CN106673951A - Method for producing cyclopentene from cyclopentadiene - Google Patents
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Abstract
The invention discloses a method for producing cyclopentene from cyclopentadiene. The method comprises the following steps: (1) a raw material containing cyclopentadiene and a solvent are mixed into a hydrogenation reaction raw material, the raw materials and hydrogen are mixed in order to carry out a fixed bed hydrogenation reaction, wherein the solvent comprises the following components in percentages by mass: 10-80% of dimethyl ether and 20-90% of diethyl ether, and the mass fraction of cyclopentadiene in the hydrogenation reaction raw materials is 1-25%, and preferably 10-25%; (2) hydrogen which is separated from hydrogenation products of the step (1) is introduced into a first rectifying tower, heavy component impurities are collected from a tower bottom, and tower top distillate which is used as a feed of a second rectifying tower is extracted; (3) the tower top distillate from the first rectifying tower in the step (2) is introduced into a second rectifying tower, cyclopentene product is collected from the tower bottom, a light component which is collected from the tower top is used as a recycled solvent, and the recycled solvent is returned to the step (1) for recycling. The method has the advantages of high conversion rate of cyclopentadiene, high yield of cyclopentene, and easy separation of the product.
Description
Technical field
The present invention relates to a kind of method for producing cyclopentenes by cyclopentadiene.
Background technology
Cyclopentenes are a kind of important fine chemical materials, can be used to prepare the high value added products such as cyclopentanol, Ketocyclopentane, glutaraldehyde, bromocyclopentane, chlorocyclopentane, but also are the primary raw materials of polycyclic alkene high molecular polymer.
At present, cyclopentenes are mainly obtained by cyclopentadiene process for selective hydrogenation.Cyclopentadiene mostlys come from cracking of ethylene by-product C5 fraction.Because at room temperature, cyclopentadiene is susceptible to self-polymeric reaction and generates relatively more stable dicyclopentadiene, therefore industrial cyclopentadiene generally with dimeric forms storage.When using, it is only necessary to which dicyclopentadiene is carried out into conventional air-distillation, fraction of the tower top temperature at 40～44 DEG C is collected, you can obtain cyclopentadiene.
Containing two active double bonds in cyclopentadiene molecules, under typical hydroconversion condition, one first double bond is hydrogenated generation cyclopentenes, the double bond in the cyclopentenes molecule of generation, it also occur that further hydrogenation reaction generates Pentamethylene..Because the reaction activity that cyclopentadiene hydrogenating generates cyclopentenes is more lower slightly than the reaction activity that cyclopentenes are hydrogenated to Pentamethylene., therefore only react at a lower temperature, could more advantageously make reaction rest on the stage for generating cyclopentenes.
Cyclopentadiene hydrogenating can be divided into autoclave interval hydrogenation technique and fixed bed continuously hydrogen adding technique by type of reactor.Such as CN1417179, CN1462734 and CN102728386, individually disclose a kind of cyclopentadiene interval hydrogenation technique of employing tank reactor.Above-mentioned interval hydrogenation technique is not suitable for large-scale continuous production due to using powder or catalyst particle, there is the difficult problem that catalyst is not readily separated with product.
Cyclopentadiene fixed bed hydrogenation technique can be divided into gas phase hydrogenation technique and liquid-phase hydrogenatin technique by reaction condition.Document（Gas chemical industry, 2012,37,20）And document（Hebei University of Technology's journal, 2011,40,40）A kind of method that cyclopentadiene gas phase hydrogenation prepares cyclopentenes is reported respectively, the method reaction temperature is usually above 100 DEG C, because reaction temperature is higher, it is unfavorable for controlling the reaction that the further hydrogenation reaction of cyclopentenes generates Pentamethylene., the Pentamethylene. of generation will certainly increase the load of follow-up separation process.Additionally, the reactor volume needed for gas phase hydrogenation technique is larger, equipment investment is costly.
Cyclopentadiene fixed bed liquid-phase hydrogenatin is the preferred technical scheme in this area（Such as US3994986 and CN1011877）.Cyclopentadiene hydrogenating is strong exothermal reaction, such as under the conditions of typical liquid-phase hydrogenatin, the mixed material being made up of 20% cyclopentadiene and 80% tert-butyl alcohol carries out hydrogenation reaction at 40 DEG C, and its adiabatic temperature rise is higher than 80 DEG C.The main deficiency that existing liquid phase hydrogenation technology is present is how to remove substantial amounts of reaction heat, makes reaction maintain to carry out at a lower temperature.A kind of conventional heat taking method is using dilution dilution agent raw material, such as document（Petrochemical technology and application, 2009,27,218）, it adopts Pentamethylene. as solvent, cyclopentadiene content is controlled in below 15wt%, with diluting reaction heat release, but due to Pentamethylene. boiling point（49.3℃）With cyclopentenes boiling point（44.2℃）It is close, adopt Pentamethylene. and increase for solvent the cost of later separation.CN1011877 discloses a kind of method that cyclopentadiene hydrogenating produces cyclopentenes, and the method takes heat using reaction effluent outer circulation, and its load is 1 with the weight ratio of circulating load：（4～12）, but the circulating load of the method is larger, certainly will increase the process load and equipment investment expense of reactor.
