WO1996023730A1 - Method for preparing iridium iodides and use thereof as catalysts - Google Patents

Method for preparing iridium iodides and use thereof as catalysts Download PDF

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Publication number
WO1996023730A1
WO1996023730A1 PCT/FR1996/000143 FR9600143W WO9623730A1 WO 1996023730 A1 WO1996023730 A1 WO 1996023730A1 FR 9600143 W FR9600143 W FR 9600143W WO 9623730 A1 WO9623730 A1 WO 9623730A1
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iodide
iridium
characterized
acid
water
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PCT/FR1996/000143
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French (fr)
Inventor
Dominique Nobel
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Rhone-Poulenc Fiber And Resin Intermediates
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06Halogens; Compounds thereof
    • B01J27/128Halogens; Compounds thereof with iron group metals or platinum group metals
    • B01J27/13Platinum group metals
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G55/00Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
    • C01G55/005Halides

Abstract

A method for preparing iridium iodides by reacting at least one iridium chloride or bromide with hydrogen iodide in a medium containing at least one carboxylic acid and/or water. The preparation of iridium iodide solutions that are particularly suitable for use as catalysts in carbonylation, isomerisation or hydroformylation reactions is also disclosed.

Description

Process for Preparing IODIDES IRIDIUM AND THEIR USE AS CATALYST

The present invention relates to an iridium iodides preparation process. It also relates to the obtaining of iridium halide solutions that can be used in particular as catalysts in carbonylation reactions, isomerization and hydroformylation.

iridium available compounds, more particularly available in sufficient quantities for possible industrial use, are essentially of iridium oxides, iridium chlorides, sodium chloro-iridates or potassium iridium bromides . These compounds are disadvantageous for certain catalytic iridium applications. And the oxides are not sufficiently soluble in solvents generally used for the carbonylation of the pentenoic acids or esters to adipic acid or its esters or for the carbonylation of methanol to acetic acid. On the other hand, the presence of chloride ions or bromides be avoided in an industrial process due to the corrosion that generate these ions.

The iridium tetraiodide, or more generally the iridium iodide since these are generally in the form of mixtures of several of them are suitable for homogeneous catalysis of carbonylation reactions indicated above. In the present text, unless otherwise stated iridium iodide term encompass the tetraiodide iridium, iridium triiodide and various mixtures of iridium iodide.

The present invention therefore consists firstly in an iridium iodide preparation process, characterized in that is reacted at least one iridium chloride or bromide with hydrogen iodide in a medium comprising at least one carboxylic acid or water or a mixture of at least one carboxylic acid and water.

As the carboxylic acid which can be used in the present process are more particularly liquid aliphatic carboxylic acids under reaction conditions such as acetic acid, propionic acid, butyric acid, valeric acid, pentenoic acids . Acetic acid is the preferred carboxylic acid for this reaction. It is of course implement a mixtures of several carboxylic acids.

Chlorides and bromides of iridium used are generally commercially available as mixtures trichloride and iridium tetrachloride or tetrabromide tribromide and iridium.

The hydrogen iodide is usually used as an aqueous solution (hydroiodic acid) including, but not limited to solution at 57% by weight. The amount of hydrogen iodide used may vary within wide limits.

Expressed in molar ratio of hydrogen iodide / iridium, it usually varies between

1 to 100 and preferably from 2 to 30.

The temperature at which is fed the process of the invention can vary widely. It is generally between 0 β C and the boiling temperature of the reaction mixture under atmospheric pressure or under pressure higher than the atmospheric pressure. As an indication, one can say that this temperature is usually between 20 ° C and 190 ° C.

The amount of carboxylic acid and / or water used is also very variable. Generally represents from 40% to 95% by weight of the total weight of the reaction mixture and preferably from 60% to 90%.

The reaction time of preparation of iridium iodide can be between a few minutes and a few days. Usually, it is between

1 hour and 48 hours without these values ​​to be limiting. The resulting iridium iodide, which is essentially of iridium tetraiodide, précipit in solid form in the reaction medium. This may be separated by any known means used in chemistry for separating a solid from a liquid, such as filtration or centrifugation.

The iodide thus obtained iridium is substantially free of chloride ions or bromide, that is to say, it contains less than 0.1000% by weight ion chlorides or bromides by weight of iridium and preferably less than 0.0500%.

This thus prepared iridium iodide is preferably dissolved to be used as carbonylation catalyst. This dissolution is carried out by contacting, usually with stirring, said iridium iodide with carbon monoxide in the presence of water. Water is present in a molar amount at least equal to the molar amount of iridium used.

