CN102766115A - Method for producing epoxycyclohexane with fixed bed reactor - Google Patents
Method for producing epoxycyclohexane with fixed bed reactor Download PDFInfo
- Publication number
- CN102766115A CN102766115A CN2012102269719A CN201210226971A CN102766115A CN 102766115 A CN102766115 A CN 102766115A CN 2012102269719 A CN2012102269719 A CN 2012102269719A CN 201210226971 A CN201210226971 A CN 201210226971A CN 102766115 A CN102766115 A CN 102766115A
- Authority
- CN
- China
- Prior art keywords
- bed reactor
- fixed
- reaction
- catalyzer
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Epoxy Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for producing epoxycyclohexane with a fixed bed reactor. The method comprises the following steps that a catalyst is filled in the fixed bed reactor, and cyclohexene and a peroxide dissolved with a catalyst are pumped into an emulsifier or mixer; the emulsified or mixed materials are pumped into the fixed bed reactor for reaction, and the reaction product is separated by an oil and water separator; the separated oil phase is distilled to obtain the epoxycyclohexane, and the new materials cyclohexene and a peroxide dissolved with a catalyst are respectively pumped into the emulsifier or mixer when the oil and water separator is used for separation; the emulsified or mixed materials are re-pumped into the fixed bed reactor for reaction, and the oil and water are re-separated; and the loop is repeated until the selectivity of the epoxycyclohexane is less than 80% to 90%, and then the reaction is stopped. In the entire reaction process, the repeated feeding and discharging operations of the catalyst are avoided, and meanwhile, the mechanical wear does not exist, the efficiency of the catalyst is improved to a great extent, and the cost of production is reduced.
Description
Technical field
The invention belongs to the technical field of preparing epoxy cyclohexane by catalytic cyclooxidation of cyclohexene, be specifically related to a kind of method of producing epoxy cyclohexane with fixed-bed reactor.
Background technology
Epoxy cyclohexane is a kind of important organic intermediate; Epoxy group(ing) on the molecular structure is very active; Be prone to generate a series of verivates, can be widely used in fields such as agricultural chemicals, medicine, paint, the high-grade thinner of epoxy resin and new chemical materials with reactions such as alcohol, phenol, carboxylic acid, mineral acids.
Blue [the CN01123652.3 of the Li Kun of Dalian Inst of Chemicophysics, Chinese Academy of Sciences; A kind of method of preparing epoxy cyclohexane by catalytic cyclooxidation of cyclohexene] etc. the people, adopt the phase-transfer catalyst epoxidation to produce epoxy cyclohexane, this type catalyst themselves is insoluble in the reaction medium; But under the hydrogen peroxide effect; Can form the active specy that dissolves in the reaction medium, be consumed and work as hydrogen peroxide, catalyzer promptly returns to initial structure and from reaction system, separates out; Through simple separation, catalyzer just can recycling use.
People such as Zhu Huayuan [CN200910308578.2; A kind of method of preparing epoxy cyclohexane by catalytic cyclooxidation of cyclohexene], make catalyzer with the synthetic HTS, use alkaline assistant; Make hydrogen peroxide and tetrahydrobenzene reaction generate epoxy cyclohexane, the recyclable repeated use of catalyzer at organic solvent.
Jiang Wei is raw material with waiting people [CN200710035351.6] with tetrahydrobenzene and superoxide, uses HTS to be the catalyst epoxidation reaction, and highly selective generates epoxy cyclohexane, and catalyzer and solvent that reaction is used can be recycled.
The Zhang Yadong of Zhengzhou University [no-solvent process of CN 200710053946.4 epoxidizing cyclohexene with hydrogen peroxide to prepare cyclohexane epoxide] produces epoxy cyclohexane.
The common feature of these methods all adopts one kettle way, after each reaction finishes, must catalyst separating be come out, feed intake again, and recycling, manpower, power consumption are big, and the production cycle is long; In the throwing repeatedly of catalyzer, discharging process; Because the oxygenizement of air, remaining material in the catalyzer duct is easy to violent oxidizing reaction takes place and catalyzer is lost activity; Thereby reduced the effective rate of utilization of catalyzer, be unfavorable for industrialization promotion.In addition, this method adopts mechanical stirring, and is comparatively serious to the wearing and tearing of catalyst matrix, further reduced the effective rate of utilization of catalyzer again, causes production cost to increase.
For embodying the Atom economy of energy-saving and cost-reducing and green chemical industry, how to improve the effective rate of utilization of the yield and the catalyzer of epoxy cyclohexane, press for thereby reduce production costs to become.
Summary of the invention
For overcome exist in the prior art because of catalyzer is thrown repeatedly, discharging; Mechanical wear and reduce the deficiency of the efficient of catalyzer the object of the present invention is to provide a kind of method of producing epoxy cyclohexane with fixed-bed reactor, and this method is in entire reaction course; Avoided that catalyzer is thrown repeatedly, the discharging operation; Simultaneously there is not mechanical wear yet, improved the efficient of catalyzer to a great extent, reduced production cost.
For realizing above-mentioned purpose, the technical scheme that the present invention takes is following:
A kind of method of producing epoxy cyclohexane with fixed-bed reactor: with catalyst loading in fixed-bed reactor; Respectively tetrahydrobenzene and the superoxide that is dissolved with promotor are squeezed into emulsor or mixing tank; Emulsification or mixed material are squeezed into fixed-bed reactor and are reacted, and reaction product is separated through water-and-oil separator, and the oil phase of after separating obtains epoxy cyclohexane through rectifying; Respectively new material tetrahydrobenzene and the superoxide that is dissolved with promotor are squeezed into emulsor or mixing tank simultaneously in that water-and-oil separator is isolating; Emulsification or mixed material are squeezed into the fixed-bed reactor reaction again, oily water separation again, so recirculation; Selectivity until epoxy cyclohexane is lower than 80 ~ 90%, stopped reaction.
Said fixed-bed reactor are the fixed-bed reactor of a plurality of series connection and/or parallel connection.
Said superoxide is the ydrogen peroxide 50 of mass percentage concentration 27.5 ~ 50%.
Tetrahydrobenzene and ydrogen peroxide 50 throughput ratio are 10 ~ 1:1, and the mass ratio of ydrogen peroxide 50 and catalyzer is 20 ~ 1:1, and the mass ratio of catalyzer and promotor is 100 ~ 1:1.
Temperature is 30 ~ 80 ℃ in the fixed-bed reactor, and the oily water separation actuator temperature remains on 0 ~ 30 ℃.
Catalyzer among the present invention and promotor are that those skilled in the art's routine is selected.Such as catalyzer is resin, molecular sieve, gac or zeyssatite; Promotor is HCO
3, halogen, SO
4, HSO
4Acid ion and Na, K, Ca, NH
4The salt that ion forms or any mixture of above salt.
Beneficial effect of the present invention: the catalyzer one-time pad in the fixed-bed reactor of the present invention; Regularly switch; Avoided that catalyzer in the entire reaction course is thrown repeatedly, the problem of discharging, realized the serialization of operation, reduced manual work and the energy consumption of launching the material catalyzer repeatedly; The mechanical wear of catalyzer has been avoided in this invention of what is more important, has improved the effective rate of utilization of catalyzer to a great extent, has reduced production cost, meets the energy-saving and cost-reducing industry policy of country, is suitable for industrialization promotion and uses.
Embodiment
Embodiment 1
Material: catalyzer--chloromethylated polystyrene props up and carries N, N-dimethyl-amino dodecane phosphorus heteropoly tungstic acid 22g, promotor--NaCl 1.2g, 50% (quality) ydrogen peroxide 50 135g, tetrahydrobenzene 300ml.
