TWI415683B - 用於乙烯之二、三及／或四聚的觸媒組合物及方法 - Google Patents

用於乙烯之二、三及／或四聚的觸媒組合物及方法 Download PDF

Info

Publication number
TWI415683B
TWI415683B TW097123207A TW97123207A TWI415683B TW I415683 B TWI415683 B TW I415683B TW 097123207 A TW097123207 A TW 097123207A TW 97123207 A TW97123207 A TW 97123207A TW I415683 B TWI415683 B TW I415683B
Authority
TW
Taiwan
Prior art keywords
catalyst composition
ethylene
group
aluminum
chromium
Prior art date
Application number
TW097123207A
Other languages
English (en)
Other versions
TW200909055A (en
Inventor
Matthias Fritz Peter
Bolt Heinz
Wohl Anina
Muller Wolfgang
Winkler Florian
Wellenhofer Anton
Rosenthal Uwe
H Muller Bernd
Hapke Marko
Peulecke Normen
Hassan Al-Hazmi Mohammed
O Aliyev Vugar
Mohammed Mosa Fuad
Original Assignee
Linde Ag
Saudi Basic Ind Corp
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 Linde Ag, Saudi Basic Ind Corp filed Critical Linde Ag
Publication of TW200909055A publication Critical patent/TW200909055A/zh
Application granted granted Critical
Publication of TWI415683B publication Critical patent/TWI415683B/zh

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2495—Ligands comprising a phosphine-P atom and one or more further complexing phosphorus atoms covered by groups B01J31/1845 - B01J31/1885, e.g. phosphine/phosphinate or phospholyl/phosphonate ligands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/1885—Ligands comprising two different formal oxidation states of phosphorus in one at least bidentate ligand, e.g. phosphite/phosphinite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/189—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/224—Phosphorus triamides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/46—Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
    • C07F9/4883—Amides or esteramides thereof, e.g. RP(NR'2)2 or RP(XR')(NR''2) (X = O, S)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
    • C07F9/6584—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having one phosphorus atom as ring hetero atom
    • C07F9/65848—Cyclic amide derivatives of acids of phosphorus, in which two nitrogen atoms belong to the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
    • C07F9/6587—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having two phosphorus atoms as ring hetero atoms in the same ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0258—Flexible ligands, e.g. mainly sp3-carbon framework as exemplified by the "tedicyp" ligand, i.e. cis-cis-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62—Chromium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/24—Phosphines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Description

用於乙烯之二、三及/或四聚的觸媒組合物及方法
本發明係關於用於乙烯之二、三及/或四聚的觸媒組合物及方法。
製造直鏈狀α－烯烴(LAOs,Linear alpha olefins)，包括共單體級1－己烯及1－辛烯之現有方法係依存於乙烯之寡聚。此等方法之共通點為產物分布於鏈長4、6、8等之乙烯寡聚物。此係由於受到競爭性鏈增長－及取代反應步驟廣泛控制之化學機制，而導致舒爾茨－弗洛里(Schulz－Flory)或卜瓦松(Poisson)產物分布。
從行銷觀點而言，此種產物分布使全範圍α－烯烴製造商面臨難以克服的挑戰。其理由為其所供應的各市場區塊在市場大小及成長性、地理位置及歧異化等方面顯現極為不同的屬性。既然在特定經濟區產物範圍之某部分可能具有高度需求，而產物之其他部分可能完全沒有銷路或只有邊際利基，因此製造商難以適應市場需要。現今，最高價值之LAO產物為使用於聚合體工業之共單體級1－己烯，同時1－辛烯需求亦以可觀之速率成長。
因此，最具經濟價值之LAOs，亦即共單體級1－己烯及1－辛烯之專門生產，呈現高度之需求。為達到對於高C6－及/或C8－選擇性之需求，已開發出新穎方法。唯一已知之選擇性C6－商業化製程已被Chevron Phillips公司採行，參 考例如J.T.Dixon、M.J.Green、F.M.Hess、D.H.Morgan之綜合評論：「選擇性乙烯三聚之進展－關鍵性之綜論」，Journal of Organometallic Chemistry 689(2004)3641－3668。
再者，Sasol所申請之專利申請案(WO 93/053891 A1)，揭示以鉻系選擇性乙烯－三聚觸媒系統，典型地為CrCl3 (雙－(2－二苯基膦基－乙基)胺)/MAO(甲基鋁氧烷)型。又，亦揭示各種配體構造(例如,雙(2－二乙基膦基－乙基)－胺、五甲基二伸乙基三胺等)。然而，所有此等錯合物產生可觀量之不期望之副產物，諸如1－己烯以外之LAOs及聚乙烯。
大量科學及專利文獻記載與以基本PNP構造為特徵之配體(例如雙(二苯基膦基)胺－配體)錯合之鉻系金屬有機錯合物(D.S.McGuinness,P.Wasserscheid,W.Keim,C.Hu,U.Englert,J.T.Dixon,C.Grove，”做為乙烯三聚之觸媒之新穎Cr－PNP錯合物”，Chem.Commun.,2003,334－335；K.Blann,A.Bollmann,J.T.Dixon,F.M.Hess,E.Killian,H.Maumela,D.H.Morgan,A.Neveling,S.Otto,M.J.Overett,，”具有大體積二膦基胺配體之高選擇性鉻系乙烯三聚觸媒”，Chem.Comm.,2005,620－621；M.J.Overett,K.Blann,A.Bollmann,J.T.Dixon,F.Hess,E.Killian,H.Maumela,D.H.Morgan,A.Neveling,S.Otto，”使用經極性取代之二膦基胺配體之乙烯三聚及四聚觸媒”，Chem.Commun.,2005,622－624；A.Jabri,P.Crewdson,S.Gambarotta,I.Korobkov,R.Duchateau，”乙烯之三及四聚之觸媒系統中陽離子性鉻(II)之分離”，Organometallics 2006,25,715－718；T.Agapie,S.J.Schofer,J.A.Labinger,J.E.Bercaw，”使用鉻－二膦觸媒之乙烯三聚反應之機制研究：涉及金屬環狀中間體之機制之實驗證據”，J.Am.Chem.Soc.2004,126,1304－1305；S.J.Schofer,M.D.Day,L.M.Henling,J.A.Labinger,J.E.Bercaw，”基於鉻與具有鄰－甲氧基芳基或鄰－甲硫基取代基之氮－橋聯二膦配體的錯合物之乙烯三聚觸媒：明確界定之觸媒前驅物及機制之探討”，Organometallics 2006,25,2743－2749；S.J.Schofer,M.D.Day,L.M.Henling,J.A.Labinger,J.E.Bercaw，”催化式乙烯三聚之鉻－二膦系統：鉻與具有鄰－甲氧基芳基取代基之氮－橋聯二膦配體之錯合物的合成及構造研究”，Organometallics 2006,25,2733－2742；P.R.Elowe,C.McCann,P.G.Pringle,S.K.Spitzmesser,J.E.Bercaw,”用於經鉻－催化的乙烯三聚及四聚之氮－連結二膦配體，其中醚附接於該氮”，Organometallics 2006,25,5255－5260；WO 2004/056578,WO 2004/056479,EP 02 794 480.0,EP 02 794 479.2；或SNS－構造(D.S.McGuinness,D.B.Brown,R.P.Tooze,F.M.Hess,J.T.Dixon,A.M.Z.Slavin,”使用Cr－PNP及Cr－SNS錯合物之乙烯三聚：配體構造、金屬氧化態及活化劑在催化上之角色的作用”，Organometallics 2006,25,3605－3610；A.Jabri,C.Temple,P.Crewdson,S.Gambarotta,I.Korobkov,R.Duchateau,”金屬氧化態在用於乙烯三聚之SNS－Cr觸媒中之角色：二及三價陽離子性中間體之分離”，J.Am.Chem.Soc.2006,128,9238－9247；C. Temple,A.Jabri,P.Crewdson,S.Gambarotta,I.Korobkov,R.Duchateau,”Cr－氧化態在做為選擇性乙烯三聚之{Cr(SNS)}觸媒之問題：未預料到之再氧化途徑”，Angewv.Chem.Int.Ed.2006,45,7050－7053)之使用，做為乙烯之三聚及四聚。過量之MAO最常被使用做為活化劑/助觸媒。
然而大部分公開之研究係依賴Cr－PNP錯合物，某些加入其他配體，例如具通式(R1)(R2)P－X－P(R3)(R4)(式中X為二價有機架橋基)者，參考WO 2005/039758 A1，或加入完全不同之錯合物，諸如二茂鈦(titanocenes)(H.Hagen,W.P.Kretschmer,F.R.van Buren,B.Hessen,D.A.van Oeffelen,”選擇性乙烯三聚：對PE形成之機制及降低之研究”，Journal of Molecular Catalysis A：Chemical 248(2006)237－247)。無論任何一種情況，主要考量通常均為選擇性及聚乙烯形成之極小化。
