WO2004022227A1 - Procede pour produire des catalyseurs a base de cyanures polymetalliques - Google Patents

Procede pour produire des catalyseurs a base de cyanures polymetalliques Download PDF

Info

Publication number
WO2004022227A1
WO2004022227A1 PCT/EP2003/008094 EP0308094W WO2004022227A1 WO 2004022227 A1 WO2004022227 A1 WO 2004022227A1 EP 0308094 W EP0308094 W EP 0308094W WO 2004022227 A1 WO2004022227 A1 WO 2004022227A1
Authority
WO
WIPO (PCT)
Prior art keywords
multimetal cyanide
poly
group
multimetal
drying
Prior art date
Application number
PCT/EP2003/008094
Other languages
German (de)
English (en)
Inventor
Edward Bohres
Friedrich Hill
Raimund Ruppel
Eva Baum
Original Assignee
Basf Aktiengesellschaft
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
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU2003250156A priority Critical patent/AU2003250156A1/en
Publication of WO2004022227A1 publication Critical patent/WO2004022227A1/fr

Links

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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J27/26—Cyanides
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying

Definitions

  • the invention relates to a process for the preparation of multimetal cyanide compounds, the multimetal cyanide compounds prepared by this process and their use as catalysts for the polymerization of alkylene oxides.
  • Polyether alcohols are used in large quantities for the production of polyurethanes. They are usually produced by catalytic addition of lower alkylene oxides, in particular ethylene oxide and propylene oxide, to H-functional starter substances. Basic metal hydroxides or salts are mostly used as catalysts, the potassium hydroxide being of the greatest practical importance.
  • DD-A-203 735 and DD-A-203 734 describe the production of polyetherols using zinc hexacyano cobaltate.
  • the production of zinc hexacyanometalates is also known.
  • These catalysts are usually prepared by solutions of metal salts, such as zinc chloride, with solutions of alkali metal or alkaline earth metal cyanometalates, such as potassium hexacyanoates. cobaltat, to be implemented.
  • a water-miscible, heteroato-containing component is generally added to the precipitation suspension formed immediately after the precipitation process. This component can also already be present in one or in both educt solutions.
  • This water-miscible component containing heteroatoms can be, for example, an ether, polyether, alcohol, ketone or a mixture thereof. Such methods are described for example in US 3,278,457, US 3,278,458, US 3,278,459 and US 5,545,601.
  • Multimetal cyanide catalysts are mostly used in the form of powder for the production of polyether alcohols.
  • No. 5,900,384 describes a process for producing multimetal cyanide catalysts with improved catalytic activity and small particle size, in which a slurry of multimetal cyanide compounds is dried in an organic solvent by means of spray drying.
  • a disadvantage of this process is that the slurrying of the multimetal cyanide compound in the organic solvent represents an additional process step, which makes the process more complicated.
  • the spray drying must be carried out under an inert gas atmosphere. Furthermore, it has been shown that the multimetal cyanide catalysts produced in this way still have an insufficient catalytic activity.
  • the object of the invention was to provide multimetal cyanide compounds which have high catalytic activity and can be prepared by a simple process.
  • multimetal cyanide compounds show an increased catalyst activity in the polymerization of alkylene oxides when they are spray-dried from an aqueous suspension and under an inert gas or air.
  • the invention accordingly relates to a process for the preparation of multimetal cyanide compounds, comprising the steps
  • step b spray drying the suspended multimetal cyanide compounds obtained in step a).
  • the invention furthermore relates to the multimetal cyanide compounds obtained by this process.
  • the invention further relates to the use of the multimetal cyanide compounds prepared by this process as catalysts for the preparation of polyether alcohols by polymerizing alkylene oxides.
  • the multimetal cyanide compounds produced by the process according to the invention preferably have the general formula (I)
  • M 1 is a metal ion selected from the group comprising Zn 2+ , Fe 2+ , Co 3+ , Ni 2+ , Mh 2 X Co 2+ , Sn 2+ , Sn 4+ , Pb 2+ , Mo 4+ , Mo 5+ , Al 3+ , V 4 X 5+ , Sr +, W 4+ , W 6+ , Cr 2 +, Cr 3+ , Cd 2+ , Cu 2+ , La 3+ ,
  • M 2 is a metal ion selected from the group containing Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Mh 2+ , Mn 3+ , Ni + V + , V 5+ , Cr 2+ , Cr 3 + , Rh 3 X Ru 2 +, Ir + ,
