CN101671224A - Preparation method of high purity dicyclopentadiene - Google Patents
Preparation method of high purity dicyclopentadiene Download PDFInfo
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- CN101671224A CN101671224A CN200910019247A CN200910019247A CN101671224A CN 101671224 A CN101671224 A CN 101671224A CN 200910019247 A CN200910019247 A CN 200910019247A CN 200910019247 A CN200910019247 A CN 200910019247A CN 101671224 A CN101671224 A CN 101671224A
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- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005336 cracking Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000005120 petroleum cracking Methods 0.000 claims abstract description 6
- 239000006227 byproduct Substances 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims description 21
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000005191 phase separation Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 10
- 238000002309 gasification Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000012691 depolymerization reaction Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
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Abstract
The invention belongs to the technical field of chemical engineering, and particularly discloses a preparation method of high purity dicyclopentadiene. The preparation method comprises the following steps: using a C5 fraction as a byproduct of ethane prepared through petroleum cracking as a raw material, cracking to prepare cyclopentadiene after gasification, and preparing the high purity dicyclopentadiene through polymeric rectification. The invention adopts a method of cracking-dimerization-rectification, and has the characteristics of low production cost, high purification precision and easy industrialization.
Description
(1) technical field
The invention belongs to chemical technology field, particularly a kind of preparation method of high purity dicyclo pentylene.
(2) background technology
Dicyclopentadiene (DCPD) is the by product of petroleum cracking system ethene and coal coking.Because DCPD contains active methylene radical and two conjugated double bonds, reactive behavior is very high, and can or participate in multiple organic chemical reactions with multiple olefin-copolymerization, make it have purposes widely at aspects such as synthetic rubber, resin, medicine, coating, fuel, softening agent, organic syntheses.
The main raw material that DCPD produces is the C 5 fraction of petroleum cracking, and in the process of petroleum cracking system ethene, the by-product C 5 fraction accounts for 12～14%, and China's ethene working ability in 2005 reaches 7,500,000 tons, can produce more than 100 ten thousand tons of C5 series product.Contain diolefins such as cyclopentadiene, isoprene, m-pentadiene in the C 5 fraction, these diolefin character are active, are important chemical material very.Both at home and abroad to these three kinds of diolefin development and use early, but the DCPD purity of producing can only be used as dicyclo resin or additive usually 70～80%, and comprehensive utilization value is single.
The production technique of existing higher degree DCPD is many to be made up of repeatedly dimerization and depolymerization reaction process and a plurality of rectifying, exists flow process complexity, a plurality of reactors of needs, facility investment greatly, catalyst performance requirement height, quality product be cannot say for sure the problem demonstrate,proved.
(3) summary of the invention
The present invention provides the preparation method of the high purity dicyclo pentylene that a kind of flow process is simple, reaction process is few in order to remedy the deficiencies in the prior art.
The present invention is achieved through the following technical solutions:
A kind of preparation method of high purity dicyclo pentylene is a raw material with the by-product C5 fraction of petroleum cracking system ethene, it is characterized in that: comprise the steps:
(1) raw material is placed the azeotropic jar, it is gasified under low-pressure steam, wherein, working pressure is 30～40KPa, and service temperature is 100～120 ℃, and liquid level is 30～70% of a tank body height.
(2) by the vapour that comes out in azeotropic jar cracking in cracking reactor, product enters phase separation tank together with water vapor, isolates cyclopentadiene, wherein, feeding temperature is 230～260 ℃ in the cracking reactor, and temperature out is 330～350 ℃, and working pressure is 30～40KPa.
(3) isolated cyclopentadiene enters polymerization in the dipolymer reactor again, the dicyclopentadiene that obtains obtains high purity product through the rectifying tower rectification under vacuum, wherein, the dipolymer reactor inlet temperature is 15～30 ℃ again, temperature out is 20～60 ℃, working pressure is 400～600KPa, and the reaction times is 1～8 hour; The rectifying tower tower top temperature is 5～10 ℃, and tower still temperature is 120～140 ℃, working pressure is-100～-50KPa.
In the step (1), raw material and low-pressure steam counter current contact help improving the utilization ratio of steam energy, shorten heat-up time, strengthen the azeotropic effect.
