EP1252262B1 - Verfahren zum erzeugen von c2- und c3- olefinen aus kohlenwasserstoffen - Google Patents

Verfahren zum erzeugen von c2- und c3- olefinen aus kohlenwasserstoffen Download PDF

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Publication number
EP1252262B1
EP1252262B1 EP01903630A EP01903630A EP1252262B1 EP 1252262 B1 EP1252262 B1 EP 1252262B1 EP 01903630 A EP01903630 A EP 01903630A EP 01903630 A EP01903630 A EP 01903630A EP 1252262 B1 EP1252262 B1 EP 1252262B1
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EP
European Patent Office
Prior art keywords
olefins
fraction
diolefins
line
mixture
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Expired - Lifetime
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EP01903630A
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German (de)
English (en)
French (fr)
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EP1252262A1 (de
Inventor
Ulrich Koss
Peter König
Martin Rothaemel
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MG Technologies AG
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MG Technologies AG
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
    • C10G51/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only
    • C10G51/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only including only thermal and catalytic cracking steps
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins

Definitions

  • the invention relates to a process for the production of C 2 - and C 3 - olefins from feed hydrocarbons by mixing these steam and by thermal steam cracking (steam cracking) in the temperature range of 700 to 1000 ° C a C 2 - to C 20 olefins and Diolefins containing cracking mixture is generated.
  • EP-A-0921179 describes a process for the catalytic cracking of olefin-rich feed hydrocarbon material at a temperature of 500 to 600 ° C to produce a feed containing one or more olefins.
  • the feed hydrocarbon material includes inter alia a C 4 cut or C 5 cut from a steam cracking unit wherein at least 95% of the C 2 to C 3 feed compounds are present as C 2 to C 3 olefins.
  • the subject of DE-A-4208907 is a process for the production of olefins from feed hydrocarbons by thermal cracking and separation of the cracking products obtained in several steps.
  • the gaseous cracking products are compressed in at least two compression stages, cooled and at least divided into individual fractions of hydrocarbons with two (C 2 ), with the (C 3 ) and with four (C 4 ) C atoms and at least the C 2 - and subjecting the C 3 fraction to selective hydrogenation.
  • the feed hydrocarbons are split into two mass flows and the mass flows are cracked at different temperatures and pressures.
  • the invention is based on the object, the method described above further develop and thereby with an obtained as an intermediate hydrocarbon mixture to work, which also has higher-boiling components.
  • This object is achieved in that separated and discharged from the cracking mixture by distillation, a first C 2 - and C 3 - olefins-containing fraction, a second C 4 - and C 6 -olefins and diolefins, eg butadiene, pentadiene, hexadiene, fraction a third fraction consisting of heavier components is separated off and discharged, the diolefins being separated and discharged from at least part of the second fraction by butadiene extraction and / or at least part of the second fraction is converted into olefins by partial hydrogenation of the diolefins, For example, butene, pentene, hexene, the residue of the extraction and / or the product of the partial hydrogenation, which consist of at least 30 wt.% Of C 4 - to C 6 - olefins, with the addition of water vapor having an inlet temperature of 300 to 700 ° C in a bed of granular, form
  • the second fraction consisting of C 4 to C 6 olefins and diolefins may contain only C 4 olefins or else C 4 diolefins or else only C 5 and C 6 olefins and C 5 and C 6 diolefins .
  • the hydrocarbon mixture which is passed into steam cracking is, for example, naphtha or ethane.
  • the diolefins must be separated to a residual content of preferably at most 5 wt.%. This is necessary because the diolefins interfere with further processing because they can contribute to the rapid coking of the shape-selective catalyst.
  • the diolefins at least partially exempt mixture, completely or partially to produce tertiary butyl methyl ether (MTBE).
  • MTBE tertiary butyl methyl ether
  • To this Purpose can be at least a part of at least partially exempted from diolefins Products by an MTBE synthesis, in particular the isobutene content on converted a known catalyst with the addition of methanol to MTBE becomes. Details of the MTBE synthesis are, for example, from companies' processes Snamprogetti and Universal Oil Products
