WO1996014286A1 - Procede de preparation d'acides carboxyliques par carbonylation en presence d'iridium - Google Patents
Procede de preparation d'acides carboxyliques par carbonylation en presence d'iridium Download PDFInfo
- Publication number
- WO1996014286A1 WO1996014286A1 PCT/FR1995/001446 FR9501446W WO9614286A1 WO 1996014286 A1 WO1996014286 A1 WO 1996014286A1 FR 9501446 W FR9501446 W FR 9501446W WO 9614286 A1 WO9614286 A1 WO 9614286A1
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- WO
- WIPO (PCT)
- Prior art keywords
- carbon monoxide
- zone
- fraction
- vaporized
- liquid
- Prior art date
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Classifications
-
- 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
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
Definitions
- the present invention relates to a process for the preparation of carboxylic acids by carbonylation of a reagent, chosen in particular from alcohols, in the presence of an iridium-based catalyst.
- the carbonylation processes using soluble iridium-based catalysts for the preparation of carboxylic acids are known processes. They are generally implemented in installations essentially comprising three zones. The first corresponds to the actual reaction zone, comprising a pressure reactor in which the carbonylation is carried out. The second consists of a separation zone for the acid formed. This operation is carried out by partial vaporization of the reaction mixture in an apparatus (called a flash) where the pressure is kept lower than in the reactor. The vaporized part is then sent to a third zone where the carboxylic acid produced is purified. This includes various distillation columns in which the carboxylic acid produced is separated from water, reagents and by-products. The part of the mixture remaining in liquid form at the outlet of the vaporization zone and comprising in particular the catalyst, is recycled to the reactor. This is typically carried out by means of a pump.
- the present invention thus ob) and method ae preparation of carboxylic acids by carbonylation in the presence of a catalyst based on iridium, wherein the catalyst in a simple and effective way is reactivated.
- the process for the preparation of carboxylic acids consists in carrying out, in a first zone, the reaction in the liquid phase, in the presence of an iridium-based catalyst, then in a second zone, in partially vaporizing the reaction mixture obtained; the vaporized fraction, comprising the carboxylic acid produced, is subsequently purified and the non-vaporized liquid fraction comprising the catalyst is recycled to the first zone.
- the characteristic of the process is that the non-vaporized liquid fraction coming from the second zone is brought into contact with carbon monoxide so that this compound does not return to the second zone.
- - Figure 1 shows a first embodiment in which the non-vaporized fraction is brought into contact with carbon monoxide in the form of a gas.
- - Figure 2 shows a second embodiment in which carbon monoxide is dissolved in part of the non-vaporized liquid fraction from the flash.
- FIG. 3 shows a variant of the previous mode in which carbon monoxide is dissolved in part of the non-vaporized liquid fraction from the flash, having been previously treated on an ion exchange resin.
- the method according to the invention makes it possible to avoid any loss of carbon monoxide, which is one of the reagents for carbonylation. Indeed, if this gas had been introduced for example in the area of the flash itself, there would have been an inevitable loss in this compound.
- this gas had been introduced for example in the area of the flash itself, there would have been an inevitable loss in this compound.
- to obtain an effective amount of carbon monoxide in order to reactivate the catalyst it is necessary to implement, industrially, very high flow rates in this gas, even if the partial pressure of carbon monoxide maintained is relatively low.
- the implementation of high flow rates can have consequences at the level of the installation itself, for example concerning the size of the equipment.
- the solubilization of carbon monoxide can only be done correctly in the presence of vigorous stirring.
- a flash does not include such means.
- the method according to the invention therefore makes it possible to reactivate the catalyst without there being any loss of carbon monoxide and without an additional significant investment being obligatory.
- the process according to the invention is used in the context of the preparation of carboxylic acids by carbonylation.
- the reagent used in this type of reaction is generally chosen from alcohols.
- alcohols capable of being used mention may be made of saturated, mono or dihydroxylated alcohols having one to ten carbon atoms.
- examples of such compounds mention may in particular be made of methanol and ethanol.
- Monohydroxylated alcohols are preferred.
- the alcohol may be present in the reaction medium as such or in masked form. Indeed, it can be either in the form of a halogen derivative and / or an ether and / or an ester obtained by reaction between said alcohol and the carboxylic acid present.
- the reaction is carried out in the presence of a catalytic system comprising on the one hand a soluble species of iridium and on the other hand, a halogen promoter.
