CN109160907A - A method of it improves propane catalyst activity co-production ketal (aldehyde) - Google Patents
A method of it improves propane catalyst activity co-production ketal (aldehyde) Download PDFInfo
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- CN109160907A CN109160907A CN201811170575.2A CN201811170575A CN109160907A CN 109160907 A CN109160907 A CN 109160907A CN 201811170575 A CN201811170575 A CN 201811170575A CN 109160907 A CN109160907 A CN 109160907A
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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
- 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
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/12—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/72—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 spiro-condensed with carbocyclic rings
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- 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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Abstract
The present invention is using the PG of by-product in propylene ring oxidation reaction as raw material, in the presence of catalyst heteropoly acid, a kind of method for realizing synthesizing epoxypropane co-production ketal (aldehyde), not only eliminate alcohols material in epoxidation reaction to the negative effect of catalyst activity, improve catalyst activity, the stabilization for realizing catalyst is applied, it expanded the downstream application of by-product PG simultaneously, provided a kind of preparation method of ketal (aldehyde), having had the advantages that reaction condition is mild, catalytic stability is good, catalyst applies that effect is good, by-product resource utilization.
Description
Technical field
The invention belongs to organic chemical industry fields, are related to a kind of raising propylene oxide (PO) catalyst activity co-production ketal
The method of (aldehyde).More particularly, to one kind using heteropoly acid as catalyst, hydrogen peroxide is the generation of oxidizer catalytic epoxidation of propylene
PO, using the method for by-product propylene glycol synthesis ketal (aldehyde) hydrolyzed of PO in epoxidation reaction, PO yield >=90% is (to hydrogen peroxide
Meter), propylene glycol conversion ratio >=98%, ketal (aldehyde) yield >=90% (to propylene glycol meter) joins by raw material of the propylene glycol of by-product
The ketal (aldehyde) of high added value is produced, effectively realizes the resource utilization of by-product, and solves alcohols material in propylene ring oxidation reaction
Negative influence to catalyst activity, the stabilization for realizing catalyst are applied, the present invention have simple process, it is easily operated, at
This low, catalyst applies the good advantage of effect, it is easy to accomplish industrialization.
Background technique
PO is that the second largest Organic chemical products of polypropylene are only second in acryloyl derivative, is synthesizing polyether glycol, poly- ammonia
The critical materials of ester, surfactant, the market demand are huge.Currently, industrially the method for production PO mainly has chlorohydrination, altogether oxygen
Change method and direct oxidation method.Chlorohydrination severe corrosion to equipment, has in production process a large amount of waste water to generate, and environmental pollution is tight
Weight;Conjugated oxidation complex process, equipment investment is big, and co-product is more.In recent years, by " Green Chemistry ", " atom economy
The influence of property " idea, direct oxidation method is gradually by the favor of researchers.So far, industrialized direct oxidation method is logical
It is catalyst frequently with TS-1, but the core technology of the catalyst rests in a small number of offshore company's hands, technical barrier is higher.
2001, the Dalian Chemistry and Physics Institute (Xi Z W, Zhou N, Sun Y, Li K L.Reaction-Controlled Phase-
Transfer Catalysis for Propylene Epoxidation to Propylene Oxide.Science,2001,
292 (5519): 1139.) proposing a kind of method using heteropoly acid as catalyst preparing epoxypropane by epoxidation of propene,
Achieve preferable catalytic effect.But the method inevitably generates by-product 1,2-PD (PG) in process of production, makes
Catalyst activity reduction influences catalyst stabilization and applies, and needs periodically to discharge it system, increases continuous production difficulty.
Therefore, it using PG as the downstream product of Material synthesis high added value, while solving the problems, such as the active reduction of epoxidation catalyst, has
Important scientific meaning and application value.