  • A is an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate or nitrate,
  • X is an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate or nitrite (N0 2 ⁇ ), and the uncharged species CO, H0 and NO, L is a water-miscible ligand selected from the group consisting of alcohols aldehydes, ketones, ethers, polyethers, esters, polyesters, polycarbonates, ureas, amides, nitriles, and sulfides or mixtures thereof,
  • P is an organic additive selected from the group consisting of polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycol glycidyl ethers, polyacrylamide, poly (acrylamide-co-acrylic acid), polyacrylic acid, poly (acrylamide-co-maleic acid), polyacrylonitrile, polyalkyl - Acrylates, polyalkyl methacrylates, polyvinyl methyl ether, poly vinyl ethyl ether, poly vinyl acetate, poly vinyl alcohol, poly-N-vinyl pyrrolidone, poly (N-vinyl pyrrolidone-co-acrylic acid), poly vinyl methyl ketone, poly (4-vinyl phenol), poly (acrylic acid co-styrene ), Oxazoline polymers, polyalkyleneimines, maleic acid and maleic anhydride copolymer, hydroxyethyl cellulose, polyacetates, ionic surfaces and surface-active compounds,
  • a, b, d, q and n are integer or fractional numbers greater than zero
  • c, f, e, h and k are integer or fractional numbers greater than zero
  • a, b, c, and d, and q and n are selected so that electroneutrality is ensured.
  • f and k may only be zero if c is non-zero and A is exclusively carboxylate, oxalate or nitrate.
  • These catalysts can be crystalline or amorphous. In the event that k is zero, crystalline double metal cyanide compounds are preferred. In the event that k is greater than zero, both crystalline, partially crystalline and substantially amorphous catalysts are preferred.
  • an aqueous solution of a cyanometalate compound in particular a cyanometalate hydrogen acid or a cyanometalate salt
  • a metal salt of the general formula M ⁇ fXJn where the symbols have the meaning explained above.
  • the molar ratio of the metal ion to the cyanometalate component is preferably from 1.1 to 7.0, preferably from 1.2 to 5.0 and particularly preferably from 1.3 to 3.0. It is advantageous to present the metal salt solution and add the cyanometalate compound, but the procedure can also be reversed. Thorough mixing, for example by stirring, is required during and after the starting material solutions have been combined.
  • the content of the cyanometalate compound in the aqueous solution, based on the mass of aqueous solution, is 0.1 to 30% by weight, preferably 0.1 to 20% by weight, in particular 0.2 to 10% by weight.
  • the content of the metal salt component in the metal salt solution, based on the mass of metal salt solution is 0.1 to 50% by weight, preferably 0.2 to 40% by weight, in particular 0.5 to 30% by weight.
  • At least one of the aqueous solutions of the starting materials preferably contains a ligand containing heteroatoms, as it is designated and explained as L in the general formula (I).
  • the ligands containing heteroatoms can also be added to the resulting suspension only after the two starting material solutions have been combined, and here too thorough mixing must be ensured.
  • the content of the ligands containing heteroatoms in the suspension formed after the precipitation should be 1 to 60% by weight, preferably 5 to 40% by weight, in particular 10 to 30% by weight.
  • the surface-active substances are already introduced in at least one of the two solutions.
  • the surface-active substances are preferably added to the solution which is initially introduced during the precipitation.
  • the content of surface-active substances in the precipitation solution is preferably between 0.01 and 40% by weight, in particular between 0.05 and 30% by weight.
  • Another preferred embodiment provides that the surface-active substances are distributed proportionally to both educt solutions.
  • the reaction of the metal salt with the cyanometalate compound takes place in two stages.
  • a catalytically inactive phase of the multimetal cyanide compound is produced and then this converted into a catalytically active phase of the multimetal cyanide compound by recrystallization.
  • the recrystallization can be carried out by various measures. It is thus possible to add further reactant solutions, in particular the solution of the metal salt, to the suspension formed after the reaction. Another possibility is to change the temperature of the precipitation suspension after the precipitation has ended, in particular to heat the suspension. Another possibility is to add further heteroatoms containing ligands and / or surface-active substances to the precipitation suspension after the precipitation has ended. Another possibility is to change the pH of the precipitation suspension.
