EP0372632A1 - Procédé de conversion d'hydrocarbures - Google Patents

Procédé de conversion d'hydrocarbures Download PDF

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Publication number
EP0372632A1
EP0372632A1 EP89203038A EP89203038A EP0372632A1 EP 0372632 A1 EP0372632 A1 EP 0372632A1 EP 89203038 A EP89203038 A EP 89203038A EP 89203038 A EP89203038 A EP 89203038A EP 0372632 A1 EP0372632 A1 EP 0372632A1
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EP
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Prior art keywords
feedstock
process according
catalyst
zeolite
conversion
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EP89203038A
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German (de)
English (en)
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EP0372632B1 (fr
Inventor
Ian Ernest Maxwell
Jaydeep Biswas
Johannes Kornelis Minderhoud
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen

Definitions

  • the present invention relates to a process for the conversion of a hydrocarbonaceous feedstock and is particularly concerned with the upgrading of certain feedstocks.
  • US 4,171,257 describes a process for upgrading a hydro­carbonaceous feedstock by contacting the feedstock with a ZSM-5 crystalline aluminosilicate catalyst at a pressure below 14 bar, a temperature of 260 to 427 °C and a space velocity of 0.1 to 15 l/l.h.
  • the feedstock exemplified as gas oil having a boiling point range of 230 to 437 °C, must contain loss than 5 ppmw of nitrogen-containing compounds, calculated as nitrogen.
  • the upgraded product includes olefinic hydrocarbons, such as propene and butenes.
  • the present invention provides a process for the conversion of a hydrotreated and/or hydrocracked heavy hydro­carbonaceous feedstock, which process comprises contacting the feedstock with a zeolitic catalyst comprising a zeolite with a pore diameter of 0.4 to 0.7 nm at a temperature of greater than 480 °C and a pressure of up to 10 bar during less than 10 seconds.
  • the feedstock is contacted with the zeolitic catalyst for less than 10 seconds.
  • the minimum contact time is 0.1 second. Very good results are obtainable with a process in which the feedstock is contacted with the zeolitic catalyst during 1 to 6 seconds.
  • the temperature during the reaction is relatively high. However, the combination of high temperature and short residence time allows a high conversion to olefins.
  • a preferred temperature range is 480 to 900 °C, more preferably 500 to 750 °C.
  • the zeolitic catalyst comprises a zeolite with a pore diameter of from 0.4 to 0.7 nm.
  • the catalyst suitably further comprises a refractory oxide that serves as binder material. Suitable refractory oxides include alumina, silica, silica-alumina, magnesia, titania, zirconia and mixtures thereof. Alumina is especially preferred.
  • the weight ratio of refractory oxide and zeolite suitably ranges from 10:90 to 90:10, preferably from 50:50 to 85:15.
  • the catalyst may comprise further zeolites with a pore diameter above 0.7 nm.
  • zeolites include the faujasite-type zeolites, zeolite beta, zeolite omega and in particular zeolite X and Y.
  • the zeolitic catalyst preferably comprises as zeolite substantially only zeolites with a pore diameter of from 0.4 to 0.7 nm.
  • zeolite in this specification is not to be regarded as comprising only crystalline aluminium silicates.
  • the term also includes crystalline silica (silicalite), silicoaluminophosphates (SAPO), chromosilicates, gallium silicates, iron silicates, aluminium phosphates (ALPO), titanium aluminosilicates (TASO), boron silicates, titanium aluminophosphates (TAPO) and iron aluminosilicates.
  • Examples of zeolites that may be used in the process of the invention and that have a pore diameter of 0.4 to 0.7 nm include SAPO-4 and SAPO-11, which are described in US-A-4,440,871, ALPO-11, described in US-A-4,310,440, TAPO-11, described in US-A-4,5OO,651, TASO-45, described in EP-A-229,295, boron silicates, described in e.g. US-A-4,254,297, aluminium silicates like erionite, ferrierite, theta and the ZSM-type zeolites such as ZSM-5, ZSM-11, ZSM-12, ZSM-35, ZSM-23, and ZSM-38.
  • SAPO-4 and SAPO-11 which are described in US-A-4,440,871, ALPO-11, described in US-A-4,310,440, TAPO-11, described in US-A-4,5OO,651, TASO-45, described in EP-A-229,29