The content of the invention
For the deficiency that existing cyclopentadiene fixed bed liquid phase hydrogenation technology is present, the invention provides a kind of method for producing cyclopentenes by cyclopentadiene, the method has cyclopentadiene high conversion rate, cyclopentenes yield high, and the advantage that product is easily isolated.
A kind of method for producing cyclopentenes by cyclopentadiene of the present invention, comprises the steps：
（1）Raw material containing cyclopentadiene mixes as hydrogenation reaction raw material with solvent, fixed bed hydrogenation reaction is carried out after mixing with hydrogen again, the solvent is made up of the dimethyl ether and 20～90% ether that mass fraction is 10～80%, preferred mass fraction is 25～80% dimethyl ether and 20～75% ether composition, the mass fraction of cyclopentadiene is 1～25%, preferably 10～25% in hydrogenation reaction raw material；
（2）By step（1）Hydrogenation products are isolated and be passed through after hydrogen first rectifying column, and bottom of towe extraction heavy constituent impurity, overhead is produced as the charging of Second distillation column；
（3）By step（2）First rectifying column overhead is passed through Second distillation column, and bottom of towe produces cyclopentenes product, and overhead extraction light component is used as circulating solvent, return to step（1）Middle recycling.
The inventive method step（1）In, described raw material containing cyclopentadiene come from dicyclopentadiene cracking institute or methyl cycle pentadiene dimer cracking, wherein the mass fraction of cyclopentadiene or methyl cyclopentadiene be more than 98%.
The inventive method step（1）In, hydrogenation catalyst is Pd/Al2O3Catalyst.Prepare using commercial goods or by this area conventional method.As the further preferred of the inventive method, described Pd/Al2O3In catalyst, Pd contents are calculated as 0.2～0.4% with metallic element mass fraction.
The inventive method step（1）In, reactor inlet temperature is 20～50 DEG C, and reaction pressure is 0.5～1.5 MPa, and mass space velocity is 1～5 h-1, hydrogen is 1.1～2.0 with the mol ratio of cyclopentadiene, and preferred reactor inlet temperature is 20～40 DEG C, and reaction pressure is 1.2～1.5 MPa, and mass space velocity is 4～5 h-1, hydrogen is 1.1～1.3 with the mol ratio of cyclopentadiene.
The inventive method step（2）In, bottom temperature is 230～265 DEG C, and tower top temperature is 65～85 DEG C, and tower top pressure is 0.45～0.65 MPa.
The inventive method step（2）In, the theoretical cam curve of described first rectifying column is 10～20 pieces.Used as the further preferred of the inventive method, the theoretical cam curve of described first rectifying column is 15 pieces.Column plate can be set in first rectifying column, it is also possible to load filler.
The inventive method step（3）In, bottom temperature is 90～120 DEG C, and tower top temperature is 55～65 DEG C, and tower top pressure is 0.35～0.75 MPa.
The inventive method step（3）In, the theoretical cam curve of described Second distillation column is 60～70 pieces.Used as the further preferred of the inventive method, the theoretical cam curve of described Second distillation column is 65 pieces.Column plate can be set in Second distillation column, it is also possible to load filler.
It is strong exothermal reaction that cyclopentadiene hydrogenating generation cyclopentenes and cyclopentenes are hydrogenated to Pentamethylene., and under the conditions of typical liquid-phase hydrogenatin, the reaction heat of the two is above 100
KJ/mol, the thermal discharge of the latter is bigger.It has been generally acknowledged that, if reaction temperature is higher than 120 DEG C, cyclopentenes are hydrogenated to the response speed of Pentamethylene. can be dramatically speeded up, on the one hand cyclopentenes selectivity is caused to decline, order can affect cyclopentenes product quality and increase the separating difficulty of subsequent product on the one hand because Pentamethylene. is close with product cyclopentenes boiling point.Therefore, taking reaction heat and control reaction away is carried out at a lower temperature, will be the key of production and separating-purifying cyclopentenes with high selectivity.