With the catalyzer fixed-bed reactor of packing into; Ydrogen peroxide 50 and the tetrahydrobenzene that will be dissolved with promotor with pump are respectively squeezed into emulsor and are carried out emulsification, and the material after the emulsification is squeezed into fixed-bed reactor and reacted, and reaction product is separated through water-and-oil separator; The oil phase of after separating obtains epoxy cyclohexane through rectifying; Water is discharged as waste liquid, in oily water separation respectively with pump with new material (be tetrahydrobenzene 300ml, be dissolved with the 135g ydrogen peroxide 50 of 1.2g promotor NaCl) through squeezing into the fixed-bed reactor reaction after the emulsor emulsification again; Again oily water separation, so recirculation.Wherein, tetrahydrobenzene flow 30mL/min, the ydrogen peroxide 50 flow is: 10mL/min, 45 ℃ of fixed bed reaction actuator temperatures, 20 ℃ of oily water separation actuator temperatures.In the reaction process profit in the water-and-oil separator is analyzed respectively mutually, oil phase adopts gc to detect, and water adopts GB GB/T6684-2002 to measure hydrogen peroxide content.When the epoxy cyclohexane selectivity is lower than 90%, stops this and take turns reaction.The epicycle reaction feeds intake 14 times altogether, reaction 20h, and the transformation efficiency of tetrahydrobenzene, the selectivity of epoxy cyclohexane is respectively:
| Test number (TN) | Transformation efficiency (%) | Selectivity (%) |
| 1 | 53.37 | 95.63 |
| 2 | 51.21 | 95.17 |
| 3 | 49.77 | 94.85 |
| 4 | 48.35 | 94.02 |
| 5 | 47.52 | 93.50 |
| 6 | 46.41 | 93.03 |
| 7 | 45.29 | 92.59 |
| 8 | 44.30 | 91.80 |
| 9 | 42.89 | 91.53 |
| 10 | 41.72 | 91.00 |
| 11 | 40.09 | 90.64 |
| 12 | 38.57 | 90.27 |
| 13 | 37.31 | 90.32 |
| 14 | 35.84 | 89.61 |
Embodiment 2:
Material: catalyzer--HTS (TS-1) 82.5g, promotor--KCl 2.5g, 50% (quality) ydrogen peroxide 50 420g, tetrahydrobenzene 1000ml.
With the catalyzer fixed-bed reactor of packing into; Ydrogen peroxide 50 and the tetrahydrobenzene that will be dissolved with promotor with pump are respectively squeezed into mixing tank and are mixed, and mixed material is squeezed into fixed-bed reactor and reacted, and reaction product is separated through water-and-oil separator; The oil phase of after separating obtains epoxy cyclohexane through rectifying; Water is discharged as waste liquid, in oily water separation respectively with pump with new material (be tetrahydrobenzene 1000ml, be dissolved with the 420g ydrogen peroxide 50 of 2.5g promotor KCl) through squeezing into the fixed-bed reactor reaction after the emulsor emulsification again; Again oily water separation, so recirculation.Wherein, tetrahydrobenzene flow 100mL/min, the ydrogen peroxide 50 flow is: 40mL/min, 50 ℃ of fixed bed reaction actuator temperatures, 10 ℃ of oily water separation actuator temperatures.In the reaction process profit in the water-and-oil separator is analyzed respectively mutually, oil phase adopts gc to detect, and water adopts GB GB/T6684-2002 to measure hydrogen peroxide content.When the epoxy cyclohexane selectivity is lower than 80%, stops this and take turns reaction.The epicycle reaction feeds intake 14 times altogether, reaction 20h, and the transformation efficiency of tetrahydrobenzene, the selectivity of epoxy cyclohexane is respectively:
| Test number (TN) | Transformation efficiency (%) | Selectivity (%) |
| 1 | 52.99 | 93.00 |
| 2 | 51.02 | 92.80 |
| 3 | 49.85 | 91.67 |
| 4 | 47.94 | 90.59 |
| 5 | 46.06 | 90.75 |
| 6 | 44.61 | 89.03 |
| 7 | 43.13 | 87.84 |
| 8 | 40.87 | 87.06 |
| 9 | 39.24 | 86.05 |
| 10 | 37.95 | 85.50 |
| 11 | 36.03 | 85.36 |
