CN109180610A - A kind of method of high efficiente callback propane catalyst co-production KA oil - Google Patents
A kind of method of high efficiente callback propane catalyst co-production KA oil Download PDFInfo
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- CN109180610A CN109180610A CN201811170586.0A CN201811170586A CN109180610A CN 109180610 A CN109180610 A CN 109180610A CN 201811170586 A CN201811170586 A CN 201811170586A CN 109180610 A CN109180610 A CN 109180610A
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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
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- 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
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The present invention provides a kind of methods of high efficiente callback propane catalyst co-production KA oil, under heteropoly acid (salt) catalysis, it controls hydrogen peroxide conversion and carries out epoxidation reaction, stratification, recycling design, catalyst are applied after separation of oil propylene oxide, using the water layer containing catalyst, hydrogen peroxide as oxidation system, it is KA oil by cyclohexane oxidation, recycles catalyst in water layer, propylene oxide yield >=87%, KA oil yield >=3%, propylene oxide selectivity >=98%, catalyst recovery yield >=99.5%.The present invention devises a kind of method for recycling propane catalyst co-production KA oil, improve catalyst recovery yield, process economy is enhanced, is a kind of simple process, clean and environmental protection, catalyst recovery yield is high, the method that good effect, good economy performance, safety are high, are easily industrialized is recycled.
Description
Technical field
The invention belongs to the technical fields of petrochemical industry, are related to a kind of high efficiente callback propane catalyst co-production KA oil
Method, more particularly, to one kind using heteropoly acid (salt) be catalyst, hydrogen peroxide as in the two phase solvent system of oxidant
Preparing epoxypropane by epoxidation of propene, the method that subsequent oxidizing ethyle alkyl prepares KA oily (cyclohexanol/cyclohexanone), improves catalysis
The KA oil product of agent rate of recovery co-production high added value, enhances the economy and safety of technique.
Background technique
Propylene oxide (PO) is important basic chemical industry raw material, mainly for the production of polyether polyol, propylene glycol and it is non-from
Subtype surfactant etc., wherein polyether polyol is polyurethane foam, thermal insulation material, elastomer, adhesive and coating etc.
Important source material, nonionic surface active agent are used widely in industries such as petroleum, chemical industry, pesticide, weaving, daily use chemicals.
Currently, industrially the method for production propylene oxide mainly has chlorohydrination, conjugated oxidation and hydrogen peroxide direct oxidation
Method.Chlorohydrination is to realize industrialized method earliest, but this method resource consumption is big, equipment seriously corroded, is generated a large amount of useless
Water waste residue, according to " industry restructuring guidance list (sheet in 2011) ", chlorohydrination has been put into limitation intermediate item, in principle not
Allow such device newly-built again.Although conjugated oxidation less pollution, the technique construction cost is big, and long flow path, co-product is more,
Material purity requires height, is influenced greatly by raw material supply, co-product market etc., restraining factors are more.Hydrogen peroxide is a kind of green
Oxidant often has the characteristics that process is simple, mild condition, reduzate are water using it as the reaction of oxidant, such is anti-
Should often environmental pollution it is small, meet the demand for development of Green Chemistry, therefore using hydrogen peroxide as the direct oxidation method of oxidant
By scientific research, the extensive concern of producers, current industrialized hydrogen peroxide direct oxidation law technology is all made of titanium silicon molecule
Sieve is catalyst, but its key technology is monopolized by a small number of offshore companies, and the country there is no autonomy-oriented device to stablize and go into operation.
Heteropoly acid (salt) is a kind of excellent olefin epoxidation catalysts, 2001, document (Xi Z W, Zhou N, Sun
Y,Li K L.Reaction-Controlled Phase-Transfer Catalysis for Propylene
2001,292 (5519): Epoxidation to Propylene Oxide.Science 1139.) is with phospho heteropoly tungstate
Catalyst realizes the epoxidation reaction of olefines of reaction-controlled phase-transfer.Under heteropolyacid salt catalysis, hydrogen peroxide can will be different
Olefin oxidation is corresponding epoxide, and after reaction, heteropolyacid salt catalyst is precipitated, recycled after separation.
(Jin nation is outstanding, Yang Hongyun, Chen Hao, Gao Huanxin, thanks and is catalyzed propylene ring in library reaction control phase transfer catalyst for document
The influence factor of oxidation reaction is catalyzed journal, 2005,26 (11): 1005-1010) point out heteropolyacid salt catalyst in oil/water two
The concentration of distribution ratio and hydrogen peroxide in phase has compared with Important Relations.Patent (CN201410597578.X) reports heteropoly acid (salt)
Catalyst has that active component is easy to run off, recycles difficulty in use, and industrialized economy is insufficient.Its reason is just
It is that hydrogen peroxide cannot convert completely, causes heteropoly acid (salt) to dissolve, discharged with water layer, causes catalyst loss, environment dirty
The problem of dye.Patent (CN1526707A) provides a kind of recovery method of homogeneous catalyst, for being not suitable for reaction controlling phase
After the completion of reaction, organic ketone or alcohol reagent is added into reaction solution makes to urge the phosphorus heteropoly tungstic acid salt catalyst of transfer catalysis
Agent Precipitation from system, but catalyst recovery yield is lower than 50%, and this method introduces novel substance, makes reaction system more
Add complexity, increase product separating difficulty, industrialization is difficult to realize.Patent (CN201310084342.1) is multiple with organic/inorganic
It closes heteropoly acid or its salt is catalyst, alkene, cyclohexyl hydroperoxide carry out liquid phase reactor；Reaction is finished, and olefin oxidation generates phase
The epoxide answered, cyclohexyl hydroperoxide are reduced to cyclohexanol and cyclohexanone, but unrecovered catalyst, and economy is insufficient,
It is difficult to realize industrialize.
KA oil (cyclohexanol/cyclohexanone) oxidation can obtain adipic acid, be the important source material for producing nylon (polyamide) 66.Patent
(US4720592) use catalysis of cobalt salt oxidizing ethyle alkyl for KA oil, reaction condition is 160 DEG C, 1-2.5MPa, has been used a large amount of
Cobalt salt is catalyst, cyclohexane conversion only 4%, KA oil total recovery only 1.75-3.85%, there are complex process, yield is low, urges
Agent is at high cost, the environmentally hazardous disadvantage of oxidant.Patent (CN101817733B) is using heteropolyacid salt as catalyst, hydrogen peroxide
It is KA oil by cyclohexane oxidation for oxidant, has the advantages that simple process, cyclohexane conversion are high, KA oil yield is high.
Currently, not exclusively causing to be catalyzed in the reaction of catalyst, often to there is hydrogen peroxide conversion with heteropoly acid (salt)
Big disadvantage is lost in agent, and economy is insufficient, it is difficult to realize industrialization；Unconverted hydrogen peroxide is removed using the method for thermal decomposition,
Heteropoly acid (salt) rate of recovery can be improved, but there are hydrogen peroxide to lose the shortcomings that big, economy reduces, and easily occurred in the process
The problem of hydrogen oxide sharply decomposes, generates security risk, and technique safety is poor.
Summary of the invention
It is an object of the invention to develop a kind of method of high efficiente callback propane catalyst co-production KA oil, has and urge
The agent rate of recovery is high, applies that effect is good, economy is strong, technique cleaning, it is easy to accomplish industrialized advantage.
The present invention provides a kind of methods of high efficiente callback propane catalyst co-production KA oil, urge in heteropoly acid (salt)
Under change, control hydrogen peroxide conversion carries out epoxidation reaction, stratification, and recycling design after separation of oil propylene oxide is urged
Agent is applied, and using the water layer containing catalyst, hydrogen peroxide as oxidation system, is urged in cyclohexane oxidation is oily for KA, recycling water layer
Agent, propylene oxide yield >=87%, KA oil yield >=3% (to hydrogen peroxide meter), propylene oxide selectivity >=98%, catalysis
The agent rate of recovery >=99.5%.The present invention devises a kind of method for recycling propane catalyst co-production KA oil, improves and urges
The agent rate of recovery, enhances process economy, is a kind of simple process, clean and environmental protection, catalyst recovery yield is high, effect is recycled
The method that fruit is good, good economy performance, safety is high, is easily industrialized.
It is an object of the invention to develop a kind of method of high efficiente callback propane catalyst co-production KA oil, has and urge
The agent rate of recovery is high, applies that effect is good, economy is strong, technique cleaning, it is easy to accomplish industrialized advantage.
A kind of method of high efficiente callback propane catalyst co-production KA oil, including the following steps:
(1) solvent, catalyst and propylene are mixed, hydrogen peroxide is added, control hydrogen peroxide conversion carries out pressure rings
Oxidation reaction, stratification；
(2) after oil reservoir distillation separation propylene oxide, kettle material direct circulation is applied；
(3) hexamethylene is added in water layer, catalyzes and synthesizes KA oil, catalyst circulation will be precipitated and be applied to epoxidation reaction.
In above-mentioned steps (1), the solvent be with the immiscible organic solvent of water, such as benzene, chlorobenzene, methylene chloride, chlorine
One or more mixtures of imitative, propionitrile, butyronitrile etc., dosage are 10-30 times of hydrogenperoxide steam generator weight；
In above-mentioned steps (1), the catalyst heteropoly acid (salt), including but not limited to phosphotungstic acid (salt), phosphomolybdic acid
One or more mixtures of (salt), P-Mo-Wo acid (salt), silico-tungstic acid (salt), molybdovanaphosphoric acid (salt) etc., dosage are propylene weight
The 5-10% of amount；
In above-mentioned steps (1), the concentration of hydrogen peroxide is 30-70%, and dosage is the 0.25-0.5 of supplied propylene
Times；
In above-mentioned steps (1), the epoxidation reaction temperature is 20-80 DEG C, reaction time 1-6h；
In above-mentioned steps (1), the control hydrogen peroxide conversion is 87-92%；
In above-mentioned steps (3), the hexamethylene dosage is 1-5 times of hydrogenperoxide steam generator weight；
In above-mentioned steps (3), the reaction temperature is 30-100 DEG C, reaction time 1-12h.
The present invention has the advantage that (1) heteropoly acid (salt) is catalyst, hydrogen peroxide is oxygen source, direct oxidation method is closed
At propylene oxide, technique cleaning, product yield are high, can directly apply solvent, catalyst after oil reservoir separation PO, recycling is convenient；(2)
Using the water layer containing hydrogen peroxide and catalyst as oxidation system, oxidizing ethyle alkyl realizes the KA oil of coproduction high added value, and
The rate of recovery, the hydrogen peroxide utilization rate of catalyst are improved, Atom economy is high, and process economy is strong；(3) anti-with redox
The hydrogen peroxide in water layer containing catalyst should be consumed, hydrogen peroxide in water layer treatment process is avoided and decomposes caused safety
Problem improves the safety of technique.
Specific embodiment
Embodiment 1
300.00g butyronitrile, 5.00g phosphotungstic acid catalyst are added in 1L autoclave, is filled with 65.00g propylene, is added
70% hydrogenperoxide steam generator of 20.00g, 70 DEG C are stirred to react 4h, cooling, pressure release, layering, hydrogen peroxide conversion 90.12%,
Propylene oxide yield 87.83% (to total hydrogen peroxide meter), propylene oxide selectivity 99.12%, after oil reservoir distillation separates PO, directly
Female connector is used.Water layer is transferred in four-hole bottle, and 50.00g hexamethylene is added, reacts 10h, hydrogen peroxide conversion in 60 DEG C of oil baths
99.87% (to total hydrogen peroxide meter), cyclohexane conversion 7.20%, KA oil yield 3.25% (to total hydrogen peroxide meter).It closes
Meter recycling catalyst 4.99g (oil reservoir catalyst-solvent+precipitation catalyst), catalyst will be precipitated in catalyst recovery yield 99.80%
Merge set with the oil reservoir after separation PO and is used for epoxidation reaction.
Embodiment 2-5
On the basis of embodiment 1, using variety classes, the solvent of dosage, acquired results are as follows:
Embodiment 6-10
On the basis of embodiment 1, using variety classes, the catalyst of dosage, acquired results are as follows:
Embodiment 11-14
On the basis of embodiment 1, using different epoxidation reaction temperatures, reaction time, acquired results are as follows:
Embodiment 15-18
On the basis of embodiment 1, using different synthesis KA oil reaction temperatures, reaction time, acquired results are as follows:
Embodiment 19-21
On the basis of embodiment 1, using the hexamethylene of different amounts, acquired results are as follows:
Embodiment 22-26
On the basis of embodiment 1, precipitation catalyst is incorporated as with the oil reservoir after separation PO during preparing KA oil
Catalyst system and solvent are recycled, experiment is applied in development, and acquired results are as follows:
Content of the present invention is not limited in embodiment content of the present invention.
Specific case used herein is expounded structure of the invention and embodiment, the explanation of above embodiments
It is merely used to help understand the core idea of the present invention.It should be pointed out that for those skilled in the art,
Without departing from the principles of the invention, can be with several improvements and modifications are made to the present invention, these improvement and modification are also fallen
Enter in the protection scope of the claims in the present invention.
Claims (8)
1. a kind of method of high efficiente callback propane catalyst co-production KA oil, characterized in that it comprises the following steps:
(1) solvent, catalyst and propylene are mixed, hydrogen peroxide is added, control hydrogen peroxide conversion carries out pressurization epoxidation
Reaction, stratification；
(2) after oil reservoir distillation separation propylene oxide, kettle material direct circulation is applied；
(3) hexamethylene is added in water layer, catalyzes and synthesizes KA oil, catalyst circulation will be precipitated and be applied to epoxidation reaction.
2. the method for high efficiente callback propane catalyst co-production KA oil according to claim 1, which is characterized in that on
State in step (1), the solvent be with the immiscible organic solvent of water, such as benzene, chlorobenzene, methylene chloride, chloroform, propionitrile, fourth
One or more mixtures of nitrile, dosage are 10-30 times of hydrogenperoxide steam generator weight.
3. the method for high efficiente callback propane catalyst co-production KA oil according to claim 1, which is characterized in that on
It states in step (1), the catalyst heteropoly acid (salt), including but not limited to phosphotungstic acid (salt), phosphomolybdic acid (salt), phosphorus molybdenum tungsten
One or more mixtures of sour (salt), silico-tungstic acid (salt), molybdovanaphosphoric acid (salt), dosage are the 5-10% of propylene weight.
4. the method for high efficiente callback propane catalyst co-production KA oil according to claim 1, which is characterized in that on
It states in step (1), the concentration of hydrogen peroxide is 30-70%, and dosage is 0.25-0.5 times of supplied propylene.
5. the method for high efficiente callback propane catalyst co-production KA oil according to claim 1, which is characterized in that on
It states in step (1), the epoxidation reaction temperature is 20-80 DEG C, reaction time 1-6h.
6. the method for high efficiente callback propane catalyst co-production KA oil according to claim 1, which is characterized in that on
It states in step (1), the control hydrogen peroxide conversion is 87-92%.
7. the method for high efficiente callback propane catalyst co-production KA oil according to claim 1, which is characterized in that on
It states in step (3), the hexamethylene dosage is 1-5 times of hydrogenperoxide steam generator weight.
8. the method for high efficiente callback propane catalyst co-production KA oil according to claim 1, which is characterized in that on
It states in step (3), the reaction temperature is 30-100 DEG C, reaction time 1-12h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811170586.0A CN109180610B (en) | 2018-10-09 | 2018-10-09 | Method for efficiently recovering propylene oxide catalyst and co-producing KA oil |
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| CN201811170586.0A CN109180610B (en) | 2018-10-09 | 2018-10-09 | Method for efficiently recovering propylene oxide catalyst and co-producing KA oil |
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| CN109180610A true CN109180610A (en) | 2019-01-11 |
| CN109180610B CN109180610B (en) | 2020-11-27 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045716A (en) * | 2006-03-27 | 2007-10-03 | 中国石油化工股份有限公司 | Production method of epoxy propane |
| CN103193589A (en) * | 2013-03-15 | 2013-07-10 | 湘潭大学 | Method for preparing epoxy compound, cyclohexanol and cyclohexanone by co-oxidation synthesis |
-
2018
- 2018-10-09 CN CN201811170586.0A patent/CN109180610B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045716A (en) * | 2006-03-27 | 2007-10-03 | 中国石油化工股份有限公司 | Production method of epoxy propane |
| CN103193589A (en) * | 2013-03-15 | 2013-07-10 | 湘潭大学 | Method for preparing epoxy compound, cyclohexanol and cyclohexanone by co-oxidation synthesis |
Non-Patent Citations (1)
| Title |
|---|
| 金国杰等: "反应控制相转移催化剂催化丙烯环氧化反应的影响因素", 《催化学报》 * |
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