BR9703083A - Sistemas de catalisadores à base de compostos do complexo de ródio com ligantes difosfina e seu emprego na preparação de aldeídos - Google Patents
Sistemas de catalisadores à base de compostos do complexo de ródio com ligantes difosfina e seu emprego na preparação de aldeídosInfo
- Publication number
- BR9703083A BR9703083A BR9703083A BR9703083A BR9703083A BR 9703083 A BR9703083 A BR 9703083A BR 9703083 A BR9703083 A BR 9703083A BR 9703083 A BR9703083 A BR 9703083A BR 9703083 A BR9703083 A BR 9703083A
- Authority
- BR
- Brazil
- Prior art keywords
- aldehydes
- preparation
- catalyst systems
- systems based
- complex compounds
- Prior art date
Links
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 title 2
- 150000001299 aldehydes Chemical class 0.000 title 1
- 239000003054 catalyst Substances 0.000 title 1
- 150000001875 compounds Chemical class 0.000 title 1
- 239000003446 ligand Substances 0.000 title 1
- 229910052703 rhodium Inorganic materials 0.000 title 1
- 239000010948 rhodium Substances 0.000 title 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
- C07F9/5054—Preparation; Separation; Purification; Stabilisation by a process in which the phosphorus atom is not involved
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
- B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
- B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
- B01J31/4038—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing noble metals
- B01J31/4046—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing noble metals containing rhodium
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4053—Regeneration or reactivation of catalysts containing metals with recovery of phosphorous catalyst system constituents
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4061—Regeneration or reactivation of catalysts containing metals involving membrane separation
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/786—Separation; Purification; Stabilisation; Use of additives by membrane separation process, e.g. pervaporation, perstraction, reverse osmosis
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0261—Complexes comprising ligands with non-tetrahedral chirality
- B01J2531/0266—Axially chiral or atropisomeric ligands, e.g. bulky biaryls such as donor-substituted binaphthalenes, e.g. "BINAP" or "BINOL"
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
-
- 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
- B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
- B01J2540/10—Non-coordinating groups comprising only oxygen beside carbon or hydrogen
- B01J2540/12—Carboxylic acid groups
-
- 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
- B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
- B01J2540/30—Non-coordinating groups comprising sulfur
- B01J2540/32—Sulfonic acid groups or their salts
-
- 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
- B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
- B01J2540/50—Non-coordinating groups comprising phosphorus
- B01J2540/52—Phosphorus acid or phosphorus acid ester groups
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
- B01J31/4038—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing noble metals
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19619527A DE19619527A1 (de) | 1996-05-15 | 1996-05-15 | Katalysatorsysteme auf der Basis von Rhodium-Komplexverbindungen mit Diphosphin-Liganden und ihre Verwendung bei der Herstellung von Aldehyden |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| BR9703083A true BR9703083A (pt) | 1998-09-08 |
Family
ID=7794347
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| BR9703083A BR9703083A (pt) | 1996-05-15 | 1997-05-07 | Sistemas de catalisadores à base de compostos do complexo de ródio com ligantes difosfina e seu emprego na preparação de aldeídos |
Country Status (13)
| Country | Link |
|---|---|
| US (2) | US5922634A (pt) |
| EP (1) | EP0811424A3 (pt) |
| JP (1) | JP3009635B2 (pt) |
| KR (1) | KR970073720A (pt) |
| CN (1) | CN1171981A (pt) |
| AU (1) | AU713496B2 (pt) |
| BR (1) | BR9703083A (pt) |
| CA (1) | CA2204675A1 (pt) |
| DE (1) | DE19619527A1 (pt) |
| ID (1) | ID17380A (pt) |
| PL (1) | PL319896A1 (pt) |
| RO (1) | RO115025B1 (pt) |
| ZA (3) | ZA973982B (pt) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR9703078A (pt) * | 1996-05-15 | 1998-11-10 | Hoechst Ag | Processo para obtenção de aldeídos |
| JP3847466B2 (ja) * | 1998-09-01 | 2006-11-22 | 三菱化学株式会社 | オレフィンのヒドロホルミル化反応方法 |
| AU2003201857A1 (en) * | 2002-03-22 | 2003-10-08 | Kuraray Co., Ltd. | Bisphosphine, process for producing the same, and use thereof |
| DE10352261B4 (de) | 2003-11-08 | 2006-08-24 | Celanese Chemicals Europe Gmbh | Verfahren zur Herstellung von TCD-Dialdehyd |
