FI114090B - Menetelmä katalyytittömän valmistusliuoksen erottamiseksi vetyperoksidin valmistukseen käytettävän antrakinoniprosessin hydrauskierrosta - Google Patents
Menetelmä katalyytittömän valmistusliuoksen erottamiseksi vetyperoksidin valmistukseen käytettävän antrakinoniprosessin hydrauskierrosta Download PDFInfo
- Publication number
- FI114090B FI114090B FI952631A FI952631A FI114090B FI 114090 B FI114090 B FI 114090B FI 952631 A FI952631 A FI 952631A FI 952631 A FI952631 A FI 952631A FI 114090 B FI114090 B FI 114090B
- Authority
- FI
- Finland
- Prior art keywords
- catalyst
- filter
- solution
- pore size
- range
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 49
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 25
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 150000004056 anthraquinones Chemical class 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims description 16
- 238000000926 separation method Methods 0.000 title abstract description 7
- 230000036571 hydration Effects 0.000 title 1
- 238000006703 hydration reaction Methods 0.000 title 1
- 238000001914 filtration Methods 0.000 claims abstract description 39
- 239000011148 porous material Substances 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 16
- 239000012528 membrane Substances 0.000 claims abstract description 13
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 239000010970 precious metal Substances 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 27
- 238000004519 manufacturing process Methods 0.000 abstract description 17
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
- 239000012224 working solution Substances 0.000 abstract description 5
- 239000003575 carbonaceous material Substances 0.000 abstract description 3
- 239000002356 single layer Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 19
- 239000000919 ceramic Substances 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000011877 solvent mixture Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- JORLUGVBYJSSAW-UHFFFAOYSA-N 2-ethyl-1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1CC(CC)CC2 JORLUGVBYJSSAW-UHFFFAOYSA-N 0.000 description 2
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 235000003913 Coccoloba uvifera Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 240000008976 Pterocarpus marsupium Species 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 210000003097 mucus Anatomy 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012465 retentate Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
- B01J19/243—Tubular reactors spirally, concentrically or zigzag wound
-
- 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
- B01J23/90—Regeneration or reactivation
- B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/022—Preparation from organic compounds
- C01B15/023—Preparation from organic compounds by the alkyl-anthraquinone process
-
- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4418931A DE4418931C2 (de) | 1994-05-31 | 1994-05-31 | Verfahren zur Abtrennung katalysatorfreier Arbeitslösung aus dem Hydrierkreislauf des Anthrachinonverfahrens zur Herstellung von Wasserstoffperoxid |
| DE4418931 | 1994-05-31 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| FI952631A0 FI952631A0 (fi) | 1995-05-30 |
| FI952631L FI952631L (fi) | 1995-12-01 |
| FI114090B true FI114090B (fi) | 2004-08-13 |
Family
ID=6519389
