KR940703780A - 과산화수소 생산 (production of hydrogen peroxide) - Google Patents
과산화수소 생산 (production of hydrogen peroxide)Info
- Publication number
- KR940703780A KR940703780A KR1019940702472A KR19940702472A KR940703780A KR 940703780 A KR940703780 A KR 940703780A KR 1019940702472 A KR1019940702472 A KR 1019940702472A KR 19940702472 A KR19940702472 A KR 19940702472A KR 940703780 A KR940703780 A KR 940703780A
- Authority
- KR
- South Korea
- Prior art keywords
- catalyst
- support
- solution
- range
- aqueous solution
- Prior art date
Links
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract 12
- 238000004519 manufacturing process Methods 0.000 title claims abstract 5
- 239000003054 catalyst Substances 0.000 claims abstract 22
- 229910052751 metal Inorganic materials 0.000 claims abstract 10
- 239000002184 metal Substances 0.000 claims abstract 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract 6
- 239000001257 hydrogen Substances 0.000 claims abstract 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract 5
- 239000000460 chlorine Substances 0.000 claims abstract 5
- 229910052801 chlorine Inorganic materials 0.000 claims abstract 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract 5
- 239000011734 sodium Substances 0.000 claims abstract 5
- -1 chlorine ions Chemical class 0.000 claims abstract 4
- 230000002209 hydrophobic effect Effects 0.000 claims abstract 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract 2
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 claims abstract 2
- 230000001590 oxidative effect Effects 0.000 claims abstract 2
- 239000001301 oxygen Substances 0.000 claims abstract 2
- 229910052760 oxygen Inorganic materials 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims 19
- 239000007864 aqueous solution Substances 0.000 claims 8
- 239000000243 solution Substances 0.000 claims 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 4
- 229910052799 carbon Inorganic materials 0.000 claims 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims 4
- 239000001509 sodium citrate Substances 0.000 claims 4
- 239000007787 solid Substances 0.000 claims 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- 239000000084 colloidal system Substances 0.000 claims 3
- 239000011780 sodium chloride Substances 0.000 claims 3
- 230000002378 acidificating effect Effects 0.000 claims 2
- 239000003153 chemical reaction reagent Substances 0.000 claims 2
- 238000003682 fluorination reaction Methods 0.000 claims 2
- 238000010438 heat treatment Methods 0.000 claims 2
- 150000003839 salts Chemical class 0.000 claims 2
- 230000008016 vaporization Effects 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 claims 1
- 150000001804 chlorine Chemical class 0.000 claims 1
- 238000004880 explosion Methods 0.000 claims 1
- 230000008014 freezing Effects 0.000 claims 1
- 238000007710 freezing Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 1
- 239000011260 aqueous acid Substances 0.000 abstract 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 abstract 1
Classifications
-
- 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
- C01B15/029—Preparation from hydrogen and oxygen
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0211—Impregnation using a colloidal suspension
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
본 발명은 산성 수용액에 산소로 수소를 직접 산화시켜 얻은 촉매와 과산화수소 제조에 관계한다. 촉매는 VIII기 금속과 부분적으로 친수성, 소수성인 서포트 가령 플로오린화된 탄소에 Pd와 같은 서포트로 구성된다. H2O2선택성과 촉매 안정성이 반응액에 나트륨과 염소이온 첨가시에 개선되고, 플로오린화 탄소 서포트의 경우에 플로오리드 이온원을 첨가한다.
Description
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음
Claims (25)
- 산성 수용액 용액에서 산소로 수소를 직접 산화시켜 과산화수소를 생산하는 공정에 있어서, 그 구성이 (a) 수소와 산성 수용액 용액을 포함하는 산소를 압력용기내에 소수성/친수성 서포트에 적어도 하나의 VIII 금속으로 구성된 촉매하에 접촉시키고, (b) 반응개시에 또는 촉매활성이 감소되는때에 산성 수용성 용액에 나트륨과 염소이온원을 제공하고, (c) 수소 폭발 제한치 이하의 수소 부분압과 용기내의 압력이 3.5MPa∼20MPa 범위내에서 용기의 압력을 유지시키고, 그리고 (d) 용액의 빙점에서 60°사이의 범위에서 온도를 유지시키는 단계로 구성된 것을 특징으로 하는 공정.
- 제1항에 있어서, 촉매 서포트는 일정범위의 플로오린화된 탄소이며, 서포트의 친수성이 촉매로부터 형성된 H2O2가 수용액으로 확산되고, 소수성이 기체성 반응물이 촉매와 접촉할 수 있도록 허용하는 것을 특징으로 하는 공정.
- 제2항에 있어서, 플로오린화 범위가 10 내지 65%F인 것을 특징으로 하는 공정.
- 제3항에 있어서, 플로오린화 범위가 20 내지 25%F인 것을 특징으로 하는 공정.
- 제4항에 있어서, 플로오린화 범위가 약 28%F인 것을 특징으로 하는 공정.
- 제1항에 있어서, VIII 금속이 Pd인 것을 특징으로 하는 공정.
- 제3항에 있어서, VIII 금속이 Pd인 것을 특징으로 하는 공정.
- 제3항에 있어서, 나트륨, 염소, 플로오리드 이온이 수용액에 NaCl와 NaF 형으로 제공되는 것을 특징으로 하는 공정.
- 제7항에 있어서, 나트륨, 염소, 플로오리드 이온이 수용액에 NaCl와 NaF 형으로 제공되는 것을 특징으로 하는 공정.
- 제9항에 있어서, NaCl는 촉매기준시에 3∼30wt 범위로, NaF는 촉매기준시에 2∼10wt% 범위로 제공되는 것을 특징으로 하는 공정.
- 제1항에 있어서, 촉매 서포트는 부분적으로 수화된 가황탄소인 것을 특징으로 하는 공정.
- 제1항에 있어서, 수용성 용액은 촉매가 표면에 부유하는 것을 막기 위해 교반시키는 것을 특징으로 하는 공정.
- 과산화수소 생산에 사용되는 촉매는 (a) 소수성, 친수성 서포트, (b) VIII기 금속, 그리고 (c) 나트륨과 염소이온 공급원으로 구성된 것을 특징으로 하는 촉매.
- 제13항에 있어서, VIII기 금속은 Pd이고 0.1∼10%wt 범위양으로 공급되는 것을 특징으로 하는 촉매.
- 제13항에 있어서, 촉매 서포트는 10-65%F 정도로 플로오린화된 탄소이거나 또는 부분적으로 수화된 가황탄소인 것을 특징으로 하는 촉매.
- 제13항에 있어서, 플로오린화 정도는 20-50%인 것을 특징으로 하는 촉매.
- 과산화수소 생산용 촉매를 만드는 방법에 있어서, (a) 수용액에 소듐 시트레이트와 VIII기 금속염을 제공하고, (b) 용액을 가열하여 VIII 금속 소듐 시트레이트 콜로이드를 형성시키고, (c) 용액을 포함하는 콜로이드에 촉매 서포트를 첨가하고, 서포트는 부분적으로 소수성이고, 부분적으로 친수성이며, (d) 고형물에서 용액을 기화시키고, 그리고 (e) 수소대기에서 생성 고형물을 환원시키는 단계로 구성된 것을 특징으로 하는 방법.
- 제17항에 있어서, VIII기 금속은 Pd이고 생성된 촉매에 0.1∼10%wt가 되도록 Pd를 제공하기 위해 충분한 량의 염소염으로 제공되는 것을 특징으로 하는 방법.
- 제18항에 있어서, 촉매 소포트는 10∼65%F 정도의 플로오린화된 탄소거나 또는 부분적으로 수화된 가황탄소인 것을 특징으로 하는 방법.
- 제19항에 있어서, 플로오린화 정도는 20 내지 50%F인 것을 특징으로 하는 방법.
- 제20항에 있어서, 플로오린화 정도는 28%F인 것을 특징으로 하는 방법.
- 제17항에 있어서, 시약은 (c) 단계에 첨가되어 용액의 밀도를 낮추어 서포트가 표면에서 부유하지 않도록 하는 것을 특징으로 하는 방법.
- 제22항에 있어서, 시약이 메탄올인 것을 특징으로 하는 방법.
- 제17항에 있어서, (e) 단계는 상승된 온도에서 실시하는 것을 특징으로 하는 방법.
- 과산화수소 생산용 촉매를 만드는 방법에 있어서, (a) 수용액에 소듐 시트레이트와 VIII기 금속염을 제공하고, (b) 용액을 가열하여 VIII 금속 소듐 시트레이트 콜로이드를 형성시키고, (c) 용액이 포함된 촉매를 서포트에 첨가시키고, (d) 고형물에서 용액을 기화시키고, 그리고 (e) 수소대기에서 생성 고형물을 환원시키는 단계로 구성된 것을 특징으로 하는 방법.※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/823,688 US5338531A (en) | 1992-01-21 | 1992-01-21 | Production of hydrogen peroxide |
| US07/823,688 | 1992-01-21 | ||
| PCT/CA1993/000027 WO1993014025A1 (en) | 1992-01-21 | 1993-01-21 | Production of hydrogen peroxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR940703780A true KR940703780A (ko) | 1994-12-12 |
Family
ID=25239423
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019940702472A KR940703780A (ko) | 1992-01-21 | 1993-01-21 | 과산화수소 생산 (production of hydrogen peroxide) |
| KR1019940702472A KR0118992B1 (ko) | 1992-01-21 | 1993-01-21 | 과산화수소 생산 |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019940702472A KR0118992B1 (ko) | 1992-01-21 | 1993-01-21 | 과산화수소 생산 |
Country Status (16)
| Country | Link |
|---|---|
| US (3) | US5338531A (ko) |
| EP (1) | EP0623095A1 (ko) |
| JP (1) | JP3375628B2 (ko) |
| KR (2) | KR940703780A (ko) |
| AU (1) | AU670058B2 (ko) |
| BR (1) | BR9305762A (ko) |
| CA (1) | CA2128430C (ko) |
| CZ (1) | CZ173794A3 (ko) |
| FI (1) | FI111708B (ko) |
| HU (1) | HU215565B (ko) |
| NO (1) | NO313091B1 (ko) |
| NZ (1) | NZ246548A (ko) |
| RO (1) | RO111175B1 (ko) |
| SK (1) | SK281953B6 (ko) |
| UA (1) | UA26158C2 (ko) |
| WO (1) | WO1993014025A1 (ko) |
Families Citing this family (65)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5338531A (en) * | 1992-01-21 | 1994-08-16 | Chuang Karl T | Production of hydrogen peroxide |
| CA2122881A1 (en) * | 1993-05-06 | 1994-11-07 | Michiya Kawakami | Process for producing hydrogen peroxide |
| SE9600884L (sv) * | 1996-03-07 | 1997-09-08 | Bengtsson Erik Process Design | Förfarande för framställning av väteperoxid genom direktsyntes mellan väte och syre i kontakt med en katalysator i ett lösningsmedel |
| SE9600885L (sv) * | 1996-03-07 | 1997-09-08 | Bengtsson Erik Process Design | Förfarande för framställning av väteperoxid genom direktsyntes mellan väte och syre i kontakt med katalysator |
| SE9602484D0 (sv) * | 1996-06-24 | 1996-06-24 | Eka Chemicals Ab | Method of producing a chemical compound |
| DE19642770A1 (de) * | 1996-10-16 | 1998-04-23 | Basf Ag | Verfahren zur Herstellung von Wasserstoffperoxid |
| US6299852B1 (en) | 1997-12-22 | 2001-10-09 | Akzo Nobel N.V. | Process for production of a chemical compound |
| US6576214B2 (en) * | 2000-12-08 | 2003-06-10 | Hydrocarbon Technologies, Inc. | Catalytic direct production of hydrogen peroxide from hydrogen and oxygen feeds |
| US6168775B1 (en) * | 1998-08-26 | 2001-01-02 | Hydrocarbon Technologies, Inc. | Catalyst and process for direct catalystic production of hydrogen peroxide, (H2O2) |
| US6346228B1 (en) * | 1999-02-19 | 2002-02-12 | Council Of Scientific And Industrial Research | Hydrophobic multicomponent catalyst useful for direct oxidation of hydrogen to hydrogen peroxide |
| IT1318550B1 (it) | 2000-06-01 | 2003-08-27 | Eni Spa | Catalizzatore e processo per la sintesi diretta di acqua ossigenata. |
| US6432376B1 (en) | 2000-09-05 | 2002-08-13 | Council Of Scientific & Industrial Research | Membrane process for the production of hydrogen peroxide by non-hazardous direct oxidation of hydrogen by oxygen using a novel hydrophobic composite Pd-membrane catalyst |
| US6448199B1 (en) | 2000-09-05 | 2002-09-10 | Council Of Scientific & Industrial Research | Hydrophobic composite Pd-membrane catalyst useful for non-hazardous direct oxidation of hydrogen by oxygen to hydrogen peroxide and method of its preparation |
| DE10048844A1 (de) * | 2000-10-02 | 2002-04-11 | Basf Ag | Verfahren zur Herstellung von Platinmetall-Katalysatoren |
| KR100383218B1 (ko) * | 2000-10-26 | 2003-05-12 | 한국화학연구원 | 과산화수소의 직접적 제조방법 |
| US6534440B2 (en) * | 2000-11-29 | 2003-03-18 | Council Of Scientific And Industrial Research | Process for the activation of a metallic palladium based catalyst useful for the direct oxidation of hydrogen to hydrogen peroxide |
| US20060131161A1 (en) * | 2001-05-07 | 2006-06-22 | Towler Gavin P | Air sanitation with hydrogen peroxide |
| US7115192B1 (en) * | 2001-05-07 | 2006-10-03 | Uop Llc | Apparatus and process for the synthesis of hydrogen peroxide directly from hydrogen and oxygen |
| JP2003050068A (ja) * | 2001-05-30 | 2003-02-21 | Permelec Electrode Ltd | 過酸化水素を含有する氷組成物及び生鮮食品の保存方法 |
| US6768013B1 (en) | 2001-06-15 | 2004-07-27 | Uop Llc | Intrinsically safe oxidation process |
| DE10153546A1 (de) * | 2001-10-30 | 2003-05-22 | Degussa | Direktsynthese von Wasserstoffperoxid und deren Integration in Oxidationsprozesse |
| EP1344747B1 (en) * | 2002-03-14 | 2012-02-08 | Repsol Quimica S.A. | Process to obtain hydrogen peroxide |
| ATE453603T1 (de) * | 2003-02-03 | 2010-01-15 | Repsol Quimica Sa | Integriertes verfahren zur selektiven oxydation von organischen verbindungen |
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|---|---|---|---|---|
| JPS514097A (en) * | 1974-07-02 | 1976-01-13 | Tokuyama Soda Kk | Kasankasuisono seizohoho |
| ATE25839T1 (de) * | 1983-06-22 | 1987-03-15 | Du Pont | Verfahren zur katalytischen herstellung von wasserstoffperoxid aus sauerstoff und wasserstoff. |
| US4681751A (en) * | 1983-06-22 | 1987-07-21 | E. I. Du Pont De Nemours And Company | Catalytic process for making H2 O2 from hydrogen and oxygen |
| US4661337A (en) * | 1985-11-18 | 1987-04-28 | The Halcon Sd Group, Inc. | Preparation of hydrogen peroxide |
| US4908198A (en) * | 1986-06-02 | 1990-03-13 | The Electrosynthesis Company, Inc. | Fluorinated carbons and methods of manufacture |
| US4772458A (en) * | 1986-11-19 | 1988-09-20 | E. I. Du Pont De Nemours And Company | Catalytic process for making hydrogen peroxide from hydrogen and oxygen employing a bromide promoter |