| DE10352260B3 (de) | 2003-11-08 | 2005-04-14 | Celanese Chemicals Europe Gmbh | Verfahren zur Herstellung von TCD-Alkohol DM |
| DE10352258B4 (de) | 2003-11-08 | 2013-06-13 | Oxea Gmbh | Verfahren zur Herstellung von TCD-Diamin |
| US7631758B2 (en) * | 2005-04-13 | 2009-12-15 | Vaporlok Technology, Llc | Shipping and storage containers |
| EP2740535A1 (en) * | 2012-12-04 | 2014-06-11 | Dow Technology Investments LLC | Bidentate ligands for hydroformylation of ethylene |
| CN104209012A (zh) * | 2013-05-29 | 2014-12-17 | 成都慧成科技有限责任公司 | 一种高通量、高盐截留率反渗透膜的制备方法 |
| CN104475161B (zh) * | 2014-12-03 | 2016-09-14 | 中国石油大学(北京) | 铁磁性纳米颗粒固载铑络合物的氢甲酰化催化剂的制法 |
| CN109453816B (zh) * | 2018-12-12 | 2020-08-25 | 四川大学 | 一种用于烯烃氢甲酰化反应的催化剂及其制备方法和应用 |
| US12064755B2 (en) | 2019-06-12 | 2024-08-20 | Evonik Oxeno Gmbh & Co. Kg | Process for separating one or more components from a mixture |
| CN113061149B (zh) * | 2021-03-29 | 2022-04-22 | 万华化学集团股份有限公司 | 一种互配型配体和氢甲酰化催化剂、及二元醇的制备方法 |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2230654B1 (pt) * | 1973-05-21 | 1975-11-21 | Rhone Poulenc Ind | |
| US4694109A (en) * | 1986-06-13 | 1987-09-15 | Eastman Kodak Company | Chelate ligands for low pressure hydroformylation catalyst and process employing same |
| US4935550A (en) * | 1988-08-12 | 1990-06-19 | Union Carbide Chemicals And Plastics Company Inc. | Catalytic metal recovery from non-polar organic solutions |
| DE3842819A1 (de) * | 1988-12-20 | 1990-06-21 | Hoechst Ag | Verfahren zur abtrennung von metallorganischen verbindungen und/oder metallcarbonylen aus ihren loesungen in organischen medien |
| US4960949A (en) * | 1988-12-22 | 1990-10-02 | Eastman Kodak Company | Low pressure rhodium catalyzed hydroformylation of olefins |
| US5118825A (en) * | 1990-12-10 | 1992-06-02 | Ethyl Corporation | Ruthenium phosphine complex |
| DE4040315A1 (de) * | 1990-12-17 | 1992-06-25 | Hoechst Ag | Verfahren zur herstellung von aldehyden |
| DE4141299C2 (de) * | 1991-12-14 | 2000-09-21 | Celanese Chem Europe Gmbh | Verfahren zur Herstellung von tertiären Phosphanen |
| TW225485B (pt) * | 1992-05-29 | 1994-06-21 | Hoechst Ag | |
| DE4415682A1 (de) * | 1994-05-04 | 1995-11-09 | Hoechst Ag | Palladium Katalysatoren mit sulfonierten Bisphosphinen als Liganden, Verfahren zu ihrer Herstellung und ihre Verwendung für Carbonylierungsreaktionen |
| DE19516968A1 (de) * | 1995-05-12 | 1996-11-14 | Basf Ag | Optisch aktive Phosphine, deren Herstellung, deren Metallkomplexe und Anwendung in der asymmetrischen Synthese |
| DE19522293A1 (de) * | 1995-06-20 | 1997-01-02 | Bayer Ag | Neue Bisphospine als Katalysatoren für asymmetrische Reaktionen |
| GB9517105D0 (en) * | 1995-08-21 | 1995-10-25 | Bp Chem Int Ltd | Catalyst compositions |
| JP3441605B2 (ja) * | 1996-10-30 | 2003-09-02 | 高砂香料工業株式会社 | 新規光学活性ジホスフィン及び該化合物より得られる遷移金属錯体及び該錯体の存在下にて光学活性体を得る方法 |
-
1996
- 1996-05-15 DE DE19619527A patent/DE19619527A1/de not_active Withdrawn
-
1997
- 1997-04-17 US US08/839,330 patent/US5922634A/en not_active Expired - Fee Related
- 1997-05-07 EP EP97107515A patent/EP0811424A3/de not_active Withdrawn
- 1997-05-07 BR BR9703083A patent/BR9703083A/pt not_active Application Discontinuation
- 1997-05-07 CA CA002204675A patent/CA2204675A1/en not_active Abandoned
- 1997-05-08 ZA ZA9703982A patent/ZA973982B/xx unknown
- 1997-05-08 ZA ZA9703986A patent/ZA973986B/xx unknown
- 1997-05-08 KR KR1019970017579A patent/KR970073720A/ko not_active Withdrawn
- 1997-05-08 ZA ZA9703999A patent/ZA973999B/xx unknown
- 1997-05-09 PL PL97319896A patent/PL319896A1/xx unknown
- 1997-05-13 RO RO97-00889A patent/RO115025B1/ro unknown
- 1997-05-13 AU AU20805/97A patent/AU713496B2/en not_active Ceased
- 1997-05-14 CN CN97111175A patent/CN1171981A/zh active Pending
- 1997-05-14 JP JP9124502A patent/JP3009635B2/ja not_active Expired - Lifetime
- 1997-05-15 ID IDP971620A patent/ID17380A/id unknown
-
1998
- 1998-07-09 US US09/112,099 patent/US6020532A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1171981A (zh) | 1998-02-04 |
| DE19619527A1 (de) | 1997-11-20 |
| JP3009635B2 (ja) | 2000-02-14 |
| ID17380A (id) | 1997-12-24 |
| US5922634A (en) | 1999-07-13 |
| EP0811424A3 (de) | 1998-06-03 |
| ZA973982B (en) | 1997-12-09 |
| EP0811424A2 (de) | 1997-12-10 |
| PL319896A1 (en) | 1997-11-24 |
| ZA973999B (en) | 1997-12-09 |
| ZA973986B (en) | 1997-12-09 |
| AU713496B2 (en) | 1999-12-02 |
| KR970073720A (ko) | 1997-12-10 |
| US6020532A (en) | 2000-02-01 |
| JPH1066877A (ja) | 1998-03-10 |
| AU2080597A (en) | 1997-11-20 |
| CA2204675A1 (en) | 1997-11-15 |
| MX9703456A (es) | 1998-06-28 |
| RO115025B1 (ro) | 1999-10-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PC | Transfer |
Free format text: CELANESE GMBH (DE) |
|
| FA10 | Dismissal: dismissal - article 33 of industrial property law | ||
| B11Y | Definitive dismissal acc. article 33 of ipl - extension of time limit for request of examination expired |