Ketal (aldehyde) is generally used to protect carbonyl or as synthetic intermediate as a kind of important compound, while
It is widely used in the blending and fixation of drinks, soft drink, ice cream, cosmetics etc., has in food and daily chemical industry certain
Demand.It can be condensed in acid condition by carbonyls and dihydric alcohol and is made, this is provided for the resource utilization of PG
Thinking.Traditional production method is to synthesize under inorganic acid catalysis, but the method there are side reactions more, poor product quality, equipment are rotten
The disadvantages of erosion is serious, pollution is high.Patent (CN200910235554.9) discloses a kind of system of -1,2 propanediol Ketal of cyclohexanone
Preparation Method uses the mesoporous material of the copper of sulfonic acid containing ethylphenyl to synthesize ketal for catalyst cyclohexanone and PG.Patent
(CN201610248042.6) ketal (aldehyde) is then synthesized as catalyst catalyzing alcohols substance with carbonyls to carry hydrogen compound.
In addition, research discovery solid super-strong acid, metal salt, solion and organic acid (such as p-methyl benzenesulfonic acid) are all anti-to ketal (aldehyde)
There should be good catalytic action.However these synthetic methods are there is expensive catalyst, the drawback that toxic and preparation is complicated,
It is unfavorable for industrial applications.It is increasingly strong with people's environmental consciousness, novel environmental close friend green catalyst-heteropoly acid and its
The research of salt is of increasing concern and has made some progress.Patent (CN 201611154729.X) is by Dawson structure
The phosphotungstate that the multicore iron of pregnancy urotropine coordination replaces is supported on ZSM-5 molecular sieve, obtains a kind of novel load
Type heteropolyacid salt catalyst, and be used for preparing acetal (ketone) fragrance, catalytic effect is good.Patent
(CN201510507416.7) equally using carried heteropoly acid as catalyst, a kind of synthesis technology of flavouring essence for tobacco is devised.But
Above-mentioned catalyst is carried heteropoly acid catalyst, and preparation process is complex.
Summary of the invention
The present invention in the presence of catalyst heteropoly acid, realizes one using the PG of by-product in propylene ring oxidation reaction as raw material
The method of kind of synthesizing epoxypropane co-production ketal (aldehyde) not only eliminates in epoxidation reaction alcohols material to catalyst activity
Negative effect, improve catalyst activity, the stabilization for realizing catalyst is applied, while the downstream for having expanded by-product PG is answered
With, provide a kind of preparation method of ketal (aldehyde), have reaction condition is mild, catalytic stability is good, catalyst applies effect
Well, the advantages of by-product resource utilization.
It is an object of the invention to develop a kind of method for improving propane catalyst activity co-production ketal (aldehyde), tool
There is the advantages of product yield height, by-product resource utilization, applying property of catalyst are good, economy is strong, are easily industrialized.
It is a kind of improve propane catalyst activity co-production ketal (aldehyde) method and its application specifically include following step
It is rapid:
(1) epoxidation reaction: solvent, catalyst, propylene and hydrogen peroxide are successively added in reaction kettle, and it is anti-to carry out epoxidation
It answers, reacts and finish distillation separation PO;
(2) ketal (aldehyde) synthetic reaction: above-mentioned distillation still material is mixed with ketone (aldehyde), and it is small to stir lower heating progress stoichiometric number
When, reaction is finished, and separating catalyst is applied to epoxidation reaction;Clear liquid distillation, obtains ketal (aldehyde) product.
In above-mentioned steps (1), the catalyst is heteropolyacid catalyst, including but not limited to phosphotungstic acid, phosphomolybdic acid, phosphorus
One of silicic acid, phosphorus vanadic acid, molybdovanaphosphoric acid, silico-tungstic acid or a variety of mixtures, dosage are the 5-50% of propylene weight;
In above-mentioned steps (1), the solvent is n-hexane, propionitrile, butyronitrile, benzene, toluene, chlorobenzene, dichloroethanes, chloroform etc.
One or more mixtures;Dosage is 2-10 times of propylene weight.
In above-mentioned steps (1), the epoxidation reaction temperature is 40-90 DEG C, reaction time 1-6h;The dioxygen
Water concentration is 25-70%, and dosage is 0.1-0.5 times of supplied propylene.
In above-mentioned steps (2), the ketone (aldehyde) is the one of cyclohexanone, cyclopentanone, butanone, benzaldehyde, butyraldehyde, citral etc.