  • k is zero in formula (I) and optionally e is also zero.
  • X is exclusively carboxylate, preferably formate, acetate and propionate.
  • multimetal cyanide compounds are described, for example, in WO 99/16775. In this embodiment, crystalline double metal cyanide catalysts are preferred.
  • Multimetal cyanide compounds which are crystalline and platelet-shaped are also preferred. Such multimetal cyanide compounds are described, for example, in WO 00/74843.
  • f, e and k in formula (I) are not equal to zero.
  • multimetal cyanide compounds which contain a water-miscible organic ligand L, mostly in amounts of 0.5 to 30% by weight, and an organic additive P, usually in amounts of 5 to 80% by weight .
  • Such multimetal cyanide compounds are described, for example, in WO 98/06312. described.
  • the precipitation of the multimetal cyanide compounds in step a) can preferably be carried out with vigorous stirring, for example at 24,000 rpm with Turrax® stirring, as described, for example, in US Pat. No. 5,158,922.
  • multimetal cyanide as described in WO 01/03830, describes contain organic sulphones or sulphoxides ⁇ .
  • Further multimetal cyanide compounds preferred for the process according to the invention can, as described in WO 01/03831, be produced by a so-called "Incipient Wetness Method".
  • Others for the inventive Preferred multimetal cyanide compounds can, as described in WO 01/04182, contain metal hexacyanometallate hexanitro metalate, or, as described in WO 01/04181, contain hexacyano cobaltate nitroferrocyanide.
  • the multimetal cyanide compounds produced in step a) can be separated from the precipitation suspension by filtration or centrifugation.
  • One or more washes of the multimetal cyanide compounds can then follow this separation.
  • the washings can be carried out with water, the ligands containing heteroatoms mentioned above or mixtures thereof.
  • the washings can be carried out on the separation device (e.g. filter device) itself or in separate apparatus by e.g. Resuspend the multimetal cyanide compound in washing liquid and separate again from the liquid. This washing can be carried out at temperatures from 10 ° C. to 150 ° C., preferably 15 ° to 60 ° C.
  • the multimetal cyanide compound thus obtained is optionally mashed with water, the solids content being adjusted in such a way that a sprayable aqueous suspension is present.
  • the solids content of the suspension is then between 5 and 40% by weight.
  • the aqueous suspension of the multimetal cyanide compounds is then converted into a powdery solid by a spray drying process, as described, for example, in Kröll, drying technology, Springer Verlag, 2nd volume, 2nd edition, pages 275-313.
  • the aqueous suspension is first divided into fine droplets in the spray dryer by means of an atomizing device, such as a one-component nozzle, two-component nozzle, or a rotary atomizer, which are then dispersed in a hot gas stream.
  • the inlet temperature of the drying gas is preferably between 120 ° C and 350 ° C. Due to the intensive heat and mass exchange of the spray droplets with the hot drying gas, the liquid evaporates from the spray droplets into the drying gas, so that a dry powdery solid is obtained. At the outlet of the spray dryer, the dried spray powder is separated from the drying gas, for example with a filter or cyclone. Since the metal cyanide compounds are dried from aqueous solution, the safety requirements for the spray drying process are considerably lower than in the presence of organic solvents. In principle, all gases which are inert to the multimetal cyanide compounds under the drying conditions can be used as drying gases. Air, nitrogen or argon are used in particular.
  • Air can be used particularly preferably as the drying gas, which leads to a significantly higher activity of the catalyst compared to nitrogen.
  • the multimetal cyanide compounds prepared by the process according to the invention are outstandingly suitable as catalysts for the synthesis of polyetherols with functionalities from 1 to 8, preferably 1 to 6 and molar masses from 500 to 50,000, preferably 800 to 15,000, by addition of alkylene oxides onto H-functional starter substances.
  • the catalyst concentrations used are less than 1% by weight, preferably less than 0.5% by weight, particularly preferably less than 1000 ppm, particularly preferably less than 500 ppm, particularly preferably less than 100 ppm, based on the total mass of the polyetherol Polyetherols can be carried out either continuously or batchwise.
  • the synthesis is carried out in a suspension mode.
  • the temperatures used in the synthesis are between 50 ° C. and 200 ° C., temperatures between 90 ° C. and 150 ° C. being preferred.
