CN109293600B - Method for removing residual hydrogen peroxide in epoxy chloropropane oil layer - Google Patents
Method for removing residual hydrogen peroxide in epoxy chloropropane oil layer Download PDFInfo
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- CN109293600B CN109293600B CN201811340527.3A CN201811340527A CN109293600B CN 109293600 B CN109293600 B CN 109293600B CN 201811340527 A CN201811340527 A CN 201811340527A CN 109293600 B CN109293600 B CN 109293600B
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- oil layer
- hydrogen peroxide
- residual hydrogen
- epichlorohydrin
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/32—Separation; Purification
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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
Abstract
The invention discloses a method for removing residual hydrogen peroxide in an epichlorohydrin oil layer, which comprises the following steps: adding a reductive solid into a fixed bed reactor, and adding a reaction oil layer into the fixed bed reactor at a constant speed through a metering pump to ensure that the reaction oil layer is fully contacted with the reductive solid; the reaction oil layer is obtained by reacting chloropropene with hydrogen peroxide under a heteropoly acid catalyst; the reaction oil layer contains chloropropene, epichlorohydrin and hydrogen peroxide. The method is simple to operate, does not introduce new impurities, is easy to implement industrially, and ensures the safety of the process for preparing the epichlorohydrin by directly epoxidizing the chloropropene and the hydrogen peroxide under the catalysis of the heteropoly acid catalyst.
Description
Technical Field
The invention belongs to the field of organic chemistry, and particularly relates to a method for removing residual hydrogen peroxide in an epichlorohydrin oil layer.
Background
The Chinese CN101987838A patent proposes that an explosive mixture is formed with chloropropene gas as a raw material due to ineffective decomposition of hydrogen peroxide in the reaction process, and adopts a zirconia oxygen analyzer to arrange a zirconia oxygen sensor above the gas phase of a reactor, carry out on-line monitoring on the oxygen concentration of the gas phase and control the oxygen concentration of the gas phase of the reactor within the range of 0-6 percent. The patent teaches that within this range the mixed gas in the reactor does not explode, effectively eliminating the risk of explosion of the gas phase in the reactor. The above patent studies the explosion risk during the reaction, but does not consider that a small amount of unreacted hydrogen peroxide remains during the post-reaction treatment, and there is still a potential explosion risk. The prior literatures and patents have very limited introduction on post-treatment, and no report on a method for removing residual hydrogen peroxide in an oil layer is found at present.
In the prior art, excessive chloropropene and hydrogen peroxide react under a heteropoly acid catalyst to obtain a reaction oil layer, excessive chloropropene is selected as a solvent in the reaction without adopting other solvents, the oil layer after the reaction contains a large amount of chloropropene and a small amount of unreacted hydrogen peroxide besides a product epoxy chloropropane, in order to obtain epoxy chloropropane liquid, the oil layer after the reaction needs to be distilled under normal pressure and reduced pressure, and in the distillation process, a small amount of hydrogen peroxide can be decomposed to generate oxygen to form an explosive mixture with the chloropropene, so that the production safety is damaged.
Therefore, it is required to provide a method for removing residual hydrogen peroxide in an epichlorohydrin oil layer before distillation of the reaction oil layer to solve the above problems.
Disclosure of Invention
The invention aims to provide a safe method for preparing epoxy chloropropane by directly epoxidizing chloropropene and hydrogen peroxide under the catalysis of a heteropolyacid catalyst, and particularly aims to provide a novel method for removing residual hydrogen peroxide from an epoxy chloropropane oil layer obtained by the reaction.
The conventional method for removing hydrogen peroxide in an oil layer is to wash the reacted oil layer with water to bring out a small amount of hydrogen peroxide, but due to the reaction characteristic of the invention, a large amount of chloropropene exists in the reacted oil layer to ensure that the density of the oil layer is very close to that of water, and the water washing can generate a serious emulsification phenomenon. Therefore, there is a need to find other ways to treat hydrogen peroxide in the oil layer of the reaction of the present invention. Through continuous attempts, the effect of decomposing residual hydrogen peroxide in an oil layer without introducing new impurities can be achieved by using some metals and chloride salts thereof and some sodium salts as reducing agents. In addition, the purpose of mass production can be achieved by utilizing the fixed bed reactor.
The technical scheme of the invention is as follows:
a method for removing residual hydrogen peroxide in an epoxy chloropropane oil layer comprises the steps of adding a certain amount of solid with reducibility into a fixed bed reactor, adding a reaction oil layer into the fixed bed reactor at a constant speed by a metering pump at a certain flow rate at a certain temperature, fully contacting the reaction oil layer with the reducibility solid, carrying out oxidation-reduction reaction on residual hydrogen peroxide in the oil layer to remove the residual hydrogen peroxide, wherein the removal rate of the hydrogen peroxide is more than 95%, and the removal effect is good.
The fixed bed reactor is a glass or stainless steel fixed bed reactor with a jacket for heat preservation, and inert fillers are filled in the upper part and the lower part of a bed layer (the upper part and the lower part of reductive solids);
the reaction oil layer in the scheme is obtained by reacting chloropropene and hydrogen peroxide under a heteropoly acid catalyst; the reaction oil layer contains chloropropene, epoxy chloropropane, hydrogen peroxide and the like;
the content of the residual hydrogen peroxide in the oil layer in the scheme is 0.1-1%;
the solid with reducibility in the scheme comprises Mg, Al, Cu and FeCl2、SnCl2、Na2S2O3、Na2SO3One or more reducing substances;
the mass of the reducing solid added in the scheme is 3-20% of the mass of the reaction oil layer, and the optimal mass is 8-10%;
the reaction temperature in the scheme is 10-40 ℃, and preferably 20-30 ℃;
the flow rate of the metering pump in the scheme is 1-10 g/min, and preferably 1-4 g/min.
The invention adopts a fixed bed reactor, provides a method for simply removing residual hydrogen peroxide in an epichlorohydrin oil layer, and achieves the purpose of removing a small amount of residual hydrogen peroxide in the oil layer by contacting the residual hydrogen peroxide in the oil layer with a reducing substance to generate an oxidation-reduction reaction, wherein the removal rate of the residual hydrogen peroxide in the oil layer is more than 95%. The method is simple to operate, does not introduce new impurities, is easy to implement industrially, and ensures the safety of the process for preparing the epichlorohydrin by directly epoxidizing the chloropropene and the hydrogen peroxide under the catalysis of the heteropoly acid catalyst.
Detailed Description
Example 1
The preparation method of the epichlorohydrin reaction oil layer comprises the following steps: 400g of chloropropene and 20g of phosphomolybdic acid catalyst are put into a 1000ml four-neck flask, the temperature is raised to 40 ℃ under stirring, 80g of 35 percent hydrogen peroxide is dripped into a constant pressure separating funnel, after dripping is finished for 4 hours, the temperature is kept for 2 hours. After the reaction is finished, cooling to room temperature, pouring the mixture into a separating funnel, standing and layering the mixture, and separating out an oil layer, a water layer and the catalyst, wherein the separated oil layer is the reaction oil layer.
The operation method for removing the residual hydrogen peroxide in the reaction oil layer comprises the following steps: the reactor adopts a glass fixed bed reactor with a jacket for heat preservation, the inner diameter is 3cm, the height is 80cm, and 20gNa is filled in the reactor2SO3The solid, the upper part and the lower part are filled with inert fillers, the temperature of the entrainment is controlled by circulating water at 30 ℃, 400g (0.5 percent of hydrogen peroxide) of an epoxidation reaction oil layer is injected into the reactor from the top end of the reactor at a constant speed by a metering pump at the flow rate of 1g/min, and the lower end of the reactor is connected with a receiving bottle to receive feed liquid. The content of hydrogen peroxide in the feed liquid is 0.0110%, and the removal rate of residual hydrogen peroxide in the oil layer is 97.8%.
Example 2
Adopts a stainless steel fixed bed reactor with a jacket for heat preservation, the inner diameter is 3cm, the height is 80cm, and 20gNa is filled in the reactor2SO3The solid, the upper and the lower part, are filled with inert fillers, the temperature of the entrainment is controlled by circulating water at 30 ℃, the metering pump is used for uniformly mixing the solid with the liquid at a flow rate of 1g/min from the top of the reactor400g (0.5% hydrogen peroxide) of the epoxidation reaction oil layer was fed into the reactor, and the lower end of the reactor was connected to a receiving bottle for receiving the feed liquid. The content of hydrogen peroxide in the feed liquid was 0.0130%, and the removal rate of residual hydrogen peroxide in the oil layer was 97.4%.
