CA1277123C - System for reducing energy consumption improving reactors for heterogeneous catalytic synthesis and relative reactors - Google Patents

System for reducing energy consumption improving reactors for heterogeneous catalytic synthesis and relative reactors

Info

Publication number
CA1277123C
CA1277123C CA000509060A CA509060A CA1277123C CA 1277123 C CA1277123 C CA 1277123C CA 000509060 A CA000509060 A CA 000509060A CA 509060 A CA509060 A CA 509060A CA 1277123 C CA1277123 C CA 1277123C
Authority
CA
Canada
Prior art keywords
beds
bed
diaphragm
diameter
height
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 - Lifetime
Application number
CA000509060A
Other languages
English (en)
French (fr)
Inventor
Umberto Zardi
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.)
Casale SA
Original Assignee
Ammonia Casale SA
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=25689517&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=CA1277123(C) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from CH3238/85A external-priority patent/CH666197A5/it
Application filed by Ammonia Casale SA filed Critical Ammonia Casale SA
Application granted granted Critical
Publication of CA1277123C publication Critical patent/CA1277123C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis in the gas phase
    • C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
    • C01C1/0417—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the synthesis reactor, e.g. arrangement of catalyst beds and heat exchangers in the reactor
    • C01C1/0423—Cold wall reactors
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0403—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal
    • B01J8/0407—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more cylindrical annular shaped beds
    • B01J8/0415—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more cylindrical annular shaped beds the beds being superimposed one above the other
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0403—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal
    • B01J8/0423—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more otherwise shaped beds
    • B01J8/0426—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more otherwise shaped beds the beds being superimposed one above the other
    • B01J8/0434—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more otherwise shaped beds the beds being superimposed one above the other in combination with two or more cylindrical annular shaped beds
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
    • B01J8/0449—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
    • B01J8/0453—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds the beds being superimposed one above the other
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
    • B01J8/0461—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical annular shaped beds
    • B01J8/0469—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical annular shaped beds the beds being superimposed one above the other
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0496—Heating or cooling the reactor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/152—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the reactor used
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00194—Tubes
    • 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
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49826—Assembling or joining

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
CA000509060A 1985-05-15 1986-05-13 System for reducing energy consumption improving reactors for heterogeneous catalytic synthesis and relative reactors Expired - Lifetime CA1277123C (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CH210085 1985-05-15
CH2100/85-0 1985-05-15
CH3238/85A CH666197A5 (it) 1985-07-25 1985-07-25 Reattore per aumentare la resa di conversione e ridurre i consumi energetici nelle sintesi eterogenee dell'ammoniaca.
CH03238/85-0 1985-07-25

Publications (1)

Publication Number Publication Date
CA1277123C true CA1277123C (en) 1990-12-04

Family

ID=25689517

Family Applications (1)

Application Number Title Priority Date Filing Date
CA000509060A Expired - Lifetime CA1277123C (en) 1985-05-15 1986-05-13 System for reducing energy consumption improving reactors for heterogeneous catalytic synthesis and relative reactors

Country Status (8)

Country Link
US (3) US4755362A (US06235095-20010522-C00021.png)
EP (1) EP0202454B2 (US06235095-20010522-C00021.png)
CN (1) CN1004611B (US06235095-20010522-C00021.png)
CA (1) CA1277123C (US06235095-20010522-C00021.png)
DE (1) DE3686783T3 (US06235095-20010522-C00021.png)
ES (1) ES8703812A1 (US06235095-20010522-C00021.png)
IN (1) IN165082B (US06235095-20010522-C00021.png)
UA (1) UA32508C2 (US06235095-20010522-C00021.png)

Families Citing this family (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0265654A1 (en) * 1986-09-25 1988-05-04 Ammonia Casale S.A. System and device to make catalytic basket walls for heterogeneous synthesis reactors
IN170330B (US06235095-20010522-C00021.png) * 1986-10-22 1992-03-14 Ammonia Casale Sa
ATE83684T1 (de) * 1986-11-03 1993-01-15 Ammonia Casale Sa Verfahren zur reduktion des energiebedarfs in mehreinheitenreaktoren fuer die heterogene synthese und verwandte reaktoren.
EP0293546A3 (en) * 1987-02-11 1989-06-07 Ammonia Casale S.A. System to deal with the efficiency of reactors for exothermic ammonia synthesis
EP0287765B1 (en) * 1987-02-26 1993-05-12 Ammonia Casale S.A. System to improve the efficiency of reactors for exothermic synthesis and more particularly for the reaction of ammonia
DE3710004A1 (de) * 1987-03-26 1988-10-06 Uhde Gmbh Vorrichtung zur katalytischen behandlung von stickstoff und wasserstoff
CN88103614A (zh) * 1987-05-14 1988-12-14 阿莫尼·卡萨尔公司 多相合成反应器的改进
ES2030940T5 (es) * 1988-06-27 1996-03-16 Ammonia Casale Sa Proceso y reactor para sintesis heterogenea exotermica con varios lechos cataliticos y con recuperacion externa de calor.
EP0359952A3 (en) * 1988-08-05 1990-07-18 Ammonia Casale S.A. System for the improvement of reactors for the synthesis of methanol and reactors obtained therefrom
US5184386A (en) * 1988-12-09 1993-02-09 Ammonia Casale S.A. Method for retrofitting carbon monoxide conversion reactors
DE68924834T2 (de) * 1988-12-09 1996-06-05 Ammonia Casale Sa Methode zur In-situ-Umrüstung eines axial durchströmten Kohlenmonoxidkonversionsreaktors.
ES2026723T3 (es) * 1988-12-09 1992-05-01 Ammonia Casale S.A. Reactor para sintesis heterogenea, exotermica y catalitica.
DE68906006T2 (de) * 1988-12-21 1993-08-12 Ammonia Casale Sa Reaktoren fuer heterogene synthesen.
CH678286A5 (US06235095-20010522-C00021.png) * 1989-03-09 1991-08-30 Ammonia Casale Sa
EP0386692A3 (en) * 1989-03-09 1991-01-09 Ammonia Casale S.A. System for modifying in situ reactors for the synthesis of ammonia
US5250270A (en) * 1992-07-17 1993-10-05 The M. W. Kellogg Company Catalytic reactor bed
DE4228147A1 (de) * 1992-08-25 1994-03-03 Solvay Fluor & Derivate Verfahren und Vorrichtung zur Herstellung von Diglycerin
DE69426517D1 (de) * 1993-10-29 2001-02-08 Ammonia Casale Sa Verfahren zur Nachrüstung eines heterogenen exothermischen Synthesereaktors
DE4446359A1 (de) * 1993-12-29 1995-07-06 Ammonia Casale Sa Verfahren zur in-situ-Modernisierung eines heterogenen exothermen Synthesereaktors, insbesondere eines sogenannten Kellog-Reaktors
RU95100777A (ru) * 1994-01-20 1996-10-27 Метанол Казале С.А. (Ch) Способ модернизации на месте реактора для проведения гетерогенных экзотермических реакций синтеза, в частности, реактора, так называемого ромбовидного типа и реактор для его осуществления
DE4439807A1 (de) * 1994-11-08 1996-05-09 Basf Ag Reaktor zur Durchführung heterogenkatalysierter Gasphasenreaktionen
EP0820345B1 (en) * 1995-04-11 2000-07-26 Floriall Holdings Limited Process and reactor for heterogeneous exothermic synthesis of formaldehyde
WO1996032189A1 (en) * 1995-04-11 1996-10-17 Floriall Holdings Limited Process and reactor for heterogeneous exothermic synthesis of formaldehyde
CN1088618C (zh) * 1996-08-21 2002-08-07 楼寿林 一种接近最佳温度的催化反应改进工艺及其合成反应器
EP0931586B1 (en) * 1997-11-28 2005-03-16 Ammonia Casale S.A. Method for in-situ modernization of a heterogeneous exothermic synthesis reactor
US6132687A (en) * 1998-05-21 2000-10-17 Kellogg Brown & Root, Inc. Horizontal ammonia converter adapted for high activity catalyst
ATE245478T1 (de) * 1999-08-31 2003-08-15 Ammonia Casale Sa Verfahren zur in-situ modernisierung eines heterogenen synthesereaktors
US20020183571A1 (en) * 2000-11-30 2002-12-05 Sud-Chemie Inc. Radial reactor loading of a dehydrogenation catalyst
US7435862B2 (en) 2000-11-30 2008-10-14 Sud-Chemie Inc. Radial reactor loading of a dehydrogenation catalyst
GB0115243D0 (en) * 2001-06-21 2001-08-15 Kvaerner Process Tech Ltd Method
US7718137B2 (en) * 2005-10-28 2010-05-18 Eastman Chemical Company Reactor with optimized internal tray design
US7867460B2 (en) * 2007-11-26 2011-01-11 Kellogg Brown & Root Llc Efficiency of ammonia processes
US20100074389A1 (en) * 2008-09-25 2010-03-25 Ge-Hitachi Nuclear Energy Americas Llc Replacement basket, a system using the replacement basket, and a method for loading the replacement basket
EP2354092A1 (en) 2010-01-29 2011-08-10 Ammonia Casale S.A. A method for modernizing the synthesis loop of an ammonia plant
MX2018015211A (es) * 2016-06-21 2019-04-25 Topsoe Haldor As Convertidor de flujo axial/radial.
AR113648A1 (es) * 2017-12-20 2020-05-27 Haldor Topsoe As Convertidor de flujo axial adiabático
AR113649A1 (es) * 2017-12-20 2020-05-27 Haldor Topsoe As Convertidor de flujo axial enfriado
WO2023163798A1 (en) 2022-02-23 2023-08-31 SANsyco Consulting, LLC Ammonia synthesis converter and method for small production units

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK106275C (da) * 1963-09-28 1967-01-16 Topsoe Haldor F A Reaktor til udførelse af gasfasereaktioner ved heterogen katalyse.
DK119652B (da) * 1964-09-11 1971-02-08 Topsoe H Reaktør til udførelse af gasfasereaktioner ved gennemledning af en gasblanding gennem et leje fyldt med katalysatørpartikler.
DE1667161C3 (de) * 1968-02-08 1973-10-31 Lentia Gmbh, Chem. U. Pharm. Erzeugnisse - Industriebedarf, 8000 Muenchen Verfahren und Vorrichtung zur Gasführung in katalytischen Hochdruck syntheseanlagen
US3918918A (en) * 1972-03-15 1975-11-11 Lummus Co Catalytic reactor
IT1041778B (it) * 1975-07-15 1980-01-10 Snam Progetti Reattore a flusso radiale per la sintesi dell ammoniaca con produzione di vapore ad alto livello termico
GB1574723A (en) * 1976-03-10 1980-09-10 Haldor Topsoe As Apparatus for the synthesis of ammonia
US4230669A (en) * 1978-07-17 1980-10-28 Pullman Incorporated Radial ammonia converter
US4346060A (en) * 1978-07-17 1982-08-24 Pullman Incorporated Radial ammonia converters
US4230680A (en) * 1978-07-17 1980-10-28 Pullman Incorporated Low energy process for synthesis of ammonia
FR2460707B1 (fr) * 1979-07-13 1986-09-05 Ammonia Casale Sa Reacteur de synthese, notamment pour la synthese catalytique d'ammoniac et de methanol
IT1141102B (it) * 1980-11-28 1986-10-01 Ammonia Casale Sa Reattore assiale-radiale per sintesi eterogenee
CH646618A5 (it) * 1981-03-26 1984-12-14 Ammonia Casale Sa Reattore per sintesi eterogenee catalitiche.
JPS5959242A (ja) * 1982-09-28 1984-04-05 Toyo Eng Corp 反応方法およびそのための反応器
US4518574A (en) * 1983-03-07 1985-05-21 Exxon Research & Engineering Co. Catalytic gas synthesis process
JPS60110328A (ja) * 1983-11-17 1985-06-15 Toyo Eng Corp 接触反応装置

Also Published As

Publication number Publication date
EP0202454B1 (en) 1992-09-23
EP0202454A2 (en) 1986-11-26
CN86103332A (zh) 1986-12-31
CN1004611B (zh) 1989-06-28
EP0202454B2 (en) 1997-03-05
UA32508C2 (uk) 2001-02-15
DE3686783T2 (de) 1993-05-06
DE3686783T3 (de) 1997-05-07
ES8703812A1 (es) 1987-03-01
US4904453A (en) 1990-02-27
ES554947A0 (es) 1987-03-01
EP0202454A3 (en) 1987-09-09
US4755362A (en) 1988-07-05
IN165082B (US06235095-20010522-C00021.png) 1989-08-12
US4952375A (en) 1990-08-28
DE3686783D1 (de) 1992-10-29

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