The water may be the only solvent of the solution heat reaction. Can also be used in the reaction medium at least one liquid carboxylic acid under the conditions réactionnelles.Cet carboxylic acid may be selected from those defined above for the preparation of iridium iodide or different. advantageously one will choose a carboxylic acid that will be present in the subsequent carbonylation reaction, that is to say either the acid will be obtained lor this carbonylation, such as acetic acid in the carbonylation of methanol, adipic acid and / or methylglutaric acid or ethylsuccinic acid and / or valeric acid in the carbonylation of pentenoic acids, or even acid subject to the carbonylation reaction, such as the pentenoic acids. The amount of water or amount of water and carboxylic acid used may vary widely. In practice, it is between 10% and 99.5% by weight of the total weight of the reaction mixture and preferably between 50% and 99%.

Although it is not essential, we can also implement the hydrogen iodide in the operation of dissolving iridium iodide, to facilitate the solution in some cases. As for the preparation of iridium iodide described above, the hydrogen iodide is generally used in the form of an aqueous solution (hydroiodic acid), in particular 57% by weight. The molar hydrogen / iridium iodide ratio is generally from 0 to 20 and preferably from 0 to 10.

The absolute partial pressure of carbon monoxide measured at room temperature (20-25 ° C) is generally between 1 bar (0.1 MPa) and 200 bar (20 MPa).

The temperature at which is performed the dissolution operation can vary very widely. Generally, as for the actual preparation of the iridium iodide, it is between 0 ° C and the boiling temperature of the reaction mixture, under the chosen pressure for the dissolution. For information, one can say that this temperature is usually between 50 ° C and 200 ° C.

The reaction time of dissolution of iridium iodide can be between a few minutes and a few days. Usually, it is between 1 hour and 48 hours without these values ​​to be limiting.

A variant of the inventive method consists in directly preparing an iridium iodide solution by performing a step in the two actual preparation operations iridium iodide and its dissolution. In this variant, the chlorides or bromides iridium which are the starting substrates are contacted with hydrogen iodide in a medium comprising water or a mixture of water and at least one acid carboxylic acid, in the presence of carbon monoxide.

The operating conditions of this embodiment are those which have been described above for the operation of dissolution of the iridium iodide.

The iridium iodide solution obtained by one step according to this variant comprises chlorides or bromides ions whose presence can be considered troublesome in the implementation of some processes, especially on an industrial scale. Thus it may be useful to remove some or all of these ions, for example by passing the solution through an ion exchange resin. Examples of such resins include strongly basic resins, usually quaternary ammonium functions such as benzyl function. One can for example use the resins sold under the trademark Amberlyst 26 (OH) E. Another object of the invention is the use of iridium iodide solutions prepared according to one or the other variants of the method, as the catalyst.

The solution may first be used as such, optionally after adding one or more cocatalysts or after solvent change to better adapt it to the intended reaction, for homogeneous phase catalysis reactions.

It can also be used to prepare a catalyseur.solide supported using conventional methods. Can also be used directly as solid catalyst the iridium iodide obtained in the first step one of the process variants.

However, the iridium iodide solution is preferably used as a catalyst or part of a catalyst system for carrying out reactions in a homogeneous phase.

These reactions are more specifically carbonylation reactions, hydroformylation and isomerization.

The carbonylation reactions in the liquid phase in the presence of carbon monoxide possible especially to obtain carboxylic acids and / or carboxylic acid anhydrides.

The reagents used for carbonylation reactions or isomerization are generally selected from alcohols such as alkanols having 1 to 10 carbon atoms or aicénols having 3 to 10 carbon atoms, ethers having 2 to 20 carbon atoms, unsaturated carboxylic acids having 3 to 10 carbon atoms, esters of carboxylic acids having 2 to 20 carbon atoms, olefins or diolefins such as butadiene. The iridium iodide solutions thus prepared are particularly suitable especially well to the carbonylation of methanol to acetic acid, as described in particular in EP-A-0618184 and EP-A-0,618,183 patent or the hydroxycarbonylation of pentenoic acid as described in EP-A-0511126 or in the carbonylation of allylic butenols such as described in EP-A-0612713 or the hydroxycarbonylation of the lactones as described in the patent EP-A-0612711 or the isomerization of carboxylic acids, especially branched dicarboxylic acids, as described in patent FR-A-2703045.

The catalyst system used for carbonylation reactions may comprise, in addition to iridium iodide prepared according to the invention, at least one iodinated promoter or bromine, such as hydrogen iodide or alkyl iodides can releasing in situ the hydrogen iodide or hydrogen bromide or alkyl bromides. The iodine-containing promoters are generally preferred. However iridium iodide generating in situ hydrogen iodide, the promoter addition is not always necessary. Generally, the carbonylation is carried out at a temperature of 50 ° C to 300 ° C and under a pressure of carbon monoxide of from 5 to 200 bar in temperature.

The carbonylation reaction is generally carried out in the presence of a solvent which may be more particularly, but not exclusively, selected from the compounds used or the compounds produced during the carbonylation.

Can be optionally simultaneously perform the dissolving iridium iodide, as described above and the carbonylation reaction when it implements for solution annealing the substrate to be carbonylated. This is particularly the case when operating the dissolving iridium iodide in a medium comprising at least one pentenoic acid.

The following examples illustrate the invention.

EXAMPLE 1 - Synthesis of iridium iodide. were charged into a glass reactor of 50 cc:

- 0.27 g of iridium trichloride (53% by weight of Ir)

- 2.0 g of an aqueous solution of hydriodic acid at 57% by weight - 10 g of acetic acid.

Is brought to reflux for 26 hours. For cooling, the precipitation of a black powder was observed (iridium iodide). The powder was filtered through a sintered glass filter of porosity 4 and dried. There is thus obtained 0.48 g of iridium iodide (78% yield) having a residual content of less than 0.0200% chlorine.

EXAMPLE 2 - Preparation of an iridium iodide solution in acetic acid was charged in a 1.5 liter autoclave: • aqueous solution of HI at 57% by weight: 90 g - Acetic acid: 911 g

Is stirred at 1500 revolutions / min and was slowly added 105 g of iridium iodide (with a 28.2% content of Ir) in order to obtain a homogeneous suspension appearance. Is pressurized to 5 bar with carbon monoxide and heated to 150 ° C for 5 h. After cooling, the solution is filtered on a sintered glass filter of porosity 4. This gives 1075 g of a red solution containing 2.7% iridium. This solution is stable over time (several months) and its handling does not require any special precautions. EXAMPLE 3 - Preparation of a solution of iridium iodide in 3-penténoïoue acid were charged into a glass tube:

- iridium iodide prepared in Example 1: 72.1 mg

- water: 2.27 g - 3-penténoiqυe acid: 25.2 g

Is pressurized to 5 bar with carbon monoxide and heated to 185 ° C in 30 min. It then adjusts the pressure to 20 bar with carbon monoxide and maintained at 185 ° C for a further 35 min. A homogeneous and stable solution straw yellow.

EXAMPLE 4 - Preparation of a solution of iridium iodide in 3-pentenoic acid e hvdroxycarbonylation 3-penténoïoue acid are charged into a glass bulb: - iridium iodide prepared in Example 1: 72.1 mg

- water: 2.27 g

- 3-pentenoic acid: 25.2 g

Bulb is introduced in an autoclave which is purged with carbon monoxide.

Is pressurized to 5 bar with carbon monoxide and heated to 185 ° C in 30 min. then the pressure is adjusted to 20 bar with carbon monoxide and maintained at 185 ° C for a further 1 h 30 min. Measuring a rate of carbonylation of pentenoic acid to 5 moles per liter of reaction mixture per hour.

Adipic acid was obtained in a yield of 97% expressed as a molar ratio of adipic / adipic acid + saturated acids to 5 carbon atoms.

Linearity expressed in molar ratio of adipic acid / total of 6 carbon atoms diacids is 80%.

EXAMPLE 5 - Hvdroxycarbonylation of methyl acetate was charged in a glass ampoule:

- iridium iodide solution prepared in Example 2: 1, 72 g

- methyl acetate: 2.90 g - methyl iodide: 1, 16 g

- water: 2.27 g

- acetic acid 19.2 g is introduced bulb in an autoclave which is purged with carbon monoxide.

10 bar of pressure is established with carbon monoxide and the temperature was raised to 190 ° C. When this temperature is reached, establishes communication with a supply of carbon monoxide equipped with a pressure regulator for maintaining the total pressure at 30 bar. The carbonylation rate of acetic acid to methyl acetate is 7.3 moles per liter of reaction mixture per hour.