Kind or a variety of mixtures, dosage are 1-4 times of propylene glycol molal quantity;
In above-mentioned steps (2), the reaction temperature is 50-100 DEG C, reaction time 1-6h;
In above-mentioned steps (2), the separating catalyst mode is one of centrifugation, filtering, sedimentation or a variety of groups
It closes.
The present invention is applied to propylene catalysis epoxidation synthesizing epoxypropane co-production ketal (aldehyde) using heteropoly acid as catalyst
Reaction in, have the following advantages that;
(1) by-product resource utilization: additional for raw material coproduction height with the propylene glycol (PG) of by-product in propylene ring oxidation reaction
The ketal (aldehyde) of value, by-product is utilized effectively, and atom utilization is high, good economy performance;
(2) realize that catalyst stabilization is applied: by-product propylene glycol reacted with aldehyde ketone solve catalyst because alcohols material is total
It deposits and causes activity reduction, is difficult to realize the problem of applying, effectively keep catalyst stability and apply activity, it is easy to accomplish industry
Change;
(3) process route is environmentally protective: effectively consuming by-product PG, realizes catalyst stabilization and apply, reduces containing urging
The waste liquid of agent, alcohols material realizes by-product resource utilization, reduces " three wastes " discharge, meets the idea of development of Green Chemistry.
Specific embodiment
Embodiment 1
Epoxidation reaction: by 500g propionitrile, 12.5g phosphotungstic acid catalyst investment 1L autoclave, it is filled with 61.8g propylene
(1.47mol) is added 50% hydrogen peroxide of 25g (0.37mol), and 70 DEG C are vigorously stirred reaction 4h, cooling, pressure release, sampling analysis.
Hydrogen peroxide conversion ratio 99.65%, PO yield 91.83%, PG yield 4.33%.Ketal (aldehyde) synthetic reaction: above-mentioned kettle material is steamed
PO out is transferred to more than kettle equipped in stirring, thermometer, water segregator, reflux condensing tube four-hole bottle, addition 3.15g cyclohexanone (hexamethylene
Ketone and PG molar ratio are that 2), control reaction temperature reflux water-dividing is separated to anhydrous, and reaction 2h finishes, and cooling, sampling analysis filters back
Catalyst is received, filtrate distillation separation solvent propionitrile, raw material cyclohexanone and product cyclohexanone 1,2-PD ketal recycle catalyst
Epoxidation reaction is applied to recycling design propionitrile.PG conversion ratio 98.48%, cyclohexanone 1,2-PD ketal yield
90.11% (PG is counted).
Embodiment 2-5
Epoxidation reaction: reaction condition changes reaction temperature, time with embodiment 1.Acquired results are as follows:
Embodiment 6-10
Epoxidation reaction: reaction condition changes the type and dosage of heteropolyacid catalyst, acquired results are such as with embodiment 1
Under:
Embodiment 11-14
Epoxidation reaction: reaction condition is reacted, acquired results are as follows with embodiment 1 using various concentration hydrogen peroxide:
Embodiment 15-19
Epoxidation reaction: reaction condition is reacted with embodiment 1 using different solvents, and acquired results are as follows:
Embodiment 20-24
Ketal (aldehyde) synthetic reaction: reaction process is (corresponding to implement using variety classes and dosage catalyst with embodiment 1
PO synthesizes used catalyst in example 6-10), acquired results are as follows:
Embodiment 25-28
Ketal (aldehyde) synthetic reaction: reaction process is carried out with embodiment 1 using the ketone (aldehyde) of variety classes, different amounts
Reaction, acquired results are as follows:
Embodiment 29-33
Catalyst is applied: on the basis of embodiment 1, catalyst is applied, acquired results are as follows:
Embodiment 34-36
Catalyst is applied: on the basis of embodiment 1, being cancelled ketal (aldehyde) synthetic reaction, is applied catalyst, acquired results
It is 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 for improving propane catalyst activity co-production ketal (aldehyde), which is characterized in that comprise the steps of:
(1) epoxidation reaction: solvent, catalyst, propylene and hydrogen peroxide are successively added in reaction kettle, carry out epoxidation reaction,
Distillation separation PO is finished in reaction;
(2) ketal (aldehyde) synthetic reaction: above-mentioned distillation still material PO is mixed with ketone (aldehyde), and it is small to stir lower heating progress stoichiometric number
When, reaction is finished, and separating catalyst is applied to epoxidation reaction;Clear liquid distillation, obtains ketal (aldehyde) product.
