CA2517261A1 - Improved distillation sequence for the purification and recovery of hydrocarbons - Google Patents

Improved distillation sequence for the purification and recovery of hydrocarbons Download PDF

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Publication number
CA2517261A1
CA2517261A1 CA002517261A CA2517261A CA2517261A1 CA 2517261 A1 CA2517261 A1 CA 2517261A1 CA 002517261 A CA002517261 A CA 002517261A CA 2517261 A CA2517261 A CA 2517261A CA 2517261 A1 CA2517261 A1 CA 2517261A1
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CA
Canada
Prior art keywords
separation column
ethylene
column
stream
mixture
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.)
Granted
Application number
CA002517261A
Other languages
French (fr)
Other versions
CA2517261C (en
Inventor
Rian Reyneke
Michael J. Foral
Christos G. Papadopoulos
Jeffery S. Logsdon
Wayne W. Y. Eng
Guang-Chung Lee
Iain Sinclair
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ineos USA LLC
Original Assignee
Bp Corporation North America Inc.
Rian Reyneke
Michael J. Foral
Christos G. Papadopoulos
Jeffery S. Logsdon
Wayne W. Y. Eng
Guang-Chung Lee
Iain Sinclair
O&D Usa Llc
Innovene Usa Llc
Ineos Usa Llc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bp Corporation North America Inc., Rian Reyneke, Michael J. Foral, Christos G. Papadopoulos, Jeffery S. Logsdon, Wayne W. Y. Eng, Guang-Chung Lee, Iain Sinclair, O&D Usa Llc, Innovene Usa Llc, Ineos Usa Llc filed Critical Bp Corporation North America Inc.
Publication of CA2517261A1 publication Critical patent/CA2517261A1/en
Application granted granted Critical
Publication of CA2517261C publication Critical patent/CA2517261C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0238Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of CnHm with 2 carbon atoms or more
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D3/00Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14Fractional distillation or use of a fractionation or rectification column
    • B01D3/143Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
    • B01D3/146Multiple effect distillation
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G70/00Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
    • C10G70/04Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G70/00Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
    • C10G70/04Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes
    • C10G70/041Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes by distillation
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0204Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the feed stream
    • F25J3/0219Refinery gas, cracking gas, coke oven gas, gaseous mixtures containing aliphatic unsaturated CnHm or gaseous mixtures of undefined nature
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0242Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of CnHm with 3 carbon atoms or more
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0252Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of hydrogen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20C2-C4 olefins
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00Processes or apparatus using separation by rectification
    • F25J2200/38Processes or apparatus using separation by rectification using pre-separation or distributed distillation before a main column system, e.g. in a at least a double column system
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00Processes characterised by the type or other details of the feed stream
    • F25J2210/12Refinery or petrochemical off-gas
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2215/00Processes characterised by the type or other details of the product stream
    • F25J2215/62Ethane or ethylene
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2215/00Processes characterised by the type or other details of the product stream
    • F25J2215/64Propane or propylene

Abstract

This invention is an improved distillation sequence for the separation and purification of ethylene from a cracked gas. A hydrocarbon feed enters a C2 distributor column. The top of the C2 distributor column is thermally coupled to an ethylene distributor column, and the bottoms liquid of a C2 distributor column feeds a deethanizer column. The C2 distributor column utilizes a conventional reboiler. The top of the ethylene distributor is thermally coupled with a demethanizer column, and the bottoms liquid of the ethylene distributor feeds a C2 splitter column. The ethylene distributor column utilizes a conventional reboiler. The deethanizer and C2 splitter columns are also thermally coupled and operated at a substantially lower pressure than the C2 distributor column, the ethylene distributor column, and the demethanizer column. Alternatively, a hydrocarbon feed enters a deethanizer column. The top of the deethanizer is thermally coupled to an ethylene distributor column, and the ethylene distributor column utilizes a conventional reboiler. The top of the ethylene distributor column is thermally coupled with a demethanizer column, and the bottoms liquid of the ethylene distributor column feeds a C2 splitter column. The C2 splitter column operates at a pressure substantially lower than the ethylene distributor column, the demethanizer column, and the deethanizer column.

