MXPA96002083A - Process for the carbonilation of alkyl alcohols and / or reactive derivatives of the mis - Google Patents
Process for the carbonilation of alkyl alcohols and / or reactive derivatives of the misInfo
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- MXPA96002083A MXPA96002083A MXPA/A/1996/002083A MX9602083A MXPA96002083A MX PA96002083 A MXPA96002083 A MX PA96002083A MX 9602083 A MX9602083 A MX 9602083A MX PA96002083 A MXPA96002083 A MX PA96002083A
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Abstract
In a process for the liquid phase carbonylation of an alkyl alcohol, such as methanol, and / or a reactive derivative thereof, to produce the corresponding carboxylic acid and / or ester, in the presence of an iridium catalyst, an alkyl halide and water , the reaction is promoted by the presence of at least one promoter selected from cadmium, mercury, zinc, gallium, indium and tungsten, optionally with a co-promoter selected from ruthenium, osmium and ren
Description
PROCESS FOR THE CARBONILACTON OF ALCOHOLS ALOUTL? COS
Y / 0 REAGENTS DERIVATIVES THEREOF Field of the Invention The present invention relates to a carbonylation process and, in particular, to a process for the carbonylation of alkyl alcohols and / or reactive derivatives thereof, in the presence of a iridium catalyst. BACKGROUND OF THE INVENTION Carbonylation processes in the presence of iridium catalysts are already known and described, for example, in US 3772380, European Patent Publication EP 0618184-A, UK Patents GB 1276326, GB 1234641 and GB 1234642. Carbonylation in the presence of an iridium catalyst and a copromotor selected from ruthenium and osmium, is described in European Patent Publication EP-0643034-A. Summary of the Invention It has now been found that a promoter selected from the group consisting of cadmium, mercury, zinc, gallium, indium and tungsten has a beneficial effect on the carbonylation rate of an alkyl alcohol and / or a reactive derivative thereof, in presence of an iridium catalyst. Therefore, according to the present invention, there is provided a process for the production of a carboxylic by carbonylation of an alkyl alcohol and / or a reactive derivative thereof, which process comprises contacting, in a carbonylation reactor, said alcohol and / or reactive derivative thereof with carbon monoxide in a liquid reaction composition comprising: (a) an iridium catalyst, (b) an alkyl halide, (c) at least a finite concentration of water and (d) ) a promoter selected from the group consisting of cadmium, mercury, zinc, gallium, indium and tungsten. Also, according to the present invention, there is provided a catalyst system for the carbonylation of an alkyl alcohol and / or a reactive derivative thereof, which catalyst system comprises (a) an iridium catalyst,
(b) an alkyl halide and (c) a promoter selected from the group consisting of cadmium, mercury, zinc, gallium, indium and tungsten. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The promoters of the present invention are not only generally more economical than promoters such as ruthenium and osmium, but it is thought that at least cadmium, mercury, zinc, gallium and indium are less likely to form species. volatile in the carbonylation reaction. Suitable alkyl alcohols comprise C.sub.1 to C.sub.C alkyl alcohols with methanol being a very preferred alkyl alcohol. Preferably, the alkyl alcohol is a primary or secondary alkyl alcohol. The product of the carbonylation of an alcohol having n carbon atoms and / or a derivative thereof is a carboxylic having n + 1 carbon atoms and / or an ester of a carboxylic having n + 1 carbon atoms and of the alcohol that has n carbon atoms. In this way, the product of the carbonylation of methanol and / or a derivative thereof is acetic and / or methyl acetate. Suitable reactive derivatives of the alkyl alcohol include the corresponding alkyl ester of the alcohol and the corresponding carboxylic product, dialkyl ethers and alkyl halides, preferably iodides or bromides.
