The way carbonyl alcohols alkylaromatics

 

(57) Abstract:

The invention relates to a process for the carbonylation alkylaromatics alcohols, in particular methanol, or ethers of alcohols in the liquid phase with the use of carbon monoxide with its partial pressure to 7 kg/cm2. The process is carried out in the presence of a rhodium catalyst, additives halide, such as iodide Quaternary ammonium or phosphonium, and a limited amount of water. In addition, the use of manganese as a stabilizer rhodium catalyst at a molar ratio of manganese : rhodium (0.2 to 20) : 1. Manganese is transferred to the active form to accelerate the reaction by contact with hydrogen. 13 C.p. f-crystals, 3 tables.

The present invention relates to a method for carbonylation alkylaromatics alcohols and/or their reactive derivatives in the presence of a rhodium catalyst.

How carbonylation in the presence of rhodium catalysts are known and are described, for example, in U.S. patent 3769329 and European patent 0055618.

In J. Molecular Catalysis, 39 (1987) 115-136 described the addition of iodides in solutions of rhodium catalyst for carbonylation of methanol at a low concentration of water (< 2M) to skiravany methanol in the presence of MnI2together with data on speed for a large number of other iodides in General excessive reaction pressure of 400 pounds per square inch. The authors of the present invention believe that in such conditions the rate of the carbonylation reaction is not limited to the partial pressure of carbon monoxide. Moreover, the molar ratio of manganese:rhodium in the described experiment using manganese is very high and is estimated (> 90): 1.

Conducting the carbonylation processes at low partial pressure of carbon monoxide is desirable because it leads to improved use of carbon monoxide as a reactant, for example, by reducing the loss of carbon monoxide from gases that are removed from the reactor.

The problem with catalyzed by rhodium carbonylation reactions is that at low partial pressure of carbon monoxide in a carbonylation reactor for, i.e. at a pressure of less than or equal to 7 bar, the rate of carbonylation may be limited to partial pressure of carbon monoxide.

The technical problem to be resolved is how carbonylation alkylaromatics alcohol and/or reaktsionnosposobnykh is.

Thus, in accordance with the present invention proposes a method of carbonylation alkylaromatics alcohol and/or its reactive derivative, comprising the stages of (I) introducing into contact in the reactor for the carbonylation of an alcohol and/or its reactive derivative with carbon monoxide in a liquid reaction mixture containing (a) a rhodium catalyst, (b) alkylhalogenide and (C) water at least in a limited concentration, and (II) the selection of the carbonylation product from a liquid reaction mixture, characterized in that at the stages of carbonyl and/or selection of product partial pressure of carbon monoxide, less than or equal to 7 bar, and these stages is carried out in the presence of mn containing stabilizer for rhodium catalyst at a molar ratio of manganese:rhodium (0.2 to 20): 1.

In the method according to the present invention using manganese stabilizer for rhodium catalyst has a beneficial effect on the rate catalyzed by rhodium carbonylation alkylaromatics alcohol and/or its reactive derivative at a partial pressure of carbon monoxide, less than or equal to 7 bar, which may limit when one of the objects of the present invention proposes a method of carbonylation alkylaromatics alcohol and/or its reactive derivative, includes introduction to the contact in the reactor for the carbonylation of an alcohol and/or its reactive derivative with carbon monoxide in a liquid reaction mixture at a partial pressure of carbon monoxide in the reactor, less than or equal to 7 bar, in which this liquid reaction mixture contains (a) a rhodium catalyst, (b) alkylhalogenide, (C) water at least in a limited concentration, and (d) a stabilizer for the rhodium catalyst containing manganese in the active to accelerate the reaction of the carbonyl form, with a molar ratio of manganese:rhodium (0.2 to 20):1.

Unexpectedly, it was found that according to the way carbonylation of the present invention manganese stabilizer has a beneficial effect on the carbonyl process in a significantly lower concentration than that specified in J. Molecular Catalysis, 39 (1987) 115-136. It was found that this beneficial effect of manganese on the carbonylation reaction in the method according to the present invention occurs at low partial pressure of carbon monoxide, less than or equal to 7 bar, which in the absence of manganese stabilizer would limit the rate of carbonylation, while the iodides such as lithium iodide, in such the trigger to the invention the presence of manganese stabilizer in the liquid reaction mixture stabilizes the rhodium catalyst, when at the stage of selection of product at a lower partial pressure of carbon monoxide than in the carbonylation reactor for the carbonylation product is separated from the rhodium catalyst and manganese contained in the liquid reaction mixture.

Thus, in accordance with another object of the present invention proposes a method of carbonylation alkylaromatics alcohol and/or its reactive derivative, comprising the stages of (I) introducing into contact in the reactor for the carbonylation of an alcohol and/or its reactive derivative with carbon monoxide in a liquid reaction mixture containing (a) a rhodium catalyst, (b) alkylhalogenide and (C) water at least in a limited concentration; (II) selection of the carbonylation product from the reaction mixture at a partial pressure of carbon monoxide, less than or equal to 7 bar, in the presence of mn containing stabilizer for rhodium catalyst at a molar ratio of manganese:rhodium (0.2 to 20):1; and (III) return rhodium catalyst and manganese stabilizer from phase (II) phase carbonylation (I).

Appropriate alkylaromatics alcohols include C1-C10-, predpochtiteljno methanol. Preferred alkylaromatics alcohol is a primary or secondary alkylaromatics alcohol. As a product of the carbonylation of an alcohol containing n carbon atoms, and/or its derivative gain carboxylic acid containing n+1 carbon atoms, and/or ether carboxylic acids containing n+1 carbon atoms, and an alcohol containing n carbon atoms. Thus, the product of the carbonylation of methanol and/or its derivative is an acetic acid and/or methyl acetate.

Acceptable reactive derivative alkylaromatics alcohol include the appropriate alkilany ester of the alcohol and the corresponding received carboxylic acid, dialkyl ethers and alkylhalogenide, preferably iodides or bromides. Acceptable reactive derivatives of methanol include methyl acetate, easy dimethyl ether and methyliodide. In the method according to the present invention as reagents may be used a mixture of alkylaromatics alcohol with its reactive derivative. As the reagent, it is preferable to use methanol and/or methyl acetate and/or dimethyl ether. At least some amount of alkylaromatics what isatou or solvent becomes difficult alkalemia esters, which, therefore, present in the liquid reaction mixture. Acceptable concentration difficult Olkiluoto ether in the liquid reaction mixture is 0.1-70 wt.%, preferably 0.5 to 50 wt.% and most preferably 0.5 to 35 wt.%.

Water can be obtained in situ in the liquid reaction mixture, for example, by the esterification reaction between alkylaromatics alcohol reactant and product - carboxylic acid. In the carbonylation reactor for water can enter together with other components of the liquid reaction mixture or separately from them. Water can be separated from other components of the reaction mixture withdrawn from the reactor, and can be returned to the cycle in controlled amounts to maintain the desired concentration of water in the liquid reaction mixture. Accordingly, the concentration of water in the liquid reaction mixture is 0.1-15 wt.%, preferably 1-15 wt.%. It is preferable to maintain the concentration of water less than 14 wt.%, more preferably less than 11 wt.% and most preferably less than 8 wt.%.

The rhodium component of the catalyst in the liquid reaction mixture can be any registersee compound which is soluble in this liquid reaction mixture. Rhodium componentname, in which it is dissolved in the liquid reaction mixture or can pass into the soluble form. As examples of acceptable registergui compounds that can be added to the liquid reaction mixture, can be called [Rh(CO)2Cl]2] , [Rh(CO)2I] 2, [Rh(Cod)Cl]2, chloride, rhodium (III) chloride trihydrate rhodium (III) bromide, rhodium (III) iodide rhodium (III) acetate, rhodium (III), decarbonylation rhodium, RhCl3PPh3)3and RhCl(CO)(PPh3)2.

The preferred concentration of the rhodium catalyst in the liquid reaction mixture is 50-5000 weight.parts/million in terms of rhodium, preferably 100-1500 weight.parts/million

Manganese stabilizer can be any mn containing compound which is soluble in the liquid reaction mixture. The stabilizer can be added to the liquid reaction mixture for the reaction of carbonyl in any acceptable form, in which it is soluble in this liquid reaction mixture or can pass into the soluble form.

Examples of usable mn containing compounds include Mn2(CO)10, manganese acetate (II), manganese acetate (III) bromide, manganese (II) bromide tetrahydrate Marga is, XID manganese (IV), Mn(CO)5Br, Mn(CO)5I.