In the step (2), water vapor uses as thinner, enters phase separation tank together with split product.
Preferred process of the present invention is:
In the step (1), the service temperature of azeotropic jar is 105～115 ℃, and liquid level is 40～60% of a tank body height; In the step (2), the temperature out of cracking reactor is 337～342 ℃; In the step (3), the inlet temperature of dipolymer reactor is 18～23 ℃ again, and temperature out is 35～60 ℃, working pressure is 480～530KPa, and the reaction times is 2～5 hours, and the tower top temperature of rectifying tower is 6～8 ℃, tower still temperature is 127～132 ℃, working pressure is-80～-60KPa.
Raw material among the present invention and product index are:
(1) raw material is formed (volume content)
Light carbon five: 2.48%, benzene: 0.93%, dipolymer: 0.49%, trimer: 10.01%, cyclopentadiene: 80.24%, tetramer: 2.82%, pentamer: 3.03%.
(2) product is formed (volume content)
Dicyclopentadiene＞95%, moisture＜0.03%.
The present invention takes the method for cracking-dimerization-rectifying, prepares high purity dicyclo pentylene by C5 fraction, and it is low to have a production cost, and purification precision height is easy to industrialized characteristics.
(4) description of drawings
The present invention is further illustrated below in conjunction with accompanying drawing.
Fig. 1 is a technological process apparatus synoptic diagram of the present invention;
Fig. 2 is a process flow diagram of the present invention.
(5) embodiment
Embodiment 1:
The C5 fraction raw material enters azeotropic jar and low-pressure steam and is counter current contact and makes its gasification, working pressure is 30KPa, service temperature is 105 ℃, liquid level is 40% of a tank body height, the vapour that comes out from the azeotropic jar enters cracking reactor and carries out cracking, feeding temperature is 240 ℃, 337 ℃ of temperature outs, working pressure is 30KPa, and split product carries out the separating ring pentadiene with sending into phase separation tank together as the water vapour of thinner, and cyclopentadiene enters and carries out polymerization in the dipolymer reactor, product is thick dicyclopentadiene, the dipolymer reactor feeding temperature is 18 ℃ again, 35 ℃ of temperature outs, working pressure 480KPa, polymerization time 2 hours, the dicyclopentadiene of coming out from poly-two reactors is again sent to rectifying tower and is carried out rectification under vacuum, and wherein tower top temperature is 6 ℃, 127 ℃ of tower still temperature, working pressure-80KPa, product obtains high purity dicyclo pentylene after decolouring, product is formed: dicyclopentadiene＞95%, moisture＜0.03%.
Embodiment 2:
The C5 fraction raw material enters azeotropic jar and low-pressure steam and is counter current contact and makes its gasification, working pressure is 35KPa, service temperature is 110 ℃, liquid level is 50% of a tank body height, the vapour that comes out from the azeotropic jar enters cracking reactor and carries out cracking, feeding temperature is 250 ℃, 340 ℃ of temperature outs, working pressure is 35KPa, and split product carries out the separating ring pentadiene with sending into phase separation tank together as the water vapour of thinner, and cyclopentadiene enters and carries out polymerization in the dipolymer reactor, product is thick dicyclopentadiene, the dipolymer reactor feeding temperature is 20 ℃ again, 45 ℃ of temperature outs, working pressure 500KPa, polymerization time 3.5 hours, the dicyclopentadiene of coming out from poly-two reactors is again sent to rectifying tower and is carried out rectification under vacuum, and wherein tower top temperature is 7 ℃, 130 ℃ of tower still temperature, working pressure-70KPa, product obtains high purity dicyclo pentylene after decolouring, product is formed: dicyclopentadiene＞95%, moisture＜0.03%.