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FI952631A FI114090B (fi) | 1994-05-31 | 1995-05-30 | Menetelmä katalyytittömän valmistusliuoksen erottamiseksi vetyperoksidin valmistukseen käytettävän antrakinoniprosessin hydrauskierrosta |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US5534149A (enExample) |
| EP (1) | EP0687649B1 (enExample) |
| JP (1) | JPH07330311A (enExample) |
| CN (1) | CN1122726A (enExample) |
| AT (1) | ATE162158T1 (enExample) |
| BR (1) | BR9502610A (enExample) |
| CA (1) | CA2150492C (enExample) |
| DE (2) | DE4418931C2 (enExample) |
| ES (1) | ES2113692T3 (enExample) |
| FI (1) | FI114090B (enExample) |
| IL (1) | IL113915A0 (enExample) |
| NZ (1) | NZ272235A (enExample) |
| TW (1) | TW287145B (enExample) |
| ZA (1) | ZA954428B (enExample) |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10052323A1 (de) * | 2000-10-21 | 2002-05-02 | Degussa | Kontinierliches Verfahren zur Hydrierung |
| FR2832937B1 (fr) * | 2001-12-04 | 2004-01-16 | Technip France | Procede et dispositif de reaction chimique entre un gaz et au moins un compose en solution, mis en oeuvre en presence d'un catalyseur solide |
| US7282148B2 (en) * | 2003-10-30 | 2007-10-16 | International Business Machines Corporation | Porous silicon composite structure as large filtration array |
| US7717001B2 (en) * | 2004-10-08 | 2010-05-18 | Sdc Materials, Inc. | Apparatus for and method of sampling and collecting powders flowing in a gas stream |
| JP5275342B2 (ja) | 2007-05-11 | 2013-08-28 | エスディーシー マテリアルズ インコーポレイテッド | 粒子生産システム及び粒子生産方法 |
| US8575059B1 (en) | 2007-10-15 | 2013-11-05 | SDCmaterials, Inc. | Method and system for forming plug and play metal compound catalysts |
| US7901036B2 (en) | 2007-11-12 | 2011-03-08 | Hon Hai Precision Industry Co., Ltd. | Print head unit and method for manufacturing patterned layer on substrate with the same |
| USD627900S1 (en) | 2008-05-07 | 2010-11-23 | SDCmaterials, Inc. | Glove box |
| US8470112B1 (en) | 2009-12-15 | 2013-06-25 | SDCmaterials, Inc. | Workflow for novel composite materials |
| US8545652B1 (en) | 2009-12-15 | 2013-10-01 | SDCmaterials, Inc. | Impact resistant material |
| US8803025B2 (en) | 2009-12-15 | 2014-08-12 | SDCmaterials, Inc. | Non-plugging D.C. plasma gun |
| US9126191B2 (en) | 2009-12-15 | 2015-09-08 | SDCmaterials, Inc. | Advanced catalysts for automotive applications |
| US9149797B2 (en) | 2009-12-15 | 2015-10-06 | SDCmaterials, Inc. | Catalyst production method and system |
| US9119309B1 (en) | 2009-12-15 | 2015-08-25 | SDCmaterials, Inc. | In situ oxide removal, dispersal and drying |
| US8557727B2 (en) | 2009-12-15 | 2013-10-15 | SDCmaterials, Inc. | Method of forming a catalyst with inhibited mobility of nano-active material |
| US8652992B2 (en) | 2009-12-15 | 2014-02-18 | SDCmaterials, Inc. | Pinning and affixing nano-active material |
| US8669202B2 (en) | 2011-02-23 | 2014-03-11 | SDCmaterials, Inc. | Wet chemical and plasma methods of forming stable PtPd catalysts |
| CN107096576A (zh) | 2011-08-19 | 2017-08-29 | Sdc材料公司 | 用于催化和催化转化器中的涂覆基质和将基质用修补基面涂料组合物涂覆的方法 |
| US9511352B2 (en) | 2012-11-21 | 2016-12-06 | SDCmaterials, Inc. | Three-way catalytic converter using nanoparticles |
| US9156025B2 (en) | 2012-11-21 | 2015-10-13 | SDCmaterials, Inc. | Three-way catalytic converter using nanoparticles |
| JP2015020940A (ja) * | 2013-07-22 | 2015-02-02 | 国立大学法人静岡大学 | 過酸化水素合成方法 |
| CN105592921A (zh) | 2013-07-25 | 2016-05-18 | Sdc材料公司 | 用于催化转化器的洗涂层和经涂覆基底及其制造和使用方法 |
| WO2015061477A1 (en) | 2013-10-22 | 2015-04-30 | SDCmaterials, Inc. | Catalyst design for heavy-duty diesel combustion engines |
| EP3068517A4 (en) | 2013-10-22 | 2017-07-05 | SDCMaterials, Inc. | Compositions of lean nox trap |
| US9687811B2 (en) | 2014-03-21 | 2017-06-27 | SDCmaterials, Inc. | Compositions for passive NOx adsorption (PNA) systems and methods of making and using same |
| CN104402142B (zh) * | 2014-11-26 | 2016-06-01 | 柳州化工股份有限公司 | 一种蒽醌法生产双氧水工业中污水预处理的方法 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1272292B (de) * | 1965-12-04 | 1968-07-11 | Degussa | Abtrennung von suspendierten traegerlosen Hydrierungs-Katalysatoren der Platinmetallgruppe aus fluessigen organischen Hydrierungsgemischen |
| NL141400B (nl) * | 1965-12-04 | 1974-03-15 | Degussa | Werkwijze voor het afscheiden van gesuspendeerde, dragerloze edelmetaalkatalysatoren uit organische vloeistoffen door middel van filters. |
| US4428923A (en) * | 1982-11-09 | 1984-01-31 | Degussa Aktiengesellschaft | Continuous process for the production of hydrogen peroxide according to the anthraquinone process |
| SE8207376L (sv) * | 1982-12-23 | 1984-06-24 | Eka Ab | Forfarande vid avskiljning av i vetska suspenderade katalysatorpartiklar |
| FI86380C (fi) * | 1990-09-10 | 1992-08-25 | Kemira Oy | Foerfarande foer rening av filter. |
| DE4217245A1 (de) * | 1992-05-25 | 1993-12-02 | Degussa | Verfahren zur Abtrennung katalysatorfreier Arbeitslösung aus dem Hydrierkreislauf des Anthrachionverfahrens zur Herstellung von Wasserstoffperoxid |
-
1994
- 1994-05-31 DE DE4418931A patent/DE4418931C2/de not_active Expired - Fee Related
-
1995
- 1995-03-20 US US08/406,519 patent/US5534149A/en not_active Expired - Lifetime
- 1995-05-10 EP EP95107071A patent/EP0687649B1/de not_active Expired - Lifetime
- 1995-05-10 ES ES95107071T patent/ES2113692T3/es not_active Expired - Lifetime
- 1995-05-10 AT AT95107071T patent/ATE162158T1/de not_active IP Right Cessation
- 1995-05-10 DE DE59501253T patent/DE59501253D1/de not_active Expired - Fee Related
- 1995-05-23 JP JP7123866A patent/JPH07330311A/ja active Pending
- 1995-05-29 TW TW084105412A patent/TW287145B/zh active
- 1995-05-29 NZ NZ272235A patent/NZ272235A/en unknown
- 1995-05-30 FI FI952631A patent/FI114090B/fi not_active IP Right Cessation
- 1995-05-30 IL IL11391595A patent/IL113915A0/xx unknown
- 1995-05-30 CA CA002150492A patent/CA2150492C/en not_active Expired - Fee Related
- 1995-05-30 CN CN95106619A patent/CN1122726A/zh active Pending
- 1995-05-30 ZA ZA954428A patent/ZA954428B/xx unknown
- 1995-05-31 BR BR9502610A patent/BR9502610A/pt not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| FI952631L (fi) | 1995-12-01 |
| ZA954428B (en) | 1996-01-24 |
| IL113915A0 (en) | 1995-08-31 |
| DE59501253D1 (de) | 1998-02-19 |
| DE4418931A1 (de) | 1995-12-07 |
| CA2150492C (en) | 2001-01-16 |
| NZ272235A (en) | 1996-05-28 |
| CA2150492A1 (en) | 1995-12-01 |
| CN1122726A (zh) | 1996-05-22 |
| JPH07330311A (ja) | 1995-12-19 |
| TW287145B (enExample) | 1996-10-01 |
| EP0687649B1 (de) | 1998-01-14 |
| BR9502610A (pt) | 1996-01-02 |
| FI952631A0 (fi) | 1995-05-30 |
| ES2113692T3 (es) | 1998-05-01 |
| ATE162158T1 (de) | 1998-01-15 |
| EP0687649A1 (de) | 1995-12-20 |
| US5534149A (en) | 1996-07-09 |
| DE4418931C2 (de) | 1997-06-19 |
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