GB1569714A - Nickel-rhenium hydrogenation catalyst and methods of preparing same and using same - Google Patents

Nickel-rhenium hydrogenation catalyst and methods of preparing same and using same Download PDF

Info

Publication number
GB1569714A
GB1569714A GB376/77A GB37677A GB1569714A GB 1569714 A GB1569714 A GB 1569714A GB 376/77 A GB376/77 A GB 376/77A GB 37677 A GB37677 A GB 37677A GB 1569714 A GB1569714 A GB 1569714A
Authority
GB
United Kingdom
Prior art keywords
nickel
rhenium
composition
catalyst
support
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.)
Expired
Application number
GB376/77A
Other languages
English (en)
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.)
Union Carbide Corp
Original Assignee
Union Carbide 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 Union Carbide Corp filed Critical Union Carbide Corp
Publication of GB1569714A publication Critical patent/GB1569714A/en
Expired legal-status Critical Current

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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8896—Rhenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
    • C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
    • C07C209/28—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with other reducing agents

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
GB376/77A 1976-01-07 1977-01-06 Nickel-rhenium hydrogenation catalyst and methods of preparing same and using same Expired GB1569714A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US05/647,065 US4123462A (en) 1976-01-07 1976-01-07 Amination process using nickel-rhenium catalysts

Publications (1)

Publication Number Publication Date
GB1569714A true GB1569714A (en) 1980-06-18

Family

ID=24595557

Family Applications (1)

Application Number Title Priority Date Filing Date
GB376/77A Expired GB1569714A (en) 1976-01-07 1977-01-06 Nickel-rhenium hydrogenation catalyst and methods of preparing same and using same

Country Status (10)

Country Link
US (2) US4123462A (https=)
JP (2) JPS6038380B2 (https=)
BE (1) BE850144A (https=)
CA (1) CA1083558A (https=)
DE (1) DE2700339C3 (https=)
FR (1) FR2337585A1 (https=)
GB (1) GB1569714A (https=)
IN (1) IN145670B (https=)
IT (1) IT1082703B (https=)
NL (1) NL180914C (https=)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0526851A3 (en) * 1991-07-31 1993-05-19 Tosoh Corporation Process and catalyst for producing an ethylenamine
WO1997012928A1 (en) * 1995-10-04 1997-04-10 The Dow Chemical Company Amine capped polyethers and process for producing same
US5817593A (en) * 1995-06-02 1998-10-06 The Dow Chemical Company Catalyst and process for producing amines
JP2012162525A (ja) * 2011-02-03 2012-08-30 Evonik Degussa Gmbh ポリアミド合成のための主鎖が線状の第１級ジアミンの製造

Families Citing this family (79)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4209424A (en) 1977-12-12 1980-06-24 Societe Chimique de la Grande Paroisse, Azote et Products Chimiques Catalyst for manufacturing amines from alcohols
FR2411030A1 (fr) * 1977-12-12 1979-07-06 Azote & Prod Chim Catalyseur et procede de fabrication d'amines a partir d'alcools
FR2430262A2 (fr) * 1978-07-04 1980-02-01 Azote & Prod Chim Catalyseur et procede de fabrication d'amines a partir d'alcools
EP0002630B2 (fr) * 1977-12-12 1986-04-16 Societe Chimique De La Grande Paroisse, Azote Et Produits Chimiques Catalyseur et procédé de fabrication d'amines à partir d'alcools
US4404405A (en) * 1981-09-30 1983-09-13 Union Carbide Corporation Process for the preparation of polyethylene polyamines
US4400539A (en) * 1981-09-30 1983-08-23 Union Carbide Corporation Process for the manufacture of ethylenediamine
US4929759A (en) * 1983-07-27 1990-05-29 Basf Aktiengesellschaft Production of amines from an olefin and ammonia or a primary or secondary amine
SE461095B (sv) * 1983-09-09 1990-01-08 Berol Kemi Ab Amineringsfoerfarande med anvaendning av en ruteniumdopad nickel och/eller kovoltkatalysator
US4625030A (en) * 1984-05-23 1986-11-25 Union Carbide Corporation Potentiated nickel catalysts for amination
US4647701A (en) * 1984-05-23 1987-03-03 Union Carbide Corporation Processes for producing diethylenetriamine from monoethanolamine
US4827037A (en) * 1985-04-04 1989-05-02 Union Carbide Corporation Quality of catalytically prepared polyalkylene polyamines
US4772750A (en) * 1985-06-14 1988-09-20 The Dow Chemical Company Method of producing amines
GB8519425D0 (en) * 1985-08-01 1985-09-04 Ici Plc Amine production
US4709034A (en) * 1986-02-14 1987-11-24 Air Products And Chemicals, Inc. Process for the synthesis of hydroxyalkyl amines and hydroxyalkyl piperazines
US4918233A (en) * 1986-07-08 1990-04-17 Air Products And Chemicals, Inc. Production of ethylenediamine from monoethanolamine and ammonia
US4774336A (en) * 1986-10-02 1988-09-27 Texaco Inc. Process for preparing N-substituted piperazines from ethylene glycol and amines
GB8707304D0 (en) * 1987-03-26 1987-04-29 Bp Chem Int Ltd Chemical process
US4795733A (en) * 1987-11-27 1989-01-03 Gaf Corporation Hydrogenation catalyst and process for its preparation
GB8819663D0 (en) * 1988-08-18 1988-09-21 Bp Chem Int Ltd Chemical process
GB8918965D0 (en) * 1989-08-19 1989-10-04 Bp Chem Int Ltd Chemical process
DE4006540A1 (de) * 1990-03-02 1991-09-05 Huels Chemische Werke Ag Katalysatoren fuer die metathese von olefinen und funktionalisierten olefinen
DE69521289T2 (de) * 1993-12-22 2002-05-02 Union Carbide Chemicals & Plastics Technology Corp., Danbury Reduktive Aminierung zur selektiven Herstellung von Aminoethylethanolamin
CA2146903C (en) * 1993-12-22 2000-01-25 Stephen Wayne King Reductive amination catalysts for the selective production of aminoethylethanolamine
US5600000A (en) * 1993-12-22 1997-02-04 Union Carbide Chemicals & Plastics Technology Corporation Reductive amination processes for the selective production of amino-ethylethanolamine
US5475138A (en) * 1994-07-07 1995-12-12 Pharm-Eco Laboratories Incorporated Method preparing amino acid-derived diaminopropanols
US6063963A (en) * 1995-07-05 2000-05-16 Pharm-Eco Laboratories, Inc. Amino acid-derived diaminopropanols
US5679862A (en) * 1996-03-25 1997-10-21 Chemical Research & Licensing Company Amination process
SE513250C2 (sv) * 1997-11-11 2000-08-07 Akzo Nobel Nv Amineringsförfarande för framställning av polyaminer
ES2229754T3 (es) * 1998-07-21 2005-04-16 Lonza A.G. Procedimiento para la preparacion de aminas.
US6534441B1 (en) * 1999-03-06 2003-03-18 Union Carbide Chemicals & Plastics Technology Corporation Nickel-rhenium catalyst for use in reductive amination processes
US6309758B1 (en) * 1999-05-06 2001-10-30 W. R. Grace & Co.-Conn. Promoted porous catalyst
WO2003076883A2 (en) * 2002-03-08 2003-09-18 Sensys Medical, Inc. Compact apparatus for noninvasive measurement of glucose through near-infrared spectroscopy
DE10145119A1 (de) * 2001-09-13 2003-04-03 Basf Ag Verfahren zur Herstellung von Aminen
US7022645B2 (en) * 2003-08-04 2006-04-04 Catalytic Distillation Technologies Ni hydrogenation catalysts, manufacture and use
US7131446B2 (en) * 2004-03-25 2006-11-07 Tang Kenneth Y Light-triggered tattoo process
US20080045749A1 (en) * 2006-06-07 2008-02-21 The Procter & Gamble Company Process for the alternating conversion of glycerol to propylene glycol or amino alcohols
US7619118B2 (en) 2006-06-07 2009-11-17 The Procter & Gamble Company Process for the conversion of glycerol to propylene glycol and amino alcohols
US7619119B2 (en) * 2006-06-07 2009-11-17 The Procter & Gamble Company Processes for converting glycerol to amino alcohols