| 12 | 34.82 | 84.98 |
| 13 | 32.79 | 84.02 |
| 14 | 31.08 | 83.79 |
Claims (5)
1. method of producing epoxy cyclohexane with fixed-bed reactor; It is characterized in that: catalyst loading in fixed-bed reactor, is squeezed into emulsor or mixing tank with tetrahydrobenzene and the superoxide that is dissolved with promotor respectively, and emulsification or mixed material are squeezed into fixed-bed reactor and are reacted; Reaction product is separated through water-and-oil separator; The oil phase of after separating obtains epoxy cyclohexane through rectifying, respectively new material tetrahydrobenzene and the superoxide that is dissolved with promotor is squeezed into emulsor or mixing tank simultaneously in that water-and-oil separator is isolating, and emulsification or mixed material are squeezed into the fixed-bed reactor reaction again; Again oily water separation; Like this recirculation is lower than 80 ~ 90%, stopped reaction until the selectivity of epoxy cyclohexane.
2. the method for claim 1 is characterized in that: said fixed-bed reactor are the fixed-bed reactor of a plurality of series connection and/or parallel connection.
3. the method for claim 1, it is characterized in that: said superoxide is the ydrogen peroxide 50 of mass percentage concentration 27.5 ~ 50%.
4. method as claimed in claim 3 is characterized in that: tetrahydrobenzene and ydrogen peroxide 50 throughput ratio are 10 ~ 1:1, and the mass ratio of ydrogen peroxide 50 and catalyzer is 20 ~ 1:1, and the mass ratio of catalyzer and promotor is 100 ~ 1:1.
5. method as claimed in claim 4 is characterized in that: temperature is 30 ~ 80 ℃ in the fixed-bed reactor, and the oily water separation actuator temperature remains on 0 ~ 30 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210226971.9A CN102766115B (en) | 2012-07-03 | 2012-07-03 | Method for producing epoxycyclohexane with fixed bed reactor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210226971.9A CN102766115B (en) | 2012-07-03 | 2012-07-03 | Method for producing epoxycyclohexane with fixed bed reactor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102766115A true CN102766115A (en) | 2012-11-07 |
| CN102766115B CN102766115B (en) | 2014-08-13 |
Family
ID=47093724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210226971.9A Expired - Fee Related CN102766115B (en) | 2012-07-03 | 2012-07-03 | Method for producing epoxycyclohexane with fixed bed reactor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102766115B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110590507A (en) * | 2018-06-12 | 2019-12-20 | 北京旭阳科技有限公司 | Method for preparing 1, 2-hexanediol by oxidizing 1-hexene |
| CN115197171A (en) * | 2021-04-13 | 2022-10-18 | 中国石油化工股份有限公司 | Method and system for producing propylene oxide |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4367342A (en) * | 1969-04-02 | 1983-01-04 | Shell Oil Company | Olefin epoxidation |
| CN1401640A (en) * | 2001-08-27 | 2003-03-12 | 中国科学院大连化学物理研究所 | Process for preparing epoxy cyclohexane by catalytic cyclooxidation of cyclohexene |
| CN101020669A (en) * | 2007-02-02 | 2007-08-22 | 郑州大学 | No-solvent process of epoxidizing cyclohexene with hydrogen peroxide to prepare cyclohexane epoxide |
| CN101691363A (en) * | 2009-10-21 | 2010-04-07 | 中国石油化工股份有限公司 | Method for preparing epoxy cyclohexane through catalytic epoxidation of cyclohexene |
| CN102295625A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Method for producing 1,2-epoxy cyclohexane and alpha, alpha-dimethyl benzyl alcohol |
| CN102295626A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Method for preparing 1,2-cyclohexene oxide and alpha, alpha-dimethyl benzyl simultaneously |
-
2012