目前在科學及專利文獻中所揭示之乙烯三聚及四聚觸媒及方法通常具有一個或多個下列缺點：． 對期望產物1－己烯及/或1－辛烯之選擇性低(亦即來自副反應管道之不期望副產物高)。
． 產物之純度有限，亦即在特定C6－或C8－部份之選擇性低(異構物化、分枝烯烴形成等)。
． 形成蠟，亦即形成重質、長鏈、高碳數產物。
． 形成聚合物(聚乙烯，分枝及/或交聯PE)，而導致可觀的產物產率損失及設備之積垢。
． 不佳的轉化率/觸媒活性，導致每公斤產物之成本提 高。
． 觸媒或配體成本高。
． 配體合成困難，導致低可利用性及高觸媒成本。
． 觸媒性能(在活性及選擇性二方面)對微量雜質敏感(觸媒損失/毒害)。
． 觸媒成份在技術環境(觸媒錯合物合成、預聚合、惰性化、觸媒或配體回收)中的操作困難。
． 嚴苛的反應條件，亦即高溫度及壓力，導致高投資、維護及能量成本。
． 高助觸媒/活化劑成本及/或消耗量
． 對助觸媒品質改變敏感；通常發生在必須使用較大量不明確的化合物(例如某些MAO－種類)做為活化劑的情況。
本發明的目的為提供一種能克服先前技術中缺點之用於乙烯之選擇性二、三及/或四聚之觸媒組合物及方法。尤其，不論製程條件為何，均可達到較高選擇性，而避免相當量之蠟及聚合物的形成。再者，本觸媒組合物對於技術製程而言亦能提供足夠高之活性轉換頻率。
易言之，可避免先前技術製程中LAO(直鏈狀α－烯烴)產物的寬廣範圍，且允許較佳、經濟上最期望之產物1－己烯之選擇性生產。視助觸媒性質及反應條件，亦可分別提供例如1－丁烯與1－己烯，及1－己烯與1－辛烯之共生產。
本目的係藉由提供一種觸媒組合物而達成，該觸媒組 合物包含：(a)鉻化合物；(b)具通式(A)R1 R2 P－N(R3 )－P(R4 )－N(R5 )－H或(B)R1 R2 P－N(R3 )－P(R4 )－N(R5 )－PR6 R7 (其中R1 、R2 、R3 、R4 、R5 、R6 及R7 各自獨立，選自鹵素、胺基、三甲基矽烷基、C1 －C10 －烷基、芳基及經取代之芳基)之配體，或(A)及(B)之任何環狀衍生物(其中PNPN－單元或PNPNP－單元之P或N原子之至少一個為一環系統之成員，該環系統係從構造(A)或(B)的一個或多個成分化合物藉由取代而形成)；以及(c)活化劑或助觸媒。
如眾所周知，任何(A)及(B)的環狀衍生物可被利用做為配體，其中PNPN－單元(構造(A))或PNPNP－單元(構造(B))之P或N原子之至少一個為環成員，該環係由構造(A)或(B)的一個或多個成分化合物藉由取代而形成，亦即形式上從每一成分化合物減去R1－R7(如定義)中之二個完整基團或H，來自R1－R7(如定義)中二基團之各個的一個原子，或者R1－R7(如定義)中之一個完整基團或H及來自R1－R7(如定義)中另一基團的一個原子，且每一成分化合物可藉由一個共價鍵形式上接合成所謂的共價不飽和位點，以於該給定位點提供與初始存在之價數相同的價數。
適合之(A)及(B)之環狀衍生物可為下列者：
該鉻化合物以選自Cr(II)或Cr(III)的有機或無機鹽、配位錯合物及有機金屬錯合物為較佳。
該鉻化合物以選自CrCl3 (THF)3 、乙烯基丙酮合Cr(III)、辛酸Cr(III)、六羰基鉻、2－乙基己酸Cr(III)及(苯)三羰基－鉻為最佳。
該R1 、R2 、R3 、R4 、R5 、R6 及R7 亦以選自氯、胺基、三甲基矽烷基、甲基、乙基、異丙基、第三丁基、苯基、苯甲基、甲苯基及二甲苯基為較佳。
適合之具有胺基－取代基之配體(A)及(B)可為下列者：
在一具體實施例中，活化劑或助觸媒係選自三甲基鋁、三乙基鋁、三異丙基鋁、三異丁基鋁、倍半氯化乙基鋁、氯化二乙基鋁、二氯化乙基鋁、甲基鋁氧烷(MAO)或其混合物。
其中該配體以選自(Ph)2 P－N(i－Pr)－P(Ph)－N(i－Pr)－H、(Ph)2 P－N(i－Pr)－P(Ph)－N(Ph)－H、(Ph)2 P－N(i－Pr)－P(Ph)－N(第三丁基)－H及(Ph)2 P－N(i－Pr)－P(Ph)－N(CH(CH3 )(Ph))－H為最佳。
觸媒組合物以包含溶劑之形式提供為較佳。
該溶劑以選自芳香烴、直鏈狀及環狀脂族烴、直鏈狀烯烴及醚為較佳，其中以甲苯、苯、乙基苯、異丙苯、二甲苯、三甲苯、己烷、辛烷、環己烷、甲基環己烷、己烯、庚烯、辛烯、***或四氫呋喃為更佳，其中以甲苯為最佳。任何此等溶劑之混合物亦可使用。
在一具體實施例中，該鉻化合物之濃度為從0.01至100 mmol/l，而以0.1至10 mmol/l為較佳。
該配體/Cr比以從0.5至50為較佳，而以0.8至2.0為更佳。
該Al/Cr比以1至1000為較佳，而以10至200為更佳。
如熟習此技藝者所熟知，提供該觸媒組合物之組份(a)至(c)多少可視為起始物質，然而亦可在該三種化合物(a)至(c)混合時轉化以形成觸媒組合物。在此種考量下，根據本發明之觸媒組合物亦可解釋係藉由組合至少下列者而得到： (a)鉻化合物；(b)具通式(A)R1 R2 P－N(R3 )－P(R4 )－N(R5 )－H或(B)R1 R2 P－N(R3 )－P(R4 )－N(R5 )－PR6 R7 (其中R1 、R2 、R3 、R4 、R5 、R6 及R7 各自獨立，選自鹵素、胺基、三甲基矽烷基、C1 －C10 －烷基、芳基及經取代之芳基)之配體，或任何(A)及(B)之環狀衍生物(其中PNPN－單元或PNPNP－單元之P或N原子之至少一個為環系統之成員，該環系統係從構造(A)或(B)的一個或多個成分化合物藉由取代而形成)；以及(c)活化劑或助觸媒。
根據本發明，亦提供一種乙烯之二、三及/或四聚的方法，其包含將本發明之觸媒組合物施用於反應器中之氣相乙烯，並進行寡聚。
其中該寡聚以在壓力1至200 bar進行為較佳，而以10至50 bar為更佳。
再者，該寡聚化在溫度10至200℃進行為較佳，而以20至100℃為更佳。
在一具體實施例中，該方法係以連續、半連續或不連續方式進行。
平均駐留時間為從10分鐘至20小時，而以1至4小時為較佳。
當組合通式(A)之配體及助觸媒時，可得到具有下列構造式之反應產物。
當然亦可不分開添加配體及助觸媒，而將上文揭示之反應產物用於觸媒組合物，此亦應在本發明之保護範圍內。
在反應條件下，PNPN－H－型配體被助觸媒在原處去質子化。在本發明之一更有利的具體實施例中，活性觸媒亦可藉由分開之去質子化/消減步驟離場形成，而產生上述構造。
尤其，如果使用較小或所佔立體空間較少之基團 R1 －R7 ，則該配體趨向於形成二聚體。此等二聚體環偶磷氮烷(cyclodiphosphazane)可被直接使用於形成活性觸媒。
所揭示之具通式(A)及(B)之配體亦可藉由以下構造式例示說明：
最佳配體構造為(Ph)2 P－N(i－Pr)－P(Ph)－N(i－Pr)－H及
令人驚異地，發現藉由本發明之觸媒組合物及乙烯之二、三及四聚之方法，可明顯地克服先前技術之缺點。尤其，本發明之方法及觸媒組合物允許1－己烯以高轉化率及高選擇性生產。再者，可得到高再現性，亦即觸媒組合物 不受來自雜質之千擾及製程條件之變動影響而保持安定。昂貴之助觸媒，諸如甲基鋁氧烷(MAO)，可全部或相當大程度被廉價之物質(以三乙基鋁為較佳)取代。再者，由於化學結構較不明確而傾向於品質不安定的助觸媒(例如MAO)可部分或全部被結構明確型的化學品(三乙基鋁)取代。依照本發明之方法，不會得到寬廣的LAO產物分布，而能選擇性地製造特定之α－烯烴。再者，可充分壓制聚合物之形成。並且，可選擇溫和的反應條件，因而使得技術規模工廠的投資成本降低，且能量成本及操作成本均降低。此外，使得相當單純、直接的製程設計成為可能。極高的1－己烯或1－己烯/1－辛烯選擇性使得產物純度高而在分離過程中無需額外的純化步驟。
本發明之進一步優點及特徵將在下述實施例章節中於參考附圖下例示說明，其中第一圖為實施例2所得到之液相之GC/FID分析。
活性觸媒可藉由將鉻源及配體在適當溶劑(以甲苯為優先)中混合，且使鉻濃度為0.01至100 mmol/L，較佳在0.1與10 mmol/L之間以及配體/Cr之比率成為0.5至50mol/mol，較佳0.8及2.0 mol/mol之間的方式製備。助觸媒(以三乙基鋁或三乙基鋁與MAO或三乙基鋁與三甲基鋁的任何混合物為較佳)係以溶於甲苯之溶液形式添加，且使Al/Cr比在l與1000 mol/mol之間。較佳之Al/Cr比為10至200 mol/mol。
溶劑甲苯可被其他溶劑取代，此等其他溶劑諸如甲苯 以外的芳香烴(苯、乙苯、異丙苯、二甲苯、三甲苯等)；脂肪族烴(直鏈狀及環狀，例如己烷、辛烷、環己烷)，直鏈烯烴類如己烯、庚烯、辛烯等，或醚類例如***或四氫呋喃。
繼而於適當的加壓反應器中，使觸媒溶液與無水乙烯的氣相於1與200 bar之間，較佳10與50 bar之間的壓力下接觸。該反應器可為任何適合提供氣相與液相充分接觸的類型，諸如氣泡管反應器、攪拌槽反應器、具有固定或分配式乙烯注入口的流動反應器等。
較佳反應溫度在10與200℃之間，最佳溫度範圍為20至100℃。選擇平均駐留時間及駐留時間分布(在連續式製成之情況)以在高選擇性下達到充分的轉化率。典型之平均駐留時間在10分鐘與20小時之間(取決於溫度及壓力)。較佳之範圍為1至4小時。
 實施例1：配體之製備
1.1雙(異丙基－胺基)－苯基膦(NPN)之製備 在異丙基胺(30 ml，352 mmol)溶於***(250 ml)之攪拌溶液中，於0℃經30分鐘期間添加二氯苯基膦(9.63 ml，71 mmol，溶於50 ml***)。總共攪拌72小時後，將溶液過濾。將殘餘物用***清洗，並將溶劑於真空除去。將殘存油在0.2 Torr/76－78℃下蒸餾，得到無色液體，產率33%(5.3 g)。31 P{H}NMR：49.0 ppm。
1.2(苯基) 2 PN(異丙基)P(苯基)NH(異丙基)(PNPN－H)之製備 將NPN類化合物(如1.1節中所製備)(2.4g，10.7 mmol)於四氫呋喃(10 ml)之溶液，於－40℃逐滴加入經攪拌之三乙基胺(6 ml)及氯二苯基膦(2.36 g，10.7 mmol)溶於四氫呋喃(40ml)之溶液中。於室溫再攪拌24小時後，將三乙基銨鹽濾除，並將殘餘物溶於正己烷，再度過濾，及將溶液保持在－30℃進行再結晶。產率52%(2.3 g，5.6 mmol)。31 P{H}NMR：41.2,68.4(寬)。
實施例2：乙烯之三聚
將設有滴加管、測溫插套、氣體運移式攪拌器、冷卻盤管、及溫度、壓力及攪拌器速度的控制單元(均連結到數據收取系統)之300 ml加壓反應器用乾氬氣洗氣並填充100 ml無水甲苯。在氬氣籠罩下，將配體1((苯基)2 PN(異丙基)P(苯基)NH(異丙基))溶於甲苯之4.017 wt%溶液1694μl與CrCl3 (thf)3 (thf＝四氫呋喃)59.2 mg混合。將此觸媒溶液連同三乙基鋁溶於甲苯之1.9 mol/L溶液3.6 ml一起在恆定氬氣流下轉移至反應器。
選擇配體/CrCl3 (thf)3 比為1.5 mol/mol且Al/Cr比為70 mol/mol時，能使鉻濃度成為1 mmol/l之體積及質量。
將反應器密封，用30 bar乾乙烯加壓並加熱至40℃。當以1200 rpm攪拌時，乙烯耗用量藉由數據收取系統及電子天平經常性地秤取乙烯加壓筒之重量而監測。經過120分鐘駐留時間後，液相反應藉由利用乙烯壓力將液體存留 物轉移至充填約100 ml水之玻璃槽中而停止。反應器頂部空間之總氣相藉由經校正之氣體測量計定量，繼而以定量方式收集於經洗氣並抽真空之氣袋中。
液體有機相分離之後，藉由秤重測定總質量。繼而，藉由GC/FID分析有機相之組成。另外將先前收集之氣相藉由GC/FID分析。
基於測得之數據，將質量天秤關閉，並測定總產率及選擇率。
為說明之目的，在第一圖中顯示液相之GC－追蹤。令人驚異地，其中發現非常高之1－己烯產率，而只有微量之1－丁烯、1－辛烯、1－癸烯及1－十二烯。在明確界定條件下之重複實驗中，未觀察到可偵測之聚合物形成。在40℃時平均C6－產率超過89%，溫度升高時稍微降低。甚至比高C6－產率更令人驚異者，為C6－部分中之1－己烯選擇率。在40℃反應溫度下測得之1－己烯選擇率趨近於100 wt%，亦即在實驗誤差範圍內與100 wt%幾無區別，因此在技術操作中無須使用確保1－己烯規格之任何精製分離單元。本發明所揭示之新穎觸媒系統可非常有效地壓制任何不期望之副反應管道，諸如烯烴異構化或重組，溶劑之佛端德－克來福特(Friedel－Crafts)烷化，共寡聚等。
一系列非最佳化實驗之典型結果之摘要示於表1中。較高溫度雖然造成C6－產率變差，然而可用於C4－及C6－烯烴之共生產，而且依然分別在C4－及C6－部分中得到高1－丁烯及1－己烯之選擇率(產物純度)。
使用不同助觸媒，及/或藉由改變配體之官能基構造或Cr/配體比，可使系統從純1－己烯，亦即乙烯－三聚觸媒，轉移至組合之三聚/四聚系統，而以高選擇率製造1－己烯及1－辛烯。
使用配體1及以三乙基鋁做為助觸媒可得到高1－己烯產率，而使用MAO則得到1－己烯及1－庚烯。
助觸媒之組合，諸如摻有少量MAO之三乙基鋁或三甲基鋁可增加總體活性(亦即轉化率)至少3倍，同時維持高產率及選擇率。
以PNPN－H為構造基礎之配體類型之其他較佳變化已成功地被合成且如上所示測試。
上述說明、申請專利範圍及圖式中所揭示之特徵，可分開或以其任何組合方式，做為以不同形式實現本發明之利器。
第一圖為根據實施例2之實驗條件所得液相之GC/FID分析。

Claims (16)

  1. 一種用於乙烯之選擇性二、三及/或四聚的觸媒組合物，其包含：(a)鉻化合物；(b)具通式(A)R1 R2 P-N(R3 )-P(R4 )-N(R5 )-H或(B)R1 R2 P-N(R3 )-P(R4 )-N(R5 )-PR6 R7 (其中R1 、R2 、R3 、R4 、R5 、R6 及R7 各自獨立，選自鹵素、胺基、三甲基矽烷基、C1 -C10 -烷基、芳基及經取代之芳基)之配體，或任何(A)及(B)之環狀衍生物(其中PNPN-單元或PNPNP-單元之P或N原子之至少一個為環系統之成員，該環系統係從構造(A)或(B)的一個或多個成分化合物藉由取代而形成)；以及(c)活化劑或助觸媒。
  2. 如申請專利範圍第1項之觸媒組合物，其中該鉻化合物係選自Cr(II)或Cr(III)的有機或無機鹽、配位錯合物及有機金屬錯合物。
  3. 如申請專利範圍第2項之觸媒組合物，其中該鉻化合物係選自CrCl3 (THF)3 、乙烯基丙酮合Cr(III)、辛酸Cr(III)、六羰基鉻、2-乙基己酸Cr(III)及(苯)三羰基-鉻。
  4. 如申請專利範圍第1項之觸媒組合物，其中R1 、R2 、R3 、R4 、R5 、R6 及R7 係選自氯、胺基、三甲基矽烷基、甲基、乙基、異丙基、第三丁基、苯基、苯甲基、甲苯基及二 甲苯基。
  5. 如申請專利範圍第1項之觸媒組合物，其中該活化劑或助觸媒係選自三甲基鋁、三乙基鋁、三異丙基鋁、三異丁基鋁、倍半氯化乙基鋁、氯化二乙基鋁、二氯化乙基鋁、甲基鋁氧烷(MAO)或其混合物。
  6. 如申請專利範圍第1項之觸媒組合物，其中該配體係選自(Ph)2 P-N(i-Pr)-P(Ph)-N(i-Pr)-H、(Ph)2 P-N(i-Pr)-P(Ph)-N(Ph)-H、(Ph)2 P-N(i-Pr)-P(Ph)-N(第三丁基)-H及(Ph)2 P-N(i-Pr)-P(Ph)-N(CH(CH3 )(Ph))-H。
  7. 如申請專利範圍第1項之觸媒組合物，其另外包含溶劑。
  8. 如申請專利範圍第7項之觸媒組合物，其中該溶劑係選自芳香烴、直鏈及環狀脂族烴、直鏈烯烴及醚。
  9. 如申請專利範圍第7項之觸媒組合物，其中該鉻化合物之濃度為0.01至100mmol/l。
  10. 如申請專利範圍第1項之觸媒組合物，其中該配體/Cr比為從0.5至50。
  11. 如申請專利範圍第5項之觸媒組合物，其中該Al/Cr比為從1：1至1000：1。
  12. 一種乙烯之二、三及/或四聚的方法，其包含將如申請專利範圍第1至11項中任一項之觸媒組合物施用於反應器中之氣相乙烯，而進行寡聚。
  13. 如申請專利範圍第12項之方法，其中該寡聚係在壓力1至200 bar進行。
  14. 如申請專利範圍第12或13項之方法，其中該寡聚係在 溫度10至200℃進行。
  15. 如申請專利範圍第13項之方法，其中該方法係連續地進行。
  16. 如申請專利範圍第13項之方法，其中平均駐留時間為10分鐘至20小時。
TW097123207A 2007-07-11 2008-06-20 用於乙烯之二、三及／或四聚的觸媒組合物及方法 TWI415683B (zh)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP07013543 2007-07-11