KR20100111712A (ko) * 2008-01-03 2010-10-15 아크조 노벨 엔.브이. 에틸렌 아민의 제조 방법
WO2009155466A2 (en) 2008-06-19 2009-12-23 Honda Motor Co. Ltd. Low temperature single-wall carbon nanotube synthesis
CN102239002B (zh) * 2008-10-06 2013-10-30 联合碳化化学品及塑料技术公司 低金属负载的氧化铝载体的催化剂组合物和氨基化方法
CN102227413B (zh) 2008-10-06 2014-11-05 联合碳化化学品及塑料技术公司 制备环状n-氨基官能化三胺的方法
EP2346810B1 (en) * 2008-10-06 2015-08-19 Dow Global Technologies LLC Methods for making ethanolamine(s) and ethyleneamine(s) from ethylene oxide and ammonia, and related methods
WO2010042161A1 (en) * 2008-10-06 2010-04-15 Union Carbide Chemicals & Plastics Technology Llc Low metal (nickel and rhenium) catalyst compositions including acidic mixed metal oxide as support
JP5774991B2 (ja) * 2008-10-06 2015-09-09 ユニオン カーバイド ケミカルズ アンド プラスティックス テクノロジー エルエルシー 不均一触媒系上でのエチレンジアミン（ｅｄａ）及び他のエチレンアミンの連続アミノ交換反応による、ジエチレントリアミン（ｄｅｔａ）又は他の望ましいエチレンアミンの選択的製造プロセス
JP2012504610A (ja) * 2008-10-06 2012-02-23 ユニオン カーバイド ケミカルズ アンド プラスティックス テクノロジー エルエルシー エチレンアミンの製造方法
US8124808B2 (en) * 2008-10-06 2012-02-28 Union Carbide Chemicals & Plastics Technology Llc Transalkoxylation of nucleophilic compounds
CN101875014B (zh) * 2009-11-17 2012-10-03 中国科学院大连化学物理研究所 一种在临氢条件下一乙醇胺和氨转化为乙二胺的催化剂
EP2571968A1 (en) 2010-05-21 2013-03-27 H R D Corporation Process for upgrading low value renewable oils
DE102011004465A1 (de) 2010-09-10 2012-03-15 Evonik Degussa Gmbh Verfahren zur direkten Aminierung sekundärer Alkohole mit Ammoniak zu primären Aminen
DE102011075162A1 (de) 2010-12-08 2012-06-14 Evonik Degussa Gmbh Verfahren zur homogen-katalysierte, hochselektiven direkten Aminierung von primären Alkoholen mit Ammoniak zu primären Aminen bei hohem Volumenverhältnis von Flüssig- zu Gasphase und/oder hohen Drücken
CN103370302B (zh) 2011-02-21 2015-06-17 赢创德固赛有限公司 借助Xantphos催化剂体系用氨将醇直接胺化成伯胺的方法
EP2794581B1 (en) * 2011-12-22 2016-05-25 Dow Global Technologies LLC Reductive amination of diethanolamine and resulting product mixture
US8952198B2 (en) 2013-01-30 2015-02-10 Ian Williams Amination process for manufacturing amines using catalyst
EP3077444B1 (en) 2013-12-02 2018-04-25 Dow Global Technologies LLC Preparation of high molecular weight, branched, acyclic polyalkyleneamines and mixtures thereof
MX378938B (es) 2016-02-12 2025-03-10 Akzo Nobel Chemicals Int Bv Proceso para preparar etilenaminas y derivados de etilenaminas superiores.
JP6671490B2 (ja) * 2016-02-12 2020-03-25 ヌーリオン ケミカルズ インターナショナル ベスローテン フェノーツハップＮｏｕｒｙｏｎ Ｃｈｅｍｉｃａｌｓ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｂ．Ｖ． 高級エチレンアミンおよびエチレンアミン誘導体を調製する方法
US10844001B2 (en) 2016-02-12 2020-11-24 Nouryon Chemicals International B.V. Process to prepare higher ethylene amines and ethylene amine derivatives
KR102445287B1 (ko) 2016-05-11 2022-09-20 레그 신써틱 퓨얼즈, 엘엘씨 바이오재생 케로신, 제트 연료, 제트 연료 혼합연료, 및 제조 방법
EP3568387B1 (en) * 2016-11-30 2021-05-05 Basf Se Process for the conversion of ethylene glycol to ethylenediamine employing a zeolite catalyst
WO2018108698A1 (de) 2016-12-15 2018-06-21 Basf Se Verfahren zur herstellung von ethanolaminen und/oder ethylenaminen
BR112019025307B1 (pt) 2017-06-09 2023-05-09 Basf Se Processo para preparar alcanolaminas e/ ou etilenoaminas na fase líquida
CN110785400B (zh) 2017-06-09 2024-01-09 巴斯夫欧洲公司 制备亚乙基胺的方法
JP7105811B2 (ja) 2017-06-09 2022-07-25 ビーエーエスエフ ソシエタス・ヨーロピア エチレンアミンの製造方法
BR112020000020B1 (pt) 2017-07-10 2023-10-17 Nouryon Chemicals International B.V Processo para preparar etileno aminas, derivado de ureia de tetraetileno pentamina, derivado de ureia de pentaetileno-hexamina e uso do derivado de ureia
CN111278801B (zh) 2017-10-27 2023-05-26 巴斯夫欧洲公司 从含eda的混合物中分离n-甲基乙二胺
JP7277454B2 (ja) 2017-10-27 2023-05-19 ビーエーエスエフ ソシエタス・ヨーロピア エチレンアミンの製造方法
JP7268016B2 (ja) 2017-10-27 2023-05-02 ビーエーエスエフ ソシエタス・ヨーロピア エチレンアミンの製造方法
CN111263746B (zh) 2017-10-27 2024-01-19 巴斯夫欧洲公司 制备亚乙基胺的方法
CN107913694A (zh) * 2017-10-31 2018-04-17 山东玉皇化工有限公司 一种胺化催化剂载体的调变方法及其应用
CN109734601B (zh) * 2019-01-25 2021-11-12 浙江师范大学 一种制备1,3-丙二胺的方法
WO2020178085A1 (en) 2019-03-06 2020-09-10 Basf Se Method for the production of ethyleneamines
EP4073026B1 (en) 2019-12-13 2024-06-05 Basf Se Separation of n-methylethylenediamine from eda-containing mixtures
EP4463435A1 (en) 2022-01-14 2024-11-20 Basf Se Method for the manufacture or conversion of alkanolamines
JP2025520810A (ja) 2022-06-29 2025-07-03 ビーエーエスエフ ソシエタス・ヨーロピア エチレンアミンの製造方法
WO2024002740A1 (en) 2022-06-29 2024-01-04 Basf Se Method for manufacture of ethyleneamines
WO2025125094A1 (en) 2023-12-14 2025-06-19 Basf Se Process for preparing diethylenetriamine and/or ethylene glycol
CN118253311A (zh) * 2024-04-08 2024-06-28 卫星化学股份有限公司 一种用于乙二胺和哌嗪制备的催化剂及其制备方法和应用
WO2026022226A1 (en) 2024-07-23 2026-01-29 Basf Se Assistance in controlling a chemical reactor

