US3719718A - Process for the production of cyclopentadiene from dicyclopentadiene - Google Patents

Process for the production of cyclopentadiene from dicyclopentadiene Download PDF

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Publication number
US3719718A
US3719718A US00135694A US3719718DA US3719718A US 3719718 A US3719718 A US 3719718A US 00135694 A US00135694 A US 00135694A US 3719718D A US3719718D A US 3719718DA US 3719718 A US3719718 A US 3719718A
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United States
Prior art keywords
cyclopentadiene
dicyclopentadiene
reactor
isoprene
percent
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Expired - Lifetime
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US00135694A
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English (en)
Inventor
F Grude
K Halcour
P Woernle
W Schwerdtel
W Swodenk
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Bayer AG
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Bayer AG
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Priority claimed from DE19702019596 external-priority patent/DE2019596C3/de
Application filed by Bayer AG filed Critical Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/22—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by depolymerisation to the original monomer, e.g. dicyclopentadiene to cyclopentadiene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated

Definitions

  • ABSTRACT The process for the production of cyclopentadiene by the substantially quantitative splitting or monomerizing of a dicyclopentadiene concentrate containing thermally stable dimers of isoprene and codimers of cyclopentadiene, isoprene and piperylene and having been obtained by the heat treatment of a C fraction of a pyrolysis petrol and its subsequent enrichment by fractional distillation, comprising heating the dicyclopentadiene concentrate in liquid phase in a reactor at a temperature of about 170 to 250 C., and maintaining a concentration of about 10 to 70 percent by weight for the thermally stable dimers of isoprene and codimers of cyclopentadiene, isoprene and piperylene in the reactor.
  • a C +fraction is obtained in addition to a C fraction and a C fraction so-called pyrolysis petrol.
  • the C +fraction of the pyrolysis petrol contains inter alia isoprene, cyclopentadiene and piperylene.
  • the cyclopentadiene is usually dimerized into dicyclopentadiene before the C fraction is subjected to further working up.
  • the two fractions can then be separately worked up; for example, the C fraction containing isoprene and piperylene can be worked up into isoprene and the dicyclopentadiene fraction can be worked up into monomeric cyclopentadiene.
  • gas-phase splitting includes the remarkably high consumption of energy attributable to the high temperature required for splitting, and the risk of reactor coking which the high reaction temperatures involve.
  • inert diluents for example inert gases or steam, but these only further increase the energy costs and complicate the working up of the reaction products (cf. US. Pat. Nos. 2,453,044; 2,801,270 and 2,508,922 and Hungarian Pat. Specification No. 151,720).
  • a process for the production of cyclopentadiene by the substantially quantitative splitting or monomerizing of a dicyclopentadiene concentrate containing thermally stable dimers of isoprene and codimers of cyclopentadiene, isoprene and piperylene and having been obtained by the heat treatment of a C fraction of a pyrolysis petrol and its subsequent enrichment by fractional distillation, comprising heating the dicyclopentadiene concentrate in liquid phase in a reactor at a temperature of about 170 to 250 C., and maintaining a concentration of about 10 to percent by weight for the thermally stable dimers of isoprene and codimers of cyclopentadiene, isoprene and piperylene in the reactor.
  • the pressure may be about normal or slightly elevated, e.g., up to about 1.5 at (7 psig) or more.
  • a concentration of up to 50 percent is maintained for the polymer fraction in the sump of the splitting apparatus.
  • a portion ot the bottom product in the reactor is continuously withdrawn and subjected to distillation, preferably using a thin-film evaporator, the thermally stable dimers and codimers coming off as distillate being recycled at least in part to the reactor.
  • the dicyclopentadiene can be dissociated in an amount of more than percent.
  • a residence time of less than about 5 hours is best maintained for the splitting reaction coupled with the highest possible heat transferred per unit surface.
  • Monomerizing can be effected either at normal pressure or under a slight excess pressure in a distillation apparatus comprising an evaporator, preferably a thermosiphon evaporator, a separator, a fractionating column with a few plates, preferably two to 10 plates, and a dephlegmator or condenser with a reflux pump.
  • a distillation apparatus comprising an evaporator, preferably a thermosiphon evaporator, a separator, a fractionating column with a few plates, preferably two to 10 plates, and a dephlegmator or condenser with a reflux pump.
  • the product to be split or monomerized containing more than about 70 percent by weight of dicyclopentadiene, which originates from the fractional distillation of dicylopentatiene-containing C cuts of a pyrolysis petrol, and the recycled codimers described below are continuously pumped into the sump or into the fractionating column.
  • the starting material contains the other C hydrocarbons known as codimers and dimers, and optionally remaining amounts of C hydrocarbons.
  • the sump product of the monomerization apparatus comprises dicyclopentadiene, thermally stable codimers of cyclopentadiene with isoprene and of cyclopentadiene with piperylene, dimers of isoprene and the cyclopentadiene polymers accumulating during splitting.
  • the sump product is heated to boiling point (170 to 200 C.), advantageously in thermosiphon or forced-circulation evaporators.
  • the residence time should be as short as possible, preferably less than 5 hours, and the heat transferred per unit surface should be as high as possible.
  • the sump level of the monomerization apparatus is kept constant by running off sump product either continuously or at intervals.
  • the throughput of dicyclopentadiene to be monomerized is so high that most of the dicyclopentadiene is immediately converted to cyclopentadiene.
  • the sump boiling under reflux promotes development in the fractionating column of a temperature and concentration profile which can be influenced by the dicyclopentadiene input, by recycling of the codimers, by the heat transferred per unit surface and also by the reflux ratio.
  • the conditions have to be selected in accordance with the puritiy in which the cyclopentadiene is required.
  • the cyclopentadiene obtained preferably contains less than 2 percent by weight of dicyclopentadiene and codimers, In cases where a dephlegmator is used, the cyclopentadiene obtained can be used directly, i.e., without condensation, for subsequent processes, for example, hydrogenation. If it is desired to obtain the cyclopentadiene in liquid form, it has to be cooled after condensation to temperatures below 20 C. (because it is quickly dimerized again at temperatures higher than this), after which it can be further treated.
  • the overall conversion amounts to between percent and percent, based on the dicyclopentadiene used, and resin formation amounts to between 5 percent and 10 percent by weight.
  • the cyclopentadiene only contains the volatile C compounds which were already present in the starting material.
  • dicyclopentadiene 82.0% by weight codimers and dimers 13.0% by weight C hydrocarbons 5.0% by weight 100.0% by weight
  • the sump was heated to boiling point (170to 180C) under atmospheric pressure by natural circulation in a steam-heated thermosiphon evaporator.
  • the boiling constituents and the cyclopentadiene formed through monomerizing of the dicyclopentadiene were rectified in a 3.50 meters long, 50 mm wide fractionating column packed with mm fillings arranged on the evaporator.
  • a temperature profile of between 180 C. and 50 C. was developed in the fractionating column.
  • the concentration of the dicyclopentadiene fell from percent by weight at the lower end to around 2 percent by weight at the upper end of the fractionating column.
  • a dephlegmator run on water heated to around 50 C. was arranged on the fractionating column. 1,205 g/hour of distillate containing 92.9 percent of cyclopentadiene were obtained downstream of the dephlegmator.
  • the yield came to 91 percent, based on the dicylopentadiene used.
  • the distillate was added to the starting dicyclopentadiene and thus re-entered the sump of the cracking apparatus. An equilibrium was formed after a short time.
  • 1,500 g per hour of 82 percent dicyclopentadiene used (A) 1,205 g/hour were run off downstream of the dephlegmator; this product contained 1,120 g of cyclopentadiene (92.9 percent by weight), 75 g of C hydrocarbons (6.2 percent by weight) and 10 g of C hydrocarbons (0.8 percent by weight) (B).
  • the cyclopentadiene yield amounted to 91 percent. It amounted to between 90 percent and 95 percent during a long-term test.
  • the proportion of polymers in the reactor amounted to 22 percent. Under these conditions, it was possible to continue the dissociation of dicylcopentadiene for a period of 1,500 hours with a cyclopentadiene yield of to percent, based on the dicyclopentadiene used. The sump product of the dissociation apparatus did not become so viscous as a result of resinification as to prevent recirculation.
  • heating is effected at a rate to convert more than 90 percent of the dicyclopentadiene in the concentrate to cyclopentadiene.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US00135694A 1970-04-23 1971-04-20 Process for the production of cyclopentadiene from dicyclopentadiene Expired - Lifetime US3719718A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19702019596 DE2019596C3 (de) 1970-04-23 Verfahren zur Herstellung von Cyclopentadien durch thermische Spaltung eines Dicylopentadien-Konzentrats aus einer thermisch nachbehandelten Pyrolyse benzlnfraktion

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US3719718A true US3719718A (en) 1973-03-06

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US00135694A Expired - Lifetime US3719718A (en) 1970-04-23 1971-04-20 Process for the production of cyclopentadiene from dicyclopentadiene

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US (1) US3719718A (de)
JP (1) JPS5235661B1 (de)
AT (1) AT310141B (de)
BE (1) BE766190A (de)
CA (1) CA964676A (de)
ES (1) ES390457A1 (de)
FR (1) FR2090676A5 (de)
GB (1) GB1342953A (de)
NL (1) NL148583B (de)
NO (1) NO133493B (de)
SE (1) SE373569B (de)
ZA (1) ZA712385B (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5659107A (en) * 1996-05-07 1997-08-19 Phillips Petroleum Company Separation of cyclopentadiene from dicyclopentadiene
WO2017103736A1 (en) 2015-12-14 2017-06-22 Sabic Global Technologies B.V. Methods and systems for recovering dicyclopentadiene from pygas
US9988324B2 (en) 2015-11-04 2018-06-05 Exxonmobil Chemical Patents Inc. Process and system for making cyclopentadiene and/or dicyclopentadiene
CN113527027A (zh) * 2020-04-15 2021-10-22 中国石油化工股份有限公司 双环戊二烯解聚制备环戊二烯的方法和设备及其应用
US20230357653A1 (en) * 2019-11-18 2023-11-09 Sabic Global Technologies B.V. Methods for integrated separation of dienes

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109665934B (zh) * 2017-10-16 2021-10-19 中国石油化工股份有限公司 一种制备双环戊二烯的方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB769813A (en) * 1954-08-28 1957-03-13 Huels Chemische Werke Ag Improvements in the production of cyclopentadiene by deploymerisation of dicyclopentadiene
US3016410A (en) * 1959-12-28 1962-01-09 Dow Chemical Co Preparation of cyclopentadiene from dicyclopentadiene

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5659107A (en) * 1996-05-07 1997-08-19 Phillips Petroleum Company Separation of cyclopentadiene from dicyclopentadiene
US9988324B2 (en) 2015-11-04 2018-06-05 Exxonmobil Chemical Patents Inc. Process and system for making cyclopentadiene and/or dicyclopentadiene
WO2017103736A1 (en) 2015-12-14 2017-06-22 Sabic Global Technologies B.V. Methods and systems for recovering dicyclopentadiene from pygas
US10611703B2 (en) 2015-12-14 2020-04-07 Sabic Global Technologies B.V. Methods and systems for recovering dicyclopentadiene from pygas
US20230357653A1 (en) * 2019-11-18 2023-11-09 Sabic Global Technologies B.V. Methods for integrated separation of dienes
US12134741B2 (en) * 2019-11-18 2024-11-05 Sabic Global Technologies B.V. Methods for integrated separation of dienes
CN113527027A (zh) * 2020-04-15 2021-10-22 中国石油化工股份有限公司 双环戊二烯解聚制备环戊二烯的方法和设备及其应用

Also Published As

Publication number Publication date
AT310141B (de) 1973-09-25
FR2090676A5 (de) 1972-01-14
CA964676A (en) 1975-03-18
DE2019596B2 (de) 1975-08-28
ES390457A1 (es) 1973-06-01
GB1342953A (en) 1974-01-10
NO133493B (de) 1976-02-02
DE2019596A1 (de) 1971-11-04
NL148583B (nl) 1976-02-16
NL7105302A (de) 1971-10-26
BE766190A (fr) 1971-10-25
ZA712385B (en) 1971-12-29
SE373569B (sv) 1975-02-10
JPS5235661B1 (de) 1977-09-10

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