- the iridium-based compounds used are chosen from the coordination complexes of this metal, which are soluble in the medium under the reaction conditions. More particularly, coordination complexes are used, the ligands of which are on the one hand carbon monoxide and on the other hand a halogen which is particularly iodine. Of course, it is possible to use soluble complexes based on organic ligands. As suitable compounds based on iridium, reference may in particular be made to US Pat. No. 3,772,380, which gives an indicative list. As regards the promoter, this corresponds more particularly to the halogenated form of the abovementioned alcohol. Preferably, the halogen is iodine. The content of halogen promoter is generally less than 10%. Furthermore, the carbonylation reaction is carried out in the presence of the ester corresponding to the alcohol and to the acid produced. , the ester content is between 2 and 40%.
- the carbonylation reaction is further carried out in the presence of water
- the water content can vary within wide limits. However, preferably it is less than 10%.
- the reaction mixture may optionally comprise a compound chosen from soluble lodides which can be introduced as such into the reaction medium or also in the form of compounds capable of forming soluble lodides.
- the lodides introduced into said mixture are chosen from mineral iodides, such as in particular alkaline earth or alkali metal lodides, or organic iodides, comprising at least one organophosphorus group and / or at least one organo-nitrogen group, reacting with iodine-based compounds present in the reaction medium, to give ionic species containing this halogen.
- mineral iodides such as in particular alkaline earth or alkali metal lodides
- organic iodides comprising at least one organophosphorus group and / or at least one organo-nitrogen group, reacting with iodine-based compounds present in the reaction medium, to give ionic species containing this halogen.
- Mention may be made, as preferred mineral iodides, of potassium iodide, lithium iodide and sodium iodide.
- organic iodides of methyltriphenyl phosphonium iodide and N-methyltriethy
- the carboxylates of alkali or alkaline earth metals such as lithium acetate in particular, are suitable.
- the quantity of iodides present in the medium is such that the atomic ratio iodides introduced / iridium (expressed in mole / mole), is between 0 excluded and 10 and more particularly between 0 excluded and 3.
- the solvent for the reaction is advantageously the carboxylic acid which it is desired to manufacture.
- the carbonylation reaction is carried out at a temperature between 150 and 250 ° C.
- the total pressure in the reactor is usually between 1 and 100 bar absolute.
- the partial pressure of carbon monoxide in the reactor varies more particularly between 1 and 50 bar absolute.
- Carbon monoxide can be introduced into the reactor in a pure form or diluted in a gas, such as hydrogen, methane or even nitrogen.
- reaction mixture is then treated continuously in the separation zone of the acid formed, in which a fraction of said reaction mixture is vaporized.
- the total pressure is lower than that of the reactor. It is generally between 1 and 20 bar absolute.
- the operation can take place without adding heat to the flash (adiabatic conditions) or with adding heat.
- the partial vaporization is carried out in an adiabatic flash.
- the vaporized fraction includes the production of carboxylic acid, but also the reactants and by-products of the reaction.
- This vaporized fraction is sent to the acid purification zone, which conventionally comprises several distillation columns in which the acid produced is purified.
- the non-vaporized liquid fraction comprising in particular the catalyst, is recovered at the bottom of the flash to be recycled in the reactor.
- the carbonylation process according to the invention therefore consists in bringing said non-vaporized fraction into contact with carbon monoxide so that this compound does not return to the second zone, that of partial vaporization of the reaction mixture.
- the introduction of carbon monoxide is such that this compound does not return to the second zone, it is intended to employ means preventing the degassing of this compound directly to the flash.
- the catalyst tends to form inactive species, in a relatively slow and reversible process. These species cause a drop in the activity of the catalyst after several passages in the recycling loop from the separation zone to that of the reaction zone.
- the introduction of carbon monoxide into this part of the process makes it possible to unexpectedly reduce the concentration of these inactive species and therefore to find a significant level of activity.
- carbon monoxide is introduced in the form of a gas.
- the introduction takes place downstream of the pump by which the non-vaporized liquid fraction is recycled to the reactor.
- Carbon monoxide can be used in a pure form or can include other gases such as hydrogen, methane, nitrogen.
- the carbon monoxide used has a sufficient purity to avoid the accumulation of too many gases which are not active for the carbonylation reaction.
- the partial pressure of the gas introduced comprising mainly carbon monoxide, varies within wide limits. It is more particularly between 1 and 100 bar absolute
- the non-vaporized fraction can also undergo any type of treatment, in particular for the purpose of purifying the latter, such as for example a treatment to remove the corrosion metals, which will be detailed below.
- the non-vaporized fraction of the reaction mixture, coming from the flash is brought into contact with a liquid stream comprising carbon monoxide in the dissolved state, before being returned to the reactor.
- This variant is advantageous in that introducing a liquid in which carbon monoxide is dissolved makes this compound instantly active.
- Carbon monoxide can again be used in a pure form or else include other gases such as hydrogen, methane, nitrogen. What was indicated on this subject during the first variant remains valid here.
- the quantity of carbon monoxide introduced is at most equal to the limit of the solubility of this gas in the liquid used, depending on the temperature and pressure conditions. More particularly, the amount of dissolved carbon monoxide is between 0 excluded and 10%, this content being linked to the temperature and the pressure of the liquid.
- the liquid stream in which the carbon monoxide is dissolved consists of the carboxylic acid and / or any other reagent used during the carbonylation.
- the carboxylic acid, or any other reagent can be used in a pure form or else come, advantageously, from the purification zone located downstream.
- the carbon monoxide is dissolved in a solution further comprising the catalyst.
- at least part of the non-vaporized liquid fraction coming from the separation zone is derived from the recycling loop to be brought into contact with carbon monoxide.
- the liquid flow thus treated is then collected with the other part of the liquid fraction leaving the flash.
- This embodiment is particularly advantageous in that a part of the catalyst is treated with carbon monoxide, thus allowing its reactivation.
- the part of the liquid fraction in which the carbon monoxide is dissolved is first treated on an ion exchange resin to remove the corrosion metals therefrom.
- an ion exchange resin to remove the corrosion metals therefrom.
- resins of the strong acid type in a hydrogen form. These resins can be in the form of a gel or else macroreticulated.
- the contacting is carried out in a fixed bed or in a fluidized bed.
- the temperature at which the treatment is carried out must of course be adapted to the resistance of the resin. In general, it is between room temperature and 100 ° C.
- the gas solubilization operation takes place in an apparatus with vigorous stirring. Any means can be used to obtain such a result, whether mechanical or not.
- the contacting temperature is between 25 and 200 ° C.
- the pressure is at least equal to the pressure prevailing in the reactor. More particularly, the pressure is between 1 and 100 bar absolute.
- the solution comprising the dissolved carbon monoxide is introduced into a part of the recycling loop so as to avoid degassing of the carbon monoxide and its entrainment towards the flash, as well as to avoid cavitation of the pump thanks to which the liquid fraction from the flash is returned to the reactor.
- the skilled person is able, with his own knowledge of engineering chemical to determine the appropriate place for the introduction of the solution comprising dissolved carbon monoxide.
- FIG. 1 describes an embodiment of the first variant, in which the non-vaporized fraction is brought into contact with carbon monoxide in the form of gas.
- carbon monoxide and alcohol are introduced into the reactor (1) comprising the catalytic system, the carboxylic acid, the ester, water and the stabilizing agent.
- the reaction mixture is expanded by means of a valve which is not shown in the diagram, which results in a partial vaporization of the mixture and introduced into the flash (2).
- the vaporized fraction is condensed so as to separate the carboxylic acid to be purified from the noncondensable products that are carbon monoxide, and the gaseous by-products of the reaction.
- the remaining liquid fraction is engaged in the recycling loop to the reactor.
- Carbon monoxide is introduced downstream of the pump used to recycle the liquid fraction
- FIG. 2 describes an embodiment of the second variant, in which part of the non-vaporized fraction is brought into contact with carbon monoxide dissolved in a liquid stream.
- the caroonylation reaction takes place as shown in the previous figure.
- the reaction mixture is introduced into the flash (2).
- the vaporized fraction is condensed to separate the carboxylic acid to be purified from noncondensable products.
- the remaining liquid fraction is engaged in the recycling loop to the reactor. Part of this flow is then diverted from the recycling loop to be introduced into a reactor (3) provided with means for stirring and for introducing carbon monoxide.
- the liquid in carbon monoxide is collected in the flow which has not been treated, after having been previously and if necessary, relaxed so as to find a pressure close to that of the reactor, by means of a valve which is not shown.
- Figure 3 describes a variant of the mode described in the previous figure.
- the difference between these two modes lies in the fact that the fraction derived from your recycling loop is treated by passing through a column (4) over an ion exchange resin before being brought into contact with carbon monoxide.
- the diversion of the flow to be brought into contact with carbon monoxide is carried out upstream of the pump allowing the recycling of the liquid to the reactor. It would not be departing from the scope of the present invention to carry out this bypass downstream of this same pump.