Claims (26)

1. A process for the separation and recovery of hydrocarbon components, comprising:
a. introducing a hydrocarbon feed comprising a mixture of hydrogen, methane, ethane, ethylene, propane, propylene and optionally heavier components into a first separation column to obtain a first top stream and a first bottom stream;
b. introducing said first top stream into a second separation column to obtain a second top stream and a second bottom stream;
c. refluxing said first separation column with a liquid draw from said second separation column;
d. reboiling said first separation column with a reboiler exchanger;
e. introducing said first bottom stream into a third separation column to obtain a third top stream and a third bottom stream;
f. introducing said second top stream into a fourth separation column to obtain a fourth top stream and a fourth bottom stream;
g. refluxing said second separation column with a liquid draw from said fourth separation column;
h. reboiling said second separation column with a reboiler exchanger;
i. chilling said fourth top stream to provide reflux for said fourth separation column;
j. introducing said second bottom stream and said third top stream into a fifth separation column to obtain a fifth top stream and a fifth bottom stream;
k. refluxing said third separation column with a liquid draw from said fifth separation column; and l. recovering said fourth bottom stream and said fifth top stream as a hydrocarbon component.
2. The process of Claim 1 wherein said third and fifth separation columns operate at a pressure substantially lower than the pressure levels of said first, second, and fourth separation columns.
3. The process of Claim 1 wherein said first separation column is a C2 distributor.
4. The process of Claim 1 wherein said first top stream comprises a mixture of hydrogen, methane, ethane, and ethylene, and further wherein said first bottom stream comprises a mixture of ethane, ethylene, propane, and propylene and optionally heavier components.
5. The process of Claim 1 wherein said second separation column is an ethylene distributor.
6. The process of Claim 1 wherein said second top stream comprises a mixture of ethylene, hydrogen, and methane, and further wherein said second bottom stream comprises a mixture of ethylene and ethane.
7. The process of Claim 1 wherein said third separation column is a deethanizer.
8. The process of Claim 1 wherein said third top stream comprises a mixture of ethylene and ethane, and further wherein said third bottom stream comprises a mixture of propylene and propane and optionally heavier components.
9. The process of Claim 1 wherein said fourth separation column is a demethanizer.
10. The process of Claim 1 wherein said fourth top stream comprises a mixture of hydrogen and methane, and further wherein said fourth bottom stream comprises a recoverable ethylene component.
11. The process of Claim 10 wherein a dephlegmator assists said demethanizer in ethylene recovery.
12. The process of Claim 1 wherein said fifth separation column is a C2 splitter.
13. The process of Claim 1 wherein said fifth top stream comprises a recoverable ethylene component, and further wherein said fifth bottom stream comprises ethane.
14. The process of Claim 9 wherein said demethanizer comprises one or more side condensers.
15. A process for the separation and recovery of hydrocarbon components comprising:
a. introducing a hydrocarbon feed comprising a mixture of hydrogen, methane, ethane, ethylene, propane, and propylene and optionally heavier components into a first separation column to produce a first top stream and a first bottom stream;
b. introducing said first top stream into a second separation column to produce a second top stream and a second bottom stream;
c. refluxing said first separation column with a liquid draw from said second separation column;
d. introducing said second top stream into a third separation column to produce a third top stream and a third bottom stream;
e. refluxing said second separation column with a liquid side draw from said third separation column;
f. reboiling said second separation column with a reboiler exchanger;
g. introducing said second bottom stream into a fourth separation column to produce a fourth top stream and a fourth bottom stream; and h. recovering said third bottom stream and said fourth top stream as a hydrocarbon component.
16. The process of Claim 15 wherein said fourth separation column operates at a pressure substantially lower than the pressure levels of said first, second, and third separation columns.
17. The process of Claim 15 wherein said first separation column is a deethanizer.
18. The process of Claim 15 wherein said first top stream comprises a mixture of ethylene, ethane, hydrogen, and methane, and further wherein said first bottom stream comprises a mixture of propylene and propane and optionally heavier components.
19. The process of Claim 15 wherein said second separation column is an ethylene distributor.
20. The process of Claim 15 wherein said second top fream comprises a mixture of ethylene, hydrogen, and methane, and further wherein said second bottom stream comprises a mixture of ethylene and ethane.
21. The process of Claim 15 wherein said third separation column is a demethanizer.
22. The process of Claim 15 wherein said third top stream comprises a mixture of hydrogen and methane, and further wherein said third bottom stream comprises a recoverable ethylene component.
23. The process of Claim 22 wherein a dephlegmator assists said demethanizer in ethylene recovery.
24. The process of Claim 15 wherein said fourth separation column is a C2 splitter.

