Continuous production of acetic acid and\or methylacetate

FIELD: chemical technology.

SUBSTANCE: invention relates to continuous method for production of acetic acid and/or methyl acetate based on known process of methanol or derivatives thereof (such as dimethyl ether, halogenated methyl or methyl acetate) carbonylation. Process is carried out in homogenous liquid phase under carbon monoxide pressure in presence of catalytic system containing rhodium-based homogeneous catalyst and halogenated promoter, in presence of water in reaction medium and in amount of not less than 14 mass %. In continuous process homogeneous catalyst composition is gradually changed by continuous or discontinuous addition of any iridium compound. Catalyst composition is transformed without process shutdown by transition from rhodium-based catalyst to rhodium/iridium-based catalyst or iridium-based catalyst. Iridium addition makes it possible to decrease water content in reaction system.

EFFECT: modified industrial process of methanol carbonylation by transformation of catalytic system.

19 cl, 7 tbl

 

The technical FIELD

The present invention relates to the field of industrial production of acetic acid and/or methyl acetate.

More specifically it refers to the method of continuous production of acetic acid and/or acetate, which is extremely soft and regularly changes the composition of the catalytic system, which allows on an industrial scale to move from catalytic systems on the basis of pure rhodium to a catalytic system based on rhodium and iridium, and even on the basis of pure iridium. This eliminates the need to stop industrial unit to perform the replacement of the catalyst.

PRIOR art

Known for numerous industrial methods of production of acetic acid and/or methyl acetate in the liquid phase under pressure with use of a homogeneous catalytic system.

The present invention relates in particular to the modification of production methods, with which the initial carbonylation of methanol or any derivative of methanol that can be carbonyliron, in the presence of a catalyst based on rhodium.

Patents Paulik, etc. that underlie the so-called technology or method Monsanto (Monsanto), describe the carbonylation reagent in liquid or gaseous AZE through homogeneous or heterogeneous catalysis, respectively, rhodium (U.S. Patent No. 3769329) or iridium (U.S. Patent No. 3772380). With this technology, the reagents are alcohols ROH, ethers, R'-O-R', esters R C(O)OR' and halides R-X, in which the total number of carbon atoms less than or equal to 20. The carbonylation reaction is conducted in the presence of one of these reagents, carbon monoxide (partial pressure between 1 and 15,000 pounds per square inch), catalyst system comprising rhodium or iridium, in the presence of a halogenated promoter and water at a temperature of from 50°to 300°C.

The first were developed ways carbonylation catalyzed coupling of rhodium in the presence of methyl halide as co-catalyst, predominantly methyl iodide. These methods systematically improved to increase the reaction rate (and hence the performance of the process), reduce the formation of impurities, increasing the stability of the catalyst in solution, and also to reduce production costs.

In particular, reducing the water content became possible to achieve by adding to the reaction environment of significant quantities of iodine ions (more than 0.3 mol/l, French patent No. 2551434) and/or by maintaining a preselected concentration of the components of the reaction medium (EP 0161874 and EP 0250189).

Studies conducted in the past is it time to replace the rhodium iridium, find the output of new production processes, the so-called low water content, catalyzed only iridium (EP 0618184, EP 0616997, EP 0786447) or iridium mixed with jointly entered accelerators catalysis, mainly ruthenium, osmium or rhenium (EP 0643034, EP 0728729, EP 0752406).

Usually these various ways carbonylation in the liquid phase with homogeneous catalysis is carried out in the installation, which includes three different zones. In the first zone, called the reaction zone, under pressure and with the simultaneous introduction of both reagents is the carbonylation reaction with carbon monoxide, methanol, or any derivative of methanol that can be carbonyliron. In the reaction medium is maintained given structure by summing both of these reagents and recycling streams withdrawn from the second and third zones. In the second zone, called the evaporation zone or area of the boil, the reaction medium is partially evaporates at a lower pressure than in the first reaction zone; the dilution is carried out with the announcement of heat or without. Evaporative fraction, mainly consisting of unreacted reagents, water, methyl iodide, methyl acetate and acetic acid, is directed in a third zone, zone of separation by distillation and purification formed is camping products: acetic acid and/or methyl acetate. Not evaporated fraction coming from the zone of boiling (No. 2), mainly consisting of acetic acid and the catalyst is reused in the reaction zone (No. 1). The third zone, usually consisting of three distillation columns, allows you to separate different components, reuse the ones that are required for the implementation of the reaction, and producing acetic acid and/or methyl acetate in purified form. In addition, the installation according to the specified methods include the treatment zone gases and/or exhaust pipe. For more information you can refer to the article: .J.Howard et al. - Catalysis today, Vol.18 (1993), str-354.

Most recently described methods carbonylation using catalytic systems consisting of both rhodium and iridium.

Patent EP 0618183 dedicated to carbonyliron alcohols or their derivatives, demonstrates energycost catalytic system composed simultaneously of rhodium and iridium with respect to catalytic systems consisting of a single metal, rhodium or iridium. This method is carried out in the presence of low concentrations of stabilizer catalysts, such as soluble iodide salts (from 0 to 5%, preferably from 0 to 2%), and even in the absence of such compounds.

Soluble iodide salts are the alkaline iodides, alkaline is Zemelny metals and Quaternary iodides of ammonium or phosphonium.

French patent 2750984 describes a method of improving completeness of the use of carbon monoxide through the introduction of the second carbonylation reactor located between the first area (main reactor) and the second zone - the zone of evaporation (boiling); catalytic system consists of iridium, if necessary in combination with rhodium.

French patent 2750985 relates to the carbonylation of methanol and offers a way to stabilize the catalytic system composed of soluble complexes of iridium and rhodium, which is to maintain the water concentration above 0.5% in the liquid fraction, not evaporated in the second zone - the zone of evaporation (boiling), which is reused in the first zone to the reaction zone.

In the published international application WO 00/27785 demonstrated energycost catalytic system composed of iridium and platinum, and in the case of rhodium with respect to catalytic systems composed of only one metal. This application includes maintaining the molar ratio between the insertion soluble iodide salts and iridium in value less than 10.