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3240782A (en) * 1966-03-15 Method of converting z-dehydro-isoeme tine into z-dehydro-emetine and inter- mediates therein
DE1034184B (de) * 1957-01-23 1958-07-17 Basf Ag Verfahren zur Herstellung von 1, 3-Propylendiamin
US3022349A (en) * 1957-12-30 1962-02-20 Union Carbide Corp Production of amines
NL248643A (https=) * 1959-02-27
DE1172268B (de) * 1962-02-21 1964-06-18 Basf Ag Verfahren zur Herstellung von Diaminen
FR1360740A (fr) * 1963-02-12 1964-05-15 British Petroleum Co Perfectionnements relatifs à l'hydrogénation des paraffines
FR1368177A (fr) * 1963-06-07 1964-07-31 Comp Generale Electricite Procédé de préparation d'un catalyseur d'hydrogénation, catalyseur ainsi obtenu et applications
US3387032A (en) * 1965-06-08 1968-06-04 Jackson D. Leonard Process for the manufacture of methylamines
US3492314A (en) * 1965-08-23 1970-01-27 Mitsubishi Petrochemical Co Process for catalytic hydrogenation of dicarboxylic acid anhydride and catalyst therefor
US3520933A (en) * 1966-10-28 1970-07-21 Basf Ag Production of amines
US3666412A (en) * 1968-10-21 1972-05-30 Du Pont Dispersed phase activated and stabilized metal catalysts
US3708539A (en) * 1970-02-06 1973-01-02 Union Oil Co Condensation of ammonia or a primary or secondary amine with an alcohol
BE765482A (fr) * 1970-04-20 1971-08-30 Du Pont Catalyseur de reforming modifie au rhenium
JPS4734181U (https=) * 1971-05-07 1972-12-16
US3739029A (en) * 1971-12-29 1973-06-12 Shell Oil Co N-alkyl amine production
FR2252330B1 (https=) * 1973-11-23 1978-06-16 Ruhrchemie Ag
US4036883A (en) * 1974-11-27 1977-07-19 Basf Aktiengesellschaft Manufacture of isomer-free 3-methylbutylamine