  • the zeolite is selected from the group consisting of crystalline metal silicates having a ZSM-5 structure, ferrierite, erionite and mixtures thereof.
  • crystalline metal silicates with ZSM-5 structure are aluminium, gallium, iron, scandium, rhodium and/or scandium silicates as described in e.g. GB-B-2,110,559.
  • the zeolites usually a significant amount of alkali metal oxide is present in the prepared zeolite.
  • the amount of alkali metal is removed by methods known in the art, such as ion exchange, optionally followed by calcination, to yield the zeolite in its hydrogen form.
  • the zeolite used in the present process is substantially in its hydrogen form.
  • Olefin production is facilitated by the absence of hydrogen or a hydrogen donor.
  • the present process is advantageously carried out in the absence of added hydrogen and/or steam. It is, of course, possible that during the reaction some small molecules, such as hydrogen molecules are formed. However, this amount is usually negligible and will be less than 0.5 %wt of the product.
  • the pressure in the present process can be varied within wide ranges. It is, however, preferred that the pressure is such that at the prevailing temperature the feedstock is substantially in its gaseous phase. Then it is easier to achieve the short contact times envisaged. Hence, the pressure is preferably relatively low. This is the more advantageous since no expensive compressors and high-pressure vessels and other equipment are necessary. Pressures up to 10 bar can be employed. Subatmospheric pressures are possible, but not preferred. The minimum pressure is suitably 1 bar. It is economically advantageous to operate at atmospheric pressure.
  • the catalyst/feedstock weight ratio may vary widely, for example up to 200 kg of catalyst per kg of feedstock. Preferably, the catalyst/feedstock weight ratio is from 2 to 200.
  • the process according to the present invention may be carried out in a fixed bed. However, this would imply that extremely high space velocities be required to attain the short contact times envisaged. Therefore, the present process is preferably carried out in a moving bed.
  • the bed of catalyst may move upwards or downwards. When the bed moves upwards a process similar to a fluidized catalytic cracking process is obtained. Preferably, the process is carried out in a downwardly moving bed.
  • the catalyst is regenerated by subjecting it, after having been contacted with the feedstock, to a treatment with an oxidizing gas, such as air.
  • a continuous regeneration similar to the regeneration carried out in a fluidized catalytic cracking process, is especially preferred.
  • the coke formation does not occur at a very high rate.
  • the contact time between feedstock and catalyst should be less than 10 seconds.
  • the contact time generally corresponds with the residence time of the feedstock.
  • the residence time of the catalyst is from 1 to 20 times the residence time of the feedstock.
  • the feedstock which is to be convert in the present process comprises hydrotreated and/or hydrocracked hydrocarbons, preferably, though not necessarily, heavy feedstocks.
  • Suitable feedstocks are obtained by hydrotreating and/or hydro­cracking heavy flashed distillate fractions from long residue or deasphalted oils obtained from short residue.
  • the feedstock is suitably fractionated to remove lower boiling fractions after hydrotreating and/or hydrocracking and prior to contacting with the zeolitic catalyst in accordance with the invention.
  • the product obtained by the process of the invention is optionally fractionated to yield an olefin-rich gas fraction, a gasoline fraction and a bottom fraction, all or part of which is optionally recycled to the feedstock upstream of the hydrotreating and/or hydrocracking unit. In this way, high conversion of the heavy deasphalted oil or heavy flashed distillate feedstock to more valuable olefin-rich gas is obtained.
  • a process for the conversion of a hydrocarbonaceous feedstock comprising hydrotreating and/or hydrocracking said feedstock in the presence of a suitable catalyst, contacting at least a part of the hydrotreated and/or hydrocracked product with a zeolitic catalyst comprising a zeolite with a pore diameter of 0.4 to 0.7 nm at a temperature of greater than 480 °C and a pressure of up to 10 bar during less than 10 seconds, fractionating the resulting converted material and recycling a heavier fraction to said hydrotreating and/or hydrocracking step.