| CA1317740C (en) * | 1988-10-24 | 1993-05-18 | Karl T. Chuang | Production of hydrogen peroxide |
| US5132099A (en) * | 1990-12-27 | 1992-07-21 | Mitsubishi Gas Chemical Company, Inc. | Method for producing hydrogen peroxide |
| US5135731A (en) * | 1991-05-15 | 1992-08-04 | E. I. Du Pont De Nemours And Company | Method for catalytic production of hydrogen peroxide |
| US5338531A (en) * | 1992-01-21 | 1994-08-16 | Chuang Karl T | Production of hydrogen peroxide |
-
1992
- 1992-01-21 US US07/823,688 patent/US5338531A/en not_active Expired - Lifetime
-
1993
- 1993-01-21 EP EP93902010A patent/EP0623095A1/en not_active Ceased
- 1993-01-21 HU HU9402151A patent/HU215565B/hu not_active IP Right Cessation
- 1993-01-21 RO RO94-01187A patent/RO111175B1/ro unknown
- 1993-01-21 KR KR1019940702472A patent/KR940703780A/ko not_active IP Right Cessation
- 1993-01-21 NZ NZ246548A patent/NZ246548A/xx not_active IP Right Cessation
- 1993-01-21 SK SK882-94A patent/SK281953B6/sk unknown
- 1993-01-21 UA UA94075647A patent/UA26158C2/uk unknown
- 1993-01-21 AU AU33423/93A patent/AU670058B2/en not_active Ceased
- 1993-01-21 CZ CZ941737A patent/CZ173794A3/cs unknown
- 1993-01-21 CA CA002128430A patent/CA2128430C/en not_active Expired - Fee Related
- 1993-01-21 BR BR9305762A patent/BR9305762A/pt not_active IP Right Cessation
- 1993-01-21 JP JP51204493A patent/JP3375628B2/ja not_active Expired - Fee Related
- 1993-01-21 WO PCT/CA1993/000027 patent/WO1993014025A1/en active IP Right Grant
- 1993-01-21 KR KR1019940702472A patent/KR0118992B1/ko active
-
1994
- 1994-07-15 FI FI943377A patent/FI111708B/fi active
- 1994-07-20 NO NO19942714A patent/NO313091B1/no unknown
-
1997
- 1997-04-24 US US08/845,571 patent/US5846898A/en not_active Expired - Fee Related
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1998
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Also Published As
| Publication number | Publication date |
|---|---|
| FI111708B (fi) | 2003-09-15 |
| AU670058B2 (en) | 1996-07-04 |
| WO1993014025A1 (en) | 1993-07-22 |
| SK88294A3 (en) | 1995-01-12 |
| US5846898A (en) | 1998-12-08 |
| US5338531A (en) | 1994-08-16 |
| CA2128430C (en) | 1998-10-27 |
| NZ246548A (en) | 1995-09-26 |
| SK281953B6 (sk) | 2001-09-11 |
| NO942714D0 (no) | 1994-07-20 |
| NO313091B1 (no) | 2002-08-12 |
| JPH07503447A (ja) | 1995-04-13 |
| EP0623095A1 (en) | 1994-11-09 |
| RO111175B1 (ro) | 1996-07-30 |
| FI943377A (fi) | 1994-07-15 |
| NO942714L (no) | 1994-07-20 |
| BR9305762A (pt) | 1997-01-28 |
| HUT69291A (en) | 1995-09-28 |
| HU215565B (hu) | 1999-01-28 |
| AU3342393A (en) | 1993-08-03 |
| CA2128430A1 (en) | 1993-07-22 |
| FI943377A0 (fi) | 1994-07-15 |
| KR0118992B1 (ko) | 1997-09-30 |
| CZ173794A3 (en) | 1995-08-16 |
| HU9402151D0 (en) | 1994-09-28 |
| UA26158C2 (uk) | 1999-06-07 |
| US5925588A (en) | 1999-07-20 |
| JP3375628B2 (ja) | 2003-02-10 |
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