- 2012-07-03 CN CN201210226971.9A patent/CN102766115B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4367342A (en) * | 1969-04-02 | 1983-01-04 | Shell Oil Company | Olefin epoxidation |
| CN1401640A (en) * | 2001-08-27 | 2003-03-12 | 中国科学院大连化学物理研究所 | Process for preparing epoxy cyclohexane by catalytic cyclooxidation of cyclohexene |
| CN101020669A (en) * | 2007-02-02 | 2007-08-22 | 郑州大学 | No-solvent process of epoxidizing cyclohexene with hydrogen peroxide to prepare cyclohexane epoxide |
| CN101691363A (en) * | 2009-10-21 | 2010-04-07 | 中国石油化工股份有限公司 | Method for preparing epoxy cyclohexane through catalytic epoxidation of cyclohexene |
| CN102295625A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Method for producing 1,2-epoxy cyclohexane and alpha, alpha-dimethyl benzyl alcohol |
| CN102295626A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Method for preparing 1,2-cyclohexene oxide and alpha, alpha-dimethyl benzyl simultaneously |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110590507A (en) * | 2018-06-12 | 2019-12-20 | 北京旭阳科技有限公司 | Method for preparing 1, 2-hexanediol by oxidizing 1-hexene |
| CN115197171A (en) * | 2021-04-13 | 2022-10-18 | 中国石油化工股份有限公司 | Method and system for producing propylene oxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102766115B (en) | 2014-08-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105001087A (en) | Method and apparatus for producing formic esters by comprehensively utilizing metronidazole hydroxylation synthesis wastewater | |
| CN104557784A (en) | Method for producing epoxypropane | |
| CN103180273A (en) | Method for producing hydrocarbons from biomass or organic waste | |
| CN102690726A (en) | Method for preparing biodiesel by fixed bed catalytic membrane reactor | |
| CN103172600A (en) | Preparation method of furfuraldehyde | |
| CN102766115B (en) | Method for producing epoxycyclohexane with fixed bed reactor | |
| CN101786943A (en) | Catalytic synthesis method for preparing cresol by toluene one-step hydroxylation reaction | |
| CN103980080A (en) | Preparation method of xylene by alkylation of mixed crude benzene and methanol | |
| CN102786499A (en) | Method for preparing cyclohexene oxide | |
| CN101863761B (en) | Method for preparing dipropylene glycol methyl ether acetate | |
| CN101993353B (en) | Method for preparing 3-methyl-3-butene-1-alcohol | |
| CN103450010B (en) | Method for preparing cyclohexanecarboxylic acid | |
| CN103435480A (en) | Production method of propylene glycol monomethyl ether acetate (PMA) | |
| CN101619026B (en) | Synthesis method for continuously producing N,N-dimethyl cyclohexyl amine | |
| CN102757406B (en) | Styrene epoxidation method for preparing styrene oxide | |
| CN104177447B (en) | A kind of method that phenols chemicals is prepared in carbon-based solid acid Catalytic lignin degraded | |
| CN102993131B (en) | Method for preparing cyclohexene oxide by cyclization of o-chlorocyclohexanol | |
| CN102786500A (en) | Preparation method of cyclohexene oxide | |
| CN101811928A (en) | Method for preparing isopropyl benzene | |
| CN104788408A (en) | Method for producing gamma-valerolactone from hemicellulose | |
| CN105439823A (en) | Method for synthesizing 3-methyl-3-butene-1-ol | |
| CN103787877B (en) | Preparation method of cyclohexyl acetate | |
| CN102786501B (en) | Method for preparing cyclohexene oxide by heterogeneous catalytic epoxidation | |
| CN105080601A (en) | Catalyst for preparing methyl ethyl ketone by dehydration of 2,3-butanediol, and preparation method of catalyst | |
| CN104387249B (en) | Acrylic aldehyde preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140813 Termination date: 20170703 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |