CN103145523B - Production method of high-purity trans-m-pentadiene - Google Patents
Production method of high-purity trans-m-pentadiene Download PDFInfo
- Publication number
- CN103145523B CN103145523B CN201310078807.2A CN201310078807A CN103145523B CN 103145523 B CN103145523 B CN 103145523B CN 201310078807 A CN201310078807 A CN 201310078807A CN 103145523 B CN103145523 B CN 103145523B
- Authority
- CN
- China
- Prior art keywords
- pentadiene
- reaction
- trans
- production method
- rectifying
- 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.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a production method of high-purity trans-m-pentadiene. The method comprises the following steps of: 1) conveying m-pentadiene raw materials in a rectifying tower, rectifying at an operating pressure of 0-3.0 bar, a tower bottom temperature of 50-70 DEG C, a tower top temperature of 40-50 DEG C, and a reflux ratio of 8-30, obtaining trans-m-pentadiene on the top of the tower, thereby obtaining heavy components which are rich in cis-m-pentadiene; 2) performing isomerization reaction on the raw materials in the tower, preparing aqueous solution from the measured Co(AC)2.4H2O under the protection of nitrogen, adding the measured potassium cyanide aqueous solution and diethylamine to react, charging the mixed gas of nitrogen and hydrogen in a reactor to react at a reaction temperature of 0-40 DEG C, a system pressure of 0.10-3.0 car, and a catalyst dosage of 1-10% occupying the mass of m-pentadiene by mass of metallic cobalt by taking the prepared reaction solution as a catalyst, and after the reaction is concluded, performing oil/water separation on the reaction solution, and cyclically applying the water phase as a catalyst; and 3) conveying the oil phase obtained by the reaction aforementioned in the rectifying tower, and rectifying under the operating conditions in the step 1). According to the production method, the raw materials containing cis-m-pentadiene and trans-m-pentadiene are subjected to rectifying separation and isomerization reaction to produce trans-m-pentadiene.
Description
Technical field
The present invention relates to a kind of production method of high-purity trans-m-pentadiene, particularly by the method for the raw material containing cis and trans-m-pentadiene by rectifying separation and isomerization reaction production high-purity trans-m-pentadiene.
Background technology
M-pentadiene produces the epoxy curing agents such as methyl hexahydrophthalic anhydride mainly for the production of synthetic rubber monomer, carbon five aliphatic petroleum resin and methyl tetrahydro phthalic anhydride and repeated hydrogenation thereof.Usual m-pentadiene product is the mixture of cis-form m-pentadiene and trans-m-pentadiene, m-pentadiene total mass content is generally between 68 ~ 72%, wherein the mass content of trans-m-pentadiene is 42 ~ 46%, the mass content of cis-form m-pentadiene is 25 ~ 27%, trans-m-pentadiene and cis-form m-pentadiene mass values are 1.67 ~ 1.74, other main component is cyclopentenes and pentamethylene, and the two mass content is respectively 17 ~ 19% and 5 ~ 8%.For the production of the m-pentadiene of carbon five aliphatic petroleum resin, owing to being acid catalyzed polymerisation reaction, therefore cis and trans-m-pentadiene can be fully used; And when producing methyl tetrahydro phthalic anhydride and methyl hexahydrophthalic anhydride, Diels-Alder can be there is with cis-butenedioic anhydride owing to only having trans-m-pentadiene to react and generate methyl tetrahydro phthalic anhydride, cis-form m-pentadiene is not but mated because of symmetry cannot participate in reaction, and cis-form m-pentadiene is not utilized effectively; When synthetic rubber is produced in the polymerization of this external anionic catalyst, Ziegler-Natta catalyst or transition-metal catalyst catalysis m-pentadiene, only have trans-m-pentadiene to be the monomer participating in polyreaction, cis-form m-pentadiene does not then participate in reaction.
US Patent No. 3,403,196 describe a kind of isomer utilizing ammonium chloride cuprous fractionation by adsorption purification cis and transconfiguration, mass ratio that is trans in m-pentadiene raw material and cis can be brought up between 6 ~ 7 by about 2.But this method is not also a kind of separation truly, cannot produce high trans m-pentadiene product.Chinese patent CN1865202 proposes a kind of method of being carried out piperyene cis, trans-isomer(ide) separation by physical process extracting rectifying, but the trans-m-pentadiene that content is 80% ~ 93.9% can only be produced, and cis-form m-pentadiene is not fully used.
Summary of the invention
The invention provides a kind of production method of high-purity trans-m-pentadiene, the technical problem that it will solve is by rectifying separation and isomerization reaction production high-purity trans-m-pentadiene by the raw material containing cis and trans-m-pentadiene.
Below the technical scheme that the present invention solves the problems of the technologies described above:
A production method for high-purity trans-m-pentadiene, the method comprises the following steps:
1) m-pentadiene raw material enters rectifying tower and carries out rectifying; The theoretical plate number of rectifying tower is 100 ~ 150 pieces; Working pressure is 0 ~ 3.0bar, and bottom temperature is 50 ~ 70 DEG C, and tower top temperature is 40 ~ 50 DEG C, and reflux ratio is 8 ~ 30; Tower top obtains trans-m-pentadiene, and tower reactor must be rich in the heavy constituent of cis-form m-pentadiene;
2) step 1) the kettle material kettle material that obtains carries out isomerization reaction; Under nitrogen protection, by the Co (AC) of metering
24H
2o is mixed with the aqueous solution, and under the mild stirring of room, add metering the potassium cyanide aqueous solution and second two amine ﹙ EN ﹚ fully react, obtained reaction solution as catalyzer, wherein [Co (CN)
xeN]
-(X-2)co in complex compound
2+﹕ CN
-the mol ratio of ﹕ EN is 1 ﹕ 3.90 ~ 4.10 ﹕ 3, x=3.9 ~ 4.1, and the concentration of cobalt ion is 0.10 ~ 2.5mol/L; Pass into nitrogen and hydrogen gas mixture in the reactor, temperature of reaction is 0 ~ 40 DEG C, system pressure is 0.10 ~ 3.0bar, in nitrogen and hydrogen gas mixture, the volumn concentration of nitrogen is 70 ~ 95%, stirring velocity is 300 ~ 800 revs/min, catalyst levels counts 1 ~ 10% of m-pentadiene quality with cobalt metal quality, and the reaction times is 10 ~ 300 minutes; After reaction terminates, reaction solution carries out oil/water separation, and upper oil phase is sent into rectifying tower and carried out rectifying, and aqueous phase is applied mechanically as catalyst recirculation.
3) by step 2) oil phase that obtains sends into rectifying tower and carries out rectifying, adopt step 1) operational condition stated carries out rectifying.
Above-mentioned steps 1) and step 3) described in working pressure be preferably normal pressure; Bottom temperature is preferably 55 ~ 65 DEG C, and tower top temperature is preferably 42 ~ 43 DEG C, and reflux ratio is preferably 15 ~ 25.
Above-mentioned steps 2) described in Co
2+﹕ CN
-the mol ratio of ﹕ EN is preferably 1 ﹕ 3.95 ~ 4.05 ﹕ 3; The concentration of cobalt ion is preferably 0.15 ~ 1.8mol/L; Temperature of reaction is preferably 10 ~ 30 DEG C; System hydrogen pressure is preferably 0.5 ~ 1.5bar; In nitrogen and hydrogen gas mixture, the volumn concentration of nitrogen is preferably 80 ~ 90%; Stirring velocity is preferably 500 ~ 700 revs/min; [Co (CN)
xeN]
-(X-2)catalyst levels cobalt metal quality meter is preferably 3 ~ 8% of m-pentadiene quality; Reaction times is preferably 30 ~ 200 minutes.
M-pentadiene described in said process can be pure cis-form m-pentadiene, also can be the mixture of conventional cis and trans-m-pentadiene.Usually, listed by the table composed as follows of above-mentioned m-pentadiene:
| Component | Content (wt%) |
| Trans-m-pentadiene | 42～46 |
| Cis-form m-pentadiene | 25～27 |
| Cyclopentenes | 17～19 |
| Pentamethylene | 5～8 |
| Other carbon five and carbon six | Surplus |
Technical scheme provided by the invention mainly includes three steps.Wherein step 1) and step 2) the most key.The present invention utilizes trans-m-pentadiene boiling point lower than the feature of cis-form m-pentadiene, is achieved the separation of piperyene cis, trans-isomer(ide) by rectifying fractionation well.The rectifying tower adopted can be packing tower or sieve-tray tower, and the theoretical plate number of rectifying tower is generally to be advisable at 100 ~ 150 pieces, and certainly higher theoretical plate number can make separating effect more desirable, but energy consumption is higher.