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0526851A3 (en) * 1991-07-31 1993-05-19 Tosoh Corporation Process and catalyst for producing an ethylenamine
US5321160A (en) * 1991-07-31 1994-06-14 Tosoh Corporation Process for producing an ethylenamine
US5817593A (en) * 1995-06-02 1998-10-06 The Dow Chemical Company Catalyst and process for producing amines
US5952529A (en) * 1995-06-02 1999-09-14 The Dow Chemical Company Catalyst and process for producing amines
WO1997012928A1 (en) * 1995-10-04 1997-04-10 The Dow Chemical Company Amine capped polyethers and process for producing same
US5789490A (en) * 1995-10-04 1998-08-04 The Dow Chemical Company Amine capped polyethers and process for producing same
JP2012162525A (ja) * 2011-02-03 2012-08-30 Evonik Degussa Gmbh ポリアミド合成のための主鎖が線状の第１級ジアミンの製造

Also Published As

Publication number Publication date
JPS5285991A (en) 1977-07-16
US4111840A (en) 1978-09-05
US4123462A (en) 1978-10-31
IT1082703B (it) 1985-05-21
JPS56108534A (en) 1981-08-28
FR2337585A1 (fr) 1977-08-05
DE2700339A1 (de) 1977-08-18
DE2700339B2 (https=) 1979-08-09
JPS6241064B2 (https=) 1987-09-01
BE850144A (fr) 1977-07-06
NL7700084A (nl) 1977-07-11
DE2700339C3 (de) 1980-06-19
FR2337585B1 (https=) 1983-10-07
IN145670B (https=) 1978-11-25
JPS6038380B2 (ja) 1985-08-31
NL180914C (nl) 1987-05-18
CA1083558A (en) 1980-08-12

Similar Documents

Publication Publication Date Title
US4123462A (en) Amination process using nickel-rhenium catalysts
CA1241629A (en) Potentiated nickel catalysts for amination
EP0828558B1 (en) Catalyst and process for producing amines
EP2340113B1 (en) Low metal (nickel and rhenium) catalyst compositions including acidic mixed metal oxide as support
US5958825A (en) Catalysts for the amination of alkylene oxides, alcohols, aldehydes and ketones
FI81027C (fi) Dopad nickel- och/eller kobolt- katalysator och dess anvaendning.
EP2352585B1 (en) Low metal loaded, alumina supported, catalyst compositions and amination process
JP5124486B2 (ja) 触媒の存在でモノエチレングリコール及びアンモニアの水素化アミノ化によるエチレンアミン及びエタノールアミンの製造方法
US7053247B2 (en) Process for the manufacture of diethylenetriamine and higher polyethylenepolyamines
CN112898163A (zh) 一种环己亚胺氨化制备1,6-己二胺的方法
US4973692A (en) Aminoethylethanolamine producers composition and method for producing same
US4977266A (en) Aminoethylethanolamine and ethylenediamine producers composition and method for producing same
US5196588A (en) Ethylenediamine and diethylenetriamine producers composition and method for producing same
US5202490A (en) Process for thr manufacture of diethylenetriamine and aminoethylethanolamine
US5068329A (en) Aminoethylethanolamine producers composition and method for producing same
US5068330A (en) Aminoethyethanolamine and ethylenediamine producers composition and method for producing same
US5202491A (en) Process for the manufacture of diethylenetriamine
FI84260C (fi) Foerfarande foer framstaellning av aminerade produkter med anvaendning av en nickel- och/eller koboltkatalysator.

Legal Events

Date Code Title Description
PS Patent sealed [section 19, patents act 1949]
PE20 Patent expired after termination of 20 years

Effective date: 19970105