Embodiment 3:
The C5 fraction raw material enters azeotropic jar and low-pressure steam and is counter current contact and makes its gasification, working pressure is 40KPa, service temperature is 115 ℃, liquid level is 60% of a tank body height, the vapour that comes out from the azeotropic jar enters cracking reactor and carries out cracking, feeding temperature is 260 ℃, 342 ℃ of temperature outs, working pressure is 40KPa, and split product carries out the separating ring pentadiene with sending into phase separation tank together as the water vapour of thinner, and cyclopentadiene enters and carries out polymerization in the dipolymer reactor, product is thick dicyclopentadiene, the dipolymer reactor feeding temperature is 23 ℃ again, 60 ℃ of temperature outs, working pressure 530KPa, polymerization time 5 hours, the dicyclopentadiene of coming out from poly-two reactors is again sent to rectifying tower and is carried out rectification under vacuum, and wherein tower top temperature is 8 ℃, 132 ℃ of tower still temperature, working pressure-60KPa, product obtains high purity dicyclo pentylene after decolouring, product is formed: dicyclopentadiene＞95%, moisture＜0.03%.
Claims (6)
1. the preparation method of a high purity dicyclo pentylene is a raw material with the by-product C5 fraction of petroleum cracking system ethene, it is characterized in that: comprise the steps:
(1) raw material is placed the azeotropic jar, it is gasified under low-pressure steam, wherein, working pressure is 30～40KPa, and service temperature is 100～120 ℃, and liquid level is 30～70% of a tank body height.
(2) by the vapour that comes out in azeotropic jar cracking in cracking reactor, product enters phase separation tank together with water vapor, isolates cyclopentadiene, wherein, feeding temperature is 230～260 ℃ in the cracking reactor, and temperature out is 330～350 ℃, and working pressure is 30～40KPa.
(3) isolated cyclopentadiene enters polymerization in the dipolymer reactor again, the dicyclopentadiene that obtains obtains high purity product through the rectifying tower rectification under vacuum, wherein, the dipolymer reactor inlet temperature is 15～30 ℃ again, temperature out is 20～60 ℃, working pressure is 400～600KPa, and the reaction times is 1～8 hour; The rectifying tower tower top temperature is 5～10 ℃, and tower still temperature is 120～140 ℃, working pressure is-100～-50KPa.
2. the preparation method of high purity dicyclo pentylene according to claim 1, it is characterized in that: in the step (1), the service temperature of described azeotropic jar is 105～115 ℃, and liquid level is 40～60% of a tank body height.
3. the preparation method of high purity dicyclo pentylene according to claim 1 and 2 is characterized in that: in the step (1), and described raw material and low-pressure steam counter current contact.
4. the preparation method of high purity dicyclo pentylene according to claim 1 and 2, it is characterized in that: in the step (2), the temperature out of described cracking reactor is 337～342 ℃.
5. the preparation method of high purity dicyclo pentylene according to claim 1 and 2, it is characterized in that: in the step (3), the inlet temperature of described dipolymer reactor again is 18～23 ℃, and temperature out is 35～60 ℃, working pressure is 480～530KPa, and the reaction times is 2～5 hours.
6. the preparation method of high purity dicyclo pentylene according to claim 1 and 2, it is characterized in that: in the step (3), the tower top temperature of described rectifying tower is 6～8 ℃, and tower still temperature is 127～132 ℃, working pressure is-80～-60KPa.
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| CN 200910019247 CN101671224B (en) | 2009-10-14 | 2009-10-14 | Preparation method of high purity dicyclopentadiene |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105820025A (en) * | 2016-04-19 | 2016-08-03 | 大连理工大学 | Method for preparing high-purity cyclopentadiene |
| US11465951B2 (en) | 2018-12-12 | 2022-10-11 | Sabic Global Technologies B.V. | Dimerization of cyclopentadiene using shell and tube heat exchanger |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9896395B2 (en) | 2015-11-04 | 2018-02-20 | Exxonmobil Chemical Patents Inc. | Process and system for making cyclopentadiene and/or dicyclopentadiene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3676509A (en) * | 1971-01-20 | 1972-07-11 | Dow Chemical Co | Recovery of dicyclopentadiene from cracked petroleum |
| CN100393676C (en) * | 2005-12-26 | 2008-06-11 | 山东玉皇化工有限公司 | Method for producing high-purity cyclopentadiene and cyclopentane by coarse piperyene |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105820025A (en) * | 2016-04-19 | 2016-08-03 | 大连理工大学 | Method for preparing high-purity cyclopentadiene |
| US11465951B2 (en) | 2018-12-12 | 2022-10-11 | Sabic Global Technologies B.V. | Dimerization of cyclopentadiene using shell and tube heat exchanger |
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