In step 2) in, the present invention is by increasing part CN
-1with Co
2+the mode of mol ratio obtains the [Co (CN) that stability significantly improves
xeN]
-(X-2)complex compound, this complex compound has the performance of good catalysis cis-form m-pentadiene isomerization reaction.In step 2) in, the present invention is by adopting the mode making isomerization reaction carry out under system pressure is 0.10 ~ 3.0bar and the existence at nitrogen and hydrogen gas mixture, the isomerization reaction of cis-form m-pentadiene can be ensured on the one hand, effectively can also to intercept in air oxygen molecule to the migration in reaction system simultaneously, and reduce the hydrogenation side reaction of m-pentadiene.
Positive effect of the present invention there are provided the separation method of a kind of desirable piperyene cis, trans-isomer(ide), and it adopts precise distillation and isomerization reaction technology production of high purity in next life trans-m-pentadiene.Reached the object of piperyene cis, trans-isomer(ide) separation by precise distillation, become trans-m-pentadiene to improve the yield of trans-m-pentadiene cis-form m-pentadiene isomery by isomerization reaction again simultaneously.Technical scheme provided by the invention is easy to realize industrial applications, overcomes the defect that prior art exists well.
Embodiment
Below by specific embodiment, the invention will be further described, but embodiment does not limit the scope of the present invention, in an embodiment, the isomerisation conversion of Cis-PD (cis-form m-pentadiene) and Trans-PD (trans-m-pentadiene) selectivity are respectively:
The m-pentadiene that each embodiment uses forms as listed in table 1:
One, rectifying [embodiment 1 ~ 4]
The m-pentadiene raw material of composition as table 1 enters a rectifying tower and carries out rectifying, and rectifying tower is packing tower, and theoretical plate number is 138.M-pentadiene raw material enters rectifying tower with the speed of 400g/h from the 80th block of column plate.Each embodiment rectifying tower operates at ambient pressure, and other main distillation operation condition is in table 2.Rectifying tower tower top obtains trans-m-pentadiene, and kettle material carries out isomerization reaction as raw material, and rectifying tower tower top and kettle material composition are in table 3.
Two, isomerization [embodiment 5 ~ 14]
1) preparation of catalyzer
Being prepared in of catalyzer is withstand voltage, and volume is carry out in 1000ml jacketed glass reactor.On glass reactor top, variable-ratio mechanical stirring device, thermocouple for measuring temperature, tensimeter, hydrogen and nitrogen inlet and charging opening are housed.Temperature of reaction controls temperature of reaction by constant temperature oil bath temperature.By the deionized water of accurate weighing, Co (AC)
24H
2o adds reactor by charging opening, starts and stirs and be stabilized in 200 turns/min, makes Co (AC)
24H
2o is dissolved in water, is mixed with the transparent aqueous solution; Use nitrogen replacement reactor, and add the potassium cyanide aqueous solution and Yi bis-An ﹙ EN ﹚ under nitrogen protection, obtained reaction solution is as catalyzer.
2) isomerization reaction
Under nitrogen protection, in above-mentioned reactor, add m-pentadiene raw material as listed in table 3.Pass into nitrogen and hydrogen gas mixture in the reactor, and be raised to required pressure and temperature and carry out isomerization reaction, after the reaction times to be achieved, cool the temperature to room temperature and carry out layering, oil phase sampling is carried out GC analysis and send rectifying tower to carry out rectifying.
The concrete reaction conditions of each embodiment is in table 4, and Cis-PD conversion rate and Trans-PD selectivity are in table 5.
Three, rectifying
Form above-mentioned isomerization reaction liquid to enter rectifying tower and carry out rectifying, rectifying tower is packing tower, and theoretical plate number is 138.Other main distillation operation condition is in table 2.Rectifying tower tower top obtains high-purity trans-m-pentadiene, and kettle material is as the raw material of separating ring amylene and pentamethylene.
Table 1.
| Sequence number | Component | Content (wt%) |
| 1 | Skellysolve A | 0.01 |
| 2 | Isoprene | 0.01 |
| 3 | Trans amylene-2 | 0.01 |
| 4 | Cis amylene-2 | 0.02 |
| 5 | 2-methyl-2-butene | 0.10 |
| 6 | Trans-m-pentadiene | 47.68 |
| 7 | Cyclopentadiene | 0.28 |
| 8 | Cis-form m-pentadiene | 25.76 |
| 9 | Cyclopentenes | 18.53 |
| 10 | Pentamethylene | 7.60 |
Table 2.
| Embodiment | Bottom temperature (DEG C) | Tower top temperature (DEG C) | Reflux ratio |
| Embodiment 1 | 50 | 42.3 | 8 |
| Embodiment 2 | 70 | 42.4 | 30 |
| Embodiment 3 | 55 | 42.2 | 15 |
| Embodiment 4 | 65 | 42.1 | 25 |
Table 3.
Table 4.
Table 5.
Claims (10)
1. a production method for high-purity trans-m-pentadiene, the method comprises the following steps:
1) m-pentadiene raw material enters rectifying tower and carries out rectifying; The theoretical plate number of rectifying tower is 100 ~ 150 pieces, and working pressure is normal pressure, and bottom temperature is 55 ~ 65 DEG C, and tower top temperature is 42 ~ 43 DEG C, and reflux ratio is 15 ~ 25;
2) step 1) kettle material that obtains carries out isomerization reaction; Under nitrogen protection, by the Co (AC) of metering
24H
2o is mixed with the aqueous solution, and under the mild stirring of room, add metering the potassium cyanide aqueous solution and quadrol fully react, obtained reaction solution as catalyzer, wherein [Co (CN)
xeN]
-(X-2)co in complex compound
2+﹕ CN
-the mol ratio of ﹕ EN is 1 ﹕ 3.90 ~ 4.10 ﹕ 3, x=3.9 ~ 4.10, and the concentration of cobalt ion is 0.10 ~ 2.5mol/L; Add step 1 in the reactor) kettle material that obtains, and pass into nitrogen and hydrogen gas mixture in the reactor, temperature of reaction is 0 ~ 40 DEG C, system pressure is 0.10 ~ 3.0bar, in nitrogen and hydrogen gas mixture, the volumn concentration of nitrogen is 70 ~ 95%, stirring velocity is 300 ~ 800 revs/min, and catalyst levels counts 1 ~ 10% of m-pentadiene quality with cobalt metal quality, and the reaction times is 10 ~ 300 minutes; After reaction terminates, reaction solution carries out oil/water separation, and upper oil phase is sent into rectifying tower and carried out rectifying, and aqueous phase is applied mechanically as catalyst recirculation;
3) by step 2) oil phase that obtains is sent into rectifying tower and is carried out rectifying in reaction, adopts step 1) described in operational condition carry out rectifying.
2. the production method of a kind of high-purity trans-m-pentadiene according to claim 1, is characterized in that step 2) described in catalyzer [Co (CN)
xeN]
-(X-2)co in complex compound
2+﹕ CN
-the mol ratio of ﹕ EN is 1 ﹕ 3.95 ~ 4.05 ﹕ 3.
3. the production method of a kind of high-purity trans-m-pentadiene according to claim 1, is characterized in that step 2) described in the concentration of catalyst cobalt ion be 0.15 ~ 1.8mol/L.
4. the production method of a kind of high-purity trans-m-pentadiene according to claim 1, is characterized in that step 2) described in temperature of reaction be 10 ~ 30 DEG C.
5. the production method of a kind of high-purity trans-m-pentadiene according to claim 1, is characterized in that step 2) described in system pressure be 0.5 ~ 1.5bar.
6. the production method of a kind of high-purity trans-m-pentadiene according to claim 1, is characterized in that step 2) described in nitrogen and hydrogen gas mixture in the volumn concentration of nitrogen be 80 ~ 90%.
7. the production method of a kind of high-purity trans-m-pentadiene according to claim 1, is characterized in that step 2) described in stirring velocity be 500 ~ 700 revs/min.
8. the production method of a kind of high-purity trans-m-pentadiene according to claim 1, is characterized in that step 2) described in catalyst levels count 3 ~ 8% of m-pentadiene quality with cobalt metal quality.
9. the production method of a kind of high-purity trans-m-pentadiene according to claim 1, is characterized in that step 2) described in reaction times be 30 ~ 200 minutes.