Suitable reactive derivatives of methanol include methyl acetate, dimethyl ether and methyl iodide. In the process of the present invention, a mixture of alkyl alcohol and reactive derivatives thereof can be used as reactants. Preferably, methanol and / or methyl acetate are used as reactants. At least part of the alkyl alcohol and / or reactive derivative thereof will be converted to, and will therefore be present as, alkyl esters in the liquid reaction composition by reaction with the product carboxylic or solvent. The concentration, in the liquid reaction composition, of the alkyl ester is suitably from 1 to 70% by weight, preferably from 2 to 50% by weight and even more preferably from 3 to 35% by weight. Water can be formed in situ in the liquid reaction composition, for example, by the esterification reaction between the alkyl alcohol reactant and the carboxylic acid product. Water can be introduced into the carbonylation reactor together or separately from other components of the liquid reaction composition. The water can be separated from the other components of the reaction composition extracted from the reactor and can be recycled in controlled amounts to maintain the required concentration of water in the liquid reaction composition. Suitably, the concentration of water in the liquid reaction composition is from 1 to 15% by weight, preferably from 1 to
% by weight, more particularly not more than 6.5% by weight. The iridium component of the catalyst in the liquid reaction composition can comprise any compound containing iridium and which is soluble in the liquid reaction composition. The iridium component of the catalyst can be added to the liquid reaction composition for the carbonylation reaction in any suitable form that is dissolved in the liquid reaction composition or can be converted to a soluble form. Examples of suitable iridium-containing compounds that can be added to the liquid reaction composition include IrCl, Irl3, IrBr3, [Ir (CO) 2I] 2, [Ir (CO) a], [Ir (CO) 2Br] 2, [Ir (CO) 2I2] -H +, [Ir (CO) 2Br2] -H +, [Ir (CO) 2I4] -H +, [Ir (CH3) I3 (CO) 2] "H +, Ir4 (CO) 12, IrCl3. 3H2O, IrBr3.3H2O, Ir4 (CO) 12, iridium metal, Ir2O3, IGO2, Ir (acac) (CO) 2, Ir (acac) 3, iridium acetate, [Ir O (OAc) g (H2O) 3] [OAc] and hexachloroiridic acid [H2IrClg], preferably iridium complexes, free of chloride, such as acetates, oxalates and acetoacetates, which are soluble in one or more of the components of the carbonylation reaction, such as water, alcohol and or carboxylic acid, in particular the crude iridium acetate which can be used in an acetic acid solution or an aqueous solution of acetic acid, preferably the concentration of the iridium catalyst in the liquid reaction composition is from 100 to 6,000 ppm by weight of iridium.
The cadmium, mercury, zinc, gallium, indium or tungsten promoter can comprise any compound containing cadmium, mercury, zinc, gallium, indium or tungsten and which is soluble in the liquid reaction composition.
The promoter can be added to the liquid reaction composition for the carbonylation reaction in any suitable form which is dissolved in the liquid reaction composition or which can be converted to a soluble form. Examples of suitable cadmium-containing compounds that can be used include Cd (OAc) 2, Cdl2, CdBr, CdC_, Cd (OH) 2 and cadmium acetylacetonate. Examples of suitable mercury-containing compounds that can be used include Hg (OAc) 2, Hgl2, HgBr2, HgCl2, Hg I2, and Hg Cl2. Examples of suitable zinc-containing compounds that can be used include Zn (OAc), Zn (OH) 2, Znl 2, ZnBr 2, ZnCl 2 and zinc acetylacetonate. Examples of suitable gallium-containing compounds that can be used include gallium acetylacetonate, gallium acetate, GaG3, GaBr3, Examples of suitable indium-containing compounds that can be used include indium acetylacetonate, indium acetate, InCl, InBr3, Inl, Inl and In (OH) 3. Examples of suitable tungsten-containing compounds that can be used include W (CO) 6, WC14, WCl6, WBr5, WI2 or C H ^ W (CO) 3 and any tungsten compounds chloro-, bromo- or iodocarbonyl. The molar ratio of each promoter: iridium catalyst is suitably (0.1 to 20): 1, preferably (0.5 to 10): 1. More than one promoter can be used. An optional co-promoter selected from the group consisting of ruthenium, osmium and rhenium and which may comprise any ruthenium, osmium or rhenium containing compound that is soluble in the liquid reaction composition may also be employed. The optional co-promoter can be added to the liquid reaction composition for the carbonylation reaction in any suitable form that is dissolved in the liquid reaction composition or can be converted to a soluble form. Examples of suitable ruthenium-containing compounds, which can be used as an optional co-promoter, include ruthenium (III) chloride, ruthenium (III) chloride trihydrate, ruthenium (IV) chloride, ruthenium (III) bromide, ruthenium metal, ruthenium oxides, ruthenium (III) format, [Ru (CO) 3I] ~ H +,
[Ru (CO) 2I2] n, [Ru (CO) 4I2], [Ru (CO) 3I2] 2, tetra (aceto) chloro-ruthenium (II, III), ruthenium acetate (III), ruthenium propionate (III) , ruthenium butyrate (III), ruthenium pentacarbonyl, trirutenium dodecacarbonyl and ruthenium mixed halocarbonyl, such as dichlorotricarbonylrruthenium (II) dimer, dibromotricarbonylrruthenium (II) dimer and other organo-ruthenium complexes such as tetrachlorobis (4-cymene) diruthenium
(II), tetrachlorobis (benzene) diruthenium (II), dichloro (cycloocta-l, 5-diene) ruthenium (II) polymer and tris (acetylacetonate) ruthenium (III).
Examples of suitable osmium-containing compounds that can be used as an optional co-promoter include hydrated and anhydrous osmium (III) chloride, osmium metal, osmium tetraoxide, triosmium dodecacarbonyl,
[Os (CO) 4I2], [Os (CO) 3I2] 2, [Os (CO) 3I] ~ H +, pentachloro-μ-nitrodiosmium and mixed osmium halocarbonyl groups such as tricarbonyldichloroosmium (II) dimer and other organosomal complexes. Examples of suitable rhenium-containing compounds that can be used as an optional co-promoter include the following Re2 (CO) ^ Q, Re (CO) 5 Cl, Re (CO) 5 Br, Re (CO) 5I, ReCl3.xH2O, [Re (CO) 4I] 2, [Re (CO) 4I2] ~ H + and Rea5.yH2O. The molar ratio of each optional co-promoter: iridium catalyst is suitably from (0.1 to 20): 1, preferably from (0.5 to 10): 1. Preferably, the compounds containing iridium, promoter and optional promoter are free of impurities that provide or generate in situ ionic iodides, which can inhibit the reaction, for example, salts of alkali metals or alkaline earth metals or salts of other metals. Ionic contaminants such as, for example, (a) corrosion metals, in particular nickel, iron and chromium and (b) phosphines or nitrogen-containing compounds or ligands, which can be quaternized in situ, should be kept to a minimum in the composition of liquid reaction, since they will have an adverse effect on the reaction by generating I ~ in the liquid reaction composition which has an adverse effect on the reaction rate. It has been found that some metallic corrosion contaminants such as, for example, molybdenum, are less susceptible to the generation of I ~. Corrosion metals that have an adverse effect on the reaction rate can be minimized by using suitable corrosion resistant construction materials. Similarly, contaminants such as alkali metal iodides, for example lithium iodide, should be kept to a minimum.
The corrosion metal and other ionic impurities can be reduced by the use of a suitable ion exchange resin bed, to treat the reaction composition, or preferably a recycle stream of catalyst. Said process is described in US 4007130. Preferably, the ionic contaminants are kept below a concentration at which they would generate 500 ppm I ~, preferably less than 250 ppm I ~, in the liquid reaction composition. Suitable alkyl halides have alkyl moieties corresponding to the alkyl moiety of the alkyl alcohol reactant and are preferably alkyl halides Ci a to Cg and even more particularly Cj to C 4. Preferably, the alkyl halide is an iodide or bromide, more particularly an iodide. A preferred alkyl halide is methyl iodide. Preferably, the concentration of alkyl halide in the liquid reaction composition is from 1 to 20%, preferably from 2 to 16% by weight. The reactant carbon monoxide may be essentially pure or may contain inert impurities such as carbon dioxide, methane, nitrogen, noble gases, water and C ^ to C4 parabolic hydrocarbons. The presence of hydrogen in the carbon monoxide fed and generated in situ by the water gas displacement reaction is preferably maintained at low values, for example, at a partial pressure of less than 1 bar, since its presence can be translated into the formation of hydrogenation products. The partial pressure of carbon monoxide in the reactor is suitably from 1 to 70 bar, preferably from 1 to 35 bar and more especially from 1 to 15 bar. The total pressure of the carbonylation reaction is suitably from 10 to 200 relative bar, preferably from 15 to 100 bar relative and more preferably from 15 bar to 50 bar relative. The temperature of the carbonylation reaction is suitably 100 to 300 ° C, preferably from 150 to 220 ° C. As the solvent for the reaction, the carboxylic acid and / or ester thereof can be used. The process of the present invention can be carried out as a batch or continuous process, preferably as a continuous process. The carboxylic acid and / or ester thereof obtained as a product can be separated from the reactor by extracting the liquid reaction composition and separating the carboxylic acid product and / or ester therefrom by one or more steps of instantaneous and fractional distillation of the other components of the product. the liquid reaction composition, such as iridium catalyst, cadmium, mercury, zinc, gallium, indium or tungsten promoter, optional co-promoter, alkyl halide, water and unconsumed reactants, which can be recycled to the reactor to maintain its concentrations in the liquid reaction composition. The product carboxylic acid and / or ester thereof can also be separated from the reactor in the form of vapor. The invention will now be illustrated, by way of example only, with reference to the following examples. Promoters of cadmium, mercury and zinc For a series of batch carbonylation experiments, a Hastelloy B2 (Registered Trade Mark) autoclave of 150 cm3 capacity was used and equipped with a Magnedrive agitator (Registered Trade Mark), liquid injector device and cooling coils . A supply of gas to the autoclave was provided from a ballast vessel, feed gas being provided to maintain the autoclave at a constant pressure. The rate of gas absorption at a given point in the experiment was used to calculate the carbonylation rate, as the number of moles of reactant consumed per liter of cold degassed composition of the reactor per hour (moles / l / h), to a composition particular of the reactor (reactor composition based on a cold degassed volume). The concentration of methyl acetate was calculated over the course of the reaction from the initial composition, assuming that one mole of methyl acetate was consumed for each mole of carbon monoxide consumed. The organic components of the head space of the autoclave were not taken into account. The data are recorded at calculated concentrations of methyl acetate of 26%, 15% and 6% corresponding to typical constant concentrations found in the liquid reaction composition in a continuous process. For a calculated concentration of methyl acetate of 15% in said continuous process, the concentration of other components of said liquid reaction composition are: methyl iodide, about 5 to 8%, generally about 5 to 6%; water, approximately 6 to 8%; and acetic acid, the rest. For each batch carbonylation experiment, the autoclave was charged with cadmium, mercury or zinc promoter, optional co-promoter and the liquid components of the liquid reaction composition excluding part of the water charge (6.5 g), in the which the iridium catalyst was dissolved (see Table
!) • The autoclave was flushed twice with nitrogen and once with carbon monoxide (being pressurized with each gas at approximately 25 bar) and then heated, by electric heating coils, to a temperature of 190 ° C under a carbon monoxide pressure bar. A fast and consistent stirring speed (1000 rpm) was used. Once the temperature was stabilized, the aqueous solution of iridium catalyst was injected into the autoclave. Simultaneously, the autoclave was pressurized to 22 bar relative to carbon monoxide fed from the ballast vessel. The pressure in the autoclave was subsequently maintained at about 22 relative bars (see Table 2) with carbon monoxide fed from the ballast vessel. The partial pressure of carbon monoxide was not measured but was estimated to be less than 15 bar. The reaction temperature was maintained within ± 1 ° C of the desired reaction temperature (190 ° C). The gas absorption of the ballast vessel was measured throughout the course of the experiment and was used to calculate the carbonylation rate. Once the absorption of carbon monoxide from the ballast vessel ceased, the autoclave was isolated from the gas supply and cooled to room temperature by means of the cooling coils. The autoclave was vented and samples of the liquid reaction composition and gases from the headspace of the autoclave were analyzed by gas chromatography. The main product of each batch carbonylation experiment according to the present invention was acetic acid. The yields of by-products are indicated in Table 2. Examples 1-10 v Experiments A-I The results indicated in Table 2 show that cadmium does not act as a carbonylation catalyst under the reaction conditions (Experiment D). The results of Table 2 also demonstrate that cadmium promotes the carbonylation of methanol catalyzed by iridium (compare Examples 1-3 with Experiments A-D). The results in Table 2 show that the carbonylation rate increases as the cadmium concentration does. The results in Table 2 show that mercury and zinc are also promoters for the carbonylation of methanol catalyzed by iridium (Examples 4-7), but they are not as effective as cadmium.
The results in Table 2 also demonstrate that cadmium and zinc promote a methylated carbonylation of iridium / ruthenium catalyzed methanol.
(compare Experiment E with Examples 8, 9 and 10). No evidence of precipitation was observed in Examples 1 to 7, which indicates that cadmium, mercury and zinc are soluble.
lahlaJ. Autoclave loads
I
2? Ibja_2 Speed, Stability and Sub-product Data
Ol I
Table 2 Cont. Speed, Stability and Sub-product Data
ia% by volume of the measured gases (CO, CH ^ and CO ^, the remainder being carbon monoxide, b no carbonylation occurred, therefore, the reactor pressure was not measured at the 15% strength acetate concentration. methyl, calculated concentration of methyl acetate: 26%, 15% and 6% by weight, corresponding to water concentrations of 9.7%, 7% and 4.6% respectively.The concentration of methyl iodide was 5% 8% approximately, in general from 5 to 6% approximately.% Error estimated in ± 10% MeOAc = methyl acetate.
Promoters of rooster c iridio. Examples 11-14 The same procedure and apparatus was used as in the case of the cadmium, mercury and zinc promoters. The autoclave charges are offered in the
Table 3 and the results in Table 4 for Examples 11-14. The main product of each batch carbonylation experiment according to the present invention consisted of acetic acid. The results indicated in Table 4 demonstrate that gallium and indium both promote the carbonylation of methanol catalyzed by iridium (compare Examples 11-12 with the AC Experiments.) The results of Table 4 also show that gallium and indium promote the carbonylation of methanol catalyzed by iridium / ruthenium (compare Experiment E with Examples 13-14) No evidence of precipitation was observed in Examples 11 and 12, indicating that gallium and indium are soluble.
Table 3 Autoclave loads
03 I
3. #} ? bja_á Speed, Stability and Sub-product Data
I vo I
to% by volume of the measured gases (CO, CH4 and CO2); the rest being carbon monoxide; b calculated concentration of methyl acetate: 26%, 15% and 6% by weight, corresponding to water concentrations of 9.7%, 7% and 4.6% respectively. The concentration of methyl iodide was about 5 to 8%, generally about 5 to 6%. Estimated% error in ± 10%. MeOAc = methyl acetate.
Tungsten Promoter • a A 300-capacity Hastelloy B2 (Registered Trade Mark) autoclave equipped with a Dispersimax (Registered Trade Mark) agitator liquid injector device and cooling coils was used for a series of batch carbonylation experiments. A supply of gas to the autoclave was provided from a ballast vessel, feed gas being provided to maintain the autoclave at a constant pressure. The rate of gas absorption at a certain point in the experiment was used to calculate the carbonylation rate, as the number of moles of reactant consumed per liter of cold degassed composition of the reactor per hour (moles / l / h), to a composition particular of the reactor (reactor composition based on a cold degassed volume). The concentration of methyl acetate was calculated during the course of the reaction from the starting composition, assuming that one mole of methyl acetate is consumed for each mole of carbon monoxide consumed.
The organic components of the head space of the autoclave were not taken into account. The data were recorded at a calculated concentration of methyl acetate of 26%, 15% and 6%, which corresponds to a constant typical concentration in the liquid reaction composition in a continuous process. For a calculated concentration of methyl acetate of 15%, the concentrations of other components of said liquid reaction composition are: methyl iodide, about 5 to 8%, generally about 5 to 6%; water, approximately 6 to 8%; and acetic acid, the rest. For each batch carbonylation experiment the autoclave was charged with tungsten promoter, optional co-promoter and the liquid components of the liquid reaction composition excluding part of the water charge (10.83 g), in which the catalyst was dissolved of iridium (see Table 5). The autoclave was once flooded with nitrogen at approximately 30 bar and twice with carbon monoxide at approximately 25 bar, and then heated, by means of electric heating coils, to a temperature of 190 ° C under a monoxide pressure. of carbon of 8 relative bars. A fast and consistent stirring speed (1500 rpm) was used. Once the temperature was stabilized, the aqueous solution of iridium catalyst was injected into the autoclave. Simultaneously, the autoclave was pressurized to 22 bar relative to carbon monoxide fed from the ballast vessel. The pressure in the autoclave was subsequently maintained at 22 bar relative to the carbon monoxide fed from the ballast vessel. The carbon monoxide partial pressure was calculated to be about 8 bars when the calculated concentration of methyl acetate was 15% by weight. The reaction temperature was maintained within ± 1 ° C of the desired reaction temperature (190 ° C). The absorption of gas from the ballast vessel was measured throughout the course of the experiment and was used to calculate the carbonylation rate. Once the absorption of carbon monoxide from the ballast vessel ceased, the autoclave was isolated from the gas supply and cooled. The autoclave was vented and samples of the liquid reaction composition were analyzed by gas chromatography. The main product of each batch carbonylation experiment according to the present invention was acetic acid. The yields in by-products are summarized in Table 6. Examples 15-21 and Experiments -N In Examples 15-17, more methyl iodide (3 molar equivalent to tungsten) was added to compensate for the probable loss of methyl iodide to tungsten iodocarbonyl components. Experiment M demonstrates that the simple addition of this extra methyl iodide to an iridium catalyzed reaction, without promoting, did not cause a significant increase in the reaction rate. The results given in Table 6 demonstrate that tungsten promotes the carbonylation of methanol catalyzed by iridium (compare Examples 15-17 with Experiments J-L). Other Experiments Other experiments were carried out (Experiment N and Examples
18-21) using the same 300 ml autoclave apparatus employed for tungsten.
Examples 18 to 20 show the effect of increasing the amount of zinc promoters and Example 1 demonstrates the effect of the cadmium promoter.
Table 5 Autoclave loads
I to? i
Iabla_6 Speed Data, Sub-products and Stability
I t * - I a) Estimated speed error ± 10% Water concentrations 9.7%, 7% and 4.6% respectively at 26, 15 and 6% methyl acetate; Methyl iodide 5-8% approximately, generally 5-6% approximately [for example, in M the initial methyl iodide is approximately 8%]
Claims (9)
- REGVTNDTCAC? QNES 1.- A process for the carbonylation of an alkyl alcohol and / or a reactive derivative thereof, characterized in that it comprises contacting, in a carbonylation reactor, said alcohol and / or a reactive derivative thereof with monoxide. carbon in a liquid reaction composition comprising: (a) an iridium catalyst, (b) an alkyl halide, (c) at least a finite concentration of water and (d) a promoter selected from the group consisting of cadmium, mercury , zinc, gallium, indium and tungsten.
- 2. A process according to claim 1, characterized in that the molar ratio of each promoter: iridium catalyst is (0.1 to 20): 1, preferably (0.5 to 10): 1.
- 3.- A process according to claim 1 or 2, characterized in that a co-promoter selected from ruthenium, osmium and rhenium is present in the liquid reaction composition.
- 4. A process according to claim 3, characterized in that the molar ratio of each co-promoter: iridium catalyst is (0.1 to 20): 1, preferably (0.5 to 10): 1.
- 5 A process according to any of the preceding claims, characterized in that the concentration of water in the liquid reaction composition is from 1 to 15% by weight, preferably from 1 to 10% by weight.
- 6. A process according to any of the preceding claims, characterized in that the alkyl ester is present in the liquid reaction composition in a concentration of 1 to 70% by weight, preferably 2 to 50% by weight and more preferably 3 to 35% by weight.
- 7. A process according to any of the preceding claims, characterized in that the concentration of alkyl halide in the liquid reaction composition is from 1 to 20% by weight, preferably from 2 to 16% by weight.
- 8. A process according to any of the preceding claims, characterized in that the partial pressure of carbon monoxide in the reactor is from 1 to 70 bar, preferably from 1 to 35 bar and more preferably from 1 to 15 bar.
- 9. A process according to any of the preceding claims, characterized in that the alkyl alcohol is methanol, the alkyl halide is methyl iodide and the product of the reaction comprises acetic acid and / or methyl acetate.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB9512606.6A GB9512606D0 (en) | 1995-06-21 | 1995-06-21 | Process |
| GB9512606.6 | 1995-06-21 | ||
| GBGB9514745.0A GB9514745D0 (en) | 1995-07-19 | 1995-07-19 | Process |
| GB9514745.0 | 1995-07-19 | ||
| GBGB9520441.8A GB9520441D0 (en) | 1995-10-06 | 1995-10-06 | Process |
| GB9520441.8 | 1995-10-06 | ||
| GB9524037.0 | 1995-11-23 | ||
| GBGB9524037.0A GB9524037D0 (en) | 1995-11-23 | 1995-11-23 | Process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| MXPA96002083A true MXPA96002083A (en) | 1997-08-01 |
| MX9602083A MX9602083A (en) | 1997-08-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| MX9602083A MX9602083A (en) | 1995-06-21 | 1996-05-31 | Process. |
| MX9602082A MX9602082A (en) | 1995-06-21 | 1996-05-31 | Process. |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| MX9602082A MX9602082A (en) | 1995-06-21 | 1996-05-31 | Process. |
Country Status (16)
| Country | Link |
|---|---|
| US (1) | US5696284A (en) |
| EP (2) | EP0749948B1 (en) |
| JP (2) | JPH092993A (en) |
| KR (2) | KR100404644B1 (en) |
| CN (2) | CN1068576C (en) |
| AR (2) | AR002559A1 (en) |
| AT (2) | ATE212970T1 (en) |
| CA (2) | CA2175028C (en) |
| DE (2) | DE69619030T2 (en) |
| MX (2) | MX9602083A (en) |
| MY (2) | MY115799A (en) |
| NO (2) | NO961723L (en) |
| NZ (2) | NZ286473A (en) |
| RU (2) | RU2167850C2 (en) |
| TW (2) | TW338763B (en) |
| UA (2) | UA46724C2 (en) |
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| GB9626317D0 (en) * | 1996-12-19 | 1997-02-05 | Bp Chem Int Ltd | Process |
| GB9626429D0 (en) * | 1996-12-19 | 1997-02-05 | Bp Chem Int Ltd | Process |
| GB9626324D0 (en) * | 1996-12-19 | 1997-02-05 | Bp Chem Int Ltd | Process |
| US5900505A (en) * | 1997-02-04 | 1999-05-04 | Eastman Chemical Company | Heterogeneous vapor phase carbonylation process |
| GB9816385D0 (en) * | 1998-07-29 | 1998-09-23 | Bp Chem Int Ltd | Process |
| GB9819079D0 (en) * | 1998-09-03 | 1998-10-28 | Bp Chem Int Ltd | Carbonylation process |
| GB9824011D0 (en) * | 1998-11-03 | 1998-12-30 | Bp Chem Int Ltd | Process for the production of acetic acid |
| GB9825424D0 (en) * | 1998-11-19 | 1999-01-13 | Bp Chem Int Ltd | Process |
| US6103934A (en) * | 1998-12-18 | 2000-08-15 | Millennium Petrochemicals, Inc. | Manufacturing and process control methods |
| US6251256B1 (en) | 1999-02-04 | 2001-06-26 | Celanese International Corporation | Process for electrochemical oxidation of an aldehyde to an ester |
| JP2002536695A (en) * | 1999-02-05 | 2002-10-29 | エイリアン・テクノロジイ・コーポレーション | Apparatus and method for forming an assembly |
| US6160163A (en) * | 1999-02-16 | 2000-12-12 | Eastman Chemical Company | Method for the vapor-phase carbonylation of lower aliphatic alcohols using a supported platinum catalyst and halide promoter |
| US6159896A (en) * | 1999-02-16 | 2000-12-12 | Eastman Chemical Company | Iridium catalyst for carbonylation of lower aliphatic alcohols |
| US6137000A (en) * | 1999-02-16 | 2000-10-24 | Eastman Chemical Company | Method for carbonylation of lower aliphatic alcohols using a supported iridium and lanthanide series catalyst |
| US6355595B1 (en) | 1999-08-25 | 2002-03-12 | Eastman Chemical Company | Group 5 metal promoted iridium carbonylation catalyst |
| US6355837B1 (en) | 1999-08-25 | 2002-03-12 | Eastman Chemical Company | Vapor phase carbonylation process using group 4 metal promoted iridium catalyst |
| US6353132B1 (en) | 1999-08-25 | 2002-03-05 | Eastman Chemical Company | Vapor phase carbonylation process using group 5 metal promoted iridium catalyst |
| GB9926855D0 (en) * | 1999-11-12 | 2000-01-12 | Bp Chem Int Ltd | Process |
| US6458995B1 (en) | 2000-03-31 | 2002-10-01 | Celanese International Corporation | Catalytic composition for carbonylation including iridium and pyridine polymers |
| US6177380B1 (en) | 2000-05-22 | 2001-01-23 | Eastman Chemical Company | Iridium-gold carbonylation co-catalysts |
| US6548444B2 (en) | 2001-06-20 | 2003-04-15 | Eastman Chemical Company | Tin promoted iridium catalyst for carbonylation of lower alkyl alcohols |
| US6617471B2 (en) | 2001-06-20 | 2003-09-09 | Eastman Chemical Company | Method for carbonylation of lower aliphatic alcohols using tin promoted iridium catalyst |
| US6646154B2 (en) | 2001-06-20 | 2003-11-11 | Eastman Chemical Company | Method for carbonylation of lower alkyl alcohols using tungsten promoted group VIII catalyst |
| US6537944B1 (en) * | 2001-06-20 | 2003-03-25 | Eastman Chemical Company | Tungsten promoted catalyst for carbonylation of lower alkyl alcohols |
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- 1996-04-18 EP EP96302733A patent/EP0749948B1/en not_active Expired - Lifetime
- 1996-04-18 EP EP96302734A patent/EP0752406B1/en not_active Expired - Lifetime
- 1996-04-18 DE DE69619030T patent/DE69619030T2/en not_active Expired - Lifetime
- 1996-04-18 AT AT96302734T patent/ATE212970T1/en not_active IP Right Cessation
- 1996-04-18 AT AT96302733T patent/ATE194825T1/en not_active IP Right Cessation
- 1996-04-18 DE DE69609381T patent/DE69609381T2/en not_active Expired - Lifetime
- 1996-04-24 MY MYPI96001567A patent/MY115799A/en unknown
- 1996-04-24 MY MYPI96001568A patent/MY113453A/en unknown
- 1996-04-25 CA CA002175028A patent/CA2175028C/en not_active Expired - Fee Related
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- 1996-04-29 TW TW085105091A patent/TW338763B/en not_active IP Right Cessation
- 1996-04-29 TW TW085105092A patent/TW396150B/en not_active IP Right Cessation
- 1996-04-29 NO NO961723A patent/NO961723L/en not_active Application Discontinuation
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- 1996-04-30 NZ NZ286473A patent/NZ286473A/en unknown
- 1996-04-30 NZ NZ286474A patent/NZ286474A/en unknown
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- 1996-05-17 KR KR1019960016758A patent/KR100404644B1/en not_active IP Right Cessation
- 1996-05-17 KR KR1019960016759A patent/KR970001296A/en not_active Application Discontinuation
- 1996-05-21 CN CN96108432A patent/CN1068576C/en not_active Expired - Fee Related
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- 1996-05-31 MX MX9602082A patent/MX9602082A/en unknown
- 1996-06-04 JP JP8142047A patent/JPH092993A/en active Pending
- 1996-06-04 JP JP14204696A patent/JP3884504B2/en not_active Expired - Fee Related
- 1996-06-20 UA UA96062442A patent/UA46724C2/en unknown
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