Claims

1) - A method of iridium iodide preparation, characterized in that is reacted at least one chloride or bromide iπdium with hydrogen iodide in a medium comprising at least one carboxylic acid or water or a mixture of at least one carboxylic acid and water
2) - Process according to claim 1, characterized in that the carboxylic acid used is chosen from carboxylic acids phatic liquid under the reaction conditions such as acetic acid, propionic acid, butyπques acids, the vaiéπque acid, pentenoic acids and is preferably acetic acid
3) - A method according to one of claims 1 or 2, characterized in that the amount of carboxylic acid and / or water used represents from 40% to 95% e the total weight of the reaction mixture and preferably from 60% to 90%.
4) - A method according to one of claims 1 to 3, characterized in that the amount of hydrogen iodide implementation expπmée in molar ratio of hydrogen iodide / indium, vane between 1 and 100 and preferably 2 to 30
5) - A method according to one of claims 1 to 4, characterized in that the temperature at which it is carried out is between 0 ° C and ébullitio temperature of the reaction mixture under atmospheric pressure or under pressure higher than the atmospheric pressure and is preferably compnse between 20 ° C and 190 ° C
6) - A method according to one of claims 1 to 5, caractéπsé in that the obtained indium iodide precipitated in solid form in the reaction medium is sépar by any known means such as filtration or ceπtπfugation
7) - A method according to claim 6, characterized in that the separate indium iodide is dissolved by contacting said indium iodide with carbon monoxide in the presence of water 8) - A process for preparing an indium iodide solution, characterized in that the contacting takes place at least one chloride or indium bromide with hydrogen iodide in a medium comprising water or a mixture of water and at least one carboxylic acid, in the presence of carbon monoxide, the amount of hydrogen iodide implementation expπmée in molar ratio of hydrogen iodide / iπdium, vaπant between 1 and 100 and preferably between 2 and 30.
9) - A process as claimed in claim 7 or 8, characterized in that water is present in a molar amount at least equal to the molar amount of iπdium implemented
10) - Method according to one of claims 7 to 9, caractéπsé in that water is the only solvent of the solution heat reaction.
11) - A method according to one of claims 7 to 9, caracténse in that it implements in the reaction medium at least one liquid carboxylic acid under the reaction conditions, such as acetic acid, propionic acid, butyric acids, valéπque acid, adipic acid, méthylglutanque acid, ethylsuccinic acid, pentenoic acids and mixtures of several of these acids
12) - A method according to one of claims 7 to 11, characterized in that the amount of water or amount of water and carboxylic acid used is between 10% and 99.5% by weight of the total weight the reaction mixture and preferably between 50% and 99%
13) - A method according to one of claims 7 and 9 to 12, caractéπsé in that it implements hydrogen iodide
14) - A method according to claim 7 and 9 to 13, caractéπsé in that the molar ratio of hydrogen iodide / iπdium is 0 to 20 and preferably from 0 to 10
15) - A method according to one of Claim 7 to 14, caractéπsé in that the partial pressure of carbon monoxide measured at room temperature is between 1 bar (0.1 MPa) and 200 bar (20 MPa), and that the temperature at which is performed the operation of dissolution is between 0 ° C and the boiling temperature of the reaction mixture, under the chosen pressure for the dissolution and is preferably compπse between 50 ° C and 200 ° C 16) - Using the iridium iodide prepared according to one of claims 1 to 15, characterized in that the iridium iodide solution is used as such, optionally after adding one or more cocatalysts or after change of solvent in order to better adapt it to the intended reaction, for homogeneous phase catalysis reactions such as carbonylation reactions, hydroformylation and isomerization.
17) - Use according to claim 16, characterized in that the iridium iodide solution is carried out for the carbonylation reactions or isomerisation of compounds selected from alcohols having 1 to 10 carbon atoms or alkenols having 3 to 10 carbon atoms, ethers having 2 to 20 carbon atoms, unsaturated carboxylic acids having 3-10 carbon atoms, esters of carboxylic acids having 2 to 20 carbon atoms, olefins or diolefins.
18) - Use according to any of claims 16 or 17, characterized in that the iridium iodide solution is used for the carbonylation reaction of methanol to acetic acid.
19) - Use according to any of claims 16 or 17, characterized in that the iridium iodide solution is used for the hydroxycarbonylation reaction of pentenoic acids for the carbonylation of allylic butenols louse the hydroxycarbonylation reaction of lactones or the isomerization reaction of branched dicarboxylic acids.
PCT/FR1996/000143 1995-02-02 1996-01-29 Method for preparing iridium iodides and use thereof as catalysts WO1996023730A1 (en)

Priority Applications (2)

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FR9501406A FR2730225B1 (en) 1995-02-02 1995-02-02 Process for the preparation of iridium iodides and their use as catalysts

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6177603A (en) * 1984-09-25 1986-04-21 Toyo Soda Mfg Co Ltd Production of iodide
EP0612713A1 (en) * 1993-02-26 1994-08-31 RHONE-POULENC FIBER & RESIN INTERMEDIATES Process for the carbonylation of allylic butenols and their esters
EP0618184A1 (en) * 1993-03-31 1994-10-05 Pardies Acetiques Process for the preparation of carboxylic acids or corresponding esters in presence of a catalyst based on rhodium and iridium

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6177603A (en) * 1984-09-25 1986-04-21 Toyo Soda Mfg Co Ltd Production of iodide
EP0612713A1 (en) * 1993-02-26 1994-08-31 RHONE-POULENC FIBER & RESIN INTERMEDIATES Process for the carbonylation of allylic butenols and their esters
EP0618184A1 (en) * 1993-03-31 1994-10-05 Pardies Acetiques Process for the preparation of carboxylic acids or corresponding esters in presence of a catalyst based on rhodium and iridium

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 8622, Derwent World Patents Index; AN 86-141338, XP002001901 *

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FR2730225A1 (en) 1996-08-09 application

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