  • the gromigen shape-selective catalyst is preferably a zeolite catalyst pentasil type having an atomic ratio of Si: Al in the range of 10: 1 to 200: 1.
  • a zeolite catalyst is z.
  • a vaporous feed hydrocarbon which may also be a hydrocarbon mixture, eg naphtha, is introduced in line (1), mixed with water vapor from line (2) and passed through a steam cracker (steam cracker). (3) led.
  • the steam cracker is heated in a conventional manner by burning a fuel, wherein the mixture to be cracked is heated by indirect heat exchange briefly to temperatures in the range of 700 to 1000 ° C. Under these conditions, larger molecules are thermally split.
  • a crack mixture is withdrawn from line (4), which usually contains C 2 to C 20 olefins and also higher boiling components.
  • a distillation (5) which can also be formed in several stages, separating the desired fractions from the supplied mixture.
  • a first fraction containing C 2 and C 2 olefins is removed in line (7) and already constitutes a crude product.
  • a second fraction containing olefins of the range C 4 to C 6 is withdrawn in the Line (8) and the heavier components fall in the line (9).
  • the second possibility of the further treatment consists of giving up the second fraction of the line (8) wholly or partly through the opened valve (15) and the line (16) of a hydrogenation (17), which is also passed through the line (18). Supplying hydrogen gas.
  • diolefins are at least partially converted to olefins.
  • the product of hydrogenation (17) and the mixture of extraction (12) are combined in line (20) to form a mixture, referred to herein as an intermediate.
  • This intermediate product consists of at least 30% by weight and preferably at least 50% by weight of C 4 to C 6 olefins.
  • a variant of the method consists of passing the intermediate product of the line (20) wholly or partly through the opened valve (25) and the line (26) into an MTBE synthesis (27).
  • MTBE is withdrawn in line (28).
  • the remaining gas mixture passes through the line (29) also to the reactor (23).
  • the reactor (23) contains a bed of a granular, shape-selective zeolite catalyst. At temperatures in the bed of 300 to 700 ° C, the introduced in the lines (22) and (29) feedstock is largely converted to C 2 - and C 3 -olefins.
  • the product mixture coming from the reactor (23) is in withdrawn from the line (30) and in a cooler (31) Temperatures of about 30 to 80 ° C cooled, leaving water and Condensate gasoline.
  • the condensate-containing mixture passes through the conduit (32) to a separator (33). From the Separator is withdrawn through the line (34) from water, in the Line (35) gives an organic gas phase, and by the line (36) is withdrawn a product gas.
  • the product gas contains the desired products ethylene and propylene. To the Recyclables ethylene and propylene separate, you can gas the line (36) of a separating device, not shown respectively.
  • the organic gas phase (35) is partially condensed in the distillation column (38) and separated into a gaseous phase containing C 4 olefins withdrawn through line (39) and into a liquid phase withdrawn through line (40).
  • Example 2 It is worked as in Example 1, but one passes the Intermediate product of the line (20) with the valve closed (21) through the line (26) in a known MTBE synthesis (27). There isobutylene is reacted with methanol to MTBE and this product is withdrawn through line (28). The remaining mixture, which in the line (29) to the reactor (23) has the in Table I, column G, indicated Composition. The reaction in the reactor (23) takes place under the same conditions as in Example 1, this also applies to the subsequent separation of ethylene and propylene.
  • This second fraction is supplied with closed valve (10) through the line (16) of a partial hydrogenation (17) on a fixed bed arranged commercial Pd / Al 2 O 3 catalyst together with hydrogen from the line (18).
  • the mixture withdrawn from the hydrogenation has the composition given in Table II, column B, it is fed through the lines (20) and (21) to the reactor (23).
  • the product flow of line (36) has the composition shown in Table II, column C and column D is the composition of the gas mixture of line (39) indicated.
  • Example 3 It works first as in Example 3 with closed Valve (10), now holds the valve (21) closed and introduces the intermediate product of line (20) - Table II, Column B - in the MTBE synthesis (27). After separating the produced MTBE is drawn in the line (29) a mixture with the composition according to Table II, column E from and If it leads to the reactor (23), one works there as in Example 1 described.
  • the composition of the product of Line (36) is shown in Table II in column F, Column G indicates the composition in the line (39).

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Thermal Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
  • Powder Metallurgy (AREA)
EP01903630A 2000-01-12 2001-01-08 Verfahren zum erzeugen von c2- und c3- olefinen aus kohlenwasserstoffen Expired - Lifetime EP1252262B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10000889 2000-01-12
DE10000889A DE10000889C2 (de) 2000-01-12 2000-01-12 Verfahren zum Erzeugen von C¶2¶- und C¶3¶-Olefinen aus Kohlenwasserstoffen
PCT/EP2001/000129 WO2001051590A1 (de) 2000-01-12 2001-01-08 Verfahren zum erzeugen von c2- und c3-olefinen aus kohlenwasserstoffen

Publications (2)

Publication Number Publication Date
EP1252262A1 EP1252262A1 (de) 2002-10-30
EP1252262B1 true EP1252262B1 (de) 2005-04-06

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EP01903630A Expired - Lifetime EP1252262B1 (de) 2000-01-12 2001-01-08 Verfahren zum erzeugen von c2- und c3- olefinen aus kohlenwasserstoffen

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US (1) US20030149322A1 (pt)
EP (1) EP1252262B1 (pt)
JP (1) JP4637434B2 (pt)
CN (1) CN1263831C (pt)
AT (1) ATE292663T1 (pt)
AU (1) AU2001231667A1 (pt)
BR (1) BR0107573B1 (pt)
CA (1) CA2396986A1 (pt)
CZ (1) CZ302128B6 (pt)
DE (2) DE10000889C2 (pt)
MX (1) MXPA02006800A (pt)
PL (1) PL196066B1 (pt)
RU (1) RU2256692C2 (pt)
SK (1) SK286459B6 (pt)
TW (1) TW538036B (pt)
WO (1) WO2001051590A1 (pt)
ZA (1) ZA200205192B (pt)

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CZ302128B6 (cs) * 2000-01-12 2010-11-03 Lurgi Gmbh Zpusob výroby C2- a C3-alkenu z uhlovodíku

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ES2316514T3 (es) * 2002-12-01 2009-04-16 Sud-Chemie Ag Uso de un catalizador a base de aluminosilicato cristalino.
DE102004008573A1 (de) * 2004-02-19 2005-09-08 Stockhausen Gmbh Ein Verfahren zur Entfernung kohlenstoffhaltiger Rückstände in einem Reaktor
CN1333052C (zh) * 2004-07-14 2007-08-22 中国石油化工股份有限公司 一种生产低碳烯烃和芳烃的方法和装置
AU2005274030B2 (en) * 2004-08-10 2008-11-20 Shell Internationale Research Maatschappij B.V. Method and apparatus for making a middle distillate product and lower olefins from a hydrocarbon feedstock
CN100418938C (zh) * 2005-09-07 2008-09-17 中国石油化工股份有限公司 分离含碳烯烃催化裂解产物的方法
US20100200460A1 (en) * 2007-04-30 2010-08-12 Shell Oil Company Systems and methods for making a middle distillate product and lower olefins from a hydrocarbon feedstock
CN101952394B (zh) * 2007-10-10 2013-09-11 国际壳牌研究有限公司 由烃原料制备中间馏分产物和低级烯烃的系统和方法
EP2231821A1 (en) * 2007-11-29 2010-09-29 Shell Internationale Research Maatschappij B.V. Systems and methods for making a middle distillate product and lower olefins from a hydrocarbon feedstock
EP2336275B1 (en) * 2008-09-17 2016-11-23 Asahi Kasei Kabushiki Kaisha Process for producing olefin
US8137631B2 (en) * 2008-12-11 2012-03-20 Uop Llc Unit, system and process for catalytic cracking
US8246914B2 (en) * 2008-12-22 2012-08-21 Uop Llc Fluid catalytic cracking system
JP5441025B2 (ja) * 2008-12-26 2014-03-12 Ｊｘ日鉱日石エネルギー株式会社 ジシクロペンタジエンの精製方法
CA2748247C (en) 2008-12-26 2019-04-02 Jx Nippon Oil & Energy Corporation Method for refining dicyclopentadiene
US8889076B2 (en) * 2008-12-29 2014-11-18 Uop Llc Fluid catalytic cracking system and process
DE102010026880A1 (de) 2010-07-12 2012-01-12 Süd-Chemie AG Verfahren zur Herstellung von Katalysatoren auf Zeolithbasis zur Umsetzung von Oxygenaten zu niederen Olefinen
RU2518080C2 (ru) * 2011-07-08 2014-06-10 Общество с ограниченной ответственностью "Премиум Инжиниринг" Способ и устройство переработки тяжелого нефтяного сырья
WO2014023418A1 (de) * 2012-08-09 2014-02-13 Linde Aktiengesellschaft Verfahren zum herstellen von olefinen durch thermisches dampfspalten
CA2877157A1 (en) * 2012-08-09 2014-02-13 Linde Aktiengesellschaft Process for converting hydrocarbon feeds to olefin-containing product streams by thermal steamcracking
EP2867337B1 (de) * 2012-08-09 2015-11-04 Linde Aktiengesellschaft Verfahren zur herstellung von olefinen durch thermisches dampfspalten in spaltöfen
JP6215936B2 (ja) * 2012-08-09 2017-10-18 リンデ アクチエンゲゼルシャフトＬｉｎｄｅ Ａｋｔｉｅｎｇｅｓｅｌｌｓｃｈａｆｔ 炭化水素供給原料の熱水蒸気分解による転化方法
BR112015010348A2 (pt) * 2012-11-08 2017-07-11 Linde Ag processo para produzir produtos que contêm olefina por craqueamento por vapor térmico
WO2016098909A1 (ja) * 2014-12-19 2016-06-23 千代田化工建設株式会社 低級オレフィンの製造方法、低級オレフィンの製造装置、低級オレフィンの製造設備の構築方法およびゼオライト触媒
JP6480726B2 (ja) * 2014-12-19 2019-03-13 千代田化工建設株式会社 低級オレフィンの製造方法、低級オレフィンの製造装置および低級オレフィンの製造設備の構築方法
US10538711B2 (en) 2015-06-02 2020-01-21 Sabic Global Technologies B.V. Process for converting naphtha
CA3069332C (en) 2017-07-18 2022-06-07 Lummus Technology Llc Integrated thermal and catalytic cracking for olefin production

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CZ302128B6 (cs) * 2000-01-12 2010-11-03 Lurgi Gmbh Zpusob výroby C2- a C3-alkenu z uhlovodíku

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Publication number Publication date
TW538036B (en) 2003-06-21
SK9972002A3 (en) 2003-09-11
DE10000889C2 (de) 2002-12-19
DE10000889A1 (de) 2001-07-26
ZA200205192B (en) 2003-09-29
AU2001231667A1 (en) 2001-07-24
EP1252262A1 (de) 2002-10-30
SK286459B6 (sk) 2008-10-07
JP2003525971A (ja) 2003-09-02
CN1395609A (zh) 2003-02-05
MXPA02006800A (es) 2002-10-17
JP4637434B2 (ja) 2011-02-23
BR0107573B1 (pt) 2011-05-03
US20030149322A1 (en) 2003-08-07
PL357673A1 (en) 2004-07-26
BR0107573A (pt) 2003-01-14
CZ302128B6 (cs) 2010-11-03
CA2396986A1 (en) 2001-07-19
ATE292663T1 (de) 2005-04-15
CN1263831C (zh) 2006-07-12
PL196066B1 (pl) 2007-11-30
CZ20022357A3 (cs) 2003-08-13
DE50105830D1 (de) 2005-05-12
RU2002121483A (ru) 2004-01-10
RU2256692C2 (ru) 2005-07-20
WO2001051590A1 (de) 2001-07-19

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