]
25. The process of Claim 15 wherein said fourth top stream comprises a recoverable ethylene component, and further wherein said fourth bottom stream comprises ethane.
26. The process of Claim 21 wherein said demethanizer comprises one or more side condensers.
CA2517261A 2003-03-20 2004-03-12 Improved distillation sequence for the purification and recovery of hydrocarbons Expired - Lifetime CA2517261C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US10/393,460 US7311813B2 (en) 2003-03-20 2003-03-20 Distillation sequence for the purification and recovery of hydrocarbons
US10/393,460 2003-03-20
PCT/US2004/007799 WO2004085577A1 (en) 2003-03-20 2004-03-12 Improved distillation sequence for the purification and recovery of hydrocarbons

Publications (2)

Publication Number Publication Date
CA2517261A1 true CA2517261A1 (en) 2004-10-07
CA2517261C CA2517261C (en) 2012-10-02

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Family Applications (1)

Application Number Title Priority Date Filing Date
CA2517261A Expired - Lifetime CA2517261C (en) 2003-03-20 2004-03-12 Improved distillation sequence for the purification and recovery of hydrocarbons

Country Status (9)

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US (1) US7311813B2 (en)
EP (1) EP1603993A1 (en)
JP (1) JP2006520785A (en)
CN (1) CN1761735A (en)
CA (1) CA2517261C (en)
RU (1) RU2005129133A (en)
TW (1) TW200502030A (en)
WO (1) WO2004085577A1 (en)
ZA (1) ZA200506951B (en)

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US20050154245A1 (en) * 2003-12-18 2005-07-14 Rian Reyneke Hydrogen recovery in a distributed distillation system
US7299643B2 (en) * 2004-09-29 2007-11-27 Chevron U.S.A. Inc. Method for recovering LPG boil off gas using LNG as a heat transfer medium
JP2008525377A (en) * 2004-12-23 2008-07-17 ソルヴェイ(ソシエテ アノニム) Process for producing 1,2-dichloroethane
EP1910501A1 (en) * 2005-07-28 2008-04-16 Innovene Usa Llc Process for recovering ethylene from an autothermal cracking reactor effluent
CN100551885C (en) * 2005-09-29 2009-10-21 中国石油化工集团公司 From the product gas of preparation alkene, reclaim the method for low-carbon alkene
US8168071B2 (en) * 2005-11-09 2012-05-01 Suncor Energy Inc. Process and apparatus for treating a heavy hydrocarbon feedstock
DE102007010874A1 (en) * 2007-03-06 2008-09-11 Linde Ag separation
US8968522B2 (en) * 2009-07-15 2015-03-03 Butamax Advanced Biofuels Llc Recovery of butanol isomers from a mixture of butanol isomers, water, and an organic extractant
US8968523B2 (en) * 2009-07-15 2015-03-03 Butamax Advanced Biofuels Llc Recovery of butanol isomers from a mixture of butanol isomers, water, and an organic extractant
US8961744B2 (en) * 2013-02-25 2015-02-24 Korex Corporation System and method for recycling high-boiling-point waste photoresist stripper
CN105602614B (en) * 2014-11-23 2017-12-15 胜帮科技股份有限公司 Dust-laden crosses gasification oil gas condensation separation method
CN105413221A (en) * 2016-01-18 2016-03-23 中国恩菲工程技术有限公司 Rectifying system
KR102162297B1 (en) * 2017-06-08 2020-10-06 주식회사 엘지화학 Method and Apparatus of separating ethylene
KR102416636B1 (en) * 2018-09-04 2022-07-01 주식회사 엘지화학 Method for preparing ethylene
CN111886062B (en) 2018-11-01 2022-04-26 株式会社Lg化学 Method for separating organic solvent from mixed solution containing organic solvent
CN111686470B (en) * 2020-06-23 2021-01-15 江西省科学院生物资源研究所 Device and method for producing specific fingerprint polycosanol

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US5880320A (en) * 1997-08-05 1999-03-09 Netzer; David Combination process for manufacturing ethylene ethylbenzene and styrene

Also Published As

Publication number Publication date
CA2517261C (en) 2012-10-02
EP1603993A1 (en) 2005-12-14
US7311813B2 (en) 2007-12-25
US20040182752A1 (en) 2004-09-23
WO2004085577A8 (en) 2005-02-17
CN1761735A (en) 2006-04-19
ZA200506951B (en) 2006-06-28
TW200502030A (en) 2005-01-16
WO2004085577A1 (en) 2004-10-07
JP2006520785A (en) 2006-09-14
RU2005129133A (en) 2006-01-27

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