10. the production method of a kind of high-purity trans-m-pentadiene according to claim 1, it is characterized in that step 3) described in employing step 1) described in operational condition be working pressure be normal pressure, bottom temperature is 55 ~ 65 DEG C, tower top temperature is 42 ~ 43 DEG C, and reflux ratio is 15 ~ 25.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310078807.2A CN103145523B (en) | 2013-03-12 | 2013-03-12 | Production method of high-purity trans-m-pentadiene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310078807.2A CN103145523B (en) | 2013-03-12 | 2013-03-12 | Production method of high-purity trans-m-pentadiene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103145523A CN103145523A (en) | 2013-06-12 |
| CN103145523B true CN103145523B (en) | 2015-03-04 |
Family
ID=48543908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310078807.2A Active CN103145523B (en) | 2013-03-12 | 2013-03-12 | Production method of high-purity trans-m-pentadiene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103145523B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113548938A (en) * | 2020-12-23 | 2021-10-26 | 江苏广域化学有限公司 | Cis-trans-inversion method of non-terminal alkene liquid crystal monomer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1865202A (en) * | 2005-05-18 | 2006-11-22 | 中国石化上海石油化工股份有限公司 | Piperyene cis and trans isomer separating method |
-
2013
- 2013-03-12 CN CN201310078807.2A patent/CN103145523B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1865202A (en) * | 2005-05-18 | 2006-11-22 | 中国石化上海石油化工股份有限公司 | Piperyene cis and trans isomer separating method |
Non-Patent Citations (1)
| Title |
|---|
| Catalytic properties of cyanoaminocobaltate complex ions in hydrogenation reactions and cis-trans transformations of 1,3-pentadienes;L. Kh. Freidlin et al.;《Bulletin of the Academy of Sciences of the USSR, Division of chemical science》;19770430;第26卷(第4期);第762-767页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103145523A (en) | 2013-06-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109912544B (en) | Method for preparing bis ((3, 4-epoxycyclohexyl) methyl) adipate by using microchannel reactor | |
| CN103086822B (en) | A kind of separation method of m-pentadiene | |
| CN104592030A (en) | Method for synthesizing phthalate compounds | |
| CN103145523B (en) | Production method of high-purity trans-m-pentadiene | |
| CN103342624B (en) | Preparation method of high purity cyclopentene | |
| CN102140107B (en) | Method for disproportionating methyl chlorosilane | |
| CN105198745B (en) | A kind of ionic liquid-catalyzed ester exchange reaction prepares the method and device of diphenyl carbonate | |
| CN108947758A (en) | A method of catalysis dibenzofurans open loop prepares biphenyl | |
| CN103204759B (en) | Comprehensive pentadiene utilization method | |
| CN101092319A (en) | Method for separating cyclopentadiene | |
| CN109761795A (en) | The method that hexafluoropropylene trimer prepares perfluor isobutyl acyl fluorides | |
| CN105439801B (en) | The preparation method of hexamethylene | |
| CN105585468B (en) | A method of cyclopentanone is prepared by raw material of cyclopentene | |
| CN105111039A (en) | Preparation method of chloroisopentene | |
| CN105585451B (en) | A kind of method that cyclopentene direct hydration prepares cyclopentanol | |
| CN103113180B (en) | Method for isomerizing cis-piperylene | |
| CN101434513B (en) | Preparation of 1-naphthalene bromide | |
| CN103145522B (en) | Method for isomerizing cis-form m-pentadiene | |
| CN204958762U (en) | Ionic liquid catalysis transesterification preparation diphenyl carbonate's device | |
| Zuohua et al. | Acetylene dimerization catalyzed by LaCl3-modified Nieuwland catalyst | |
| CN1268593C (en) | Method for isomerizating 1,4-dichloro-2-butylenes from syn form to anti form | |
| CN109535007A (en) | A kind of diamino-dicyclohexyl methane isomer separation method | |
| CN102964200A (en) | Purifying method of coking toluene | |
| CN115057787B (en) | Preparation method of monoethanol diisopropanolamine | |
| CN116082113B (en) | Method for producing high-purity cyclopentane and methylcyclopentane by hydrogenating nine light components of carbon |
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 | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 201512 No. 299 Chunhua Road, Jinshanwei Town, Jinshan District, Shanghai Patentee after: SHANGHAI PEARLK CHEMICAL Co.,Ltd. Address before: 201512 No. 299 Chunhua Road, Jinshan fine chemical park, Jinshan District, Shanghai Patentee before: SHANGHAI PEARLK CHEMICALS Co.,Ltd. |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A production method of high purity trans m-pentadiene Effective date of registration: 20210918 Granted publication date: 20150304 Pledgee: Chen Hong Pledgor: SHANGHAI PEARLK CHEMICAL Co.,Ltd. Registration number: Y2021310000074 |