Example 3
Adopts a stainless steel fixed bed reactor with a jacket for heat preservation, the inner diameter is 3cm, the height is 80cm, and 5gNa is filled in the reactor2SO3The solid, upper and lower parts were filled with inert fillers, the temperature of the entrainment was controlled at 30 ℃ with circulating water, 400g (0.5% hydrogen peroxide) of the epoxidation reaction oil layer prepared in example 1 was injected into the reactor at a constant rate from the top of the reactor by a metering pump at a flow rate of 1g/min, and the lower end of the reactor was connected to a receiving flask to receive the feed liquid. The content of hydrogen peroxide in the feed liquid was 0.0150%, and the removal rate of residual hydrogen peroxide in the oil layer was 97.0%.
Examples 4 to 10
The procedure was the same as in example 1, except that the type and amount of reducing substance used were different, and the following results were obtained:
examples 11 to 16
The procedure was the same as in example 1, except that the quality of the epoxidation reaction oil layer and the content of residual hydrogen peroxide therein were different, and the following results were obtained:
| examples | Oil layer mass/g | Hydrogen peroxide content/% before treatment | Receiving feed liquid hydrogen peroxide content/%) | Removal rate/%) |
| 11 | 600 | 0.1 | 0.0042 | 95.8 |
| 12 | 500 | 0.3 | 0.0108 | 96.4 |
| 13 | 400 | 0.4 | 0.0100 | 97.5 |
| 14 | 300 | 0.6 | 0.0102 | 98.3 |
| 15 | 200 | 0.8 | 0.0120 | 98.5 |
| 16 | 100 | 1.0 | 0.0170 | 98.3 |
Examples 17 to 24
The procedure was as in example 1, except that the temperature and flow rate of the reaction were varied, and the following results were obtained:
| examples | Temperature/. degree.C | Flow rate/g.min-1 | Receiving feed liquid hydrogen peroxide content% | Removal rate/%) |
| 17 | 10 | 3 | 0.0225 | 95.5 |
| 18 | 20 | 4 | 0.0160 | 96.8 |
| 19 | 25 | 5 | 0.0140 | 97.2 |
| 20 | 30 | 7 | 0.0115 | 97.7 |
| 21 | 30 | 6 | 0.0085 | 98.3 |
| 22 | 35 | 8 | 0.0060 | 98.8 |
| 23 | 40 | 5 | 0.0090 | 98.2 |
| 24 | 40 | 10 | 0.0120 | 97.6 |
Comparative example 1
Adding 400g of an oil layer (0.5% of hydrogen peroxide) after epoxidation into a 500ml four-neck flask, adding 40g of deionized water at 30 ℃, stirring for 10min, then pouring into a 500ml separating funnel, standing, seriously emulsifying and not obviously layering, washing for 2 times, delivering the washed oil layer, measuring the content of residual hydrogen peroxide in the oil layer to be 0.1585%, and calculating the washing rate of residual hydrogen peroxide in the oil layer to be 68.3%.
Comparative example 2
The experimental procedure and conditions were the same as in example 1, except that the reducing substance used was changed to Na2S, the removal rate of residual hydrogen peroxide in the oil layer was 97.7%. Gas chromatography-mass spectrometry analysis of the reacted oil layer showed that isobutylmercaptan impurity was generated in an amount of 0.5%.
This comparative example 2 illustrates the use of Na2S is used as a reducing agent to react, new impurities enter an oil layer, and the purity of the final epoxy chloropropane product is influenced. Therefore, not all conventional reducing substances are suitable for achieving the technical effects of the present invention.
The invention is not limited to the embodiments of the invention described.
The structure and the implementation of the present invention are described herein by using specific examples, and the above description of the examples is only used to help understand the core idea of the present invention. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (7)
1. A method for removing residual hydrogen peroxide in an epichlorohydrin oil layer is characterized by comprising the following steps:
adding a reductive solid into a fixed bed reactor, and adding a reaction oil layer into the fixed bed reactor at a constant speed through a metering pump to ensure that the reaction oil layer is fully contacted with the reductive solid; the reaction oil layer is obtained by reacting chloropropene with hydrogen peroxide under a heteropoly acid catalyst; the reaction oil layer contains chloropropene, epoxy chloropropane and hydrogen peroxide;
said reductiveThe solid is Mg, Al, Cu, FeCl2、SnCl2、Na2S2O3、Na2SO3One or more of the above;
the content of the residual hydrogen peroxide in the reaction oil layer is 0.1-1%; the mass of the reducing solid is 3-20% of the mass of the reaction oil layer.