2. the method according to claim 1 for improving propane catalyst activity co-production ketal (aldehyde), feature exist
In in above-mentioned steps (1), the catalyst is heteropolyacid catalyst, including phosphotungstic acid, phosphomolybdic acid, phosphorus silicic acid, phosphorus vanadic acid, phosphorus
One of molybdenum vanadic acid, silico-tungstic acid or a variety of mixtures, dosage are the 5-50% of propylene weight.
3. the method according to claim 1 for improving propane catalyst activity co-production ketal (aldehyde), feature exist
In in above-mentioned steps (1), the solvent is the one of n-hexane, propionitrile, butyronitrile, benzene, toluene, chlorobenzene, dichloroethanes, chloroform etc.
Kind or a variety of mixtures, dosage are 2-10 times of propylene weight.
4. the method according to claim 1 for improving propane catalyst activity co-production ketal (aldehyde), feature exist
In in above-mentioned steps (1), the hydrogen peroxide concentration is 25-70%, and dosage is 0.1-0.5 times of supplied propylene.
5. the method according to claim 1 for improving propane catalyst activity co-production ketal (aldehyde), feature exist
In in above-mentioned steps (1), the epoxidation reaction temperature is 40-90 DEG C, reaction time 1-6h.
6. the method according to claim 1 for improving propane catalyst activity co-production ketal (aldehyde), feature exist
In, in above-mentioned steps (2), the ketone (aldehyde) be cyclohexanone, cyclopentanone, butanone, benzaldehyde, butyraldehyde, citral etc. one kind or
A variety of mixtures, dosage are 1-4 times of propylene glycol molal quantity.
7. the method according to claim 1 for improving propane catalyst activity co-production ketal (aldehyde), feature exist
In in above-mentioned steps (2), the reaction temperature is 50-100 DEG C, reaction time 1-6h.
8. the method according to claim 1 for improving propane catalyst activity co-production ketal (aldehyde), feature exist
In in above-mentioned steps (2), the separating catalyst mode is one of centrifugation, filtering, sedimentation or a variety of combinations.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1526707A (en) * | 2003-03-03 | 2004-09-08 | 中国科学院大连化学物理研究所 | Homogeneous catalyst recovering process |
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 |
CN101786008A (en) * | 2010-02-10 | 2010-07-28 | 东南大学 | Load-type heteropolyacid catalyst for aldolization and preparation method thereof |
CN106669838A (en) * | 2016-12-14 | 2017-05-17 | 盐城市春竹香料有限公司 | Supported heteropolyacid salt catalyst and application thereof to preparation of acetals(ketals) perfumes |
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2018
- 2018-10-09 CN CN201811170575.2A patent/CN109160907B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1526707A (en) * | 2003-03-03 | 2004-09-08 | 中国科学院大连化学物理研究所 | Homogeneous catalyst recovering process |
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 |
CN101786008A (en) * | 2010-02-10 | 2010-07-28 | 东南大学 | Load-type heteropolyacid catalyst for aldolization and preparation method thereof |
CN106669838A (en) * | 2016-12-14 | 2017-05-17 | 盐城市春竹香料有限公司 | Supported heteropolyacid salt catalyst and application thereof to preparation of acetals(ketals) perfumes |
Non-Patent Citations (2)
Title |
---|
CAI WENJIA,ET AL.: "Catalytic epoxidation of cyclohexene over mesoporous‐silica immobilized Keggin‐type tungstophosphoric acid", 《CHINESE JOURNAL OF CATALYSIS》 * |
XI ZUWEI,ET AL.: "Reaction-Controlled Phase-Transfer Catalysis for Propylene Epoxidation to Propylene Oxide", 《SCIENCE》 * |
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