- the point of contact between the liquid comprising the dissolved carbon monoxide and that which has not been treated with this gas is located downstream of the aforementioned pump. Again, this would not go beyond the scope of the present invention by doing this upstream of the pump.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/817,701 US5770768A (en) | 1994-11-04 | 1995-11-03 | Method for preparing carboxylic acids by carbonylation in the presence of iridium |
AU41193/96A AU4119396A (en) | 1994-11-04 | 1995-11-03 | Method for preparing carboxylic acids by carbonylation in the presence of iridium |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR94/13175 | 1994-11-04 | ||
FR9413175A FR2726556B1 (fr) | 1994-11-04 | 1994-11-04 | Procede de preparation d'acides carboxyliques par carbonylation en presence d'iridium |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996014286A1 true WO1996014286A1 (fr) | 1996-05-17 |
Family
ID=9468494
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR1995/001446 WO1996014286A1 (fr) | 1994-11-04 | 1995-11-03 | Procede de preparation d'acides carboxyliques par carbonylation en presence d'iridium |
Country Status (6)
Country | Link |
---|---|
US (1) | US5770768A (fr) |
KR (1) | KR100401901B1 (fr) |
CN (1) | CN1068302C (fr) |
AU (1) | AU4119396A (fr) |
FR (1) | FR2726556B1 (fr) |
WO (1) | WO1996014286A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5932764A (en) * | 1996-12-05 | 1999-08-03 | Bp Chemicals Limited | Iridium-catalyzed carbonylation process for the production of a carboxylic acid |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB0211560D0 (en) | 2002-05-20 | 2002-06-26 | Bp Chem Int Ltd | Process |
MX2010011850A (es) | 2008-04-29 | 2010-11-30 | Celanese Int Corp | Sistema de carbonilacion de metanol que tiene un absorbedor con multiples opciones de disolvente. |
US7820855B2 (en) | 2008-04-29 | 2010-10-26 | Celanese International Corporation | Method and apparatus for carbonylating methanol with acetic acid enriched flash stream |
US7884237B2 (en) | 2008-11-07 | 2011-02-08 | Celanese International Corp. | Methanol carbonylation with improved aldehyde removal |
US8168822B2 (en) | 2009-07-07 | 2012-05-01 | Celanese International Corporation | Acetic acid production by way of carbonylation with enhanced reaction and flashing |
US8455685B2 (en) | 2009-07-07 | 2013-06-04 | Celanese International Corporation | Acetic anhydride production by way of carbonylation with enhanced reaction and flashing |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3772380A (en) * | 1970-03-12 | 1973-11-13 | Monsanto Co | Production of carboxylic acids and esters |
EP0441260A1 (fr) * | 1990-02-09 | 1991-08-14 | Quantum Chemical Corporation | Procédé catalytique de carbonylisation |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55142543A (en) * | 1979-04-03 | 1980-11-07 | Mitsubishi Gas Chem Co Inc | Method for prevention of decomposition of catalyst |
US5237097A (en) * | 1990-02-09 | 1993-08-17 | Quantum Chemical Corporation | Catalytic carbonylation process |
-
1994
- 1994-11-04 FR FR9413175A patent/FR2726556B1/fr not_active Expired - Fee Related
-
1995
- 1995-11-03 AU AU41193/96A patent/AU4119396A/en not_active Abandoned
- 1995-11-03 CN CN95196033A patent/CN1068302C/zh not_active Expired - Fee Related
- 1995-11-03 US US08/817,701 patent/US5770768A/en not_active Expired - Lifetime
- 1995-11-03 KR KR1019970702955A patent/KR100401901B1/ko not_active IP Right Cessation
- 1995-11-03 WO PCT/FR1995/001446 patent/WO1996014286A1/fr active IP Right Grant
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3772380A (en) * | 1970-03-12 | 1973-11-13 | Monsanto Co | Production of carboxylic acids and esters |
EP0441260A1 (fr) * | 1990-02-09 | 1991-08-14 | Quantum Chemical Corporation | Procédé catalytique de carbonylisation |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5932764A (en) * | 1996-12-05 | 1999-08-03 | Bp Chemicals Limited | Iridium-catalyzed carbonylation process for the production of a carboxylic acid |
Also Published As
Publication number | Publication date |
---|---|
CN1162302A (zh) | 1997-10-15 |
KR100401901B1 (ko) | 2004-03-24 |
US5770768A (en) | 1998-06-23 |
AU4119396A (en) | 1996-05-31 |
KR970707067A (ko) | 1997-12-01 |
FR2726556A1 (fr) | 1996-05-10 |
FR2726556B1 (fr) | 1996-12-20 |
CN1068302C (zh) | 2001-07-11 |
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