One of key of the present invention is that the solvent that the present invention is adopted is made up of dimethyl ether and ether.Dimethyl ether the present invention adopt reaction pressure under boiling point for 51.2～60.6 DEG C.Under the reaction condition that the present invention is adopted, cyclopentadiene hydrogenating heat release makes dimethyl ether gasify, and using the gasification latent heat of dimethyl ether reaction bed temperature is controlled.The content of dimethyl ether, can be such that reaction bed temperature stably controls at 50～60 DEG C in by adjusting solvent, to suppress the further hydrogenation reaction of product cyclopentenes, Pentamethylene. by-product selectivity is controlled below 0.5%.
Further, since the solvent that the present invention is adopted is made up of dimethyl ether and ether, the two boiling point at ambient pressure is below cyclopentadiene raw material and cyclopentenes product so that product separation process is greatly simplified.Compared with the existing technology, the inventive method eliminates solvent separating step, solvent and unreacted cyclopentadiene raw material are produced with the tower top light component of Second distillation column jointly, on the one hand on the other hand also unreacted cyclopentadiene raw material can be taken back hydrogenation reactor and continue to react as the circulating solvent of the present invention.After device reaches stable state, the unreacted cyclopentadiene raw material of solvent and part is circulated in a device, can improve the conversion ratio of cyclopentadiene in fresh feed, and without the need for supplementing fresh solvent.
Description of the drawings
Fig. 1 is schematic flow sheet of the present invention.
Wherein, 1- raw material storage tanks, 2- feed pumps, 3- hydrogenation reactors, 4- gas-liquid separators, 5- feed pumps, 6- first rectifying columns, 7- Second distillation columns.
101～111 is logistics, wherein 101- raw materials containing cyclopentadiene, 102- fresh solvents, 103- hydrogenation reaction raw materials, 104- hydrogen, 105- hydrogenation reaction effluents, 106- circulating hydrogens, the charging of 107- first rectifying columns, 108- heavy constituent impurity, 109- Second distillation columns feed, 110- cyclopentenes products, 111- circulating solvents.
Specific embodiment
Below in conjunction with the accompanying drawings and embodiment the invention will be further described.It is only below the present invention preferably specific embodiment, but protection scope of the present invention is not limited to this, and any those familiar with the art can readily occur in change or replacement, all should cover in the protection domain of this patent.
Raw material containing cyclopentadiene as shown in Figure 1（101）With fresh solvent（102）And circulating solvent（111）After mixing in raw material storage tank 1, hydrogenation reaction raw material is constituted（103）；The flow of each stock material is adjusted, the mass fraction for making cyclopentadiene in hydrogenating materials is 10～25%, the mass fraction of dimethyl ether is 25～80% in solvent；Hydrogenation reaction raw material（103）Jing and hydrogen（104）Hydrogenation reactor 2 is entered after mixing, in Pd/Al2O3It it is 20～40 DEG C in reactor inlet temperature in the presence of catalyst, reaction pressure is 1.3～1.5 MPa, mass space velocity is 4～5 h-1, the mol ratio of hydrogen and cyclopentadiene is under conditions of 1.1～1.3, cyclopentadiene selective hydrogenation occurs；The hydrogenation reaction effluent of generation（105）Gas-liquid separation is carried out in knockout drum 4, hydrogen is isolated（106）Can be recycled；Liquid-phase hydrogenatin product is isolated as the charging of first rectifying column 6（107）, it is 230～265 DEG C in bottom temperature, tower top temperature is 65～85 DEG C, and tower top pressure is to operate under conditions of 0.45～0.65 MPa, bottom of towe extraction heavy constituent impurity（108）；Charging of the first rectifying column overhead as Second distillation column（109）, it is 90～120 DEG C in bottom temperature, tower top temperature is 55～65 DEG C, and tower top pressure is to operate under conditions of 0.35～0.75 MPa, bottom of towe extraction cyclopentenes product（110）, tower top distillates light component as circulating solvent（111）, return in raw material storage tank 1 and recycle.
The effect of the present invention is further illustrated with reference to embodiments.
Embodiment 1-5
Raw material containing cyclopentadiene used by various embodiments of the present invention comes from dicyclopentadiene cracking, and the wherein mass fraction of cyclopentadiene is 98%, and remaining is dicyclopentadiene.
The technological process that various embodiments of the present invention are adopted is as shown in Figure 1.Table 1 lists the hydrogenation reaction raw material of each embodiment（103）Composition.
Table 1
Table 2 lists the operating condition of various embodiments of the present invention hydrogenation reactor.
Table 2
In order to illustrate the effect of the inventive method, using beneficial effect of the one way selective presentation the inventive method of cyclopentadiene conversion per pass, the one way selectivity of cyclopentenes and Pentamethylene. to cyclopentadiene selective hydrogenation.
Table 3 lists various embodiments of the present invention cyclopentadiene selective hydrogenation one way reaction result.The mass fraction that the inventive method passes through dimethyl ether in control solvent, dimethyl ether is set to absorb cyclopentadiene hydrogenating reaction liberated heat under the conditions of the reaction according to the invention and gasify, reaction bed temperature is controlled using the gasification latent heat of dimethyl ether, makes hydrogenation reaction maintain to carry out at a lower temperature.As shown in table 3, using the inventive method hydrogenation reactor outlet temperature can be made to control at 50～60 DEG C, therefore the one way selectivity that cyclopentadiene deep hydrogenation generates Pentamethylene. is controlled below 0.5%, to obtain higher cyclopentenes product selectivity.
Table 3
Table 4 lists the hydrogenation products of various embodiments of the present invention and separates and process for refining condition, and technological process is as shown in Figure 1.The theoretical cam curve of first rectifying column is 15 pieces, and the theoretical cam curve of Second distillation column is 65 pieces.The rectifying column that various embodiments of the present invention are adopted can arrange distillation tray, it is also possible to load filler.The technology contents that plate column and packed tower are well known to the skilled person.Various embodiments of the present invention adopt packed tower, and filler used is metal Pall ring filler.
Table 4
Table 5 lists cyclopentenes product（110）And circulating solvent（111）Composition.The device invested to build using the inventive method is reached after stable state, without the need for being supplemented with fresh solvent.As shown in table 6, another beneficial effect of the invention is that unreacted cyclopentadiene returns hydrogenation reactor and continues reaction with circulating solvent, the total conversion of cyclopentadiene can be improved into more than 99%, and cyclopentenes total yield of products is improved to more than 98%.
Table 5
Table 6
Claims (14)
1. it is a kind of by cyclopentadiene produce cyclopentenes method, it is characterised in that：Comprise the steps：
（1）Raw material containing cyclopentadiene mixes as hydrogenation reaction raw material with solvent, fixed bed hydrogenation reaction is carried out after mixing with hydrogen again, the solvent is made up of the dimethyl ether and 20～90% ether that mass fraction is 10～80%, and the mass fraction of cyclopentadiene is 1～25% in hydrogenation reaction raw material；
（2）By step（1）Hydrogenation products are isolated and be passed through after hydrogen first rectifying column, and bottom of towe extraction heavy constituent impurity, overhead is produced as the charging of Second distillation column；
（3）By step（2）First rectifying column overhead is passed through Second distillation column, and bottom of towe produces cyclopentenes product, and overhead extraction light component is used as circulating solvent, return to step（1）Middle recycling.
2. method according to claim 1, it is characterised in that：Step（1）Middle solvent is made up of the dimethyl ether and 20～75% ether that mass fraction is 25～80%, and the mass fraction of cyclopentadiene is 10～25% in hydrogenation reaction raw material.
3. method according to claim 1, it is characterised in that：Step（1）In raw material containing cyclopentadiene come from dicyclopentadiene cracking, wherein the mass fraction of cyclopentadiene be more than 98%.
4. method according to claim 1, it is characterised in that：Step（1）Middle hydrogenation catalyst is Pd/Al2O3Catalyst.
5. method according to claim 4, it is characterised in that：Pd/Al2O3Catalyst is prepared using commercial goods or according to a conventional method.
6. method according to claim 5, it is characterised in that： Pd/Al2O3Pd contents are calculated as 0.2～0.4% with metallic element mass fraction in catalyst.
7. method according to claim 1, it is characterised in that：Step（1）Middle reactor inlet temperature is 20～50 DEG C, and reaction pressure is 0.5～1.5 MPa, and mass space velocity is 1～5 h-1, hydrogen is 1.1～2.0 with the mol ratio of cyclopentadiene.
8. method according to claim 7, it is characterised in that：Reactor inlet temperature is 20～40 DEG C, and reaction pressure is 1.2～1.5 MPa, and mass space velocity is 4～5 h-1, hydrogen is 1.1～1.3 with the mol ratio of cyclopentadiene.
9. method according to claim 1, it is characterised in that：Step（2）Middle bottom temperature is 230～265 DEG C, and tower top temperature is 65～85 DEG C, and tower top pressure is 0.45～0.65 MPa.
10. method according to claim 1, it is characterised in that：Step（2）The theoretical cam curve of middle first rectifying column is 10～20 pieces.
11. methods according to claim 1, it is characterised in that：Column plate is set in first rectifying column or filler is loaded.