I believe that manganese stabilizer is an active component for accelerating the reaction of carbonyl when it contains manganese in nizkoemissionnoi condition, such as Mn(O) and/or Mn(I). Thus, if manganese is added in the reaction mixture in this highly oxidised state, in particular in such as Mn (II), it may not have a promoting effect on the carbonylation reaction, if, or until, until it transformed into nizkoemissionnoi state, for example, by introducing into contact with an appropriate reducing agent, such as hydrogen.

The molar ratio of manganese stabilizer:rhodium catalyst amounts (0.2 to 20):1, preferably (0.5 to 10):1.

Acceptable alkylhalogenide contain alkyl residues, the corresponding alkyl residue alkylaromatics alcohol reagent, and preferably represents a C1-C10-, more preferably C1-C6and most preferably C1-C4alkylhalogenide. The preferred alkylhalogenide is iodide or bromide, more preferably iodide. The preferred concentration of alkylhalogenide in the liquid reaction slator catalyst in the liquid reaction mixture may also contain iodide. This iodide salt may be an iodide salt of any metal iodide salt of Quaternary ammonium or Quaternary iodide of phosphonium. The preferred metal iodide iodide is an alkaline or alkaline earth metal, more preferably the iodide of lithium, sodium, potassium or cesium. To fit the Quaternary ammonium iodides include iodides quaternionic amine, pyridine, pyrrolidine and/or imidazole, for example, N,N'-dimethylimidazolidin. Acceptable iodides of Quaternary phosphonium include methyltriphenylphosphonium, tetrabutylphosphonium, methyltriphenylphosphonium etc. iodides Such as stabilizers are described, for example, in European patent EP-A-0573189.

Operatorkey reagent may be almost pure or may contain inert impurities such as carbon dioxide, methane, nitrogen, noble gases, water and C1-C4paraffin hydrocarbons. The content of hydrogen in the carbon monoxide and released in situ due to the reaction of conversion of water gas is preferably maintained at a low level, for example, at the level of the partial pressure less than 1 bar, as its presence can lead to the formation of hydrogenation products. Party is 7 bar, in these conditions, it was found that the use of manganese stabilizer in the reactor in accordance with the method of the present invention has a positive effect on the carbonylation reaction due to stabilization of the catalyst and to maintain the reaction rate.

Acceptable overpressure during the carbonylation reaction is between 10 to 200 bar, preferably between 10 and 100 bar, more preferably 15-50 bar. Acceptable temperature of the carbonylation reaction is 100-300oC, preferably 150-220oC, more preferably 170 to 200oC.

As the solvent for this reaction can be used carboxylic acid and/or its ester.

The method according to the present invention can be accomplished by periodic or continuous process, preferably a continuous process.

Carboxylic acid and/or ester as the product of the carbonylation can recover from a liquid reaction mixture, removing the liquid reaction mixture from the reactor and separating the carbonylation product by implementing one or more stages of a single equilibrium and/or fractional distillation from the other components of the liquid reactions the major reagents, you can return to the reactor to maintain their concentrations in the liquid reaction mixture. The carbonylation product can also be removed from the reactor in the form of steam.

In a preferred embodiment, the liquid reaction mixture containing the obtained carboxylic acid, rhodium catalyst, manganese stabilizer, alkylhalogenide, water, ester alkylating alcohol and unused reagents, away from the reactor and sent to the area of a single equilibrium distillation under a lower total pressure than the reactor for carbonylation, where with the addition of heat or without liquid reaction mixture formed steam and liquid fractions, and steam fraction obtained contains carboxylic acid, alkylhalogenide, water, unused reagents and ester, and the liquid fraction obtained contains carboxylic acid, rhodium catalyst, manganese stabilizer and water, together with certain amounts of alkylhalogenide and complex ester. This liquid fraction is returned to the reactor for carbonylation, and the resulting carboxylic acid is recovered from the steam fraction by implementing one or several stages of distillation, and alkylhalogenide, water, slo is carbon monoxide in the area of a single equilibrium distillation less than in the reactor for carbonylation, and is, for example, less than 0.25 bar.

Further, the invention is illustrated in more detail by the following examples without limiting its scope.

In the experiments described below, manganese was detected in the liquid reaction mixture at the end of the periodic process of carbonyl in a concentration of approximately 6 parts per million without adding manganese stabilizer, which is believed to be caused by corrosion. This corresponds to a molar ratio of manganese:rhodium (a lot less than 0.05):1. Thus, suppose that in the experiments described above is similar to the manganese content, which corresponds to a molar ratio of manganese:rhodium (a lot less than 0.05):1 can be expected without adding manganese stabilizer.

The following experiments were conducted using a 150-ml autoclave made of Hastelloy B2 (trademark) equipped with a Magnedrive stirrer (trade mark), a device for input of liquid and coil refrigerators. The gas in the autoclave was made of the capacity to compensate for changes in pressure, and the gas was applied in such a way as to maintain in the autoclave constant pressure. In particular mew, as expected, 1%) in the form of numerical values of moles of the spent reagent per liter of cold degassed mixture in the reactor per hour (mol/l/h) at a particular composition of the reaction mixture (reaction mixture in terms of the amount of cold degassed mixture).

During the reaction the concentration of acetate was calculated by the original composition, assuming that each mole of consumed carbon monoxide consumed one mole of acetate. Organic components in the free space of the autoclave above the liquid in the calculation was not accepted.

At the end of each experiment by gas chromatography was analyzed samples of liquid and gas from the autoclave.

For each experiment periodic carbonylation in the autoclave was loaded manganese stabilizer (when it was used), the liquid components of the liquid reaction mixture, excluding the part methylacetate and/or explicitating components, in which was dissolved rhodium catalyst.

The autoclave was twice purged with nitrogen and then heated with stirring (1000 rpm) to 185oC. Upon reaching temperature 185oC to create the required pressure autoclave, which was below the pressure at the end of reaccelerate. After stabilization system for about 30 min in an autoclave using excess pressure of carbon monoxide was introduced rhodium catalyst dissolved in methyl acetate and/or acetic acid. Feed as necessary gaseous carbon monoxide from the tank to compensate for changes in pressure using tool to enter the liquid in the autoclave was maintained practically constant excess pressure, and this pressure ranged from 27 to 28 bar. Then the initial partial pressure of carbon monoxide used in the experiment was calculated by subtraction of the final pressure in the reactor of the pressure that was measured when the input in an autoclave with nitrogen.

Once every 30 seconds and measured the absorption of gas from the tank to compensate for the pressure change and the data obtained used to calculate the rate of carbonylation. After stopping the absorption of carbon monoxide from the tank to compensate for changes in pressure or after 40 min of reaction (depending on what came before), the autoclave was disconnected from the source of gas supply. Subsequently, the autoclave was cooled to room temperature, the gases in the space of the autoclave above the liquid gently dropped out amaturely and analyzed for the content of liquid products and by-products.

To obtain reliable baseline can have a number of identical basic experiments in order to bring the autoclave to the desired conditions thus, in order to obtain consistent parameters. Period to bring the required conditions for different autoclaves often different and may depend on previous work carried out in them.

In the experiments and examples of periodic processes in the autoclave, the concentration of components in the reaction in the experiment were changed. For example, the concentration methylacetate derived methanol reagent with a decrease in the water content decreased. With increasing volume of the liquid reaction mixture due to the formation of carboxylic acid as product concentration methyliodide promoter decreased. The initial concentration of acetate (approximately 18 wt.%) was higher than that, as expected, can be used during a typical continuous process (in particular from about 0.1 to 5 wt.%), moreover, this concentration can be achieved in the experiment with periodic process upon completion of the conversion of acetate.

The contents of the autoclave, Edstaveni in table 1.

The results of the analysis of non-condensable gases discharged into the atmosphere upon completion of the experiments are shown in table 2. Analysis of the liquid reaction mixtures showed that in all cases, acetic acid is the main product (> 99%). All reactions were carried out at 185oC.

Experiment AND

The basic experiment was carried out at relatively high concentrations of water formed during the reaction of 17.1-11.7 wt.%. The initial partial pressure of carbon monoxide in a carbonylation reactor for amounted to 4.8 bar.

After 5 min the reaction rate calculated by the absorption of carbon monoxide was 3.6 mol/l/hour, the Reaction was stopped after from the tank to compensate for pressure changes were submitted 104 mmole of carbon monoxide. This is consistent with carbonyliron 43% methylacetate substrate. When opening the autoclave was detected obvious intense deposition of the catalyst.

This example is not consistent with the present invention, since the liquid reaction mixture was added manganese stabilizer. This experiment showed that in such conditions with a low partial pressure of carbon monoxide in the reactor DL is correctly stopped due to decontamination and/or instability of the rhodium catalyst in the reactor for carbonylation. The reaction rate was below that which can be expected (approximately 7.5-8 mol/l/h) in the same conditions, but without adding in an autoclave with nitrogen, i.e., at a partial pressure of carbon monoxide in excess of 7 bar.

