US3674883A - Recovering cyclopentadiene values from c{11 {11 fractions - Google Patents

Recovering cyclopentadiene values from c{11 {11 fractions Download PDF

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Publication number
US3674883A
US3674883A US62937A US3674883DA US3674883A US 3674883 A US3674883 A US 3674883A US 62937 A US62937 A US 62937A US 3674883D A US3674883D A US 3674883DA US 3674883 A US3674883 A US 3674883A
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cyclopentadiene
solvent
dicyclopentadiene
process according
percent
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US62937A
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English (en)
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Bernhard Schleppinghoff
Helmut Scherb
Hans Puxbaumer
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Erdoelchemie GmbH
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Erdoelchemie GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/005—Processes comprising at least two steps in series
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/10—Purification; Separation; Use of additives by extraction, i.e. purification or separation of liquid hydrocarbons with the aid of liquids
    • 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 A process for recovering the cyclopentadiene values from a [21] Appl 62937 cyclopentadiene-containing C fraction consisting of a mixture of paraffinic, olefinic and diolefinic hydrocarbons, which [30] Foreign Application Priority Data comprises subjecting the fraction to treatment to dimerize the cyclopentadiene to dicyclopentadiene; subjecting the fraction 1969 Germany 19 41 7040 to a liquid-liquid extraction with a selective solvent whereby [52] Us Cl 260/666 A 208/255 260/6815 there is formed a solvent phase containing the dioleflnic 51 ln t. Cl.
  • a petroleum fraction known as cracked gasoline, containing relatively large quantities of diolefins, and particularly isoprene and cyclopentadiene, is formed during the high-temperature cracking of mineral oils and their fractions.
  • a C, fraction i.e. a hydrocarbon fraction essentially containing hydrocarbons with five carbon atoms, is obtained from this cracked gasoline during further processing by distillation.
  • These C hydrocarbons consist essentially of a mixture of parafiinic, olefinic and diolefinic hydrocarbons.
  • the cyclopentadiene which is also present in a cracked petroleum fraction of this kind causes considerable difficulties during the separation process due to its pronounced tendency towards dimerization and trimerization when the cracked petroleum fraction is subsequently processed, preferentially with a view to recovering isoprene which is generally achieved through a combination of distillation, extraction and extractive distillation. Furthermore, the purity requirements which a polymerizable grade isoprene has to satisfy permit a cyclopentadiene content of only a few ppm.
  • the process according to the invention can be carried out in any conventional extraction plant.
  • the liquidliquid extraction can be carried out in pulsating sieve-plate columns, in centrifugal extractors or in a mixer-settler arrangement.
  • Suitable selective solvents include those of the kind which separate the diolefins on the one hand from the parafiins and olefins on the other hand with sufficient selectivity in a liquidliquid extraction, for example N-methyl pyrrolidone, loxo-lmethyl phospholine, phospholine, N-methyl oxazolidone, acetonitrile, dimethyl sulfoxide, furfurol, dimethyl acetamide, sulfolane, dimethyl formamide, or mixtures thereof, in which case the dicyclopentadiene passes into the paraffin-olefin phase rather than into the diolefin phase.
  • the quantity in which the selective solvent is employed should at least be sufficient to dissolve all the constituents to be extracted.
  • Suitable ratios by volume of the solvent to the starting material are in the range of from about 3:1 to 12:1.
  • the solvent may have a water content of from about 3 to 20 percent and preferably from about 5 to percent by volume to improve the phase separation and to increase selectivity.
  • the extraction temperature can vary within a wide range, provided that, under the temperature and pressure conditions applied, it is lower than that temperature at which bubbles are formed in the mixture and provided that it is above the solidification temperature of the selective solvent. In most cases, a temperature of from about 10 to 40 C. is used. A slight positive pressure is usually maintained in the extraction column, in which case the optimum working temperature is substantially about 35 C.
  • the dimerization is effected as described by V. N. Timkin et a]. in Petroleum Chemistry (Russ) No. 3 (1964) pages 435-440, i.e. heating in a closed vessel under autogenous pressure for about 1 to 4 hours at about to 130 C.
  • the selective solvent flows countercurrent to the starting material in the extraction column and dissolves the diolefins out of it, while dicyclopentadiene together with the paraffins and monoolefins is run off from the head of the extraction column as the raffinate 6.
  • the solvent 7 containing the diolefins is run off at the lower end of the extractor and, by boiling in a separation column 8, is freed from the dissolved hydrocarbons which leave at 9 and are recycled to the extractor 4.
  • the residue from still 8 leaves through line 14 and is boiled in column 15, driving off residual C diolefins and some water at 16 with the now purified selective solvent being recycled through line 5 to extractor 4.
  • the raffinate 6 from extractor 4 still containing a little solvent which is run off from the head of the extractor, is delivered to a raffinate washer 10 which consists optionally of a mixer-settler complex or a trickle column filled with a packing.
  • the washing liquid 11, in the present case water, is delivered to the head of the washing column, the solvent-containing wash water 12 is run off from the lower end of the column and delivered to the diolefin-containing solvent stream 7.
  • the solvent-free raffinate 13 run off from the head of the washer 10 is distilled without depolymerization of the dicyclopentadiene by initially distilling ofi most of the C hydrocarbons in a column 17 at normal pressure and at sump or pot temperatures below 100 C., the C hydrocarbons leaving at 18.
  • the residue from still 17 passes through pipe 19 to still 20 operating at the same sump temperature but at an absolute pressure of about 30 mm Hg additional C hydrocarbons being boiled off at 21, the residue comprising more concentrated dicyclopentadiene.
  • This residue leaves through pipe 22 and in still 23 operating at about 30 mm Hg and 100 C. is boiled off at 24 in the form of dicyclopentadiene of very high purity.
  • the residue, leaving at 25, comprises polymeric impurities.
  • 100 kg/hour of the dicyclopentadiene-containing material are continuously delivered via 3 into the sixth chamber from the bottom of an extraction apparatus 4 consisting of an arrangement of 18 superimposed mixing and settling chambers.
  • 530 kg per hour of N-methyl pyrrolidone containing 8 percent of water are delivered into the uppermost chamber via line 5.
  • the extract is run E from the bottom of the extraction apparatus at 7 in a quantity of 646 kg/hour (C hydrocarbon content 18 percent by weight).
  • This extract is heated in a following column 8, the so-called extract recycle column, until the dissolved parrafins and olefins and also some of the dienes have been distilled off as the head product and, upon condensation, are delivered into the lowermost chamber of the extractor via line 9.
  • the extract with a residual C hydrocarbon content of approximately 5.4 percent is run off at 14 from the sump of the extract recycle column.
  • column 15 the solvent is completely freed of hydrocarbons by heating and, after intermediate cooling, is recirculated via 5 to the top of the extractor 4.
  • a substantially cyclopentadiene-free C diolefin fraction is removed from the head of the column 15 in a quantity of 30 kg per hour along with 3 kg per hour of water.
  • 73 kg per hour of the raffinate containing 11.0 percent by weight of dicyclopentadiene accumulate at the head of the extractor 4.
  • more dicyclopentadiene has been formed from the residual monomers during extraction, also passing into the raffinate.
  • the rafiinate contains 4 percent by weight of N-methyl pyrrolidone in solution. It is passed via line 6 through a wash column 10 filled with Raschig rings to which 3 kg per hour of fresh water are continuously delivered at 11. Wash water is continuously run off from the lower end of the washing column 10 via line 12 in a quantity of approximately 6 kg per hour.
  • the raffinate is removed from the head of the washing tower at 13 with an N- methyl pyrrolidone content of 200 ppm.
  • the raffinate is distilled at atmospheric pressure in a first distillation stage 17 and the dicyclopentadiene concentrated to 85 percent in the sump at a temperature of 90 C.
  • a process for recovering the cyclopentadiene values from a cyclopentadiene-containing C fraction consisting of a mixture of parafiinic, olefinic and diolefinic hydrocarbons which comprises subjecting the fraction to treatment to dimerize the cyclopentadiene to dicyclopentadiene, subjecting the fraction to a liquid-liquid extraction with a selective solvent whereby there is formed a solvent phase containing the diolefinic hydrocarbons and a parafiin-olefm phase containing the dicyclopentadiene, and recovering the dicyclopentadiene from said paraffin-olefin phase by distillation.
  • said solvent comprises N-methyl pyrrolidone, l-oxo- 1 -methyl phospholine, phospholine, N-methyl oxazolidone, acetonitrile, dimethyl sulfoxide, furfurol, dimethyl acetamide, sulfolane, dimethyl formamide, or mixtures thereof.
  • dimerization of the cyclopentadiene is effected by heating, wherein the solvent comprises N-methyl pyrrolidone and contains about 3 to 20 percent of water by weight, and wherein the parafiin-olefin phase is washed with water prior to its distillation to remove therefrom dissolved N-methyl pyrrolidone solvent.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US62937A 1969-08-16 1970-08-11 Recovering cyclopentadiene values from c{11 {11 fractions Expired - Lifetime US3674883A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19691941704 DE1941704A1 (de) 1969-08-16 1969-08-16 Verfahren zur Entfernung von Cyclopentadien aus C5-Fraktionen

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US (1) US3674883A (fr)
BE (1) BE754878A (fr)
DE (1) DE1941704A1 (fr)
FR (1) FR2058087A5 (fr)
GB (1) GB1331985A (fr)
NL (1) NL7011852A (fr)

Cited By (4)

* 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
US9896395B2 (en) 2015-11-04 2018-02-20 Exxonmobil Chemical Patents Inc. Process and system for making cyclopentadiene and/or dicyclopentadiene
CN108349833A (zh) * 2015-11-04 2018-07-31 埃克森美孚化学专利公司 环戊二烯和/或双环戊二烯的制备方法和系统
US20190225560A1 (en) * 2015-12-14 2019-07-25 Sabic Global Technologies B.V. Methods and systems for recovering dicyclopentadiene from pygas

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2266887C1 (ru) * 2004-06-29 2005-12-27 Открытое акционерное общество "Нижнекамскнефтехим" Способ очистки c5-углеводородов

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3344198A (en) * 1964-03-06 1967-09-26 Basf Ag Separating and recovering cyclopentadiene

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3344198A (en) * 1964-03-06 1967-09-26 Basf Ag Separating and recovering cyclopentadiene

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
US9896395B2 (en) 2015-11-04 2018-02-20 Exxonmobil Chemical Patents Inc. Process and system for making cyclopentadiene and/or dicyclopentadiene
US9896396B2 (en) 2015-11-04 2018-02-20 Exxonmobil Chemical Patents Inc. Process and system for making cyclopentadiene and/or dicyclopentadiene
CN108349833A (zh) * 2015-11-04 2018-07-31 埃克森美孚化学专利公司 环戊二烯和/或双环戊二烯的制备方法和系统
EP3371132A4 (fr) * 2015-11-04 2018-10-17 ExxonMobil Chemical Patents Inc. Procédé et système de fabrication de cyclopentadiène et/ou de dicyclopentadiène
US20190225560A1 (en) * 2015-12-14 2019-07-25 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

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Publication number Publication date
FR2058087A5 (fr) 1971-05-21
NL7011852A (fr) 1971-02-18
BE754878A (fr) 1971-02-15
GB1331985A (en) 1973-09-26
DE1941704A1 (de) 1971-02-25

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