WO1997002091A1 - Supported carbonylation catalyst - Google Patents
Supported carbonylation catalyst Download PDFInfo
- Publication number
- WO1997002091A1 WO1997002091A1 PCT/NL1996/000272 NL9600272W WO9702091A1 WO 1997002091 A1 WO1997002091 A1 WO 1997002091A1 NL 9600272 W NL9600272 W NL 9600272W WO 9702091 A1 WO9702091 A1 WO 9702091A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group viii
- activated carbon
- supported catalyst
- catalyst
- viii metal
- Prior art date
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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
-
- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
- B01J27/13—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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic 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
- 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
Definitions
- the invention relates to a supported catalyst, in which a metal of Group VIII of the periodic system (CAS version as printed in Chemical Engineering News, 63(5), 27, 1985) is immobilized on a carbon support.
- the invention also relates to the preparation of the supported catalyst and its use in a carbonylation process.
- the use of an iodide or bromide promoted rhodium catalyst system is disclosed in the carbonylation of butadiene to pentenoic acid in the presence of acetic acid and water.
- the rhodium source is preferably [Rh(CO) 2 Cl ] 2 , [Rh(cyclooctadiene)Cl 2 ] 2 , [Rh(cyclooctadiene)- (acetylacetonate)], Rhl 3 and Rh(CO) 2 I 3 .
- the rhodium is present in the reaction mixture as a component of a homogeneous catalyst system.
- Semi-heterogeneous catalyst systems are also mentioned. These systems have as a rhodium source a supported rhodium catalyst, for example Rh/C and Rh/alumina.
- the object of this invention is to provide a Group VIII metal-supported catalyst which is stable over a longer period of time when used as carbonylation catalyst.
- the catalyst comprises halogen atoms, the Group VIII metal and an activated carbon support which support has a more hydrophobic surface than normal activated carbon, obtainable by subjecting the activated carbon to a temperature treatment in an inert medium, in which the temperature is between 500 and 1100°C.
- the catalyst according to the invention is more stable than the conventional Group VIII metal-supported carbon catalyst.
- the leaching of the Group VIII is almost totally avoided.
- almost no adipic acid is formed as by-product when carbonylating butadiene to pentenoic acid using a Rh- supported catalyst according to the invention in the process of EP-B-405433.
- a considerable amount of adipic acid is formed.
- the low selectivity to adipic acid is advantageous if the preferred product is pentenoic acid.
- US-A-4158643 describes the preparation of a heterogenerous catalyst in which activated carbon is used as support for a catalyst composition, particularly PdCl 2 - CuCl 2 , with which modified activated carbon is to be impregnated.
- the modification of the activated carbon comprises of an oxidative modification in which chemisorption of the oxygen by the activated carbon support takes place.
- the present invention is different in that a temperature treatment of the activated carbon is performed.
- the catalyst has a structure according the following general formula (1): (1) n
- X represents a halogen atom
- Me represents a Group VIII metal atom
- A represents one or more different organic or anorganic ligand groups in which n is 0 - 4 and m is 0 - 3.
- the Group VIII metal (Me) can be for example rhodium, palladium, platinum, ruthenium, iridium, nickel or cobalt.
- the halogen atom (X) can be for example F, Cl, Br, or I.
- X is Br, I or Cl and more preferably I.
- Group A may be one or more coordinating ligand groups, for example CO, H, halogen, for example F, Cl, Br, or I, or alkenes, for example the alkenically unsaturated substrate of the carbonylation reaction in which the supported catalyst is used for example butadiene. It is not fully understood how the halogen and
- Group VIII metal atoms are bonded to the activated carbon surface. Electrostatic and/or covalent bounds are believed to exist in this system.
- the catalyst is stable under reducing conditions. Oxidizing conditions may deactivate the catalyst.
- the catalyst is preferably stored under reducing conditions, for example, optionally in a solvent, under a carbon monoxide, nitrogen and/or hydrogen atmosphere.