The presence of a precipitate of the catalyst at the end of the experiment indicated that during the process in which the obtained carboxylic acid under reduced partial pressure of carbon monoxide is separated in the reaction mixture from the rhodium catalyst, the stability of the rhodium catalyst may be slow.

Experiment B

Another basic experiment was carried out at lower partial pressures of carbon monoxide than in experiment A.

After 5 min the reaction rate calculated by the absorption of carbon monoxide was 2.4 mol/l/hour, the Reaction was stopped after from the tank to compensate for pressure changes were submitted 56 mmol of carbon monoxide. This is consistent with carbonyliron 23% methylacetate substrate. When opening the autoclave, there has been a noticeable deposition of the catalyst.

This example is not consistent with the present invention, since the liquid reaction mixture is added emergenciesfacility catalyst during the separation of the obtained carboxylic acid from rhodium catalyst.

Example 1

Repeated the experiment B, except that the autoclave was also loaded 1.97 mmole Mn2(CO)10. After 5 min the rate of carbonylation according to calculations made 8.0 mol/l/hour, a Rate of absorption of carbon monoxide (mol/h) of capacity to compensate for changes in pressure were constant up until in the course of the reaction is not spent more than 90% of the acetate (based on the absorption of carbon monoxide). Moreover, when opening the autoclave at the end of the reaction the signs of deposition of the catalyst was absent.

This example corresponds to the present invention, because it showed that the addition of manganese stabilizer Mn2(CO)10in the mix for the carbonylation at low partial pressure of carbon monoxide increased the reaction rate of the carbonylation, and proved that this speed was maintained throughout the reaction, suggesting that the increased stability of the rhodium catalyst in the reactor. In addition, because the conditions in the experiment with periodic process in the autoclave was more stringent test of the stability of the catalyst than those that would normally be expected in the reaction mixture during the separation to the ora large), the lack of sediment showed that the presence of manganese stabilizer should stabilize the rhodium catalyst during the process, where in the reaction mixture of carboxylic acid is separated from the rhodium catalyst at a partial pressure of carbon monoxide less than in the reactor.

Example 2

Repeating example 1 except that the reaction was carried out at constant pressure 27,4 bar and the initial partial pressure of carbon monoxide of 4.7 bar. After 5 min the rate of carbonylation according to the calculations was 7.5 mol/l/hour, a Rate of absorption of carbon monoxide (mol/h) of capacity to compensate for changes in pressure were constant during the whole reaction (about the end of the experiment was tried by the absorption of carbon monoxide from the tank to compensate for pressure changes). When opening the autoclave at the end of the reaction there was also no evidence of deposition of the catalyst.

This example corresponds to the present invention, and additionally shows that the addition of manganese stabilizer Mn2(CO)10in the mixture for the reaction of carbonyl allows you to achieve the benefits of increasing the rate of carbonylation and stabilurobas acid from rhodium catalyst.

Experiment

The experiment was carried out at a lower concentration of water than in experiments a and B, formed during the reaction of 5.1-0.5 wt.%. The reaction was carried out at constant pressure 27,3 bar and the initial partial pressure of carbon monoxide of 4.3 bar.

After 5 min the calculated reaction rate was 0.9 mol/l/h on the basis of absorption of carbon monoxide. The reaction was stopped after the filing of the capacity to compensate for changes in pressure only 14 mmol of carbon monoxide. This is consistent with carbonyliron 6% methylacetate substrate. When opening the autoclave was found indications of abundant deposition of the catalyst.

This example is not consistent with the present invention, since the liquid reaction mixture was added manganese stabilizer. This experiment indicated low reaction rate, early termination of the reaction and the possibility of instability of the catalyst, when the water concentration in the liquid reaction mixture and the partial pressure of carbon monoxide was found to be low.

Experiment G

Repeated the experiment with the addition of lithium iodide (iodide as a stabilizer).

On istechenii same as in experiment C. the Reaction was stopped after the consumption of only 40 mmol of carbon monoxide. This is consistent with carbonyliron 16% methylacetate substrate. When opening the autoclave at the end of reaction indications of abundant deposition of the catalyst was absent.

This example is not consistent with the present invention, since the liquid reaction mixture was added manganese stabilizer. This experiment showed that although lithium iodide stabilized rhodium catalyst, preventing his deposition, he did not give the advantages of increasing the rate of carbonylation in conditions of low partial pressure of carbon monoxide.

Example 3

Repeated the experiment G except that instead of lithium iodide in the autoclave was added 2.00 mmole manganese stabilizer Mn2(CO)10. After 5 min, the calculated rate of carbonylation was 4.9 mol/l/h In the course of the reaction the rate of carbonylation gradually decreased, and the reaction, which was still going after 40 min stopped.

At the end of the experiment observed the formation of a certain amount of solid material, which, as I thought, was a rather margantsevorudny in experiments a and B.

This example corresponds to the present invention. He showed that the addition of manganese stabilizer Mn2(CO)10in the mix for the carbonylation at low partial pressure of carbon monoxide increased the rate of the carbonylation reaction.

As described above, no precipitate rhodium catalyst was also indicated that the presence of manganese stabilizer stabilizes the rhodium catalyst in a process in which carboxylic acid is separated from the rhodium catalyst at a partial pressure of carbon monoxide less than in the reactor.

Moreover, this example showed that at low partial pressure of carbon monoxide in equimolar concentrations of manganese exceeded LiI.

Experiment D

The basic experiment was carried out at a low concentration of water (comprised of 5.1-0.5 weight. %), as in experiment C. However, before the introduction of carbon monoxide into the autoclave nitrogen was not added, resulting in the partial pressure of carbon monoxide, although it is not expected that exceed 7 bar. After 5 min the rate of carbonylation was $ 6.9 mol/l/hour, a Rate of carbonylation in reaction time was not constant and gradually decreased until at Atara with decreasing concentration of water during the experiment.

This example is not consistent with the present invention, since the liquid reaction mixture was added manganese stabilizer.

Experiment E

Repeated the experiment D except that the reaction mixture was added 3,81 mmole of lithium iodide. In the course of the reaction the rate of carbonylation was not constant, but gradually decreased from the initial value of 6.8 mol/l/h, measured after 5 min before stopping the reaction after 40 minutes

This example is not consistent with the present invention, since the liquid reaction mixture was added manganese stabilizer. This experiment showed that the addition of lithium iodide (known stabilizer of the carbonylation catalyst in the liquid reaction mixture did not eliminate the disadvantage in reducing the rate of carbonylation (and, therefore, catalytic activity) during this experiment. After 5 min the reaction rate of carbonylation is also not increased.

Experiment W

Repeated the experiment D except that the autoclave was also loaded 1,95 mmole Mn2(CO)10.

The rate of carbonylation during providentiality 5 min, up until after 40 min the reaction was stopped.

This example is not consistent with the present invention, since the partial pressure of carbon monoxide exceed 7 bar. The experiment showed that under these conditions, the manganese was not accelerated the carbonylation reaction.

Additional experiments

The experiments were conducted in the same manner as in experiments A-F and examples 1-3, using a 300-ml autoclave made of Hastelloy B2 (trademark). Every 2 seconds (instead of every 30 seconds, as described above) measured the absorption of gas from the tank to compensate for the pressure change and the data obtained used to calculate the rate of carbonylation. The reaction was carried out at constant pressure within 26-28 bar.

The contents of the autoclave are shown below in table 3.

Experiment C

We conducted an experiment in which the liquid reaction mixture in the initial concentration of 10.4 weight. % contained lithium iodide. During the reaction the concentration of water in the liquid reaction mixture was 5.1-0.5 wt.%. This reaction was carried out at constant pressure 28,2 bar and when the initial partial pressure of carbon monoxide 5.5 bar.

The calculated reaction rate is compensation changes in pressure only 11 mmol of carbon monoxide.

This example is not consistent with the present invention, since the liquid reaction mixture was added manganese. This experiment showed that even when the content of lithium iodide in a high concentration at low partial pressure of carbon monoxide is achieved by a low reaction rate.

Experiment AND

Repeated the experiment C, except that before heating to 185oC in the autoclave was introduced hydrogen (1 bar). The reaction was carried out at constant initial pressure of 26.1 bar and the initial partial pressure of carbon monoxide of 5.3 bar.

When the measured water concentration of 4.5 wt.% the calculated reaction rate was 3.5 mol/l/hour, the Reaction was stopped after consumption of the capacity to compensate for changes in pressure 320 mmol of carbon monoxide.

