CN1194594A - Supported carbonylation catalyst - Google Patents
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- CN1194594A CN1194594A CN96196660A CN96196660A CN1194594A CN 1194594 A CN1194594 A CN 1194594A CN 96196660 A CN96196660 A CN 96196660A CN 96196660 A CN96196660 A CN 96196660A CN 1194594 A CN1194594 A CN 1194594A
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Abstract
The invention relates to a supported catalyst, in which a metal of Group VIII of the periodic system is immobilized on a carbon support, wherein 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, and to the use of such a catalyst in a carbonylation reaction of an organic compound, preferably in the carbonylation reaction of butadiene to pentenoic acid, a Nylon-precursor.
Description
The present invention relates to a kind of carried catalyst, in this catalyzer, a kind of metal of periodictable group VIII (see " chemical engineering news ", in 63 (5), 27,1985, the version of CAS-U.S. chemical abstract service center) be fixed on the carbon support.The invention still further relates to the preparation method of this carried catalyst and the application in carbonylation process thereof.
Disclose among the EP-B-405433 in the presence of acetic acid and water, helped the application of catalytic rhodium catalyst system in divinyl carbonylation generation pentenoic acid process by iodide or bromide.According to the disclosure content, the rhodium source is [Rh (CO) preferably
2Cl]
2, [Rh (cyclooctadiene) Cl
2]
2, [Rh (cyclooctadiene)-(acetylacetonate)], RhI
3And Rh (CO)
2I
3Therefore, rhodium is as a kind of component of homogeneous catalyst system and be present in the reaction mixture.Also introduced half homogeneous catalyst system in this patent.As a kind of rhodium source, there is a kind of carrier rhodium catalyst in this system, for example, and Rh/C and Rh/ aluminum oxide.
Although homogeneous catalyst system has tangible advantage, in general, homogeneous catalyst system preferably is used for the process that EP-B-405433 describes.This tangible advantage is that the catalyzer-product separation of homogeneous catalyst system is fairly simple.The reason of why doing this selection is that in one long period, the homogeneous carbonylation catalyst system usually is unsettled.The bad major cause of catalyst stability is the leaching of group VIII metal.
The purpose of this invention is to provide a kind of group VIII metal carrier catalyst, when this catalyzer is used as carbonylating catalyst, is stable in longer for some time.
Catalyzer contains halogen atom, group VIII metal and a kind of activity carbon carrier just can reach this purpose, this carrier has more hydrophobic surface than common activated carbon, activated carbon in inert media, is just heat-treated under 500～1100 ℃ and can be obtained above-mentioned activity carbon carrier.
Catalyzer of the present invention is more stable than traditional group VIII metal carbon carrier catalyst.Almost completely avoided the leaching of group VIII metal.And, have been found that in the process of EP-B-405433, when the Rh-carried catalyst that adopts this invention makes the divinyl carbonyl change into pentenoic acid, generate the hexanodioic acid by product hardly.And when adopting homogeneous catalyst system in the process of EP-B-405433, then can generate a large amount of hexanodioic acids.If the product of wanting is a pentenoic acid, it is favourable that the selectivity of hexanodioic acid is hanged down.
Described a kind of preparation method of homogeneous catalyst in the US-A-4158643 patent, wherein, activated carbon is the carrier as catalyst composition, specifically as PdCl
2-CuCl
2Carrier, the activated carbon of improvement just floods with this catalyst composition.The improvement of activated carbon comprises the oxidation improvement, and in this course, the sorption of oxygen has taken place activity carbon carrier.Difference of the present invention is activated carbon has been carried out thermal treatment.
Be not limited to theoretical explanation, it is believed that this catalyzer has the structure of following general formula (1): absorbent charcoal carrier
X represents halogen atom in the formula, and Me represents the group VIII atoms metal, and A represents one or more different organic or inorganic ligands, and n wherein is 0-4, and m is 0-3.
Group VIII metal (Me) can be, for example rhodium, palladium, platinum, ruthenium, iridium, nickel or cobalt.Halogen atom can be, for example F, Cl, Br or I.Preferred X is Br, I or Cl, more preferably I.
The A group can be one or more coordination ligands, for example CO, H, halogen, and for example F, Cl, Br or I, or alkene, the unsaturated matrix of the alkene of carbonylation reaction for example, in this reaction, carried catalyst is to be used for, for example the reaction of divinyl.
Also not clear fully now, halogen atom and group VIII atoms metal are how to be attached to activated carbon surface.It is believed that and in this system, exist electrostatic and/or covalent linkage.This catalyzer is stable under reduced state.Oxidizing condition may make this catalyst deactivation.This catalyzer preferably is stored under the reduced state, for example, can randomly be stored in the solvent under atmosphere such as carbon monoxide, nitrogen and/or hydrogen.
A kind of interesting carried catalyst example of the present invention is a kind of like this catalyzer, and promptly the group VIII metal in this catalyzer is a rhodium, and X is I (iodine), and m wherein preferably 0,1 or 2.Other example is (Me/X): (Pd/Cl)-carried catalyst, wherein m preferably 0 or 1; (Rh/Br)-and carried catalyst, wherein m preferably 0,1 or 2.Patent specification will be described in more detail the Rh/I-carried catalyst.This is not that the present invention only limits to this concrete carried catalyst.Below the preparation method of described composition and (Rh/I)-carried catalyst, also can be used for other carried catalyst of the present invention in general.
It is believed that in carbonylation processes (Rh/I), the active configuration of carried catalyst can represent by following general formula (m=1, n=3): absorbent charcoal carrier
On active carrier, may exist not and any rhodium atom bonded iodine atom.Therefore, the amount of the iodine atom on the carrier generally will be more than the amount of the atom of rhodium, and this amount can be calculated according to formula (1).The amount of iodine can be, 50～3000mmol/kg for example, and the amount of rhodium can be, for example 10～1000mmol/kg carried catalyst.
The carbon support of catalyzer can be begun to make by any common gac.The preparation method of activated carbon exists, for example in the existing narration of " gac " book, the author of this book is J.B.Donnet, R.C.Bansal and F.Stoecklin, Marcel Dekker, published in New York in 1988: during the preparation gac generally is at first will contain the carbonaceous material, and for example (fruit stone) carbon, wood, sugar or vegetables oil carry out carbonization.Carbonization process generally is heated in inert atmosphere and is no more than 600 ℃ and finishes containing carbonaceous material.Resulting carbonated product activates in the presence of suitable oxygenant such as mixture of steam, air, oxygen or carbonic acid gas or these gases with that under 400～900 ℃.Active oxygen in the activator is used as the most reactive materials in the carbon skeleton as carbon monoxide and is burnt.General known gac has two kinds: low temperature (400～575 ℃) and high temperature (575～900 ℃) gac.These activity carbon carriers can have been bought from following company, for example Lurgi (DESOREX ED47
), American Norit company (NORIT.RB-1, SORBONORIT B-3) or Kennecott company (CARBORUNDUM GAC-616GA) (being name of product in the bracket).Other surface treatment method is to use HNO
3, H
3PO
4Or hydrogen peroxide carries out the liquid phase processing.Preferably make carbon support with the high temperature active charcoal.Other example of carbon support material is the graphite protofibril.In the presence of suitable oxygenant, the hydrophobicity of heat-treating the carbon that is obtained under 400～900 ℃ is exactly the hydrophobicity of the present invention's " common gac ".
Absorbent charcoal carrier had better not contain high-load impurity, for example SiO
2, Fe
2O
3Or Al
2O
3The total amount of these impurity preferably should be less than 1 weight %.These impurity for example may be present in the commercial gac, and this is original in the fruit stone carbon.
In order to obtain the most stable (being meant the leaching of group VIII metal) carried catalyst of the present invention, we have found that the selection of carbon support and pre-treatment are very important.This pretreatment process will be described below.
As mentioned above, SiO in the carbon support
2, Fe
2O
3And/or Al
2O
3Content Deng impurity preferably should be lower than 1 weight %.When using the contaminated gac of this class, this carbon to be handled earlier, so that remove these impurity.L.Daza, people such as S.Mendrioroz and J.A.Pajares once described the example of this processing on " carbon " 24,1986,33 pages.This treating processes comprised for two steps: the 1st step was to handle with 20% aqueous NaOH of heat, removed (Al) silicate; The 2nd step was to come extracting with moisture HCl, removed transition metal oxide.
Gac is placed a kind of inert media, under 500～1100 ℃, preferably under 600～1000 ℃, heat-treat, just can obtain the gac that its hydrophobic surface is Duoed than common gac.Inert media generally is a kind of rare gas element, for example nitrogen.
Absorbent charcoal carrier by above-mentioned heat treating method obtains preferably will carry out one time the demulcent oxygenizement, preferably allows activated carbon contact with oxygen in water.For example in water, mix this carrier granule and under about room temperature and normal pressure, rouse oxygen bubbles by this mixture.
The absorbent charcoal carrier that is used for preparing carried catalyst does not preferably contain any free oxygen (O2).In order to remove free oxygen, preferably absorbent charcoal carrier is being heated under the vacuum and between 200～2000 ℃, and using a kind of rare gas element, for example nitrogen washes several times.In order to obtain the highest active catalyzer, during actual load halogen and group VIII metal, also should avoid existing any free oxygen.In preparation catalyzer process, use inertia or (having certain oxygen) reactant gas, for example nitrogen, or hydrogen and/or carbon monoxide can guarantee not have free oxygen and exist.
Actual group VIII metal carrier catalyst preferably prepares by this method, promptly at first allows carbon support contact with the strong acid of pKa＜3, to helping catalysis through pretreated activity carbon carrier.The reaction conditions of this first step is not strict.Temperature of reaction generally is 20～250 ℃.Reaction pressure generally is about normal pressure or a little higher than normal pressure.The molten system of use may be favourable in the first step reaction process.Suitable solvent is water and the above-mentioned solvent that can be used for the group VIII metal load.Acid generally is mineral acid, for example sulfuric acid or phosphoric acid.Acid preferably corresponding hydrohalogen (HX), for example HI, HBr, HCl or HF.When adopting corresponding hydrohalogen, carrier is helped catalysis simultaneously, and carries upward halogen atom.Different when sour when using, halogen atom can be carried in next step, for example can be loaded with the group VIII metal and finish simultaneously.Make through helping catalytic carrier to contact the difference load that just can finish halogen atom with hydrohalogen.
In next step, allow carbon support contact with a kind of mixture, just can with the group VIII metal load to resulting halogen-carbon support, contain the group VIII source metal (Me) that is dissolved in a kind of suitable solvent in the said mixture.
The group VIII source metal can be any material that can produce VIII family metal ion when this mixture contacts with carbon support.Salt, oxide compound that they are arranged in the material that can be used as the group VIII source metal, the coordination compound of group VIII metal carbonyl and group VIII metal.The example in Rh source is RhI
3, Rh (CO)
2I
3, Rh (III) nitrate trihydrate, Rh (CO) I
3, Rh
4(CO)
12, Rh
6(CO)
16, Rh (acac)
3, Rh (CO)
2(acac), Rh (C
2H
4)
2(acac), [Rh (C
2H
4)
2Cl]
2, [Rh (CO)
2Cl]
2, [Rh (COD) Cl]
2, Rh
2[O
2C (CH
2)
6CH
3] 4, Rh
2(acetate)
4, [Rh
2Cl
2(CO)
4] or RhCl
33H
2O, acac wherein is an acetylacetonate, COD is 1, the 5-cyclooctadiene.
Suitable solvent is that the group VIII source metal is easy to be dissolved in wherein solvent under mixture and condition that carbon support contacts.Choice of Solvent is not strict.Have been found that the solvent that can be used for the described carbonylation reaction of above-mentioned EP-B-405433 also is the examples of solvents that is applicable to group VIII metal load step.The example of solvent is water, acetone, C
2-C
10Halocarbon solvent, for example chlorination carbon solvent, for example methylene dichloride or vinylchlorid and C
2-C
20Carbonyl acid and composition thereof.Suitable carboxylic acid is aliphatic C
2-C
20Monocarboxylic acid, aliphatic C
4-C
20Dicarboxylic acid, phenylformic acid, C
1-C
3Alkyl substituted benzoic acid and composition thereof.Preferred carboxylic acid is aliphatic C
2-C
6Monocarboxylic acid, C
4-C
7Dicarboxylic acid, phenylformic acid and composition thereof.Most preferred acid is acetic acid, propionic acid, butyric acid, acid dimethyl, valeric acid and caproic acid and composition thereof.
The concentration of group VIII source metal is not strict.Concentration is higher to be favourable, because the load of VIII family metal can be more effective.Maximum concentration will depend on the solubleness of group VIII source metal in mixture.
It may be favourable finishing in a step halogen and group VIII metal load are helped catalytic step in carrier and carrier.In order in a step, to finish this process, in dissolved group VIII metal mixture, add corresponding hydrohalogen.
Hydrohalogen concentration in helping catalytic process and/or group VIII metal load process is 1～100mmol/l preferably.
Carry out preferably 20～250 ℃ of the temperature of group VIII metal load.It is possible adopting lower temperature, but this can increase duration of contact, and this does not have Practical significance.
The load of group VIII metal preferably in the presence of hydrogen, is finished under the pressure of 0.1～10MPa.This is favourable, because therefore any undesired (III) class rhodium all can be transformed into Rh (I) class of wanting.
The load of group VIII metal is preferably under the carbon monoxide existence and finishes, because can obtain stable catalyst more like this.The pressure of carbon monoxide is 0.1～10MPa preferably.When adopting the group VIII source metal, and when having 2 or more group VIII atoms metals in the molecule of group VIII source metal, it is particularly advantageous using carbon monoxide.The rhodium source Rh that may use for example
2(μ-Cl)
2(CO)
4Just there are 2 rhodium atoms in the example, at the rhodium source that another kind may use: RhI
31 rhodium atom of middle existence.And, if handle the active carbonyl group catalyzer that catalyzer just can obtain general formula (2) with carbon monoxide.Yet, when the active carrier catalyzer begins preparation by a kind of carried catalyst, and be another ligand rather than carbon monoxide when being attached on the group VIII metal in this carried catalyst, this active carrier catalyzer also can form during carbonylation reaction on the spot.In other words, at carried catalyst transportation or lay up period, except that carbon monoxide, may also there be other ligand.
Mol ratio in the mixture between group VIII source metal and the hydrohalogen preferably 1: 1～1: 20.
From the advantageous results that this catalyzer obtained, the invention still further relates to the carried catalyst that is stated from the carbon support material, this solid support material can make by above-mentioned method for preparing catalyst.
Carried catalyst of the present invention can be used as the catalyzer of the various different carbonylation processes of organic compound effectively.A possible carbonyl reaction example is the unsaturated matrix of alkene or alkiodide, carbon monoxide and reactive compounds, for example water or carboxylic acid, alkanol, for example reaction between methyl alcohol, ethanol or the propyl alcohol.Suitable alkiodide example is C
1-C
15Alkiodide, for example methyl iodide, 2-iodate butane, 1-iodate butane, 2-iodate butylene, 1-iodate butylene or iodine valeric acid and isomer thereof.Suitable alkene unsaturated organic compound example is C
1-C
15Alkene, for example ethene, propylene, butene-1, divinyl, amylene-1, heptene-1 or octene-1 or functionalized C
1-C
15Allylic cpd, for example 1-methoxyl group 2-butylene, 3-methoxyl group 1-butylene, 1-oxyethyl group 2-butylene, 3-methoxyl group 1-butylene, acetic acid 2-butylene ester, 1-butylene 3-carbonic ether, 2-butylene 1-carbonic ether, 3-hydroxyl 1-butylene and 1-hydroxyl 2-butylene.Another possible carbonylation reaction example is the methyl alcohol of preparation in acetic acid, ritalin or the acetic anhydride process and the liquid-phase carbonylation of carbon monoxide and hydriodide or methyl iodide reacts.
In the process of preparation corresponding carboxylic acid or alkyl ester, when adopting carried catalyst to carry out the carbonylation reaction of alkene unsaturated organic compound, this catalyzer is particularly advantageous.
Adopt the preferred carbonylation process of Rh/I carried catalyst of the present invention to be, described in for example top EP-B-405433, by the fourth ethene of bromide or iodide-promoted and the carbonylation reaction of water.Resulting pentenoic acid is the important intermediate of preparation hexanodioic acid (precursor of nylon-6 .6) or ε-Ji Neixianan (precursor of nylon-6) process.Pentenoic acid also can carry out esterification with alkanol and generate alkyl pentenoates.The reaction conditions that carries out carbonylation is usually described in the EP-B-405433 patent of front.Pentenoic acid be the divinyl, carbon monoxide and the water that are dissolved in a kind of solvent Rh/I carried catalyst of the present invention and be selected from bromide and the promotor of iodide in the presence of react and make, temperature of reaction is that 40～200 ℃ of carbon monoxide pressure of tension in a kind of suitable solvent are 0.520MPa.Operable solvent is identical with above-mentioned group VIII metal load process solvent for use.Solvent by-product saturated carboxylic acid that preferably acetic acid, carbonylation process generated and high boiling point carboxylic acid (its boiling point is higher than the boiling point of pentenoic acid).For example hexanodioic acid, valeric acid and/or C
9-carboxylic acid, alkiodide, for example methyl iodide, 2-iodate butane, 1-iodate butane, 2-iodo butylene or 1-iodate butylene.
Promotor can be that those promotors described in the EP-B-405433 (obviously do not comprise RhI
3) and H
2SO, HBF
4Or HFSO
3Preferred promotor is HI, HBr or methyl iodide.The mol ratio of promotor and (homogeneous) rhodium (on carried catalyst) preferably 1: 1～20: 1 is pressed reaction mixture and carried catalyst volume calculation.
The concentration of promotor is 0～5000PPM preferably.
The water that exists preferably should be excessive not too many.Preferred water amount is to be less than 15 weight %, and more preferably is less than 10 weight %, comprising the liquid reaction mixture total of solvent, promotor and reaction product, but does not comprise carried catalyst in its total amount.
This process can, for example finish in slurry-phase reactor or the packed-bed reactor.After the reaction, pentenoic acid can pass through, and for example method for extracting is emanated.
The present invention will set forth by following non-limiting example.Example 1
With aqueous NaOH (20%) solution 100 gram gacs (the DESOREX ED47 of Lurgi company) are carried out the processing in 2 weeks down at 90 ℃.Then water is done Suo Gelisi (Soxleth) extracting in 1 week to this gac.Then with 2NHCl this carbon is done the Suo Gelisi extracting in 4 weeks again.And then water is done the Soxhlet extracting in 3 weeks to this carbon.The SiO of the carbon that is obtained
2, Fe
2O
3And Al
2O
3Be less than 1 weight % Deng foreign matter content.
Then the carbon that obtains is carried out drying, and heating in inert nitrogen atmosphere (0.3MPa), in heat-processed, per hour temperature is improved 100 ℃, until 600 ℃.600 ℃ of temperature will keep 16 hours.After the cooling, carbon will contact for 2 weeks with water, in the meantime, will lead to the oxygen bubbling in the water mixture.
In the 100ml autoclave, allow this carbon support of 15g and 50ml acetic acid, 0.67g56%HI (3.0mmol) and 146mg[Rh
2(CO)
4Cl
2] (0.38mmol) solution is at 0.3MPa H
2With 1.7MPa CO pressure with 130 ℃ under contact 72 hours.Liquor is removed from catalyzer, and meanwhile pressure will remain on 0.5MPa.The catalyzer that obtains so just is called T-600.See also table 1.Example 2
Repeat example 1, but temperature is to be promoted to 900 ℃ at the same rate, rather than 600 ℃, and under this temperature, kept 16 hours.The catalyzer that obtains so just is called T-900.See also table 1.Example 3
Repeat example 1, but temperature is to rise to 1100 ℃ at the same rate, rather than 600 ℃, and under this temperature, kept 16 hours.Resulting catalyzer just is called T-1100.Referring to table 1.Comparative experiment A
Repeat example 1, but before Rh load, do not heat-treat.Resulting catalyzer just is called T-0.Referring to table 1.Table 1
Example 1V
| Example | A | I | II | III |
| Catalyzer | T-0 | T-600 | T-900 | T-1100 |
| I(mmol/g) | 370 | 650 | 770 | 310 |
| Rh(mmol/g) | 29 | 61 | 79 | 17 |
Be equipped with at example 2 and add 39g acetic acid (99.8%), 0.51g H in the autoclave of about 15g Rh carried catalyst (T-900)
2O, the solution of 292mg (56%) HI (1.28mmol) and 240mg pentenoic acid (internal standard).With CO the pressure of autoclave is risen to 4.0MPa, and be heated to 130 ℃.Inject divinyl (0.6g) at once, and make pressure be increased to 7.0MPa with the CO that replenishes.Take a sample after 300 minutes, and analyze with gas-chromatography.Subsequently pressure is let out to 0.5MPa, and in the catalyzer from remain in autoclave liquor is separated.The aforesaid operations program repeats (consequently to test sequence number 1-8) more than 7 times.The result sees also table 2.Contrast experiment B
Repeated experiments 1V, but be to use specifically the autoclave of carried catalyst (T-0) is housed among this experiment A.The results are shown in Table shown in 2.
Table 2
| Example | B | IV |
| Catalyzer | T-0 | T-900 |
| Selecteed 3PA (1) in the 1st test | 91 | 91 |
| Selecteed hexanodioic acid (2) | 0 | 0 |
| The transformation efficiency (%) of divinyl in the 1st test | 70 | 70 |
| Test the leaching amount after the test (3) 1 times | 10 | 1.2 |
| After 4 tests | 9.5 | 0.8 |
| After 6 tests | 9.5 | 0.4 |
| After 8 tests | 8.8 | 0.4 |
(1) with the pentenoic acid selectivity of (mol pentenoic acid)/(mol transform divinyl) expression
*100%
(2) selectivity of hexanodioic acid.Referring to (1)
(3) leaching of PPM Rh in the single test afterreaction mixture.
Concentration at 130 ℃ of following sampling and measuring Rh of reaction conditions.
Claims (13)
1. carried catalyst, wherein, a kind of metal of periodictable group VIII is fixed on the carbon support, it is characterized in that comprising in this catalyzer halogen atom, group VIII metal and absorbent charcoal carrier, this carrier is than the bigger hydrophobic surface of common gac tool, this carrier is heat-treated and is obtained gac in inert media, and heat treated temperature is 500～1100 ℃.
2. the carried catalyst of claim 1 is characterized in that the group VIII metal is to be attached on the absorbent charcoal carrier, shown in following general formula: absorbent charcoal carrier
X represents halogen atom in the formula, and Me represents the group VIII metal, and A is organic formula inorganic group, and n is 0～4, and m is 0～3.
3. the carried catalyst of each claim in the claim 1～2 is characterized in that this group VIII metal is a rhodium.
4. the carried catalyst of each claim in the claim 1～2 is characterized in that this halogen is iodine, bromine or chlorine.
5. method for preparing carried catalyst, its method is, (a) gac is placed a kind of inert media heat-treat, thermal treatment temp is 500～1100 ℃, following step is separately to finish or finish simultaneously: carbon support is contacted with the strong acid of pKa＜3, treated activity carbon carrier is helped catalysis, (c) make through helping catalytic carrier and contacting, (d) just contact through a kind of group VIII source metal mixture in helping catalytic carbon support and being dissolved in solvent with the corresponding hydrohalogen of catalyzer halogen atom.
6. the method for claim 5 is characterized in that this strong acid is the hydrohalogen in the step (c), and step (b) and step (c) then are merged into a step.
7. the method for each claim in the claim 5～6 is characterized in that having carbon monoxide in the step (d).
8. the method for each claim in the claim 5～7, it is characterized in that: with contacting of group VIII source metal is to carry out in the presence of the hydrogen and under the pressure at 0.1～10MPa.
9. each method in the claim 5～8 is characterized in that this strong acid and hydrohalogen are that the metal of HI, group VIII source metal is a rhodium.
10. the method for each claim in the claim 5～9, it is characterized in that: resulting activated carbon just contacts with oxygen in water before in step (b) in the step (a).
11. by the obtainable carried catalyst that is stated from the carbon support material of each method in the claim 5～10.
12. the carried catalyst of each or claim 11 in the claim 1～4, or the carried catalyst that obtains according to each method in the claim 5～10 is as the application of carbonylation reaction catalyst.
13. one kind is helped the carbonylation reaction of catalysis divinyl and carbon monoxide and water to prepare the method for pentenoic acid by bromide or iodide, the carried catalyst of that wherein used in the claim 1～4 each or claim 11, or according to the prepared carried catalyst of the method for each claim in the claim 5～10, group VIII metal wherein is Rh, and halogen is I.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96196660A CN1194594A (en) | 1995-07-05 | 1996-07-02 | Supported carbonylation catalyst |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP95201837.2 | 1995-07-05 | ||
| CN96196660A CN1194594A (en) | 1995-07-05 | 1996-07-02 | Supported carbonylation catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1194594A true CN1194594A (en) | 1998-09-30 |
Family
ID=5129147
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96196660A Pending CN1194594A (en) | 1995-07-05 | 1996-07-02 | Supported carbonylation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1194594A (en) |
-
1996
- 1996-07-02 CN CN96196660A patent/CN1194594A/en active Pending
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