12. methods according to claim 1, it is characterised in that：Step（3）Middle bottom temperature is 90～120 DEG C, and tower top temperature is 55～65 DEG C, and tower top pressure is 0.35～0.75 MPa.
13. methods according to claim 1, it is characterised in that：Step（3）The theoretical cam curve of middle Second distillation column is 60～70 pieces.
14. methods according to claim 1, it is characterised in that：Column plate is set in Second distillation column or filler is loaded.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110721681A (en) * | 2019-11-12 | 2020-01-24 | 西安凯立新材料股份有限公司 | Catalyst for preparing cyclopentene by cyclopentadiene hydrogenation, preparation method and application |
| CN115806477A (en) * | 2021-09-14 | 2023-03-17 | 中国科学院大连化学物理研究所 | Method and device for producing cyclopentanone product |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB805865A (en) * | 1957-01-15 | 1958-12-17 | Exxon Research Engineering Co | Preparation of cyclopentene |
| US3598877A (en) * | 1970-06-05 | 1971-08-10 | Shell Oil Co | Cyclodiolefin hydrogenation |
| US3751497A (en) * | 1970-05-25 | 1973-08-07 | Bayer Ag | Process for the production of cyclopentene from cyclopentadiene |
| CN1417179A (en) * | 2001-11-08 | 2003-05-14 | 中国石化上海石油化工股份有限公司 | Cyclopentadiene hydrogenating precess of preparing cyclopentene |
| CN1462734A (en) * | 2003-06-16 | 2003-12-24 | 大连理工大学 | Method for industrialized reparing cyclopentene |
| CZ298994B6 (en) * | 2005-03-18 | 2008-03-26 | Vysoká škola chemicko - technologická | Process for continuously preparing cyclopentene of polymerization purity |
| CN102728386A (en) * | 2012-06-25 | 2012-10-17 | 合肥工业大学 | Pd-Ni/Al2O3 catalyst, its preparation method and application thereof |
| CN102850174A (en) * | 2012-08-29 | 2013-01-02 | 宁波职业技术学院 | Method for preparing cyclopentene from ethylene cracking C9 heavy fraction |
| CN102911001A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Method for preparing cyclopentene from dicyclopentadiene |
| CN103342624A (en) * | 2013-07-24 | 2013-10-09 | 上海派尔科化工材料有限公司 | Preparation method of high purity cyclopentene |
-
2015
- 2015-11-09 CN CN201510751427.XA patent/CN106673951B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB805865A (en) * | 1957-01-15 | 1958-12-17 | Exxon Research Engineering Co | Preparation of cyclopentene |
| US3751497A (en) * | 1970-05-25 | 1973-08-07 | Bayer Ag | Process for the production of cyclopentene from cyclopentadiene |
| US3598877A (en) * | 1970-06-05 | 1971-08-10 | Shell Oil Co | Cyclodiolefin hydrogenation |
| CN1417179A (en) * | 2001-11-08 | 2003-05-14 | 中国石化上海石油化工股份有限公司 | Cyclopentadiene hydrogenating precess of preparing cyclopentene |
| CN1462734A (en) * | 2003-06-16 | 2003-12-24 | 大连理工大学 | Method for industrialized reparing cyclopentene |
| CZ298994B6 (en) * | 2005-03-18 | 2008-03-26 | Vysoká škola chemicko - technologická | Process for continuously preparing cyclopentene of polymerization purity |
| CN102911001A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Method for preparing cyclopentene from dicyclopentadiene |
| CN102728386A (en) * | 2012-06-25 | 2012-10-17 | 合肥工业大学 | Pd-Ni/Al2O3 catalyst, its preparation method and application thereof |
| CN102850174A (en) * | 2012-08-29 | 2013-01-02 | 宁波职业技术学院 | Method for preparing cyclopentene from ethylene cracking C9 heavy fraction |
| CN103342624A (en) * | 2013-07-24 | 2013-10-09 | 上海派尔科化工材料有限公司 | Preparation method of high purity cyclopentene |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110721681A (en) * | 2019-11-12 | 2020-01-24 | 西安凯立新材料股份有限公司 | Catalyst for preparing cyclopentene by cyclopentadiene hydrogenation, preparation method and application |
| CN110721681B (en) * | 2019-11-12 | 2023-01-24 | 西安凯立新材料股份有限公司 | Catalyst for preparing cyclopentene by cyclopentadiene hydrogenation, preparation method and application |
| CN115806477A (en) * | 2021-09-14 | 2023-03-17 | 中国科学院大连化学物理研究所 | Method and device for producing cyclopentanone product |
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