Publications (2)

Publication Number Publication Date
TW200909055A TW200909055A (en) 2009-03-01
TWI415683B true TWI415683B (zh) 2013-11-21

Family

ID=38863117

Family Applications (1)

Application Number Title Priority Date Filing Date
TW097123207A TWI415683B (zh) 2007-07-11 2008-06-20 用於乙烯之二、三及／或四聚的觸媒組合物及方法

Country Status (13)

Country Link
US (2) US8637721B2 (zh)
EP (1) EP2167231B8 (zh)
JP (1) JP5158726B2 (zh)
KR (1) KR101241656B1 (zh)
CN (1) CN101720253B (zh)
BR (1) BRPI0813779B1 (zh)
CA (1) CA2692533C (zh)
ES (1) ES2394866T3 (zh)
MY (1) MY148675A (zh)
RU (1) RU2456078C2 (zh)
SG (1) SG183005A1 (zh)
TW (1) TWI415683B (zh)
WO (1) WO2009006979A2 (zh)

Families Citing this family (70)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MX2010005266A (es) * 2007-11-28 2010-06-02 Linde Ag Composicion catalizadora y proceso para oligomerizacion de etileno.
ES2371218T3 (es) * 2009-04-09 2011-12-28 Saudi Basic Industries Corporation Composición de catalizador y procedimiento para la oligomerización de etileno.
CA2777323C (en) 2009-10-16 2017-07-11 Sasol Technology (Proprietary) Limited Separation of components from a multi-component hydrocarbon stream which includes ethylene
WO2011085951A1 (en) 2010-01-15 2011-07-21 Basell Polyolefine Gmbh Oligomerization of olefins
EP2354113A1 (en) 2010-02-04 2011-08-10 Linde AG Method for deactivation of a catalyst
CN102451759B (zh) * 2010-10-22 2015-09-09 中国石油化工股份有限公司 乙烯四聚催化剂、其制备和应用
CN102451758B (zh) * 2010-10-22 2015-12-16 中国石油化工股份有限公司 乙烯四聚催化剂、其制备和应用
WO2012055943A2 (en) 2010-10-28 2012-05-03 Basell Polyolefine Gmbh Oligomerization of olefins
WO2012072178A1 (en) 2010-11-30 2012-06-07 Linde Aktiengesellschaft Method for cleaning a reactor and/or equipment thereof
EP2489431B1 (en) 2011-02-16 2013-05-01 Linde AG Method for preparing a catalyst composition for oligomerization of ethylene and respective catalyst composition pre-formation unit
CN103100420A (zh) * 2011-11-09 2013-05-15 中国石油化工股份有限公司 用于乙烯四聚的催化剂组合物及其中配体的制备方法
JP5844636B2 (ja) * 2011-12-27 2016-01-20 出光興産株式会社 α−オレフィンの製造方法
KR101846031B1 (ko) 2012-03-16 2018-04-05 에스케이이노베이션 주식회사 에틸렌으로부터 1-헥센 및/또는 1-옥텐을 제조하기 위한 촉매계
SG11201406965UA (en) 2012-05-09 2014-11-27 Sasol Tech Pty Ltd Separation of components from a multi-component hydrocarbon stream
CN104284714B (zh) 2012-05-09 2016-06-29 沙索技术有限公司 用于使烃低聚以形成至少一种共聚单体产物的方法
ES2750659T3 (es) 2012-05-09 2020-03-26 Sasol Tech Pty Ltd Tetramerización de etileno
ES2656088T3 (es) 2012-05-09 2018-02-23 Sasol Technology (Proprietary) Limited Tetramerización de etileno
KR102088445B1 (ko) 2012-05-09 2020-03-13 사솔 테크날러지 (프로프라이어터리) 리미티드 중합체 형성이 감소된 올레핀 화합물의 올리고머화
EP2684857A1 (en) 2012-07-10 2014-01-15 Saudi Basic Industries Corporation Method for oligomerization of ethylene
KR101483248B1 (ko) 2012-11-15 2015-01-16 주식회사 엘지화학 리간드 화합물, 유기크롬 화합물, 에틸렌 올리고머화용 촉매계, 이의 제조 방법 및 이를 이용한 에틸렌 올리고머화 방법
EP2738151B8 (en) * 2012-11-28 2014-12-17 Saudi Basic Industries Corporation Process for oligomerization of ethylene
CA2800268C (en) * 2012-12-21 2020-02-25 Nova Chemicals Corporation Continuous ethylene tetramerization process
EP2764915B1 (en) 2013-02-11 2017-03-22 Linde AG Purification method for a crude PNPNH compound
EP2764913A1 (en) 2013-02-11 2014-08-13 Linde AG Method for purifying a crude PNPNH compound
EP2764914A1 (en) 2013-02-11 2014-08-13 Linde AG Metalated PNPNH ligand, catalyst composition and use thereof in the oligomerization of ethylene
KR101483247B1 (ko) * 2013-04-23 2015-01-16 주식회사 엘지화학 폴리올레핀 중합용 촉매의 제조 방법 및 폴리올레핀 제조방법
SG11201508463VA (en) 2013-05-09 2015-11-27 Sasol Tech Pty Ltd Tetramerisation of ethylene
KR20160006192A (ko) 2013-05-09 2016-01-18 사솔 테크날러지 (프로프라이어터리) 리미티드 에틸렌의 1-헥센 및 1-옥텐의 혼합물로의 올리고머화 방법
CA2908559C (en) 2013-05-09 2021-08-17 Sasol Technology (Proprietary) Limited Oligomerisation of ethylene to mixtures of 1-hexene and 1-octene
EP2832445A1 (en) * 2013-07-29 2015-02-04 Linde AG Catalyst composition and process for oligomerization of ethylene
KR101638980B1 (ko) 2013-09-30 2016-07-12 주식회사 엘지화학 리간드 화합물, 유기크롬 화합물, 에틸렌 올리고머화용 촉매 시스템, 및 이를 이용한 에틸렌 올리고머화 방법
CN104511311B (zh) * 2013-09-30 2017-07-07 华东理工大学 一种高选择性的乙烯三聚、四聚催化剂体系及其使用方法
KR101601936B1 (ko) 2013-11-19 2016-03-09 주식회사 엘지화학 리간드 화합물, 올레핀 올리고머화용 촉매계, 및 이를 이용한 올레핀 올리고머화 방법
EP3092074A2 (en) * 2014-01-06 2016-11-16 Saudi Basic Industries Corporation Modified preformation method for catalyst activation in ethylene reactions
CN106573236B (zh) * 2014-07-24 2020-05-29 沙特基础工业全球技术有限公司 用于乙烯的低聚以产生1-己烯和/或1-辛烯的催化剂组合物和方法
KR101646178B1 (ko) * 2014-11-25 2016-08-05 롯데케미칼 주식회사 올레핀 올리고머화용 촉매계, 및 이를 이용한 올레핀 올리고머화 방법
KR101645611B1 (ko) * 2014-11-26 2016-08-05 롯데케미칼 주식회사 올레핀 올리고머화용 촉매계, 및 이를 이용한 올레핀 올리고머화 방법
KR101679515B1 (ko) * 2015-02-12 2016-11-24 주식회사 엘지화학 올리고머화 촉매계의 제조방법 및 이에 의해 제조된 올리고머화 촉매계
EP3243847B1 (en) * 2015-05-15 2020-08-26 LG Chem, Ltd. Catalytic composition and method of preparing polyolefin using same
KR101768194B1 (ko) 2015-05-15 2017-08-16 주식회사 엘지화학 촉매 조성물 및 이를 이용한 폴리올레핀의 제조방법
KR101757835B1 (ko) 2015-06-12 2017-07-13 주식회사 엘지화학 리간드 화합물, 유기 크롬 화합물, 올레핀 올리고머화용 촉매 시스템, 및 이를 이용한 올레핀의 올리고머화 방법
US10407359B2 (en) * 2015-09-16 2019-09-10 Sabic Global Technologies B.V. Process for deactivation of an olefin oligomerization catalyst
EP3394011B1 (en) 2015-12-22 2020-07-22 SABIC Global Technologies B.V. Methods for toluene recovery from linear alpha olefin production
KR101818180B1 (ko) * 2016-05-13 2018-02-21 한국화학연구원 에틸렌 올리고머화 방법
RU2749592C2 (ru) * 2016-12-30 2021-06-15 Сабик Глобал Текнолоджис Б.В. Способ получения раствора катализатора для селективного производства 1-гексена
KR102472153B1 (ko) 2016-12-30 2022-11-28 사빅 글로벌 테크놀러지스 비.브이. 선택적인 1-헥센 제조용 균질 촉매의 제조 방법
WO2019074304A1 (ko) * 2017-10-11 2019-04-18 롯데케미칼 주식회사 올레핀 올리고머화용 촉매계 및 이를 이용하는 올레핀 올리고머 제조방법
CN109289928A (zh) * 2018-10-09 2019-02-01 天津科技大学 一种用于乙烯齐聚的催化剂及其制备方法
KR20210091748A (ko) * 2018-11-12 2021-07-22 사빅 글로벌 테크놀러지스 비.브이. 크롬 보조된 1-헥센의 생성을 위한 리간드 및 이를 이용한 에틸렌 올리고머화 방법
WO2020147372A1 (zh) * 2019-01-15 2020-07-23 中国石油化工股份有限公司 含卤素化合物及其作为催化剂配体在乙烯齐聚中的用途
CN111434670B (zh) * 2019-01-15 2021-07-30 中国石油化工股份有限公司 含氟化合物及用途和乙烯齐聚催化剂组合物及乙烯齐聚方法和乙烯三聚方法和乙烯四聚方法
CN111434668B (zh) * 2019-01-15 2021-08-03 中国石油化工股份有限公司 含卤素化合物及用途和催化剂组合物及乙烯齐聚方法和乙烯三聚方法和乙烯四聚方法
KR20210116515A (ko) 2019-01-15 2021-09-27 차이나 페트로리움 앤드 케미컬 코포레이션 할로겐 함유 화합물 및 용도 및 촉매 조성물 및 에틸렌 올리고머화 방법 및 에틸렌 삼량체화 방법 및 에틸렌 사량체화 방법
CN110479382B (zh) * 2019-08-19 2022-04-29 迈瑞尔实验设备（上海）有限公司 一种用于乙烯选择性齐聚制1-辛烯的催化剂体系及其制备方法与应用
CN111889142B (zh) * 2020-07-23 2023-02-07 天津科技大学 一种乙烯选择性齐聚的催化剂体系、反应方法及其应用
CN112473741B (zh) * 2020-10-22 2023-09-01 杭州小菱科技有限公司 一种乙烯齐聚催化剂体系及其制备方法与用途
US11440857B2 (en) 2020-11-30 2022-09-13 Saudi Arabian Oil Company Catalyst systems
US11623208B2 (en) 2020-11-30 2023-04-11 Saudi Arabian Oil Company Catalyst systems
US11458463B2 (en) 2020-11-30 2022-10-04 Saudi Arabian Oil Company Catalyst systems
US11458462B2 (en) 2020-11-30 2022-10-04 Saudi Arabian Oil Company Catalyst systems
WO2022115748A1 (en) 2020-11-30 2022-06-02 Saudi Arabian Oil Company Catalyst systems
JP7280623B2 (ja) * 2020-12-28 2023-05-24 株式会社アビー 細胞凍結保存液、及び細胞凍結方法
EP4294564A1 (en) 2021-03-12 2023-12-27 Saudi Arabian Oil Company Catalyst systems
US11484871B1 (en) 2021-08-26 2022-11-01 Saudi Arabian Oil Company Catalyst systems
CN114163475B (zh) * 2021-12-01 2023-07-28 浙江智英石化技术有限公司 含吡咯基刚性结构多位点配体的催化剂体系、制备方法及应用
WO2023118226A1 (en) 2021-12-23 2023-06-29 Sabic Global Technologies B.V. Catalyst composition for oligomerization reaction
US11639321B1 (en) 2022-08-31 2023-05-02 Saudi Arabian Oil Company Catalyst systems that include meta-alkoxy substituted n-aryl bis-diphosphinoamine ligands
US11623901B1 (en) 2022-08-31 2023-04-11 Saudi Arabian Oil Company Catalyst systems that include silyl ether moieties
WO2024047612A1 (en) 2022-09-02 2024-03-07 Sabic Global Technologies B.V. Methods for producing 1-hexene
US12037301B1 (en) 2022-12-20 2024-07-16 King Fahd University Of Petroleum And Minerals Chromium-catalyzed ethylene oligomerization with bulky functionalized N-aryl bisphosphineamine ligands

