DE187600T1 - Verfahren zur herstellung von methan in gegenwart eines schwefelwiderstandsfaehigen katalysators sowie in diesem verfahren zu verwendender katalysator. - Google Patents
Verfahren zur herstellung von methan in gegenwart eines schwefelwiderstandsfaehigen katalysators sowie in diesem verfahren zu verwendender katalysator.Info
- Publication number
- DE187600T1 DE187600T1 DE198585402631T DE85402631T DE187600T1 DE 187600 T1 DE187600 T1 DE 187600T1 DE 198585402631 T DE198585402631 T DE 198585402631T DE 85402631 T DE85402631 T DE 85402631T DE 187600 T1 DE187600 T1 DE 187600T1
- Authority
- DE
- Germany
- Prior art keywords
- catalyst
- lying
- metal
- atomic ratio
- carbon monoxide
- 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.)
- Pending
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract 12
- 239000003054 catalyst Substances 0.000 title claims abstract 10
- 238000000034 method Methods 0.000 title claims abstract 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract 3
- 229910052717 sulfur Inorganic materials 0.000 title claims 2
- 239000011593 sulfur Substances 0.000 title claims 2
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract 7
- 229910052751 metal Inorganic materials 0.000 claims abstract 6
- 239000002184 metal Substances 0.000 claims abstract 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract 4
- 239000001257 hydrogen Substances 0.000 claims abstract 4
- 239000000203 mixture Substances 0.000 claims abstract 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract 3
- 239000011733 molybdenum Substances 0.000 claims abstract 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract 3
- 239000010937 tungsten Substances 0.000 claims abstract 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims abstract 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract 2
- 229910017052 cobalt Inorganic materials 0.000 claims abstract 2
- 239000010941 cobalt Substances 0.000 claims abstract 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052759 nickel Inorganic materials 0.000 claims abstract 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052684 Cerium Inorganic materials 0.000 claims 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
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
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/0445—Preparation; Activation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/20—Vanadium, niobium or tantalum
- C07C2523/22—Vanadium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/28—Molybdenum
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/30—Tungsten
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/75—Cobalt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/755—Nickel
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Orthopedics, Nursing, And Contraception (AREA)
- Respiratory Apparatuses And Protective Means (AREA)
Claims (5)
1. Verfahren zur Erzeugung von Methan oder eines Methan aufweisenden
Gasgemisches aus einem insbesondere Kohlenmonoxyd, Wasserstoff und schwefelhaltige Verbindungen aufweisenden Ausgangsgemisch,
dadurch gekennzeichnet, dass man das besagte Ausgangsgemisch mit einem thiobeständigen Katalysator in Berührung
bringt, welcher ein unter Molybdän, Vanadium und Wolfram gewähltes Metall und ggf. einen aus Kobalt und/oder Nickel
bestehenden Tätigkeitspromotor aufweist, welcher Katalysator, auf einem Träger aus Ceriumoxyd bei einer zwischen ungefähr
250 und 65O0C liegenden Temperatur und einem zwischen ungefähr
5 und 140 bars liegenden Druck aufgetragen wird.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Reaktion bei einer zwischen ungefähr 100 und 15 000 Stunden
liegenden Raumgeschwindigkeit und mit einem wenigstens 0,3 und vorzugsweise 1 betragenden molaren Wasserstoff/Kohlenmonoxydverhältnis
durchgeführt wird.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Reaktion bei einer Raumgeschwindigkeit von 4750 Stunden
und mit einem molaren Wasserstoff/Kohlenmonoxydverhältnis gleich 1, bei einem Druck von 30 bars und bei einer zwischen 300 und
6000C liegenden und vorzugsweise 5000C betragenden Temperatur
durchgeführt wird.
4. Katalysator zur Verwendung des Verfahrens nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass er der Formel
X/CeO2, X/Co/Ce02, X/Ni/CeO2 oder X/Co/Ni/Ce02 in welcher
X Molybdän, Vanadium oder Wolfram ist, entspricht und dass der besagte Katalysator durch die folgenden Merkmale festgesetzt
wird :
- spezifischen Flächeninhalt BET des Trägers aus Ce0„ höher als
10 m2/g;
- zwischen ungefähr 0,15 und 0,5 cm /g liegendes poröses Gesamtvolumen
;
- zwischen ungefähr 0,5 und 2,5 liegende gestampfte Füllungsdichte;
- zwischen etwa 1/50 und 1/4 liegendes Atomverhältnis des vorgenannten
X-Metalles zum Cerium,und;
- zwischen 0 und 1 liegendes Atomverhältnis des Tätigkeitspromotormetalles
(Co und/oder Ni) zum X-Metall.
5. Katalysator nach Anspruch 4, dadurch gekennzeichnet, dass
2 der vorgenannte spezifische Flächeninhalt BET 50 m /g beträgt,
3 das vorgenannte poröse Gesamtvolumen zwischen 0,3 und 0,4 cm /g
liegt, die gestampfte Füllungsdichte zwischen 1 und 2 liegt, das X/Cerium-Atomverhältnis zwischen 1/20 und 1/7 liegt und das
Promotormetall X/Atomverhältnis zwischen 0,1 und 0,5 liegt.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8420069A FR2575464B1 (fr) | 1984-12-28 | 1984-12-28 | Procede de production du methane a l'aide d'un catalyseur thioresistant et catalyseur pour la mise en oeuvre de ce procede |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE187600T1 true DE187600T1 (de) | 1986-11-06 |
Family
ID=9311125
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE8585402631T Expired DE3562897D1 (en) | 1984-12-28 | 1985-12-24 | Process for the preparation of methane in the presence of a thioresistant catalyst, and catalyst to be used in such a process |
| DE198585402631T Pending DE187600T1 (de) | 1984-12-28 | 1985-12-24 | Verfahren zur herstellung von methan in gegenwart eines schwefelwiderstandsfaehigen katalysators sowie in diesem verfahren zu verwendender katalysator. |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE8585402631T Expired DE3562897D1 (en) | 1984-12-28 | 1985-12-24 | Process for the preparation of methane in the presence of a thioresistant catalyst, and catalyst to be used in such a process |
Country Status (12)
| Country | Link |
|---|---|
| US (2) | US4774261A (de) |
| EP (1) | EP0187600B1 (de) |
| JP (1) | JPH075485B2 (de) |
| CN (2) | CN1006547B (de) |
| AT (1) | ATE34560T1 (de) |
| AU (1) | AU582810B2 (de) |
| CA (1) | CA1260450A (de) |
| DE (2) | DE3562897D1 (de) |
| DK (1) | DK166492C (de) |
| FI (1) | FI855165L (de) |
| FR (1) | FR2575464B1 (de) |
| ZA (1) | ZA859790B (de) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2575463B1 (fr) * | 1984-12-28 | 1987-03-20 | Gaz De France | Procede de production du methane a l'aide d'un catalyseur thioresistant et catalyseur pour la mise en oeuvre de ce procede |
| FR2575453B1 (fr) * | 1984-12-28 | 1990-03-02 | Pro Catalyse | Procede de conversion du monoxyde de carbone par la vapeur d'eau a l'aide d'un catalyseur thioresistant |
| FR2600556A1 (fr) * | 1986-06-27 | 1987-12-31 | Rhone Poulenc Chim Base | Nouveau catalyseur a base de nickel et/ou de cobalt, sa preparation et son utilisation a la production de methane |
| GB2291819B (en) * | 1991-06-19 | 1996-04-24 | Inst Francais Du Petrole | Process for the synthesis of hydrocarbons from synthesis gases in the presence of a cobalt-based catalyst |
| US5639798A (en) * | 1994-12-15 | 1997-06-17 | Wexford P.A. Syncrude Limited Partnership | Process and catalyst for production of hydrocarbons |
| KR100758377B1 (ko) * | 2005-11-22 | 2007-09-14 | 주식회사 엘지화학 | 습식 밀링을 이용한 메틸벤젠류 부분산화용 촉매의제조방법 |
| CN100409940C (zh) * | 2006-07-17 | 2008-08-13 | 大连理工大学 | 一种同时脱除汽车尾气中氮氧化物和一氧化碳的催化剂 |
| CN101199939B (zh) * | 2007-12-21 | 2010-09-29 | 中国科学院山西煤炭化学研究所 | 一种甲烷氧化合成甲醇和甲醛的催化剂及制法和应用 |
| CN101618327B (zh) * | 2007-12-21 | 2011-06-08 | 中国科学院山西煤炭化学研究所 | 一种甲烷氧化合成甲醇和甲醛的催化剂及制法和应用 |
| US7955588B2 (en) * | 2009-05-26 | 2011-06-07 | Conocophillips Company | Metal sulfide catalysts and methods of making same |
| KR101242852B1 (ko) | 2010-09-28 | 2013-03-12 | 주식회사 포스코 | 몰리브데늄 촉매 및 그 제조방법과 상기 촉매를 이용한 메탄 제조방법 |
| CN102040441B (zh) * | 2010-10-20 | 2013-04-17 | 北京低碳清洁能源研究所 | 生产富含ch4气体的系统以及用该系统生产富含ch4气体的方法 |
| CN103372451B (zh) * | 2012-04-20 | 2015-11-25 | 神华集团有限责任公司 | 一种负载型催化剂的制备方法 |
| JP6203375B2 (ja) | 2013-03-28 | 2017-09-27 | エージェンシー フォー サイエンス， テクノロジー アンド リサーチ | メタン化触媒 |
| CN103191720B (zh) * | 2013-04-26 | 2015-10-21 | 神华集团有限责任公司 | 一种镁铝尖晶石负载的耐硫甲烷化催化剂 |
| SG2013050877A (en) * | 2013-06-28 | 2015-01-29 | Agency Science Tech & Res | Methanation catalyst |
| CN105582969B (zh) * | 2014-10-24 | 2018-08-17 | 中国石油化工股份有限公司 | 耐硫甲烷化催化剂及制备方法 |
| CN105013472A (zh) * | 2015-06-16 | 2015-11-04 | 中国科学院山西煤炭化学研究所 | 一种适用于高浓度co甲烷化的耐硫催化剂及制法和应用 |
| CN106423140B (zh) * | 2015-08-10 | 2019-04-09 | 神华集团有限责任公司 | 甲烷化催化剂及其制备方法和应用以及甲烷化方法 |
| CN110152651A (zh) * | 2019-05-17 | 2019-08-23 | 太原理工大学 | 应用于合成气甲烷化的耐硫催化剂及其制法和应用 |
| CN117463318A (zh) * | 2023-10-28 | 2024-01-30 | 中国科学院大连化学物理研究所 | 一种催化加氢制备γ-戊内酯的催化剂及其应用 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4151191A (en) * | 1977-11-14 | 1979-04-24 | The American Gas Association | Sulfur resistant molybdenum catalysts for methanation |
| US4260553A (en) * | 1979-03-05 | 1981-04-07 | Gas Research Institute | Alumina-containing methanation catalysts |
| DK144530C (da) * | 1979-12-18 | 1982-09-06 | Topsoee H A S | Fremgangsmaade til fremstilling af en gasblanding med hoejt indhold af metan |
| US4491639A (en) * | 1982-09-30 | 1985-01-01 | Gas Research Institute | Methods of making high activity transition metal catalysts |
| FR2575453B1 (fr) * | 1984-12-28 | 1990-03-02 | Pro Catalyse | Procede de conversion du monoxyde de carbone par la vapeur d'eau a l'aide d'un catalyseur thioresistant |
-
1984
- 1984-12-28 FR FR8420069A patent/FR2575464B1/fr not_active Expired
-
1985
- 1985-12-23 ZA ZA859790A patent/ZA859790B/xx unknown
- 1985-12-23 CA CA000498502A patent/CA1260450A/en not_active Expired
- 1985-12-23 DK DK605085A patent/DK166492C/da not_active IP Right Cessation
- 1985-12-24 DE DE8585402631T patent/DE3562897D1/de not_active Expired
- 1985-12-24 EP EP85402631A patent/EP0187600B1/de not_active Expired
- 1985-12-24 DE DE198585402631T patent/DE187600T1/de active Pending
- 1985-12-24 AT AT85402631T patent/ATE34560T1/de not_active IP Right Cessation
- 1985-12-24 AU AU51639/85A patent/AU582810B2/en not_active Ceased
- 1985-12-27 JP JP60299752A patent/JPH075485B2/ja not_active Expired - Lifetime
- 1985-12-27 FI FI855165A patent/FI855165L/fi not_active Application Discontinuation
- 1985-12-28 CN CN85109423A patent/CN1006547B/zh not_active Expired
-
1987
- 1987-07-24 US US07/077,694 patent/US4774261A/en not_active Expired - Fee Related
-
1988
- 1988-06-15 US US07/207,300 patent/US4833112A/en not_active Expired - Fee Related
- 1988-12-20 CN CN88105187A patent/CN1007703B/zh not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| EP0187600B1 (de) | 1988-05-25 |
| CN1007703B (zh) | 1990-04-25 |
| FI855165A0 (fi) | 1985-12-27 |
| DK605085D0 (da) | 1985-12-23 |
| FI855165A7 (fi) | 1986-06-29 |
| US4833112A (en) | 1989-05-23 |
| ATE34560T1 (de) | 1988-06-15 |
| AU5163985A (en) | 1986-07-03 |
| DK605085A (da) | 1986-06-29 |
| JPS61161228A (ja) | 1986-07-21 |
| EP0187600A1 (de) | 1986-07-16 |
| AU582810B2 (en) | 1989-04-13 |
| FI855165L (fi) | 1986-06-29 |
| FR2575464A1 (fr) | 1986-07-04 |
| CN1006547B (zh) | 1990-01-24 |
| DK166492C (da) | 1993-10-18 |
| DK166492B (da) | 1993-06-01 |
| DE3562897D1 (en) | 1988-06-30 |
| CN85109423A (zh) | 1986-06-10 |
| CN1033580A (zh) | 1989-07-05 |
| JPH075485B2 (ja) | 1995-01-25 |
| ZA859790B (en) | 1986-09-24 |
| FR2575464B1 (fr) | 1987-03-20 |
| US4774261A (en) | 1988-09-27 |
| CA1260450A (en) | 1989-09-26 |
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