  • compounds having at least one alkyl oxide group such as, for example, ethylene oxide, 1, -epoxypropane (propylene oxide), 1, 2-methyl-2-methylpropane, 1,2-epoxybutane (butylene oxide), 2, 3-epoxybutane, 1,2-epoxy-3-methylbutane, 1,2-epoxypentane, 1,2-epoxy-3-methylpentane, 1, 2-epoxyhexane, 1, 2-epoxyheptane, 1, 2-epoxyoctane, 1, 2-epoxynonan, 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, styrene oxide, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, (2,3-epoxypropyl) benzene, vinyloxirane, 3- Phenoxy-1,2-epoxypropane
  • the polyether alcohols according to the invention mostly have a functionality of 2 to 8, preferably 2 to 4 and in particular 2 to 3 and an equivalent weight of more than 500 g / mol.
  • the starting substances used as higher-functional starting substances are, in particular, sugar alcohols, for example sorbitol, hexitol and sucrose, but mostly two- and / or three-functional alcohols or water, either as a single substance or as a mixture of at least 2 of the starting substances mentioned.
  • Examples of bifunctional starter substances are ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol-1, 4 and pentantanedio -1, 5.
  • bifunctional start substances are trimethylolpropane, pentaerythritol and in particular glycerin.
  • the StartSubsces can also be used in the form of alkoxylates, in particular those with a molecular weight M w in the range from 62 to 15000 g / mol.
  • These alkoxylates can be prepared in a separate process step, and catalysts other than multimetal cyanide compounds, for example alkali metal hydroxides, can also be used for their preparation.
  • catalysts other than multimetal cyanide compounds for example alkali metal hydroxides
  • alkali metal hydroxides it is necessary to remove the catalyst almost completely, since alkali metal hydroxides can deactivate the multimetal cyanide catalysts.
  • the advantage of using alkoxylates as starter substances is that the reaction starts faster, the disadvantage is the introduction of an additional process step and, as stated, the time-consuming cleaning of the alkoxylate.
  • the polyether alcohols produced using the DMC catalysts according to the invention are preferably used for the production of polyurethanes, in particular polyurethane foams and in particular flexible polyurethane foams.
  • the polyurethanes are produced by reacting the polyether alcohols with polyisocyanates in the presence of catalysts, blowing agents and, if appropriate, other customary auxiliaries and / or additives.
  • the invention is illustrated by the following examples.
  • aqueous hexacyanocobaltaic acid (cobalt content: 9 g / 1 Cobalt) and heated to 50 ° C with stirring.
  • 587 g of aqueous zinc acetate dihydrate solution (zinc content: 2.6% by weight), which was also heated to 50 ° C., were then added within 45 minutes with stirring.
  • a solution of 20 g of a surface-active compound (Pluronic® PE.6200 from BASF Aktiengesellschaft) in 30 g of water was then added.
  • the mixture was heated to 60 ° C. and further stirred at this temperature for 2 hours.
  • 186.1 g of aqueous zinc acetate dihydrate solution (zinc content: 2.6% by weight) were metered in with stirring at 60 ° C. within 20 min. After a few minutes, the conductivity started to drop.
  • the suspension was stirred at a temperature of 60 ° C. until the pH of the suspension had dropped from 4.0 to 2.9 and remained constant.
  • the precipitate suspension thus obtained was filtered off and washed with about 600 ml of water. A white powder was obtained.
  • Example 2 Spray drying of the multimetal cyanide compound from water with air as the drying and atomizing medium
  • Example 1 with a proportion of multimetal cyanide compound from
  • Example 3 Spray drying of the multimetal cyanide compound from t-butanol using nitrogen as the drying and atomizing medium
  • the two-fluid nozzle was operated at a pre-pressure of 2 bar and a nitrogen throughput of 3 m3 / h.
  • a Exit of the spray tower the dry multimetal cyanide compound was separated from the drying medium with a cyclone.
  • Catalyst 1 water air 100 10.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé pour produire des catalyseurs à base de cyanures polymétalliques, comprenant les étapes suivantes : a) réaction de la solution aqueuse d'un sel métallique avec la solution aqueuse d'un composé cyanométallate, b) séchage par pulvérisation des composés cyanures polymétalliques en suspension, obtenus à l'étape a).
PCT/EP2003/008094 2002-08-15 2003-07-24 Procede pour produire des catalyseurs a base de cyanures polymetalliques WO2004022227A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003250156A AU2003250156A1 (en) 2002-08-15 2003-07-24 Method for the production of multimetal cyanide catalysts