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7022788B2 (en) * 1999-08-06 2006-04-04 Bp Chemicals Limited Polymerization process catalyzed by a bidentate bisphosphine-group VIII metal complex
US20060173226A1 (en) * 2002-12-20 2006-08-03 Kevin Blann Tetramerization of olefins

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5259939A (en) 1991-08-30 1993-11-09 Beckman Instruments, Inc. Capillary electrophoresis buffer
US5811618A (en) * 1991-10-16 1998-09-22 Amoco Corporation Ethylene trimerization
GB9517105D0 (en) * 1995-08-21 1995-10-25 Bp Chem Int Ltd Catalyst compositions
ES2216137T3 (es) * 1996-04-04 2004-10-16 Bp Chemicals Limited Un compuesto que puede utilizarse en una composicion catalitica.
US6337297B1 (en) * 1998-10-12 2002-01-08 Tosoh Corporation Catalyst for trimerization of ethylene and process for trimerizing ethylene using the catalyst
GB0016895D0 (en) * 2000-07-11 2000-08-30 Bp Chem Int Ltd Olefin oligomerisation
US7300904B2 (en) 2001-12-20 2007-11-27 Sasol Technology (Pty) Ltd. Trimerisation and oligomerisation of olefins using a chromium based catalyst
CA2510190C (en) 2002-12-20 2011-10-11 Sasol Technology (Pty) Limited Trimerisation of olefins
US7273959B2 (en) 2003-10-10 2007-09-25 Shell Oil Company Catalytic trimerization of olefinic monomers
KR20080080570A (ko) * 2005-11-21 2008-09-04 셀 인터나쵸나아레 레사아치 마아츠샤피 비이부이 올레핀 단량체의 올리고머화를 위한 촉매법
CN100386149C (zh) * 2006-06-26 2008-05-07 中国石油天然气股份有限公司 一种乙烯三聚催化剂及其应用
DE102009027375A1 (de) 2009-07-01 2011-03-10 Robert Bosch Gmbh Diagnoseverfahren zum Durchführen einer Diagnose eines Systems

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7022788B2 (en) * 1999-08-06 2006-04-04 Bp Chemicals Limited Polymerization process catalyzed by a bidentate bisphosphine-group VIII metal complex
US20060173226A1 (en) * 2002-12-20 2006-08-03 Kevin Blann Tetramerization of olefins

Also Published As

Publication number Publication date
BRPI0813779B1 (pt) 2018-06-26
RU2456078C2 (ru) 2012-07-20
CA2692533A1 (en) 2009-01-15
JP2010532711A (ja) 2010-10-14
WO2009006979A2 (en) 2009-01-15
EP2167231A2 (en) 2010-03-31
EP2167231B8 (en) 2013-03-06
WO2009006979A3 (en) 2009-03-26
SG183005A1 (en) 2012-08-30
CN101720253B (zh) 2013-07-17
MY148675A (en) 2013-05-31
BRPI0813779A2 (pt) 2014-12-30
US9555404B2 (en) 2017-01-31
RU2010104668A (ru) 2011-08-20
ES2394866T3 (es) 2013-02-06
CA2692533C (en) 2013-03-05
KR101241656B1 (ko) 2013-03-11
US20100190939A1 (en) 2010-07-29
US20140179970A1 (en) 2014-06-26
JP5158726B2 (ja) 2013-03-06
TW200909055A (en) 2009-03-01
CN101720253A (zh) 2010-06-02
US8637721B2 (en) 2014-01-28
KR20100046170A (ko) 2010-05-06
EP2167231B1 (en) 2012-09-26
WO2009006979A8 (en) 2009-12-23

Similar Documents

Publication Publication Date Title
TWI415683B (zh) 用於乙烯之二、三及／或四聚的觸媒組合物及方法
JP5571769B2 (ja) エチレンのオリゴマー化のための触媒組成物およびプロセス
KR101495389B1 (ko) 에틸렌의 올리고머화를 위한 촉매, 그것을 제조하기 위한 방법 및 그것을 사용하는 올리고머화를 위한 공정
KR101445431B1 (ko) 촉매 조성물 및 에틸렌의 올리고머화를 위한 공정
JP2012523306A5 (zh)
JP7502289B2 (ja) クロム補助エチレンオリゴマー化プロセスにおける１－ヘキセンの生成のための配位子
KR20210087528A (ko) 크롬 보조된 1-옥텐의 생성을 위한 리간드 및 이를 이용한 에틸렌 올리고머화 방법
RU2821953C2 (ru) Лиганды для получения 1-гексена в хром-катализируемом процессе олигомеризации этилена

Legal Events

Date Code Title Description
MM4A Annulment or lapse of patent due to non-payment of fees