- An example of an interesting supported catalyst according to the invention is a catalyst in which the
- Group VIII metal is rhodium and X is I (iodine), in which m is preferably 0, 1 or 2.
- Other examples are (Me/X): the (Pd/Cl)-supported catalyst, in which m is preferably 0 or 1 and the (Rh/Br)-supported catalyst, in which m is preferably 0, 1 or 2.
- the description shall describe the Rh/I-supported catalyst in more detail. This does not mean that the invention is limited to this particular supported catalyst.
- the below described composition and the process to prepare the (Rh/I)-supported catalyst will in general also apply to other supported catalysts according to the invention.
- iodine atoms may be present which do not bind with any rhodium atom. Therefore the amount of iodine atoms on the support will generally be larger than the amount of rhodium atoms which can be calculated according to formula (1).
- the amount of iodine can be for example between 50 and 3000 mmol/kg and the amount of rhodium can be for example between 10 and 1000 mmol/kg of supported catalyst.
- the carbon support of the catalyst can be made starting from any ordinary activated carbon.
- the preparation of activated carbon is for example described in Active Carbon, by J.B. Donnet, R.C. Bansal and F.Stoecklin, Marcel Dekker, New York 1988:
- Activated carbon is usually prepared by first carbonization of any source of carbonaceous raw material, e.g. (pit)coal, wood, sugar or vegetable oil. The carbonization is generally accomplished by heating the source in an inert atmosphere to a temperature not exceeding 600°C.
- the thus carbonized product is subseguently activated at temperatures between 400 and 900°C in the presence of a suitable oxidizing agent, e.g. steam, air, oxygen or carbon dioxide or any mixtures of these gasses.
- a suitable oxidizing agent e.g. steam, air, oxygen or carbon dioxide or any mixtures of these gasses.
- the active oxygen in the activating agent burns away the more reactive portions of the carbon skeleton as carbon monoxide.
- Two types of activated carbon are generally known: Low (400-575°C) and High (575-900°C) Temperature Activated Carbon. These Activated Carbon supports can be obtained from companies like for example Lurgi (DESOREX ED 47®), American Norit Company (NORIT RB-1, SORBONORIT B-3) or the Kennecott Corporation (CARBORUNDUM GAC-616GA) (product names between brackets).
- Other surface treatments are liguid phase treatments with HN0 3 , H 3 P0 4 or hydrogen peroxide.
- Preferably High Temperature Activated Carbon is used as the carbon support.
- Other examples of carbon support material are graphite and graphite fibrils.
- the hydrophobicity of the carbon, obtained by heat treatment between 400-900°C in the presence of a suitable oxidizing agent is the hydrophobicity of "normal activated carbon" according to this invention.
- the activated carbon support should not contain high amounts of impurities, for example Si0 2 , Fe 2 0 3 or A1 2 0 3 .
- the total amount of these impurities should be less than 1 wt%. These impurities may for example be present in commercially available activated carbon which is originally obtained from pitcoal.
- the content of Si0 2 , Fe 2 0 3 and/or A1 2 0 3 impurities in the carbon support should preferably be lower than 1 wt%.
- the carbon should first be treated in order to remove these impurities.
- An example of such treatment is described by L. Daza, S. Mendrioroz and J.A. Pajares, Carbon, 24, 1986, page 33. This treatment comprises two steps in which first the (Al) silicates are removed by a treatment with hot 20% agueous NaOH and second the transition metal oxides are removed by extraction with agueous HCl.
- Activated carbon with a more hydrophobic surface than normal activated carbon is obtainable by subjecting the activated carbon to a temperature treatment in an inert medium, in which the temperature is between 500 and 1100°C and preferably between 600 and 1000°C.
- the inert medium is usually an inert gas, for example nitrogen.
- the activated carbon supported obtained with the above temperature treatment is subjected to a mild oxidation, preferably by contacting the activated carbon with oxygen in water.
- a mild oxidation preferably by mixing the support particles in water and bubbling oxygen through this mixture at about room temperature and atmospheric pressure.
- the activated carbon support used to prepare the supported catalyst is preferably free of any free oxygen (0 2 ).
- the activated carbon support is preferably heated under vacuum at a temperature between 20 and 200°C and flushed several times with an inert gas, for example nitrogen.
- an inert gas for example nitrogen.
- the use of inert or (with oxygen) reactive gases, for example nitrogen, or hydrogen and/or carbon monoxide, during the preparation may ensure that no free oxygen is present.
- the actual Group VIII metal-supported catalyst is preferably prepared by first promoting the thus pre ⁇ treated activated carbon support by contacting the carbon support with a strong acid with a pKa ⁇ 3.
- the reaction conditions of this first step are not very critical.
- the temperature will generally be between 20 and 250°C.
- the pressure will generally be about atmospheric or slightly higher. It may be advantageous to use a solvent during this first step. Suitable solvents are water, and the solvents mentioned which can be used for the Group VIII metal loading.
- the acid is generally an anorganic acid, for example sulphuric acid or phosphoric acid.
- the acid is the corresponding hydrogen halide (HX), for example HI, HBr, HCl or HF.
- the support When using the corresponding hydrogen halide the support is simultaneously promoted and loaded with the halogen atoms.
- the halogen atoms may be loaded in a next step, for example, simultaneously with the Group VIII metal loading. Separate loading of the halogen atoms is performed by contacting the promoted support with hydrogen halide.
- the Group VIII metal is loaded on to the thus obtained halogen-carbon support by contacting the carbon support with a mixture comprising a Group VIII metal (Me) source dissolved in a suitable solvent.
- the Group VIII metal source can be any material which will produce Group VIII metal ions when contacting the mixture with the carbon support.
- materials which can be employed as the source of the Group VIII metal are their salts, oxides, Group VIII metal carbonyl compounds and coordination compounds of the Group VIII metals.
- Rh-sources are Rhl 3 , Rh(CO) 2 I 3 ,
- Rh(III)nitrate trihydrate Rh(C0)I 3 , Rh 4 (CO) 12 , Rh 6 (CO) 16 , Rh(acac) 3 , Rh(CO) 2 (acac) , Rh(C 2 H 4 ) 2 (acac) , [Rh(C 2 H 4 ) 2 C1] 2 , [Rh(CO) 2 Cl] 2 , [Rh(COD)Cl] 2 , Rh 2 [0 2 C(CH 2 ) 6 CH 3 ] 4 , Rh 2 (acetate) 4 , [Rh 2 Cl 2 (C0) 4 ] or RhCl 3 .3H 2 0, where acac is acetylacetonate and COD is 1,5-cyclooctadiene.
- Suitable solvents are solvents in which the Group VIII metal source can readily dissolve under the conditions of contacting the mixture with the carbon support.
- the choice of the solvent is not critical. It has been found that the solvents which can be used in the carbonylation reaction as described in the earlier mentioned EP-B-405433 are also examples of suitable solvents for the Group VIII metal loading step.
- solvents are water, acetone, halocarbon solvents, for example the chlorocarbon solvents, for example methylene chloride or ethylene chloride and C 2 -C 20 carboxylic acids and mixtures thereof.
- Suitable carboxylic acids are aliphatic C 2 -C 20 monocarboxylic acid, aliphatic c 4 -C 2 o dicarboxylic acids, benzoic acid, C J.
- the concentration of the Group VIII metal source is not critical. Higher concentrations are favorable because the loading of the Group VIII metal will be more efficient. The maximum concentration will depend on the solubility of the Group VIII metal source in the mixture.
- the promoting step and the loading of the support with the halogen and Group VIII metal may be advantageously performed in one step. To perform this in one step the corresponding hydrogen halide is added to the mixture of the dissolved Group VIII metal.
- the concentration of hydrogen halide during promoting and/or during the Group VIII metal loading is preferably between 1 and 100 mmol/1.
- the temperature at which the Group VIII metal loading is performed is preferably between 20 and 250°C. Lower temperatures are possible but the increased contact time would not be practical.
- the Group VIII metal loading is performed in the presence of hydrogen at a pressure of between 0.1 and 10 MPa. This is advantageous because any unwanted Rh(III) species are thus converted to the preferred Rh(I) species.
- the loading of the Group VIII metal is performed in the presence of carbon monoxide, because a more stable catalyst is obtained.
- carbon monoxide pressure is between 0.1 and 10 MPa.
- the use of carbon monoxide is especially advantageous when a Group VIII metal source is used in which 2 or more Group VIII metal atoms are present in the molecule of the Group VIII metal source.
- 2 rhodium atoms are present in an example of a possible rhodium source Rh 2 ( ⁇ -Cl) 2 (CO) 4 and 1 rhodium atom is present in another possible rhodium source: Rhl 3 .
- Rhl 3 rhodium source
- Such an active supported catalyst may however also be formed in situ during the carbonylation reaction when starting from a supported catalyst in which othe ligand groups than carbon monoxide are bound to the Group VIII metal. This means that during transportation or storage of the supported catalyst other ligand groups than carbon monoxide may be present.
- the molar ratio between the Group VIII metal source and the hydrogen halide in the mixture is preferably between 1 : 1 and 1 : 20.
- the invention also relates to a supported catalyst on a carbon support material obtainable by the method of preparing the catalyst as described above.
- the supported catalyst according to the invention can advantageously be used as catalyst for various carbonylation reactions of organic compounds.
- An example of a possible carbonylation reaction is a reaction between an alkenically unsaturated substrate or an alkyliodide, carbon monoxide and a reactive compound, for example water or carboxylic acids, alkanols, for example methanol, ethanol or propanol.
- suitable alkyliodides are C x -C 15 alkyliodides, for example methyliodide, 2-iodobutane, 1-iodobutane, 2-iodobutene, 1- iodobutene or iodovaleric acid and isomers thereof.
- alkenically unsaturated organic compounds are C ⁇ C ⁇ alkenes, for example ethene, propene, 1-butene, butadiene, 1-hexene, 1-heptene or 1-octene or functionalized C ⁇ C ⁇ allylic compounds, for example 1- methoxy 2-butene, 3-methoxy 1-butene, 1-ethoxy 2-butene, 3-methoxy 1-butene, 2-butenyl acetate, 1-butene 3- carbonate, 2-butene 1-carbonate, 3-hydroxy 1-butene and 1- hydroxy 2-butene.
- C ⁇ C ⁇ alkenes for example ethene, propene, 1-butene, butadiene, 1-hexene, 1-heptene or 1-octene or functionalized C ⁇ C ⁇ allylic compounds, for example 1- methoxy 2-butene, 3-methoxy 1-butene, 1-ethoxy 2-butene, 3-methoxy 1-butene, 2-butenyl acetate
- Another example of a possible carbonylation reaction is the carbonylation in the liquid phase of methanol with carbon monoxide and a hydrogen iodide or methyl iodide in a process to prepare acetic acid, methyl acetate or acetic acid anhydride.
- the supported catalyst is especially advantageous when used for the carbonylation of alkenically unsaturated organic compounds in a process to prepare the corresponding carboxylic acids or alkyl esters.
- a preferred carbonylation process, in which the Rh/I-supported catalyst according to the invention is used, is the bromide or iodide promoted carbonylation of butadiene and water as for example described in the above mentioned EP-B-405433.
- the resulting pentenoic acid is an important intermediate in a process to prepare adipic acid (precursor for Nylon-6.6) or ⁇ -caprolactam (precursor for Nylon-6).
- the pentenoic acid may also be esterified with an alkanol to an alkyl pentenoate.
- the reaction conditions to perform the carbonylation are generally as described in the aforementioned EP-B-405433.
- the pentenoic acid is prepared by reacting butadiene in a solvent, carbon monoxide and water in the presence of the Rh/I-supported catalyst according the invention and a promoter selected from the class consisting of bromide and iodide, at a temperature in the range of 40 to 200°C and at a carbon monoxide partial pressure in the range of 0.5 to 20 MPa in a suitable organic solvent.
- the solvent which can be used are the same as described above for the solvents which may be used during the Group VIII metal loading.
- the solvent is preferably acetic acid, the saturated carboxylic acids which are formed as by-products in the carbonylation and high boiling carboxylic acids (with a boiling point higher than that of pentenoic acid).
- adipic acid, valeric acid and/or C 9 -carboxylic acids alkyliodides, for example methyliodide, 2-iodobutane, 1-iodobutane, 2- iodobutene or 1-iodobutene.
- the promoter can be those promoters as mentioned in EP-B-405433 (with the exception of the Rhl 3 for obvious reasons) and H 2 S0 4 , HBF 4 or HFS0 3 .
- Preferred promoters are HI, HBr or methyliodide.
- the molar ratio (dissolved) promoter and (heterogeneous) rhodium (on the supported catalyst) is preferably between 1:1 and 20:1 calculated for a volume of reaction mixture and supported catalyst.
- the concentration of promoter is preferably between 0 and 5000 ppm.
- Water should preferably not be present in a large excess. Preferably water is present in less than-15 wt% and more preferably in less than 10 wt% calculated on the total liquid reaction mixture including the solvent(s), promoter(s) and reactants but without the supported catalyst.
- the process may be performed in for example a slurry reactor or a packed bed reactor. After the reaction the pentenoic acid can be isolated by for example extraction.
- the carbon support obtained was subsequently dried and heated in an inert nitrogen atmosphere (0.3 MPa), in which the temperature was increased with 100°C per hour to 600°C. The temperature was kept at 600°C for 16 hours. After cooling the carbon was contacted with water for two weeks in which water mixture oxygen was bubbled through.
- Example I was repeated except that the temperature was increased at the same rate to 900°C instead of 600°C and kept at that temperature for 16 hours.
- the thus obtained catalyst will be referred to as T-900. See also Table 1.
- Example III Example I was repeated except that the temperature was increased at the same rate to 1100°C instead of 600°C and kept at that temperature for 16 hours.
- the thus obtained catalyst will be referred to as T-1100. See also Table 1.
- Example I was repeated except that no temperature treatment was performed prior to the Rh- loading.
- the thus obtained catalyst will be referred to as T-0. See also Table 1.
- Example II which contained about 15 g of the Rh supported catalyst (T-900), was filled with a solution of 39 g acetic acid (99.8%), 0.51 g H 2 0, 292 mg (56%) HI (1.28 mmol) and 240 mg of propionic acid (internal standard).
- the autoclave was pressurized to 4.0 MPa with CO and heated to 130°C.
- Butadiene (0.6 g) ⁇ was injected immediately and the pressure was increased to 7.0 MPa with additional CO. After 300 minutes a sample was taken and analyzed by gas chromatography. Subsequently the pressure was let off to 0.5 MPa and the liquid solution was separated from the catalyst which remained in the autoclave. The above sequence was repeated 7 more times (resulting in runs 1-8). See table 2 for results.
- Example IV was repeated, except that now the autoclave containing the supported catalyst (T-O) obtained in Comparative experiment A was used. The results are shown in Table 2.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96921163A EP0837728A1 (en) | 1995-07-05 | 1996-07-02 | Supported carbonylation catalyst |
AU62452/96A AU6245296A (en) | 1995-07-05 | 1996-07-02 | Supported carbonylation catalyst |
JP9505029A JPH11508487A (en) | 1995-07-05 | 1996-07-02 | Supported carbonylation catalyst |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP95201837 | 1995-07-05 | ||
EP95201837.2 | 1995-07-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997002091A1 true WO1997002091A1 (en) | 1997-01-23 |
Family
ID=8220458
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/NL1996/000272 WO1997002091A1 (en) | 1995-07-05 | 1996-07-02 | Supported carbonylation catalyst |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0837728A1 (en) |
JP (1) | JPH11508487A (en) |
KR (1) | KR19990028798A (en) |
AU (1) | AU6245296A (en) |
CA (1) | CA2226146A1 (en) |
WO (1) | WO1997002091A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5886236A (en) * | 1997-04-15 | 1999-03-23 | Union Carbide Chemicals & Plastics Technology Corporation | Process for producing aldehyde acid salts |
WO1999033779A1 (en) * | 1997-12-29 | 1999-07-08 | Dsm N.V. | Process for the preparation of a carboxylic acid |
US5962680A (en) * | 1997-04-15 | 1999-10-05 | Union Carbide Chemicals & Plastics Technology Corporation | Processes for producing epsilon caprolactams |
US6365717B1 (en) | 1992-03-13 | 2002-04-02 | Akzo Nobel, N.V. | Peptides and nucleic acid sequences related to the Epstein Barr virus |
TWI593457B (en) * | 2016-04-25 | 2017-08-01 | 國立臺灣大學 | Low-temperature catalytic incineration of cooking-oil fume using hydrophobic noble-metal catalyst supported on honeycomb |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB877906A (en) * | 1958-05-01 | 1961-09-20 | Nitto Chemical Industry Co Ltd | A process for the manufacture of cyanuric chloride |
US4158643A (en) * | 1976-07-15 | 1979-06-19 | Calgon Corporation | Catalytic carbon for oxidation of carbon monoxide in the presence of sulfur dioxide |
WO1981000856A1 (en) * | 1979-10-01 | 1981-04-02 | Texaco Development Corp | Production of carboxylic acids and their esters |
US4978650A (en) * | 1988-08-15 | 1990-12-18 | Symbiotech Incorporated | Desensitizing activated carbon sorbents to the effects of humidity |
EP0405433A1 (en) * | 1989-06-26 | 1991-01-02 | E.I. Du Pont De Nemours And Company | Improved process for the manufacture of 3-pentenoic acid |
EP0418573A1 (en) * | 1989-08-29 | 1991-03-27 | BASF Corporation | Process for treating new or aged graphite powder to improve its effectiveness as a support for metal catalysts |
-
1996
- 1996-07-02 EP EP96921163A patent/EP0837728A1/en not_active Ceased
- 1996-07-02 JP JP9505029A patent/JPH11508487A/en not_active Ceased
- 1996-07-02 CA CA002226146A patent/CA2226146A1/en not_active Abandoned
- 1996-07-02 WO PCT/NL1996/000272 patent/WO1997002091A1/en not_active Application Discontinuation
- 1996-07-02 KR KR1019980700098A patent/KR19990028798A/en not_active Application Discontinuation
- 1996-07-02 AU AU62452/96A patent/AU6245296A/en not_active Abandoned
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB877906A (en) * | 1958-05-01 | 1961-09-20 | Nitto Chemical Industry Co Ltd | A process for the manufacture of cyanuric chloride |
US4158643A (en) * | 1976-07-15 | 1979-06-19 | Calgon Corporation | Catalytic carbon for oxidation of carbon monoxide in the presence of sulfur dioxide |
WO1981000856A1 (en) * | 1979-10-01 | 1981-04-02 | Texaco Development Corp | Production of carboxylic acids and their esters |
US4978650A (en) * | 1988-08-15 | 1990-12-18 | Symbiotech Incorporated | Desensitizing activated carbon sorbents to the effects of humidity |
EP0405433A1 (en) * | 1989-06-26 | 1991-01-02 | E.I. Du Pont De Nemours And Company | Improved process for the manufacture of 3-pentenoic acid |
EP0418573A1 (en) * | 1989-08-29 | 1991-03-27 | BASF Corporation | Process for treating new or aged graphite powder to improve its effectiveness as a support for metal catalysts |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6365717B1 (en) | 1992-03-13 | 2002-04-02 | Akzo Nobel, N.V. | Peptides and nucleic acid sequences related to the Epstein Barr virus |
US7507804B2 (en) | 1992-03-13 | 2009-03-24 | Akzo Nobel, N.V. | Peptides and nucleic acid sequences related to the Epstein Barr Virus |
US5886236A (en) * | 1997-04-15 | 1999-03-23 | Union Carbide Chemicals & Plastics Technology Corporation | Process for producing aldehyde acid salts |
US5962680A (en) * | 1997-04-15 | 1999-10-05 | Union Carbide Chemicals & Plastics Technology Corporation | Processes for producing epsilon caprolactams |
WO1999033779A1 (en) * | 1997-12-29 | 1999-07-08 | Dsm N.V. | Process for the preparation of a carboxylic acid |
EP0933347A1 (en) * | 1997-12-29 | 1999-08-04 | Dsm N.V. | Process for the preparation of a carboxylic acid |
TWI593457B (en) * | 2016-04-25 | 2017-08-01 | 國立臺灣大學 | Low-temperature catalytic incineration of cooking-oil fume using hydrophobic noble-metal catalyst supported on honeycomb |
Also Published As
Publication number | Publication date |
---|---|
KR19990028798A (en) | 1999-04-15 |
JPH11508487A (en) | 1999-07-27 |
CA2226146A1 (en) | 1997-01-23 |
AU6245296A (en) | 1997-02-05 |
EP0837728A1 (en) | 1998-04-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4394299A (en) | Palladium-rhodium catalyst for purification of crude terephthalic acid | |
US3717670A (en) | Production of carboxylic acids and esters | |
US3689533A (en) | Production of carboxylic acids and esters | |
CA1262719A (en) | Alcohols production by hydrogenation of carboxylic acids | |
US4467110A (en) | Process for purification of crude terephthalic acid | |
US4415479A (en) | Palladium on carbon catalyst for purification of crude terephthalic acid | |
EP0274076B1 (en) | Acid accelerated hydrocarboxylation | |
EP0405433A1 (en) | Improved process for the manufacture of 3-pentenoic acid | |
KR930005303B1 (en) | Rhodium on carbon catalyst | |
EP0837728A1 (en) | Supported carbonylation catalyst | |
JPH02231448A (en) | Method for treating acetic acid with hydrogen in the presence of hydrogenation catalyst | |
US5155266A (en) | Purification of acetic acid with ozone in the presence of an oxidation catalyst | |
GB2279348A (en) | Preparation of adipic acid or pentenoic acid | |
RU2138328C1 (en) | Method of preparing iridium-based solution and utilization thereof as catalyst | |
JPH05995A (en) | Production of acetic acid | |
JPH03220156A (en) | Carbonylation of allylbutenols and butenol esters | |
CN1194594A (en) | Supported carbonylation catalyst | |
KR102652195B1 (en) | metal particle mixture for purifying feedstock for olefin metathesis and purification method using the same | |
JPH07149686A (en) | Isomerization of carboxylic acid | |
EP0343598B1 (en) | Preparation of 4-pentenoates by isomerization | |
US4980503A (en) | Conversion of glycol formates to monocarboxylic acids | |
JP2704165B2 (en) | Method for preparing catalyst for producing organic oxygenated compound | |
CN117899933A (en) | Supported single-atom Rh or Ir-based catalyst and preparation method and application thereof | |
JPH0411530B2 (en) | ||
JP3814840B2 (en) | Catalyst for oxidative dehydrogenation and process for producing α, β-unsaturated carbonyl compounds |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 96196660.2 Country of ref document: CN |
|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AL AU BB BG BR CA CN CZ EE GE HU IL IS JP KP KR LK LR LT LV MG MK MN MX NO NZ PL RO SG SI SK TR TT UA US UZ VN AM AZ BY KG KZ MD RU TJ TM |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN 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 | ||
ENP | Entry into the national phase |
Ref document number: 2226146 Country of ref document: CA Ref document number: 2226146 Country of ref document: CA Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 1997 505029 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1019980700098 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1996921163 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1996921163 Country of ref document: EP |
|
WWR | Wipo information: refused in national office |
Ref document number: 1996921163 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1996921163 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1019980700098 Country of ref document: KR |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1019980700098 Country of ref document: KR |