  • the said hydrotreating step is known in the art and may be carried out at known conditions. Suitable conditions include a temperature of 150 to 400 °C, a hydrogen (partial) pressure of 30 to 150 bar, a space velocity of 0.5 to 4.0 kg/l.h and a hydrogen/feedstock ratio of 100 to 2000 Nl/kg.
  • Suitable hydro­treating catalysts comprise nickel, cobalt, tungsten, molybdenum, platinum, palladium or mixtures thereof on a carrier, such as alumina, silica-alumina, silica, zirconia, zeolites and the like.
  • the catalyst may further comprise fluorine, phosphorus and/or boron.
  • the temperature, gas rate and space velocity can be selected by the person skilled in the art, suitably from the range given above.
  • Hydrocracking is also known in the art and may be carried out under known conditions, such as over a hydrocracking catalyst at a temperature of 300 to 450 °C, a hydrogen (partial) pressure of 50 to 200 bar, a space velocity of 0.5 to 2.0 kg/l.catalyst.h and a H2/mineral oil fraction ratio of 500 to 2000 Nl/kg.
  • the hydro­cracking catalyst can be selected from any hydrocracking catalyst known in the art.
  • the hydrocracking catalyst comprises a carrier and at least one hydrogenating metal or a compound thereof, which carrier has been selected from the group consisting of silica, alumina, silica-alumina and the faujasite-type zeolites.
  • the most preferred faujasite-type zeolite is zeolite Y.
  • the most preferred hydrogenating metals are nickel, cobalt, tungsten and molybdenum and mixtures thereof, but platinum and/or palladium may also be used.
  • the catalyst may further comprise fluorine and/or phosphorus and/or boron.
  • nickel, cobalt, molybdenum and/or tungsten are used as hydrogenating metal, they are preferably present in the form of their sulphides.
  • a feedstock with a nitrogen content greater than 5 ppmw may be used with substantially no effect on the catalyst activity.
  • Suitable feedstocks may have a nitrogen content of more than 10 ppmw, calculated as nitrogen.
  • the feedstock may even have a nitrogen content of 1000 ppmw or more, calculated as nitrogen.
  • the feedstock in this example was a hydrotreated Arabian light deasphalted oil having the following properties: IBP, °C 453 50 %wt 591 67 %wt 620 density 70/4 0.8532 kg/l sulphur 232 ppmw nitrogen 12 ppmw
  • the DAO feedstock was upgraded in a downflow reactor by passing it downwards co-currently with a flow of catalyst particles.
  • the catalyst comprised ZSM-5 in an alumina matrix (weight ratio ZSM-5/alumina 1:3).
  • the experiment was carried out at atmospheric pressure. Further process conditions and the results of the experiment are given in Table 1 below.
  • the feedstock in this example was a hydrocracked heavy flashed distillate having the following properties:
  • Feedstock was introduced on line 1, after mixing with hydrogen from line 2, to a hydrotreating/hydrocracking unit 3 operated at 90 bar hydrogen partial pressure at 400 °C with a suitable Ni/Mo/alumina hydrotreating catalyst.
  • the hydrotreated product was fractionated in unit 4 into a gaseous fraction 5, a naphtha fraction 6, a kerosine fraction 7, a gas oil fraction 8 and a bottoms fraction 9.
  • bottoms fraction 9 was passed to a downflow reactor 10 as described in Example 1, containing catalyst as described in Example 1 and provided with suitable regeneration means from which coke can be removed in line 11 when necessary, while gaseous and liquid product is separated in fractionation unit 12 into a gaseous product 13, a gasoline product 14 and a bottoms stream 15, which is recycled to the feedstock in line 1 for re-processing.
  • Bottoms fraction 9 which is upgraded in reactor 10 comprises about 69% by weight based on the initial feed in line 1 when fractionated in unit 12.
  • the composition of the fraction obtained from unit 12 is given in Table 3 below:
EP19890203038 1988-12-02 1989-11-29 Procédé de conversion d'hydrocarbures Revoked EP0372632B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8828206 1988-12-02
GB888828206A GB8828206D0 (en) 1988-12-02 1988-12-02 Process for conversion of hydrocarbonaceous feedstock

Publications (2)

Publication Number Publication Date
EP0372632A1 true EP0372632A1 (fr) 1990-06-13
EP0372632B1 EP0372632B1 (fr) 1996-01-31

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Family Applications (1)

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EP19890203038 Revoked EP0372632B1 (fr) 1988-12-02 1989-11-29 Procédé de conversion d'hydrocarbures

Country Status (11)

Country Link
EP (1) EP0372632B1 (fr)
JP (1) JPH02212594A (fr)
CN (1) CN1025216C (fr)
AU (1) AU621169B2 (fr)
BR (1) BR8906158A (fr)
CA (1) CA2004390A1 (fr)
DE (1) DE68925574T2 (fr)
ES (1) ES2082769T3 (fr)
GB (1) GB8828206D0 (fr)
PH (1) PH27238A (fr)
RU (1) RU2017790C1 (fr)

Cited By (25)

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US5380690A (en) * 1993-03-29 1995-01-10 China Petro-Chemical Corporation Cracking catalyst for the production of light olefins
US5670037A (en) * 1993-11-05 1997-09-23 China Petro-Chemical Corporation Process for producing light olefins by catalytic conversion of hydrocarbons
EP0955091A1 (fr) * 1998-05-06 1999-11-10 Institut Francais Du Petrole Catalyseur à base de zéolithe y contenant de silicium, utilisable en hydrocraquage
EP0955092A1 (fr) * 1998-05-06 1999-11-10 Institut Francais Du Petrole Catalyseur à base de zeolithe y non globalement désaluminée, de bore et/ou de silicium et procédé d'hydrocraquage
FR2778582A1 (fr) * 1998-05-13 1999-11-19 Inst Francais Du Petrole Procede pour l'amelioration du point d'ecoulement et catalyseur a base d'au moins une zeolithe mtt, ton, fer
EP2077269A1 (fr) 2008-01-07 2009-07-08 SK Energy Co., Ltd. Complexes de métal de transition, compositions de catalyseur les contenant et procédés pour la préparation de polymères d'éthylène les utilisant
EP2077270A1 (fr) 2008-01-07 2009-07-08 SK Energy Co., Ltd. Complexes métalliques de transition, compositions de catalyseur pour la préparation d'homopolymères ou copolymères d'éthylène
US7589042B2 (en) 2005-07-01 2009-09-15 Sk Corporation Arylphenoxy catalyst system for producing ethylene homopolymer or copolymers of ethylene and α-olefins
WO2010053264A2 (fr) 2008-11-05 2010-05-14 Sk Energy Co., Ltd. Procédé de fabrication de copolymères élastomères de l'éthylène et d'α-oléfines
US7928173B2 (en) 2008-09-25 2011-04-19 Sk Energy Co., Ltd. Transition metal catalytic systems and methods for preparing ethylene homopolymers or copolymers of ethylene and α-olefins using the same
WO2012169811A2 (fr) 2011-06-09 2012-12-13 Sk Innovation Co., Ltd. Composé inédit de type métal de transition à base de cyclopenta[b]fluorényle, composition de catalyseur en contenant et procédé de préparation d'un homopolymère d'éthylène ou d'un copolymère d'éthylène et d'α-oléfine l'utilisant
WO2012176946A1 (fr) 2011-06-24 2012-12-27 Sk 이노베이션 주식회사 SYSTÈME DE CATALYSEUR DE MÉTAUX DE TRANSITION PRÉSENTANT UNE EXCELLENTE COPOLYMÉRISATION ET PROCÉDÉ DE PRÉPARATION D'UN HOMOPOLYMÈRE D'ÉTHYLÈNE OU D'UN COPOLYMÈRE D'ÉTHYLÈNE ET D'α-OLÉFINE UTILISANT CE SYSTÈME
US8344081B2 (en) 2007-12-31 2013-01-01 Sk Innovation Co., Ltd. Transition metal complexes, catalysts composition containing the same, and process for preparing ethylene homopolymers or copolymers of ethylene and alpha-olefins using the same
KR20150138042A (ko) 2014-05-29 2015-12-09 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 새로운 전이금속 화합물, 이를 포함한 올레핀 중합용 전이금속 촉매 조성물 및 이를 이용한 에틸렌 단독중합체 또는 에틸렌과 α-올레핀의 공중합체의 제조방법
US9260667B2 (en) 2007-12-20 2016-02-16 China Petroleum & Chemical Corporation Combined process of hydrotreating and catalytic cracking of hydrocarbon oils
KR20180079181A (ko) 2016-12-30 2018-07-10 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 신규한 시클로펜타[ｂ]티오펜일 전이금속 화합물, 이를 포함하는 전이금속 촉매 조성물, 및 이를 이용한 에틸렌 단독중합체 또는 에틸렌과 α-올레핀의 공중합체의 제조방법
KR20180081448A (ko) 2017-01-06 2018-07-16 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 신규한 인덴계 전이금속 화합물, 이를 포함하는 촉매 조성물, 및 이를 이용한 에틸렌 단독중합체 또는 에틸렌과 α-올레핀의 공중합체의 제조방법
KR20180082314A (ko) 2017-01-09 2018-07-18 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 신규한 전이금속 화합물, 이를 포함하는 촉매 조성물, 및 이를 이용한 에틸렌 단독중합체 또는 에틸렌과 α-올레핀의 공중합체의 제조방법
WO2019064247A1 (fr) 2017-09-29 2019-04-04 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 Nouveau composé de métal de transition à base d'indène, composition de catalyseur de métal de transition le contenant, et procédé de préparation d'homopolymère ou de copolymère d'éthylène et d'alpha-oléfine en utilisant cette composition
WO2019123028A1 (fr) 2017-12-21 2019-06-27 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 Complexe métal-ligand, composition catalytique comprenant celui-ci pour une polymérisation à base d'éthylène et procédé de préparation de polymère à base d'éthylène faisant appel à celle-ci
WO2020174346A1 (fr) 2019-02-28 2020-09-03 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 Nouveau composé de tétraarylborate, composition de catalyseur le contenant, et procédé de préparation d'homopolymères ou de copolymères d'éthylène et d'alpha-oléfine l'utilisant
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US10919992B2 (en) 2017-09-29 2021-02-16 Sabic Sk Nexlene Company Pte. Ltd. Indene-based transition metal compound, transition metal catalyst composition comprising same, and method for preparing ethylene homopolymer or copolymer of ethylene and alpha-olefin by using same
US11339230B2 (en) 2017-08-21 2022-05-24 Sabic Sk Nexlene Company Pte. Ltd. Transition metal compound, catalyst composition including the same, and method for preparing ethylene homopolymer or copolymer of ethylene and α-olefin using the same
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US6835863B2 (en) 1999-07-12 2004-12-28 Exxonmobil Oil Corporation Catalytic production of light olefins from naphtha feed
US6222087B1 (en) 1999-07-12 2001-04-24 Mobil Oil Corporation Catalytic production of light olefins rich in propylene
CN101210200B (zh) 2006-12-27 2010-10-20 中国石油化工股份有限公司 一种渣油加氢处理与催化裂化组合工艺方法
US10689586B2 (en) 2015-12-21 2020-06-23 Sabic Global Technologies B.V. Methods and systems for producing olefins and aromatics from coker naphtha
KR20240045992A (ko) 2022-09-30 2024-04-08 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 전이금속 화합물, 이를 포함하는 촉매 조성물 및 이를 이용하는 올레핀 중합체의 제조방법

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EP0955092A1 (fr) * 1998-05-06 1999-11-10 Institut Francais Du Petrole Catalyseur à base de zeolithe y non globalement désaluminée, de bore et/ou de silicium et procédé d'hydrocraquage
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US6235960B1 (en) 1998-05-13 2001-05-22 Institut Francais Du Petrole Process for improving the pour point, and a catalyst based on at least one MTT, Ton or Fer zeolite
FR2778582A1 (fr) * 1998-05-13 1999-11-19 Inst Francais Du Petrole Procede pour l'amelioration du point d'ecoulement et catalyseur a base d'au moins une zeolithe mtt, ton, fer
US7589042B2 (en) 2005-07-01 2009-09-15 Sk Corporation Arylphenoxy catalyst system for producing ethylene homopolymer or copolymers of ethylene and α-olefins
US9309467B2 (en) 2007-12-20 2016-04-12 China Petroleum And Chemical Corp. Integrated process for hydrogenation and catalytic cracking of hydrocarbon oil
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US8344081B2 (en) 2007-12-31 2013-01-01 Sk Innovation Co., Ltd. Transition metal complexes, catalysts composition containing the same, and process for preparing ethylene homopolymers or copolymers of ethylene and alpha-olefins using the same
EP2077269A1 (fr) 2008-01-07 2009-07-08 SK Energy Co., Ltd. Complexes de métal de transition, compositions de catalyseur les contenant et procédés pour la préparation de polymères d'éthylène les utilisant
EP2077270A1 (fr) 2008-01-07 2009-07-08 SK Energy Co., Ltd. Complexes métalliques de transition, compositions de catalyseur pour la préparation d'homopolymères ou copolymères d'éthylène
US7645844B2 (en) 2008-01-07 2010-01-12 Sk Energy Co., Ltd. Transition metal complexes, catalyst compositions containing the same, and methods for preparing ethylene homopolymers or copolymers of ethylene and α-olefins using the same
US7847039B2 (en) 2008-01-07 2010-12-07 Sk Energy Co., Ltd. Transition metal complexes, and catalysts compositions for preparing ethylene homopolymers or copolymers
US8232359B2 (en) 2008-09-25 2012-07-31 Sk Innovation Co., Ltd. Process for preparing ethylene homopolymers or copolymers of ethylene with α-olefin by using the transition metal compound
US7928173B2 (en) 2008-09-25 2011-04-19 Sk Energy Co., Ltd. Transition metal catalytic systems and methods for preparing ethylene homopolymers or copolymers of ethylene and α-olefins using the same
WO2010053264A2 (fr) 2008-11-05 2010-05-14 Sk Energy Co., Ltd. Procédé de fabrication de copolymères élastomères de l'éthylène et d'α-oléfines
US8013086B2 (en) 2008-11-05 2011-09-06 Sk Energy Co., Ltd. Method for preparing elastomeric copolymers of ethylene and α-olefins
US8921499B2 (en) 2011-06-09 2014-12-30 Sk Innovation Co., Ltd. Method of preparing ethylene-α-olefin-diene copolymer
US9120884B2 (en) 2011-06-09 2015-09-01 Sk Innovation Co., Ltd. Cyclopenta[b]fluorenyl transition metal compound, catalyst composition containing the same, and method of preparing ethylene homopolymer or copolymer of ethylene and α-olefin using the same
US10323111B2 (en) 2011-06-09 2019-06-18 Sabic Sk Nexlene Company Pte. Ltd. Cyclopenta[b]fluorenyl transition metal compound, catalyst composition containing the same, and method of preparing ethylene homopolymer or copolymer of ethylene and alpha-olefin using the same
US9926394B2 (en) 2011-06-09 2018-03-27 Sabic Sk Nexlene Company Pte. Ltd. Cyclopenta[b]fluorenyl transition metal compound, catalyst composition containing the same, and method of preparing ethylene homopolymer or copolymer of ethylene and alpha-olefin using the same
WO2012169811A2 (fr) 2011-06-09 2012-12-13 Sk Innovation Co., Ltd. Composé inédit de type métal de transition à base de cyclopenta[b]fluorényle, composition de catalyseur en contenant et procédé de préparation d'un homopolymère d'éthylène ou d'un copolymère d'éthylène et d'α-oléfine l'utilisant