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10238141 2002-08-15
DE10238141.0 2002-08-15

Publications (1)

Publication Number Publication Date
WO2004022227A1 true WO2004022227A1 (fr) 2004-03-18

Family

ID=31968979

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2003/008094 WO2004022227A1 (fr) 2002-08-15 2003-07-24 Procede pour produire des catalyseurs a base de cyanures polymetalliques

Country Status (2)

Country Link
AU (1) AU2003250156A1 (fr)
WO (1) WO2004022227A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011047780A1 (fr) 2009-10-19 2011-04-28 Basf Se Conditionnement de catalyseurs cyanures métalliques doubles
WO2011160797A1 (fr) 2010-06-23 2011-12-29 Basf Se Catalyseurs modifiés de type double cyanure métallique (dmc), procédé de synthèse par traitement d'un catalyseur de type dmc cristallin par un acide de brønsted et leurs applications

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5891818A (en) * 1997-07-31 1999-04-06 Arco Chemical Technology, L.P. Cyanide complex catalyst manufacturing process
US5900384A (en) * 1996-07-18 1999-05-04 Arco Chemical Technology L.P. Double metal cyanide catalysts
WO2001080994A1 (fr) * 2000-04-20 2001-11-01 Bayer Aktiengesellschaft Procede de production de catalyseurs a base de cyanure metallique double
US20010046940A1 (en) * 2000-04-28 2001-11-29 O'connor James M. Double metal cyanide catalysts containing polyglycol ether complexing agents
WO2003042280A1 (fr) * 2001-11-15 2003-05-22 Basf Aktiengesellschaft Procede de production d'alcools de polyether

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5900384A (en) * 1996-07-18 1999-05-04 Arco Chemical Technology L.P. Double metal cyanide catalysts
US5998672A (en) * 1996-07-18 1999-12-07 Arco Chemical Technology, L.P. Double metal cyanide catalysts
US5891818A (en) * 1997-07-31 1999-04-06 Arco Chemical Technology, L.P. Cyanide complex catalyst manufacturing process
WO2001080994A1 (fr) * 2000-04-20 2001-11-01 Bayer Aktiengesellschaft Procede de production de catalyseurs a base de cyanure metallique double
US20010046940A1 (en) * 2000-04-28 2001-11-29 O'connor James M. Double metal cyanide catalysts containing polyglycol ether complexing agents
WO2003042280A1 (fr) * 2001-11-15 2003-05-22 Basf Aktiengesellschaft Procede de production d'alcools de polyether

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011047780A1 (fr) 2009-10-19 2011-04-28 Basf Se Conditionnement de catalyseurs cyanures métalliques doubles
US9114380B2 (en) 2009-10-19 2015-08-25 Basf Se Conditioning of double metal cyanide catalysts
WO2011160797A1 (fr) 2010-06-23 2011-12-29 Basf Se Catalyseurs modifiés de type double cyanure métallique (dmc), procédé de synthèse par traitement d'un catalyseur de type dmc cristallin par un acide de brønsted et leurs applications

Also Published As

Publication number Publication date
AU2003250156A1 (en) 2004-03-29

Similar Documents

Publication Publication Date Title
AU716394B2 (en) Highly active double metal cyanide catalysts
EP1034035B1 (fr) Catalyseurs cristallins a base de cyanure de metaux doubles pour la production de polyether polyols
US6806393B2 (en) Multimetal cyanide compounds, their preparation and their use
DE69433826T2 (de) Doppelmetallkatalysatoren zur Herstellung von Polyolen
JPH0959373A (ja) 改良されたポリエーテル含有二重金属シアン化物触媒
WO2007082596A1 (fr) Procédé de fabrication de composes de cyanures multimétalliques
US11813595B2 (en) Method for producing double metal cyanide catalysts
DE602004004531T2 (de) Nanoskalige dmc-katalysatorpartikel
US6800583B2 (en) Suspension of multimetal cyanide compounds, their preparation and their use
EP1448664B1 (fr) Procede de production d'alcools de polyether
EP1534426A1 (fr) Composes de cyanure polymetallique
EP1517940B1 (fr) Procede de production de catalyseurs dmc
WO2004022227A1 (fr) Procede pour produire des catalyseurs a base de cyanures polymetalliques
EP1185367B1 (fr) Procede de preparation de polyether polyols en presence de catalyseurs a base de cyanure polymetallique cristallin
EP4093539B1 (fr) Procédé de fabrication de catalyseurs au cyanure métallique double
WO1999044940A1 (fr) Procede de production de catalyseurs de cyanure metallique double
CA2252398C (fr) Catalyseurs a haute activite a base de cyanure metallique double
DE102004048735A1 (de) Verfahren zur kontinuierlichen Herstellung von DMC-Katalysatoren
EP4302874A1 (fr) Procédé de production de catalyseurs au cyanure métallique double

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP