like are used for carrying out secondary extraction on the 3-chloro-1, 2-propanediol in raffinate water, organic matters in the water are basically removed through twice extraction, and the catalyst can be separated out from the water layer and can be recovered through simple filtration.

Description

Method for recovering chloropropene epoxidation water layer dissolved catalyst
Technical Field
The invention relates to a method for recovering a dissolved catalyst in a chloropropene epoxidation water layer, in particular to a method for recovering a catalyst by removing organic matters in a water layer.
Background
CN106865879, describes a process for separating catalyst in waste water by micro-cyclone. However, the catalyst particles precipitated in the aqueous layer were separated, and the catalyst dissolved in the aqueous layer could not be recovered. In addition, the epoxidation water layer contains epichlorohydrin and 3-chloro-1, 2-propanediol, wherein the boiling point of 3-chloro-1, 2-propanediol is above 200 ℃, the heteropoly acid catalyst is decomposed above 80 ℃, direct distillation causes decomposition of the catalyst, and other methods are required.
Disclosure of Invention
The invention aims to provide a method for recovering a chloropropene epoxidation water layer dissolved catalyst, which has the advantages that the structure of the catalyst cannot be damaged due to low operation temperature, the activity of the recovered catalyst cannot be reduced, and the recovery rate of the catalyst is improved by over 10 percent.
The invention provides a method for recovering a chloropropene epoxidation water layer dissolved catalyst, which is characterized in that chloropropene, hydrogen peroxide and a heteropoly acid catalyst are subjected to oxidation reaction to obtain a water layer containing epichlorohydrin and 3-chloro-1, 2-propanediol, a certain amount of chloropropene is used for extracting the epichlorohydrin in the water layer, a certain amount of ether organic solvents such as ether and the like are used for carrying out secondary extraction on the 3-chloro-1, 2-propanediol in raffinate water, organic matters in the water are basically removed through twice extraction, and the catalyst can be separated out from the water layer and can be recovered through simple filtration.
The principle of the technical scheme is as follows: the main reason why the catalyst is dissolved in water is that epichlorohydrin and 3-chloro-1, 2-propanediol exist in a water layer, and the two organic matters can form a certain binding force with the catalyst, so that the water solubility of the catalyst is improved. The organic matter in the water layer is removed by two extractions, and the catalyst is separated out. The recovery of the dissolved catalyst is realized at a lower temperature by adopting the two-time extraction process, and the structure of the catalyst is not damaged.
The ether organic solvent in the technical scheme can be diethyl ether, n-butyl ether, methyl tert-butyl ether, anisole and the like.
The epichlorohydrin content in the epoxidation reaction water layer may be 0 to 10% by weight, preferably 1 to 6% by weight, most preferably 1 to 3% by weight; the content of 3-chloro-1, 2-propanediol in the aqueous layer may be 0 to 15% by weight, preferably 1 to 10% by weight, most preferably 2 to 6% by weight.
The structure of the heteropoly acid catalyst is [ (C)nH2n+1)N(CH3)3]3PW4O16Wherein n is 0-18;
the addition amount of chloropropene in the first extraction can be 0-50 wt%, preferably 0-30 wt%, and most preferably 0-20 wt% of the weight of the water layer; the amount of the ether solvent added in the second extraction may be 0 to 50 wt%, preferably 0 to 30 wt%, most preferably 0 to 20 wt% based on the weight of the aqueous layer; the extraction temperature may be from 5 to 40 deg.C, preferably from 10 to 35 deg.C, most preferably from 20 to 30 deg.C.
The recovery rate of the catalyst is improved: after the treatment, the catalyst dissolved in the water layer can be recovered, the recovery rate of the catalyst is improved by more than 10 percent, and the consumption of the catalyst is reduced.
The separation of epoxy chloropropane and 3-chloro-1, 2-propanediol in the wastewater is realized: the separation of the epichlorohydrin and the 3-chloro-1, 2-propanediol is realized by two-time extraction, and the high-purity byproduct 3-chloro-1, 2-propanediol is obtained.
The treatment difficulty of the wastewater is reduced: by recovering the organic matter, the COD of the wastewater is greatly reduced, and the biodegradability is greatly improved.
Drawings
FIG. 1 is a flow chart of the present invention.
Detailed Description
Example 1
Into a 500ml four-necked flask was placed 300g of an epoxidation reaction water layer (epichlorohydrin: 1.8 wt%, 3-chloro-1, 2-propanediol: 5 wt%, H)2O20.2wt percent) and adding 60g of chloropropene in two times, stirring and mixing for 15min at 20 ℃, standing and layering, combining the two extracted oil layers to be used as a chloropropene raw material for recycling, and extracting a residual water layer (containing epichlorohydrin)0.05 wt% of 3-chloro-1, 2-propanediol 5.9 wt%), adding 100g of diethyl ether for three times, stirring and mixing for 15min at 20 ℃, standing and layering, wherein catalyst solids are separated out from the bottom of a water layer, merging extraction oil layers for three times, distilling and recovering diethyl ether for recycling, and obtaining the 3-chloro-1, 2-propanediol as a byproduct. And filtering the raffinate water layer to recover the catalyst, returning the catalyst to the reaction system, and directly carrying out biochemical treatment on the filtrate which hardly contains organic matters and salts and has the COD of 1000 ppm.
Example 2
Into a 500ml four-necked flask was placed 250g of an epoxidation reaction water layer (epichlorohydrin: 1.8 wt%, 3-chloro-1, 2-propanediol: 5 wt%, H)2O20.2wt percent) of the crude product, adding 50g of chloropropene twice, stirring and mixing for 15min at 25 ℃, standing and layering, combining the two extracted oil layers to be used as a chloropropene raw material for recycling, adding 100g of anisole three times into a raffinate water layer (containing 0.1wt percent of epichlorohydrin and 5.5wt percent of 3-chloro-1, 2-propanediol) for stirring and mixing for 15min at 20 ℃, standing and layering, finding that catalyst solids are separated out at the bottom of the water layer, combining the three extracted oil layers, distilling and recovering diethyl ether for recycling, and obtaining the byproduct 3-chloro-1, 2-propanediol. And filtering the raffinate water layer to recover the catalyst, returning the catalyst to the reaction system, and directly carrying out biochemical treatment on the filtrate which almost contains no organic matters and salts and has COD of 1280 ppm.
Example 3
Into a 500ml four-necked flask was placed 320g of an epoxidation reaction water layer (epichlorohydrin: 1.8 wt%, 3-chloro-1, 2-propanediol: 5 wt%, H)2O20.2 wt%), adding 55g of chloropropene twice, stirring and mixing for 15min at 20 ℃, standing for layering, combining the two extracted oil layers, recycling the extracted oil layers as a chloropropene raw material, adding 90g of n-butyl ether into the raffinate water layer for three times, stirring and mixing for 15min at 20 ℃, standing for layering, finding that catalyst solids are separated out at the bottom of the water layer, combining the three extracted oil layers, distilling and recovering ether for recycling, and obtaining the byproduct 3-chloro-1, 2-propanediol. And filtering the raffinate water layer to recover the catalyst, returning the catalyst to the reaction system, and directly carrying out biochemical treatment on the filtrate which hardly contains organic matters and salts and has COD (chemical oxygen demand) of 900 ppm.
Example 4
Into a 500ml four-necked flask was placed 300g of an epoxidation reaction water layer (epichlorohydrin: 1.8 wt%, 3-chloro-1, 2-propanediol: 5 wt%, H)2O20.2 wt%), adding 60g of chloropropene twice, stirring and mixing for 15min at 20 ℃, standing for layering, combining the two extracted oil layers, recycling the extracted oil layers as a chloropropene raw material, adding 100g of methyl tert-butyl ether three times into the raffinate water layer, stirring and mixing for 15min at 20 ℃, standing for layering, finding that catalyst solids are separated out at the bottom of the water layer, combining the three extracted oil layers, distilling and recovering diethyl ether for recycling, and obtaining the byproduct 3-chloro-1, 2-propanediol. And filtering the raffinate water layer to recover the catalyst, returning the catalyst to the reaction system, and directly carrying out biochemical treatment on the filtrate which hardly contains organic matters and salts and has COD (chemical oxygen demand) of 880 ppm.

Claims (7)

1. A method for recovering chloropropene epoxidation water layer dissolved catalyst is characterized in that chloropropene, hydrogen peroxide and heteropoly acid catalyst are subjected to oxidation reaction to obtain a water layer containing epichlorohydrin and 3-chloro-1, 2-propanediol, a certain amount of chloropropene is used for extracting the epichlorohydrin in the water layer, a certain amount of ether solvent is used for carrying out secondary extraction on the 3-chloro-1, 2-propanediol in raffinate water, organic matters in water are basically removed through twice extraction, the catalyst can be separated out from the water layer at the moment, the catalyst can be recovered through simple filtration, and the heteropoly acid catalyst has a structure of [ (C)nH2n+1)N(CH3)3]3PW4O16Wherein n is 0-18, and the ether solvent is diethyl ether, n-butyl ether, methyl tert-butyl ether or anisole.
2. The method for recovering a chloropropene epoxidation aqueous layer dissolved catalyst as claimed in claim 1, wherein the content of chloropropylene oxide in the epoxidation aqueous layer is 0-10 wt%; the content of 3-chloro-1, 2-propanediol in the water layer is 0-15 wt%, wherein the content of epichlorohydrin and 3-chloro-1, 2-propanediol is not 0.
3. The method for recovering a chloropropene epoxidation aqueous layer dissolved catalyst as claimed in claim 2, wherein the content of chloropropylene oxide in the epoxidation aqueous layer is 1-6 wt%; the content of 3-chloro-1, 2-propanediol in the water layer is 1-10 wt%.
4. The method for recovering a chloropropene epoxidation aqueous layer dissolved catalyst as claimed in claim 3, wherein the content of chloropropylene oxide in the epoxidation aqueous layer is 1-3 wt%; the content of 3-chloro-1, 2-propanediol in the water layer is 2-6 wt%.
5. The method for recovering a chloropropene epoxidation water layer dissolution catalyst as claimed in claim 1, wherein the amount of chloropropene added in the first extraction is 0-50 wt% of the weight of the water layer; the addition amount of the ether solvent is 0-50 wt% of the weight of the water layer during the secondary extraction; the extraction temperature is 5-40 ℃, wherein the addition amount of chloropropene and ether solvents is not 0.
6. The method for recovering a chloropropene epoxidation water layer dissolution catalyst as claimed in claim 5, wherein the amount of chloropropene added in the first extraction is 0-30 wt% of the weight of the water layer; the addition amount of the ether solvent is 0-30 wt% of the weight of the water layer during the secondary extraction; the extraction temperature is 10-35 ℃, wherein the addition amount of chloropropene and ether solvents is not 0.
7. The method for recovering a chloropropene epoxidation water layer dissolution catalyst as claimed in claim 6, wherein the amount of chloropropene added in the first extraction is 0-20 wt% of the weight of the water layer; the addition amount of the ether solvent is 0-20 wt% of the weight of the water layer during the secondary extraction; the extraction temperature is 20-30 ℃, wherein the addition amount of chloropropene and ether solvents is not 0.
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CN110938046B (en) * 2018-09-21 2022-08-02 中国科学院大连化学物理研究所 Method for inhibiting reaction to control hydrolysis of epoxy chloropropane produced by phase transfer catalysis
CN111233191B (en) * 2018-11-29 2021-06-29 中国科学院大连化学物理研究所 Method for treating wastewater generated in process of preparing epoxy chloropropane by epoxidation of chloropropene
CN110156726A (en) * 2019-06-03 2019-08-23 江苏扬农化工集团有限公司 A kind of method of the residual comprehensive utilization of epoxychloropropane rectifying still
CN112300097A (en) * 2019-07-26 2021-02-02 中国科学院大连化学物理研究所 Treatment method of reaction control phase transfer catalyst
CN113185036B (en) * 2021-06-07 2023-03-14 定南大华新材料资源有限公司 Waste water purification equipment is used in tombarthite production

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JP2005154340A (en) * 2003-11-26 2005-06-16 Toagosei Co Ltd Method for producing epichlorohydrins
CN100516056C (en) * 2006-12-22 2009-07-22 中国石油化工集团公司 Method of preparing and separating epichlorohydrin by chloropropene epoxidation
CN102453006B (en) * 2010-10-27 2013-12-11 中国科学院大连化学物理研究所 Method for preparing epoxy chloropropane
CN106865879A (en) * 2015-12-11 2017-06-20 中国科学院大连化学物理研究所 The method that catalyst is reclaimed from epoxychloropropane waste water

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