2. The process for removing residual hydrogen peroxide from an epichlorohydrin oil layer according to claim 1, wherein the mass of the reducing solid is 8% to 10% of the mass of the reaction oil layer.
3. The process for removing residual hydrogen peroxide from an epichlorohydrin oil layer according to claim 1, wherein the reaction temperature is 10 ℃ to 40 ℃.
4. The process for removing residual hydrogen peroxide from an epichlorohydrin oil layer according to claim 3, wherein the reaction temperature is 20 ℃ to 30 ℃.
5. The method for removing residual hydrogen peroxide from an epichlorohydrin oil layer according to claim 1, wherein the metering pump flow rate is 1g/min to 10 g/min.
6. The method for removing residual hydrogen peroxide from an epichlorohydrin oil layer according to claim 5, wherein the metering pump flow rate is 1g/min to 4 g/min.
7. The method for removing residual hydrogen peroxide in an epichlorohydrin oil layer as claimed in claim 1, wherein the fixed bed reactor is a glass or stainless steel fixed bed reactor with jacket heat preservation, and inert fillers are filled above and below a bed layer.
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| CN201811340527.3A CN109293600B (en) | 2018-11-12 | 2018-11-12 | Method for removing residual hydrogen peroxide in epoxy chloropropane oil layer |
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| CN111774064B (en) * | 2019-04-04 | 2023-04-11 | 中国石油化工股份有限公司 | Catalyst for decomposing hydrogen peroxide in epoxidation reaction product of 3-chloropropene and hydrogen peroxide |
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| WO2005113452A1 (en) * | 2004-04-22 | 2005-12-01 | Sidel Participations | Method for producing quality water from an effluent containing a mixture of peroxygenated oxidizing reagents and use in an installation for decontaminating objects |
| JP2015130844A (en) * | 2014-01-15 | 2015-07-23 | 株式会社片山化学工業研究所 | Decomposition treatment method for hydrogen peroxide |
| CN105481644A (en) * | 2015-12-02 | 2016-04-13 | 中国天辰工程有限公司 | Method for removing hydrogen peroxide from organic solvent-water solution |
| CN106140186A (en) * | 2015-04-18 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of method of decomposition of hydrogen peroxide in decomposition catalyst and epoxidation reaction product thereof |
| CN106140139A (en) * | 2015-04-18 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of catalyst decomposed for hydrogen peroxide and application process |
| CN106140178A (en) * | 2015-04-18 | 2016-11-23 | 中国石油化工股份有限公司 | The catalyst of decomposition of hydrogen peroxide and for decomposing the method for hydrogen peroxide in epoxidation reaction product |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005113452A1 (en) * | 2004-04-22 | 2005-12-01 | Sidel Participations | Method for producing quality water from an effluent containing a mixture of peroxygenated oxidizing reagents and use in an installation for decontaminating objects |
| JP2015130844A (en) * | 2014-01-15 | 2015-07-23 | 株式会社片山化学工業研究所 | Decomposition treatment method for hydrogen peroxide |
| CN106140186A (en) * | 2015-04-18 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of method of decomposition of hydrogen peroxide in decomposition catalyst and epoxidation reaction product thereof |
| CN106140139A (en) * | 2015-04-18 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of catalyst decomposed for hydrogen peroxide and application process |
| CN106140178A (en) * | 2015-04-18 | 2016-11-23 | 中国石油化工股份有限公司 | The catalyst of decomposition of hydrogen peroxide and for decomposing the method for hydrogen peroxide in epoxidation reaction product |
| CN105481644A (en) * | 2015-12-02 | 2016-04-13 | 中国天辰工程有限公司 | Method for removing hydrogen peroxide from organic solvent-water solution |
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Address after: 222065 No.28, Shihua 7th Road, Lianyungang City, Jiangsu Province Patentee after: JIANGSU RUIHENG NEW MATERIAL TECHNOLOGY Co.,Ltd. Patentee after: Jiangsu Yangnong Chemical Group Co.,Ltd. Patentee after: JIANGSU RUIXIANG CHEMICAL Co.,Ltd. Address before: 222065 room 316, building 2, Jiangsu Avenue SME Park, Xuwei New District, Lianyungang City, Jiangsu Province Patentee before: JIANGSU RUIHENG NEW MATERIAL TECHNOLOGY Co.,Ltd. Patentee before: Jiangsu Yangnong Chemical Group Co.,Ltd. Patentee before: JIANGSU RUIXIANG CHEMICAL Co.,Ltd. |