Experiment And does not correspond to the present invention, however, it was shown that at low partial pressure of carbon monoxide hydrogen exerted on the reaction rate improve some limited impact.

Example 4

Repeated the experiment C with the addition 3,90 mmole Mn2(CO)10. Excessive pressure in the autoclave was 27 bar, and the initial partial on the odes of 4.5 wt.% the rate of carbonylation was 8.0 mol/l/h

Example 4 corresponds to the present invention. He showed that the addition of manganese stabilizer Mn2(CO)10increased the rate of carbonylation at low partial pressure of carbon monoxide in the presence of lithium iodide. In addition, he showed that by improving the action of this manganese stabilizer surpassed hydrogen (1 bar, measured under normal conditions) in respect of the acceleration of the carbonylation reaction.

Example 5

Example 5(a)

Repeating example 4, except that manganese stabilizer used 7,84 mmole MnI2. Excess pressure in the reactor was 28,5 bar and the partial pressure of carbon monoxide in the beginning rate of 6.0 bar.

The reaction rate measured at a concentration of water of 4.5 wt.%, was 2.0 mol/l/h

This experiment shows that manganese (II) the stabilizer has been found to be ineffective in speeding up the carbonylation reaction for the period of this reaction in the autoclave batch.

Example 5(b)

Repeating example 5(a) except that the autoclave before heating to the reaction temperature of the injected hydrogen (1 bar). Excessive dalla 5,1 bar.

The reaction rate measured at a concentration of water of 4.5 wt.%, was 4.2 mol/l/h

This example corresponds to the present invention, because it showed that hydrogen can be used to activate manganese (II) of the stabilizer at low partial pressure of carbon monoxide. Moreover, the reaction rate was higher than the rate that was observed in experiment I.

1. The way carbonylation alkylaromatics alcohol and/or its reactive derivative, comprising the stages of (I) introducing into contact in the reactor for the carbonylation of an alcohol and/or its reactive derivative with carbon monoxide in a liquid reaction mixture containing (a) a rhodium catalyst, (b) alkylhalogenide and (C) water at least in an organic concentration, and (II) the selection of the carbonylation product from a liquid reaction mixture, characterized in that what stages of carbonyl and/or selection of product partial pressure of carbon monoxide less than or equal to 7 bar and these stages is carried out in the presence of mn containing stabilizer for rhodium catalyst at a molar ratio of manganese : rhodium (0.2 to 20) : 1.

2. The method according to p. 1, in which the molar sootie for carbonylation of an alcohol and/or its reactive derivative with carbon monoxide in a liquid reaction mixture at a partial pressure of carbon monoxide in the reactor, less than or equal to 7 bar, in which this liquid reaction mixture contains (a) a rhodium catalyst, (b) alkylhalogenide, (C) water at least in a limited concentration and (d) a stabilizer for the rhodium catalyst containing manganese in the active to accelerate the reaction of the carbonyl form, with a molar ratio of manganese : rhodium (0.2 to 20) : 1.

4. The method according to p. 3, in which the manganese stabilizer contained in the liquid reaction mixture, using manganese (1).

5. The method according to p. 3 or 4, in which the liquid reaction mixture contains water in a concentration of less than 14 wt.%, preferably less than 11 wt.%, more preferably less than 8 wt.%.

6. The method according to any of paragraphs.3 to 5, in which the liquid reaction mixture additionally contains iodide as a stabilizer selected from the group including iodides of metals, Quaternary ammonium iodides and iodide of Quaternary phosphonium.

7. The method according to p. 6, in which the metal iodide as a stabilizer selected from the group including iodides of alkali metals and iodides of alkaline-earth metals, preferably from the group including iodides of lithium, sodium, potassium and cesium; the Quaternary ammonium iodide selected from the group Oh N N'-dimethylimidazolidin, and iodide of Quaternary phosphonium selected from the group including methyltriphenylphosphonium, tetrabutylphosphonium and methyltriphenylphosphonium.

8. The method according to any of paragraphs.3 to 7, in which the molar ratio of manganese : rhodium in the liquid reaction mixture is (0.5 to 10) : 1.

9. The method according to any of paragraphs.3 to 8, in which manganese stabilizer converted into active form by introducing into contact with hydrogen.

10. The method according to any of the preceding paragraphs which includes the introduction in the contact reactor for carbonylation of methanol and/or methyl acetate with carbon monoxide in a liquid reaction mixture at a partial pressure of carbon monoxide in the reactor, less than or equal to 7 bar, in which this liquid reaction mixture contains (a) a rhodium catalyst concentration in the liquid reaction mixture of 100 to 1500 weight. hours/million rhodium, (b) 2 to 16 wt.% methyliodide, (C) less than 8 wt.% water and (d) a stabilizer for the rhodium catalyst containing manganese in the active to accelerate the reaction of the carbonyl form, with a molar ratio of manganese stabilizer : rhodium catalyst (0.5 to 10) : 1.

11. The method according to p. 1, which includes stages (I) introducing into contact in recreacional mixture, containing (a) a rhodium catalyst, (b) alkylhalogenide and (C) water at least in a limited concentration; (II) selection of the carbonylation product from the reaction mixture at a partial pressure of carbon monoxide, less than or equal to 7 bar, in the presence of mn containing stabilizer for rhodium catalyst at a molar ratio of manganese : rhodium (0.2 to 20) : 1, and (III) return rhodium catalyst and manganese stabilizer from phase (II) phase carbonylation (I).

12. The method according to p. 11, in which the molar ratio of manganese : rhodium on stage (II) is (0.5 to 10) : 1.

13. The method according to p. 11 or 12, in which the partial pressure of carbon monoxide at stage (II) is less than 0.25 bar.

14. The method according to any of the preceding paragraphs, in which alkylaromatics alcohol represents methanol, and the product of the carbonylation is acetic acid.

 

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The invention relates to improvements in the carbonylation of methanol to acetic acid with a low content of water in the presence of registeruser catalyst component and an alkali metal for the removal of corrosion products metal

The invention relates to processes for acetic acid carbonyliron methanol, dimethyl ether or acetate

The invention relates to a method of purification of fraction2-C11carboxylic acids obtained by carbonyliron in the liquid phase WITH1-C10Olkiluoto alcohol and/or its reactive derivative, in which impurities volatile iridium and/or volatile copromotor turn into a non-volatile form in their interaction with iodide in the presence of carbon monoxide at its partial pressure lower than that of the carbonylation reaction

The invention relates to methods for extraction of carboxylic acids having from one to ten carbon atoms, and in particular, formic acid, acetic acid and mixtures of formic and acetic acids containing from their aqueous solutions

The invention relates to a method of obtaining a product in the liquid carbonylation reaction mixture, in particular relates to a method of regeneration of the carbonylation product from a liquid reaction mixture of the carbonyl process, containing a catalyst of the free or bound for iridium carbonylation

The invention relates to a method for producing acetic acid from ethylene and oxygen on single-stage catalytic reaction

The invention relates to a method for carbonylation of methanol or its reactive derivative in the presence of a halide promoter and a catalyst system comprising rhodium component and bicentenary phosphorus-sulphur ligand

The invention relates to the production of carboxylic acids (C2- C11or the corresponding esters by the interaction of carbon monoxide with at least one reagent selected among alcohols, alkylhalogenide, simple or complex esters, in the presence of a catalytic system comprising at least one rhodium compound and at least one iridium compound or at least one compound containing both metal and at least one halogenated promoter
The invention relates to an industrial method of production of furfural and acetic acid from pentasaccharide raw materials, such as hardwood, treatment with superheated steam at a pressure of 0.7 to 1.4 MPa and a temperature of 200 - 250C in the presence as catalyst of a solution of salt or mixture of salts that form when dissociation of the cations with a charge of not less than two, with the degree of saturation of 20 - 90% up to 15% by weight of dry raw materials

The invention relates to processes for acetic acid carbonyliron methanol, dimethyl ether or acetate

The invention relates to a method for producing carboxylic acids by carbonyliron C1-C10saturated mono - or diatomic alcohol or its derivative selected from the group of halide derivative, simple and/or complex ester with carbon monoxide in the presence of a catalyst based on rhodium

The invention relates to a method for carbonylation of methanol or its reactive derivative in the presence of a halide promoter and a catalyst system comprising rhodium component and bicentenary phosphorus-sulphur ligand

The invention relates to the production of carboxylic acids (C2- C11or the corresponding esters by the interaction of carbon monoxide with at least one reagent selected among alcohols, alkylhalogenide, simple or complex esters, in the presence of a catalytic system comprising at least one rhodium compound and at least one iridium compound or at least one compound containing both metal and at least one halogenated promoter

The invention relates to the field of technologies for industrial organic synthesis, in particular, to methods for producing methylformate
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