US10487163B2 (en) 2011-06-09 2019-11-26 Sabic Sk Nexlene Company Pte. Ltd. Cyclopenta[b]fluorenyl transition metal compound, catalyst composition containing the same, and method of preparing ethylene homopolymer or copolymer of ethylene and alpha-olefin using the same
WO2012176946A1 (fr) 2011-06-24 2012-12-27 Sk 이노베이션 주식회사 SYSTÈME DE CATALYSEUR DE MÉTAUX DE TRANSITION PRÉSENTANT UNE EXCELLENTE COPOLYMÉRISATION ET PROCÉDÉ DE PRÉPARATION D'UN HOMOPOLYMÈRE D'ÉTHYLÈNE OU D'UN COPOLYMÈRE D'ÉTHYLÈNE ET D'α-OLÉFINE UTILISANT CE SYSTÈME
KR20150138042A (ko) 2014-05-29 2015-12-09 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 새로운 전이금속 화합물, 이를 포함한 올레핀 중합용 전이금속 촉매 조성물 및 이를 이용한 에틸렌 단독중합체 또는 에틸렌과 α-올레핀의 공중합체의 제조방법
US10053481B2 (en) 2014-05-29 2018-08-21 Sabic Sk Nexlene Company Pte. Ltd. Transition metal compound, transition metal catalyst composition for polymerizing olefin, containing same, and method for preparing ethylene homopolymer or copolymer of ethylene and alpha-olefin by using same
KR20180079181A (ko) 2016-12-30 2018-07-10 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 신규한 시클로펜타[ｂ]티오펜일 전이금속 화합물, 이를 포함하는 전이금속 촉매 조성물, 및 이를 이용한 에틸렌 단독중합체 또는 에틸렌과 α-올레핀의 공중합체의 제조방법
KR20180081448A (ko) 2017-01-06 2018-07-16 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 신규한 인덴계 전이금속 화합물, 이를 포함하는 촉매 조성물, 및 이를 이용한 에틸렌 단독중합체 또는 에틸렌과 α-올레핀의 공중합체의 제조방법
KR20180082314A (ko) 2017-01-09 2018-07-18 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 신규한 전이금속 화합물, 이를 포함하는 촉매 조성물, 및 이를 이용한 에틸렌 단독중합체 또는 에틸렌과 α-올레핀의 공중합체의 제조방법
US11339230B2 (en) 2017-08-21 2022-05-24 Sabic Sk Nexlene Company Pte. Ltd. Transition metal compound, catalyst composition including the same, and method for preparing ethylene homopolymer or copolymer of ethylene and α-olefin using the same
WO2019064247A1 (fr) 2017-09-29 2019-04-04 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 Nouveau composé de métal de transition à base d'indène, composition de catalyseur de métal de transition le contenant, et procédé de préparation d'homopolymère ou de copolymère d'éthylène et d'alpha-oléfine en utilisant cette composition
US10919992B2 (en) 2017-09-29 2021-02-16 Sabic Sk Nexlene Company Pte. Ltd. Indene-based transition metal compound, transition metal catalyst composition comprising same, and method for preparing ethylene homopolymer or copolymer of ethylene and alpha-olefin by using same
WO2019123028A1 (fr) 2017-12-21 2019-06-27 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 Complexe métal-ligand, composition catalytique comprenant celui-ci pour une polymérisation à base d'éthylène et procédé de préparation de polymère à base d'éthylène faisant appel à celle-ci
US11505563B2 (en) 2017-12-21 2022-11-22 Sabic Sk Nexlene Company Pte. Ltd. Metal-ligand complex, catalyst composition for ethylene-based polymerization including the same, and method for preparing ethylene-based polymer using the same
WO2020174346A1 (fr) 2019-02-28 2020-09-03 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 Nouveau composé de tétraarylborate, composition de catalyseur le contenant, et procédé de préparation d'homopolymères ou de copolymères d'éthylène et d'alpha-oléfine l'utilisant
KR20200105409A (ko) 2019-02-28 2020-09-07 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 신규한 테트라아릴보레이트 화합물, 이를 포함하는 촉매 조성물, 및 이를 이용한 에틸렌 단독중합체 또는 에틸렌과 α-올레핀의 공중합체의 제조방법

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BR8906158A (pt) 1990-07-31
GB8828206D0 (en) 1989-01-05
PH27238A (en) 1993-05-04
RU2017790C1 (ru) 1994-08-15
DE68925574D1 (de) 1996-03-14
DE68925574T2 (de) 1996-08-08
CN1043156A (zh) 1990-06-20
JPH02212594A (ja) 1990-08-23
AU621169B2 (en) 1992-03-05
CN1025216C (zh) 1994-06-29
ES2082769T3 (es) 1996-04-01
CA2004390A1 (fr) 1990-06-02
EP0372632B1 (fr) 1996-01-31
AU4579989A (en) 1990-06-07

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