International publication WO 00/78700 for the production of acetic acid by reaction of isomerization of methylformate and at the same time carbonylation of methanol in the presence of iridium and if necessary the spine of rhodium. In this proposal it is proposed to stabilize the catalytic system by maintaining the concentration of formyl radical (mailformat + formic acid) over 1% in neizprotamas fraction from the second zone (zone of evaporation). It is also proposed to maintain in this environment, iodides in soluble ionic form, without specifying their areas of concentration.

International publication WO 00/24701 describes the carbonylation of methanol using a catalyst system composed of both rhodium and iridium in the presence of iodine ions as stabilizers/ co-injected accelerators catalysis (co-initiators of these catalysts. The composition of the reaction medium is kept constant: water <14% (preferably from 0.1% to 8%); methyl iodide from 5% to 30%; methyl acetate from 0.5% to 30%; iodide salts from 2% to 20% (preferably lithium iodide); catalysts from 100 to 5000 ppm (ppm, ppm) for each metal; in addition, the catalytic system can include a salt of a transition metal, preferably ruthenium.

The above-mentioned patents and patent applications describe the reaction medium for the carbonylation based catalytic systems composed of both rhodium and iridium, the contents of which are optimized to achieve the results desired in these inventions. None of these documents the clients does not specify or recommend conversion from catalytic system, consisting only of rhodium, a catalytic system based on a mixture of catalysts rhodium + iridium.

In addition, it is known that if such a change is necessary to take into account the role of metals corrosion, usually and constantly present in the reaction media carbonylation (iron, Nickel, chromium, molybdenum, tungsten, zirconium, and any other metal that participates in the corrosion of industrial equipment; these metals can be recycled in the reactor in the process). Basically, as described in particular in French patent No. 2551434, they are considered extremely harmful for catalysis to clean radii, because they accelerate the reaction of conversion or reaction gas in water (abbreviated also denoted WGSR-Water Gas Shift Reaction - shift reaction the water - gas):

H2O+WITH→H2+CO2

Touching all the same catalysis on the net radii, more specialized patent EP 0384652 provides for the removal of iron and Nickel, leaving only the metal side of the sixth subgroup of the group (Mo, W, Cr)that have a positive effect on the rate of carbonylation, and hence on the performance of the process. One option is to add these metals corrosion side of the sixth subgroup of the group in the reaction environment for carbonylation.

On the contrary, when the catalysis of pure iridium p is oblama metals corrosion is more simple: it is necessary to limit their concentration in the reaction medium a few hundred (ppm) (French patent 2750984), even the size of below 200 ppm (publications of international applications WO 00/27785 and WO 00/78700) order limitations:

on the one hand, the reaction gas in the water, as in the case of rhodium;

on the other hand, the concentration of iodine ions, regarded as a catalytic poison for the carbonylation reaction, catalyzed by iridium. Indeed, iodine ions, having different origins, partly derived from the sphere of reaction in salt, which are the iodides of metals corrosion. In French Patent No. 2750984 and the application WO 00/27785 serves to maintain the molar ratio of iodine ions, and iridium at a value lower than 10.

As is evident from the above, simultaneously taking into account different depending on the catalytic system impact as the concentration of metals corrosion and ion concentration of iodine in various ways continuous production of acetic acid by carbonylation of methanol or any of its derivatives that can be carbonyliron, the only solution that was considered by the experts to this day if necessary to replace the catalyst and to move from a catalytic systems on the basis of rhodium to a catalytic system based on rhodium, significantly enriched in iridium, or only iridium, was to stop the installation to change reacciona the environment such in particular, to adjust the concentration of metals corrosion and iodides to values that would not violate the normal functioning of the process when a new catalytic system.

At the same time, contrary to every expectation, the authors present invention has now shown that it is possible, without stopping production, to change the composition of the catalyst, adding in regular and increasing the amount of the catalyst based on iridium to the reaction medium, in which the carbonyl is initially catalyzed by a catalyst based on rhodium and has a classical structure, known in accordance with the technology of Monsanto, that is, in a reaction medium containing at least 14% water, not more than 15% iodine, 2% methyl acetate and several hundred ppm of rhodium, the presence of several thousand ppm of metal corrosion, the rest of acetic acid.

Thus, the present invention proposes to modify (modify) the catalytic system in the traditional industrial method of production of acetic acid, the so-called method Monsanto, using as catalyst rhodium, by replacing at least a partial rhodium iridium, and modification of the catalytic system is:

without stop about the ECCA to implement the replacement of the catalytic system, based only on radii, rhodium + iridium;

without deep changes in the composition of the reaction medium, in particular the content naturally present of iodine ions and metal corrosion;

- without distorting the stability of the catalytic system;

- while maintaining and even increasing the rate of carbonylation, and hence the performance of the process;

- while reducing production costs by reducing the water content in the reaction medium, which saves energy during distillation.

Other advantages will be revealed more clearly when reading the following detailed description.

The INVENTION

It turned out in particular that the modification of the catalytic system can be made extremely gentle way and without stopping the production process, which represents a first advantage of the economic order, as it allows to avoid a full stop of the production process with the aim of replacing the reaction medium. Moreover, in the course of such modification of the catalytic system by enriching its iridium was possible to significantly lower the water content, which represents a second advantage of the economic order, which differs method according to the present invention, in Addition, this change of water content in the reaction medium allows to consider on an industrial scale question on the implementation simultaneously with the original carbonyliron isomerization reactions of methylformate, which also leads to the formation of acetic acid and/or methyl acetate; you can even limit the production of acetic acid and/or methyl acetate exclusively in the production, based on the reaction of isomerization of methylformate, and all these changes can be made without stopping the production process, which is a significant economic benefits.

Thus, the present invention, according to one of its essential characteristics relates to a method of continuous production of acetic acid and/or methyl acetate, characterized in that on the basis of a continuous production process, called the source, carbonylation of methanol or any derivative of methanol that can be carbonyliron, such as dimethyl ether, methyl halides or methyl acetate, in a homogeneous liquid phase under pressure of carbon monoxide in the presence of a catalytic system comprising a homogeneous catalyst based on rhodium and halogenated promoter and in the presence in the reaction medium of water at a concentration of greater than or equal to 14%, process cont the continuing work of the production installation is a gradual transformation of the composition specified homogeneous catalyst through a series of successive additions of compounds of iridium.

Thus, the method according to the present invention consists in a consistent, gradual change of the composition of the catalytic system, based on manufacturing process, called the source, which is derived from the way Monsanto, i.e. the way in which acetic acid and/or methyl acetate are produced in a continuous process by carbonylation of methanol or any derivative of methanol that can be carbonyliron, in the liquid phase under pressure in the presence of a homogeneous catalyst containing rhodium.

The method according to the present invention includes one significant step, hereinafter referred to as phase transformation, in which the catalytic system is converted by adding compounds based on iridium without stopping production, i.e. without stopping the industrial installation, bypassing the need to empty the last, bypassing the need to rinse, to clean it or to process any way to implement the replacement of the catalytic system.

As mentioned previously, the method according to the invention has application to any of the original method, derived from the way Monsanto initially functioning using a catalytic system comprising homogenisation based on rhodium and homogeneous promoter, which, in particular, may represent methyl iodide.

This original system, like any system type Monsanto operates with the reaction medium, the water content of which is greater than or equal to 14%.

Phase transformations in the method according to the present invention can be distributed in time, and the timing of that distribution can be different, depending on the destination, the desired catalytic system, and on average can range from several months to approximately 5 years.

Completion of phase transformations in the method according to the present invention allows to move from a system catalyzed only by rhodium to the system, catalyzed by homogeneous catalyst based on a mixture of rhodium from iridium and even one-catalyzed only iridium.

Completion of phase transformations according to the present method can be easily determined by the expert as estimated by the analyses, such as those described in the section "Description of embodiments of the invention" of this document, and the results obtained during phase transformation and improvement in both productivity and kinetics of the production process of acetic acid and/or methyl acetate.

Thus, after the phase transformation can directly continue the continuous production of UKS the red acid and/or acetate, maintaining the composition of the catalytic system as it was at the end of phase transformation. This new phase will be referred to as the stabilization phase.

In this phase, which follows the phase of transformation, the concentration of rhodium and iridium in the reaction environment is supported as usual in this field, by adding compounds of rhodium and/or iridium compounds to compensate for the loss of catalyst during the processes occurring during continuous production, in particular loss, possibly caused by the entrainment of the catalyst, which is hard to avoid, despite the different types of recycling carried out during the production process.

Usually in the process of carbonylation catalyzed only by rhodium or iridium), the catalytic activity in the reaction zone is maintained and regulated by a more or less frequent addition of rhodium (or iridium). This addition is intended, in particular, to maintain the same level of concentration of active catalyst in the reaction medium by means of replacement catalyst losses resulting drop it in the sediment (inactive catalyst) or as a result of his Hobbies bubbles of vapor during evaporation and distillation, which is carried out in zones of boiling and PE is Agency/cleanup.

In the case of the present invention, any addition of compounds of iridium during the phase transformation can be carried out in various ways, in particular it can be made a regular or irregular manner, continuously or in individual portions, but in any case, without stopping production.

According to one of embodiments of the present invention, the addition is carried out as a pre-dissolved (solubilizing) iridium, in particular in the form of iridium, dissolved (solubilizing) in any solution that is compatible with the reaction medium. This option has the advantage that it can be easily implemented in production. The solution can be prepared from solid compounds commonly used in the processes catalyzed by iridium (metal, oxide or hydroxide complex salt and the like) Such solubilization (dissolution) can be produced in all possible ways, known in the art, in accordance with the process conditions, in particular using the methods described in patents EP 0657386 and EP 0737103 that offer ways of preparation of catalytic solutions, which directly can be entered and used in carbonylation reactions.

Generally preferred are the methods of translation of iridium in a soluble state,compatible with industrial installations, used in the normal way carbonylation to translate rhodium in a soluble state.

In accordance with another variant, the connection iridium can be introduced in the form of a solid derivative of iridium, which is dissolved directly in the reaction medium (in situ).

In this case, the derived iridium is introduced directly into the reactor, and dissolution, as well as the synthesis of catalytically active units are carried out in a reaction medium in the presence of halogenated promoter, in particular methyl iodide, and under pressure of carbon monoxide.

In any case, the result is the carbonylation reaction, catalyzed by a mixture of rhodium and iridium, which concentrations in the reaction medium at any time can be adjusted by adding a rhodium or iridium, or both of them together.

Thus, as shown previously, the introduction of the iridium compounds in the reaction environment can be implemented in various physical forms.

It can also be implemented in various ways.

In accordance with the first variant, more or less frequent adding rhodium produced in the original process, can easily be replaced by appropriate addition of iridium in the continuation phase transformation.

Thus, according to this variant, the addition of compounds of iridium is t is to, in order to compensate the loss of rhodium by replacing the lost rhodium iridium.

In accordance with another variant, the addition of compounds of iridium is continuous.

In accordance with another variant, the addition of iridium is discrete.

As shown previously, in all cases, the approximate analysis and control as reaction kinetics, and system performance will allow us to determine the completion of phase transformations and phase stabilization of the catalytic system at a certain molar ratio Ir/Rh.

In various embodiments, the introduction of compounds of iridium, once reached the desired proportions in the catalytic system, it is possible to maintain or regulate the concentration of rhodium and iridium in the reaction medium by adding compounds of rhodium and/or iridium.

According to one variant of the invention has special advantages, if necessary adding and rhodium and iridium for maintaining and/or adjusting the concentration of rhodium and iridium in the reaction medium is produced by the simultaneous introduction of both of these catalytic metals in the form of a previously prepared solution containing them. This technique has many advantages and, in particular, the advantage that it leads to simplification of the process the operations and reduce costs, because it avoids the separate production of both catalytic solutions and separate their introduction into the reaction medium, allowing the introduction at the same time and rhodium and iridium.

The catalytic solution can be prepared by any method that allows the simultaneous addition of rhodium and iridium in the form of the catalyst solution in which the dissolution of rhodium and iridium carried out jointly and simultaneously, based on the compounds of rhodium and iridium.

Of the examples cited by the authors of the present invention, it follows that the simultaneous dissolution of rhodium and iridium, in particular in the form of rhodium iodide and iodine iridium, can be carried out under normal conditions, such as those spelled out in the way Monsanto only for rhodium iodide.

In General, in phase transformations and phase stabilization of the catalytic system in the reaction medium mainly supported molar concentration of rhodium is between 0.1 and 50 mmol/l, and the molar concentration of iridium is between 0.1 and 25 mmol/L.

In addition, the atomic ratio of iridium/rhodium mainly supported is between 1/99 and 99/1.

It is also possible, as shown earlier, continue adding compounds of iridium in the phase transformation down to the state, when iridium will be the only metal in homogeneous cat the political system.

The method according to the present invention in particular relates to a process for continuous production of acetic acid and/or methyl acetate, carried out at the facility, which includes a reaction zone (zone I), where the value of the maintained temperature is in the range between 150°, 250°and the total pressure is in the range between 5·105PA and 200·105PA; zone boil (zone II), in which the products leaving the reaction zone (zone I), partially evaporated at a pressure lower than the pressure in zone I (the reaction zone); while not evaporated fraction at the outlet of zone II zone boil) recycle to zone I (the reaction zone), and evaporated fraction is cleared in zone III zone separation by distillation and purification of the formed acetic acid and/or methyl acetate.

Introduction to the field reaction of compounds of iridium in whatever physical form may be effected in various ways, as shown previously, but also in different parts of the production plant, such as those described above, for example in three main areas.

According to one variant, the compounds of iridium in solid form or in solution can be introduced directly into the reaction medium zone I (the reaction zone) or not evaporated fraction from zone II zone boil), or calreticulin this not evaporated fraction from zone II to zone I, the latter option is preferred.

Thus, the compounds of iridium can be entered either directly in the reaction medium zone I or in the recirculation flow from zones II or III in the direction of zone I (the reaction zone).

As shown previously, there is no need (except by common practice) to remove metals corrosion for the implementation of additives iridium.

Technical conditions to normal process determines that the content of metal corrosion in the reaction medium should not exceed 5000 mg/kg (ppm, ppm, ppm).

This condition can be saved and the addition of iridium, and consequently, for the process of carbonylation in the continuation phase transformation, as well as in the continuation phase of stabilization.

Maintaining this concentration of metals corrosion in a value less than or equal to 5000 mg/kg may be carried out all the usual methods known in the art and are already widely used in catalytic processes on the basis of rhodium or only iridium:

- selective precipitation,

liquid-liquid extraction,

treatment ion exchange resins,

- osmosis,

processing through a selective membrane, etc.

As has been shown earlier, except technical and practical importance, the present is invention is accompanied by savings and cost reduction in comparison with the classical method, who is to stop production in order emptying installation, removal of the reaction medium on the basis of rhodium and replace it with another reactionary environment based on a pair of rhodium + iridium or only iridia.

This allows you to avoid production losses during shutdown of the plant, losses or difficulties associated with the replacement of rhodium, difficulty in restarting the installation related to the fact that the specifics of a new installation, functioning on a mixed catalyst system based on iridium and rhodium, differs from the specifics of the old installation, which worked only on radii.

As shown previously, another advantage of the present invention, of particular interest is the fact that it allows to reduce the water content of the reaction medium below the normal values, constituting 14% relative to the weight of the reaction medium, as merely adding iridium.

This water content can be reduced down to values below 5% without distortion performance of the carbonyl process catalyzed by a mixture of rhodium + iridium, which is an additional benefit.

In fact, specialists are well aware that the rate of carbonylation increases with increasing water content in the usual reaction medium catalyzed only by rhodium. Speed carbon is the stimulation reaches a maximum value at the concentration of water is about 14%-15% (10 mmol/l), as described in the patent EP 0055618 and publishing HJORTKJAER, JENSEN, - Ind. Eng. Chem. Prod. Res. Dev, 1977, volume 16, No. 4, str-285 and remains constant even when the water content over 14%-15%. Thanks to the present invention is able to reduce the water content in the case of catalytic systems on the basis of rhodium from iridium, while maintaining the same speed, carbonylation, which is achieved with rhodium-plated with 14% of the water can significantly reduce energy costs for the removal of water in zone III zone separation /distillation/ purification of produced acetic acid and/or methyl acetate.

An additional advantage derived from the ability to reduce the water content in the reaction medium and, in particular, of the opportunities to lower it to below 5 wt.% in relation to the weight of this reaction medium, is that all of this is to allow for more production of acetic acid and/or methyl acetate in the course of simultaneously occurring reactions of isomerization of methylformate under pressure of carbon monoxide, in addition to carbonyliron methanol. This allows, in particular, to increase the production of acetic acid in an existing installation without the need for carbon monoxide, and a significant saving of energy during the stages of distillation.

Thus, once the value of the concentration in the water in the reaction medium falls below the value less than or equal to 5 wt.% in relation to the weight of the reaction medium, you can easily enter methylformate in the reaction medium and to carry out simultaneously the carbonylation reaction of methanol or its derivative that can be carbonyliron, and isomerization of methylformate under pressure of carbon monoxide, as it follows from the published international patent application WO 97/35828.

In these circumstances it is also possible to gradually stop the introduction into the reaction medium of methanol or derived methanol, giving in to carbonyliron, in order to access the system, functioning only on the isomerization of methylformate under pressure of carbon monoxide (as it follows from the published international patent application WO 97/3582).

Finally, it was found that if the catalytic system, originally based on radii, modified according to the present invention, that is extremely mild conditions converted in a catalytic system based on a mixture of rhodium from iridium and even in a catalytic system consisting entirely of iridium, it is possible to further convert this catalytic system aimed at the gradual introduction of platinum compounds so that a gradual transition to the production process of acetic acid and/or methyl acetate in the presence of a homogeneous catalyst, sostavlennoj the iridium and platinum in proportions allows you to receive the benefits described in the patent application WO 00/27785. In this case, the concentration of platinum is preferably supported in a value between 1 and 25 mmol per liter of reaction medium.

DESCRIPTION of embodiments of the INVENTION

Were carried out series of tests artificial solutions (recreated reaction medium carbonylation) and industrial real reaction medium carbonylation (50-ml samples taken directly from the carbonylation reactor, from zone I (the reaction zone)), identical within each series, except for the composition of the catalytic system and/or the concentration of metals corrosion and/or concentration of the water.

Unless otherwise stated, amounts of catalyst (Rh or Ir) is denoted by [Rh] or [Ir] and expressed in mmol (mmol).

The results of these various series of tests are presented for each test in the form of speed carbonyl calculated as consumption, measured after 10 minutes of reaction (Vcarb 10'), corresponding to the number of educated acetyl radicals (acetic acid + methyl acetate). Vcarb expressed in moles per liter of the final reaction medium per hour = mol/(l·h).

The stability of the catalytic system was evaluated by monitoring the final reaction mass after cooling to ambient temperature the ment environment and degassing to atmospheric pressure - on the subject of the presence or absence of metal deposits or metal mobiles.

1. TYPICAL operating MODES

1.1 operating mode for artificial solutions

- Preparation of the catalyst solution:

In the autoclave of 100 ml Hastelloy® B2 is introduced rhodium iodide, iodine iridium, metal corrosion, 9 g of pure acetic acid and 3 g of water. The autoclave is set to an absolute pressure of 5 bar (5·105PA) at ambient temperature. The temperature rises to 190°, which requires about 1 hour, and the environment is maintained in the course of 10 minutes at 190°when samostanowienia pressure (10 bar, which corresponds to 10·105PA).

The carbonylation reaction (carried out directly after this).

With the tank placed under the autoclave, under pressure FROM the injected mixture consisting of water, methyl iodide, methyl acetate, acetic acid and methanol. The composition of the reaction medium without methanol is as follows: water 14%, methyl iodide (9%), acetate 2%, rhodium, iridium, metal corrosion in accordance with the requirements of the experiment, acetic acid up to 100%. Weight of artificial reaction medium without methanol is approximately 56-57 g, and methanol is added 10% of this mass, which is 5.6,

The temperature rises again up to 190°and the reactions the carbonylation is carried out at an absolute pressure of 30 bar (30· 105PA), established by injection WITH at 190±0,5°in the course of 10 minutes. Then the autoclave is cooled, emptied and set the presence or absence of metal deposits.

- The presentation of data in tables.

The concentration of catalysts, rhodium and iridium, expressed in mmol of the corresponding metal in the reaction medium of this experience.

Metals corrosion [MétCor] are introduced in the form of a metal iodide or metal carbonyl; total concentration is expressed in mg/kg (ppm) relative to the weight of the reaction medium without methanol (56-57 g). Mass fraction of metals corrosion is as follows:

iron 20%, Nickel 30%, chromium 20%, molybdenum 30%.

1.2 operating mode for the industrial reaction medium

- Preparation of the reaction medium carbonylation

Samples of 50 ml was taken in a sealed vials through analytical intake industrial reactor carbonylation of methanol catalysis only on radii and kept in a dark place at ambient temperature. Analytical intake is located on the piping connecting the reactor zone I - vaporizer - zone II - about the reactor; the sampling was carried out tightly through a system DOPAK®. 50 ml of the reaction medium was introduced into the autoclave 100 ml Hastelloy® B2 (this was approximately 56-57 g).

Industrial reaction medium who meet the following composition: water 14%, iodine bromide 9%acetate 2%, rhodium 600 mg/kg, metal corrosion (naturally present in industrial reaction medium as a result of corrosion of the materials from which is comprised of industrial equipment) 5000 mg/kg (iron 1000, Nickel 1500, chromium 1000, molybdenum 1500 mg/kg), acetic acid up to 100%. Depending on the tests is injected iodine iridium.

The autoclave was closed and it establishes an absolute pressure of 5 bar (5·105PA)at ambient temperature.

The mixture is heated to 190°when samostanowienia pressure (10 bar, which corresponds to 10·105PA), which requires approximately 1 hour, and maintained in the course of 10 minutes at 190°C. Then, using pressurised tank WITH added approximately 5.6 g of methanol (representing approximately 10% by weight of the reaction mixture). The mixture is heated to 190°and the carbonylation reaction is carried out at an absolute pressure of 30 bar (30·105PA), established by injection, at 190±0,5°in the course of 10 minutes. The autoclave is cooled, emptied, and then set the presence or absence of metal deposits.

The presentation of data in tables (see above 1.1).

2. EXPERIMENTS WITH ARTIFICIAL SOLUTIONS

2.1 Zero concentration of metals corros and

These studies were carried out using standard operating mode, presented in §1.1.

These studies, carried out in the absence of metals corrosion ([MétCor] = 0), should be regarded as comparative experiments designed to serve as a point of reference in the following experiments, where [MétCor]>0. Nevertheless, these experiments show the effect of increasing additives iridium from 0 to 0.8 mmol at a constant concentration of rhodium, equal to 0.33-0.34 mmol. Speed carbonyl constant when the molar ratio of Rh/Ir from 100/0 to 70/30 and component 5-6 mol/l·hour, then increases to 7.5 and 10 mol/l·the hour when the molar ratio of Rh/Ir, equal 50/50 and 30/70.

Experiments in the presence of a mixture of rhodium from iridium show very good stability of the catalytic system is the absence of metal deposits, in contrast to the tests carried out only with rhodium.

Conditions and results are summarized in table 1, are presented in the end of the description.

2.2 Concentration of metals corrosion from 0 to 4000 mg/kg

These studies are carried out in accordance with standard operating mode, presented in 1.1.

For each molar ratio of rhodium to iridium between 100/0 and 30/70 concentration of metals corrosion was studied in the range from 0 to 4000 mg/kg

The set of conditions and results of the studies is presented in table 2, at the end of this description.

All research conducted at zero concentration of metals corrosion, conducted for comparison.

2.2.1 Research at a constant concentration of rhodium and variable concentrations of iridium

- The molar ratio of Rh/Ir=100/0; [Rh]=0,33-0.34 mmol, [Ir]=0.

Comparative studies outside the scope of the invention, since the concentration of iridium is equal to zero, is given for a sample.

- The molar ratio of Rh/Ir=90/10; [Rh]=0,33-0.34 mmol; [Ir]≃0.04 mmol.

- The molar ratio of Rh/Ir=80/20; [Rh]=0,33 -0,34 mmol; [Ir]≃0,08-0,09 mmol.

- The molar ratio of Rh/Ir=70/30; [Rh]=0,33 -0,34 mmol; [Ir]≃0.14 mmol.

- The molar ratio of Rh/Ir=50/50; [Rh]=0,33 -0,34 mmol; [Ir]≃0.33 mmol.

- The molar ratio of Rh/Ir=30/70; [Rh]=0,33 -0,34 mmol; [Ir]≃0.8 mmol.

From all these studies we can conclude the following:

1) For the molar ratio of Rh/Ir between 90/10 and 50/50 (exclusively) the rate of carbonylation system Rh+Ir is saved in comparison with the reaction rate for the system only with rhodium (Rh/Ir=100/0), whatever the concentrations of metals corrosion in the range of 0 to 4000 mg/kg (5 to 6 mol/l·h).

2) For the molar ratio of Rh/Ir from 50/50 to 30/70 speed carbonylation system Rh+Ir decreases with increase in the concentration of metals corrosion from 0 to 4000 mg/kg (Rh/Ir=50/50 from 7.5 to 5.5 mol/l·h, and Rh/Ir=30/70 - from 10 to mol/l· hours).

3) the stability of the catalytic system:

In studies, only with rhodium metal deposits are present, but at concentrations of metals corrosion 4000 mg/kg

In all other studies, in the presence of a mixture of rhodium from iridium metal deposits are absent, whatever the concentration of metals corrosion.

2.2.2 Studies with [Rh]+[Ir]=const=0.33-0.34 mmol

- The molar ratio of Rh/Ir=100/0; [Rh]=0,33-0.34 mmol; it is also a control series of studies conducted for comparison as the [Ir]=0.

- The molar ratio of Rh/Ir=70/30; [Rh]≃0.23 mmol; [Ir]≃0.11 mmol.

- The molar ratio of Rh/Ir=50/50; [Rh]≃0,165 mmol; [Ir]≃0,166 mmol.

- The molar ratio of Rh/Ir=30/70; [Rh]≃0.10 mmol; [Ir]≃0.23 mmol.

It can be argued that:

1) For the molar ratio of Rh/Ir between 70/30 and 50/50 (inclusive) rate of carbonylation in the system Rh+Ir only slightly changed or not changed even when the concentration of metals corrosion from 0 to 4000 mg/kg (or at least not more than in control Rh/Ir=100/0).

This slight loss in speed of the carbonylation reaction, when the concentration of metals corrosion goes from 0 to 4000 mg/kg, estimated at 5% for Rh/Ir=100/0, 12% at 70/30, 0% at 50/50 and 33% in studies in which Rh/Ir=30/70.

2) the stability of the catalytic system:

Conclusions similar to that shown in PA is the agraffe 2.2.1.

3. EXPERIMENTS WITH INDUSTRIAL REACTIONARY ENVIRONMENT

These studies were carried out using standard operating mode, presented in §1.2.

3.1 Optimization of the amount of input of methanol

In this series of studies conducted for comparison (in the absence of iridium), the concentration of the added methanol was changed in the range between 5% and 15% (10% from the reaction medium in a typical operating mode). All other parameters are identical, in particular [Rh]=0,33-0.34 mmol, [MétCor]=5000 mg/kg, and the concentration of water is equal to 14%. Maximum speed carbonyl - 7 mol/l·the hour was achieved when 10% of the added methanol; it is very slightly decreases when the concentration of methanol increases to 12% and even up to 15% (6 mol/l·h).

The conditions and results of these studies are shown in table 3.1.

3.2 Research at a constant concentration of rhodium and variable concentrations of iridium

In this series of studies, the results and conditions are shown in table 3.2, was carried out adding iridium in increasing quantities to the original production reaction medium of constant composition, where, in particular, the water concentration was 14%, metals corrosion - 5000 mg/kg, rhodium is 0.33-0.34 mmol.

The molar ratio of rhodium to iridium was regulated by adding iridium in ascending to the number:

- Rh/Ir=100/0 Studies for comparison (in the absence of iridium).

- Rh/Ir=90/10, 80/20, 70/30, 50/50 and 30/70. Research in accordance with the present invention.

Note 1: Research for the same ratio Rh/Ir, as a rule, were duplicated.

Note 2: In the study of 602 (Rh/Ir=30/70) 10% methanol were replaced with 25% acetate, this was not observed any change Vcarb.

You can add increasing amounts of iridium in the actual production of the reaction medium (the usual catalyzed only by rhodium) without sacrificing performance and without compromising the stability of the catalytic system.

The rate of carbonylation for only rhodium (from 6 to 7 mol/l·h) is retained until the molar ratio of rhodium to iridium equal to 50/50, and even increases when the ratio of 30/70 (Vcarb=8-8,5 mol/l·h).

There is no metal deposits, whatever the molar ratio of Rh/Ir between 100/0 and 30/70.

3.3 Influence of water concentration and relationships Rh/Ir

Typical operating mode 1-2 was used in the next version:

In studies that require it, the water concentration was established in the amount of x % (x=12%, or 10%, or 8%, or 6%) through the introduction of acetic anhydride in the amount calculated on the basis of the initial concentration of water, equal to 14% (a 14 %) and a sample volume of industrial reaction is Reda, 50 ml of This amount of acetic anhydride were introduced into a 50 ml reaction medium at the beginning of the experience, before closing the autoclave, and a pressure of carbon monoxide at 5 bar (5·105PA). Then resumed the standard operating mode.

In these four series of studies was maintained constant initial concentration of the reaction medium, in which [MétCor]=5000 mg/kg and almost the concentration of catalyst [Rh]+[Ir]=0,33-0.44 mmol (note: in the 4th series of experiments with 734 in 739 - number of the reaction medium is reduced to 43 ml/48 g and, therefore, methanol is added in the amount of 4.8 g).

Conditions and results are summarized in table 3.3 at the end of the description.

- The molar ratio of Rh/Ir=100/0; [Rh]=0,33-0.34 mmol; [Ir]=0.

These studies were conducted for comparative purposes and are outside the scope of the present invention, since the [Ir]=0; they are applicable as a control.

- The molar ratio of Rh/Ir=90/10; [Rh]=0,33-0.34 mmol; [Ir]≃0.04 mmol.

- The molar ratio of Rh/Ir=80/20; [Rh]=0.35 to 0.36 mmol; [Ir]≃0.09 mmol.

- The molar ratio of Rh/Ir=70/30; [Rh]=0,23-0,24 mmol; [Ir]≃0.10 mmol.

Thus, [Rh]+[Ir]=0,33-0.44 mmol.

These various studies directly comparable, because the concentration of rhodium and iridium amounts to almost a constant value, in particular a series of studies with Rh/Ir=100/0 and 70/30, gesumaria concentration of rhodium and iridium equals to 0.33-0.34 mmol.

In General, we can conclude that:

1) Reduction of water content causes a reduction in the rate of carbonylation in each series, whatever the molar ratio of Rh/Ir between 100/0 and 70/30.

2) in Virtually any concentration of water, the rate of carbonylation are grouped in the following order:

Rh/Ir=100/0≤Rh/Ir=90/10≤Rh/Ir=80/20<Rh/Ir=70/30.

3) low concentrations of water from 14% to 12% and even 10% is accompanied by only a very small reduction in the rate of carbonylation: Vcarb (Rh/Ir=70/30, water = 12%)=Vcarb (Rh/Ir=100/0, water = 14%).

4) Not observed any visible negative impact of the presence of metal corrosion in the amount of 5000 mg/kg when adding iridium in increasing quantities nor on the rate of carbonylation, nor on the stability of the catalytic system Rh+Ir (no metal deposits).

4. Simultaneous dissolution of rhodium and iridium

These examples describe the simultaneous dissolution of rhodium and iridium in the form of rhodium iodide and iodine iridium - terms derived from classical conditions, like written in the way Monsanto only for rhodium iodide. Thus obtained solutions are catalytic solutions, designed for simultaneous add both catalysts, rhodium and iridium in the reaction medium carbonylation.

In the autoclave of 100 ml Hastelloy® B2 is introduced rhodium iodide, iodine iridium, water and acetic acid in amounts corresponding to those shown in table 4.1, which shows the conditions of the experiment. In the autoclave under pressure is forced FROM at ambient temperature, which further increases to 110°C, the pressure is regulated is 5·105PA (5 bar) and is further supported by the same value, and the reaction is carried out at 110°for 5 or 8 hours depending on the experiment.

Next, the autoclave is cooled, the catalytic solution is collected and weighed to ensure there are no leaks and confirm thus the reliability of the conducted expertise.

The catalytic solution is analyzed for the following parameters:

appearance, the presence or absence of sediment, the concentration of rhodium and iridium, determined by atomic absorption spectrometry.

The autoclave is checked to verify the presence or absence of metal deposits. The results of these tests are given in table 4.2.

Transparent appearance catalytic solutions, as well as a comparison of the concentrations identified in the analysis of the obtained solution with theoretical concentrations prove the full transition of rhodium and iridium in the solution.

Thus it is possible th is towith the following types of catalytic solutions:

- concentrated - 950 mg of rhodium per kilogram of solution and from 950 to 2600 mg of iridium per kilogram of solution (experiments 780, 787 785).

or very concentrated, as in the experience 788 - 1 wt.% rhodium and 1.4 wt.% iridium.

TABLE 1
EXPERIMENTS WITH ARTIFICIAL SOLUTIONS
ZERO CONCENTRATION of METALS CORROSION
no experienceType of experienceThe deposition of metalMet. Corr. mg/kgRh mmollr mmolRh mol %Ir mol %Vcarb 10' mol/l·hour
606For EUR.Prisutstvie.00,334010005,5
719For EUR.Prisutstvie.0of 0.337010004,5
610For EUR.No.0of 0.3330,03790105,3
611For EUR.No.00,3360,08480206
721For EUR.No.00,3340,14570305
726For EUR.No.00,334of 0.33250507,5
730For EUR.No.0of 0.3330,777307010,5
599For EUR.No.00,3340,801307010

td align="center"> 5,5
TABLE 2
EXPERIMENTS WITH ARTIFICIAL SOLUTIONS
The CONCENTRATION of METALS CORROSION from 0 to 4000 mg/kg
no experienceType of experienceThe deposition of metalMet. Corr. mg/kgRh mmolIr mmolRh mol %Ir mol %Vcarb 10' Ir/Rh=0/100
606For EUR.Prisutstvie.00,33401000
719For EUR.Prisutstvie.0of 0.337010004,5
715For EUR.Prisutstvie.1000,335010006
716For EUR.Prisutstvie.1000of 0.333010005
717For EUR.Prisutstvie.2000of 0.333010005
720For EUR.No.40000,335010005
no experienceType of experienceThe deposition of metalMet. Corr. mg/kgRh mmolIr mmolRh mol %Ir mol %Vcarb 10' Ir/Rh=10/90
610For EUR.No.0of 0.3330,03790 105,3
612Soglio.No.1000,3360,03790105
613The agreements. imageNo.10000,3340,03790106
614Soglio.No.2000of 0.3330,03790105,3
615Soglio.No.40000,3350,04290105,3
no experienceType of experienceThe deposition of metalMet. Corr. mg/kgRh mmolIr mmolRh mol %Ir mol%Vcarb 10' Ir/Rh=20/80
611For EUR.No.00,3360,08480206
616Soglio.No.1000,335 0,08380206
617The agreements. Fig.No.10000,3350,08980206
618The agreements. Fig.No.20000,3340,08580205,5
622Soglio.No.40000,3340,08380206
no experienceType of experienceThe deposition of metalMet. Corr. mg/kgRh mmolIr mmolRh mol %Ir mol %Vcarb 10' Ir/Rh=30/70
721For EUR.No.00,3340,14570305
722Soglio.No.1000,3350,14370306
723Soglio.No. of 0.3330,14470305,5
724For EUR.No.00,235to 0.10870304
725Soglio.No.40000,2330,10770303,5
no experienceType of experienceThe deposition of metalMet. Corr. mg/kgRh mmolIr mmolRh mol %Ir mol %Vcarb 10' Ir/Rh=50/50
726For EUR.No.00,334of 0.33250507,5
727Soglio.No.4000of 0.3330,33450505,5
728For EUR.No.00,1650,16650503
729Soglio. No.40000,1650,16650503
no experienceType of experienceThe deposition of metalMet. Corr. mg/kgRh mmolIr mmolRh mol %Ir mol %Vcarb 10' Ir/Rh=70/30
599For EUR.No.00,3340,801307010
730For EUR.No.0of 0.3330,777307010,5
731Soglio.No.4000of 0.3330,77730708
732For EUR.No.00,0990,23330703
733Soglio.No.40000,1030,23330702

The velocity of the carbonyl of the simulation are expressed in moles per liter per hour (mol/l· h)

td align="center" namest="c11" nameend="c12"> 100
TABLE 3.1
EXPERIMENTS WITH INDUSTRIAL REACTION MEDIUM
OPTIMIZATION of the AMOUNT of INPUT of METHANOL
no experienceType of experienceMeon %Met. Corr. mg/kgRh mmolIr mmolRh mol %Ir mol %Vcarb 10' mol/l·hour
583For EUR.550000,336010002
581For EUR.1050000,329010007
604For EUR.1250000,3290100 06,4
605For EUR.1550000,327010006
TABLE 3.2
EXPERIMENTS WITH INDUSTRIAL REACTION MEDIUM
EXPERIMENTS with[Rh] is a constant; [Ir] - variable
no experienceType of experienceThe deposition of metalMet. Corr. mg/kgRh mmolIr mmolRh mol %Ir mol %Vcarb 10' mol/l·hour
581For EUR.No.50000,329010007
603For EUR.No.50000,341007
655For EUR.No.50000,329010006,5
656Soglio.No.50000,3380,03790107
661Soglio.No.5000of 0.3320,03890106,5
657Soglio.No.50000,3380,08580206,5
662Soglio.No.5000of 0.3330,083 80206
664Soglio.No.50000,3310,14370306,5
663Soglio.No.50000,3390,14470307
659Soglio.No.50000,3380,33650507
660Soglio.No.50000,3350,78230708,5
602 (25% Asome)Soglio.No.5000of 0.3330,774 30708

TABLE 3.3
EXPERIMENTS WITH INDUSTRIAL REACTION MEDIUM
The INFLUENCE of WATER CONTENT AND the RATIO Rh/Ir
no experienceType of experienceThe deposition of metalWater %Rh mmolIr mmolRh mol %Ir mol %Vcarb 10' mol/l·hour
700For EUR.No.140,338010007
699For EUR.No.120,339010006
698For EUR.No.10of 0.332010004,5
696For against,No.80,335010004
697Alacran. No.60,342010003
no experienceType of experienceThe deposition of metalWater %Rh mmolIr mmolRh mol %Ir mol %Vcarb 10' mol/l·hour
701Soglio.No.14of 0.3320,03890107
702Soglio.No.120,3430,03890106
706Soglio.No.100,3310,03990105
704Soglio.No.80,3430,03890104,3
705Soglio.No.60,3350,03890103,2
Ȋ
no experienceType of experienceThe deposition of metalWater %Rh mmolIr mmolRh mol %Ir mol %Vcarb 10' mol/l·hour
707Soglio.No.140,3550,08880206,5
708Soglio.No.120,3460,08880206
709Soglio.No.100,3520,08680205
710Soglio.No.80,3530,08880204
711Soglio.No.60,3600,08680204
no experienceType of experienceThe deposition of metalWater %Rh mmol Ir mmolRh mol %Ir mol %Vcarb 10' mol/l·hour
734Soglio.No.140,2330,10070307,5
738Soglio.No.120,2350,10070307
736Soglio.No.100,233is 0.10270305,6
737Soglio.No.80,2330,10170304,3
739Soglio.No.60,2330,10170304

The appearance of the solution after reaction
TABLE 4.1
SIMULTANEOUS DISSOLUTION of RHODIUM AND IRIDIUM
TABLE WORKING CONDITIONS
no experienceWater, gAcetic acid, g Iodine iridium, gIodide, rhodium, gReaction time, hoursPressure, barTemperature, °
78015,7458,040,2280,32955110
78715,7458,040,423of 0.33255110
78515,7458,040,6390,32955110
7889,0028,222,0002,00085110
TABLE 4.2
SIMULTANEOUS DISSOLUTION of RHODIUM AND IRIDIUM
RESULTS TABLE
no experienceIridium calculation, mg/kgIridium fact, mg/kgRhodium calculation, mg/kgRhodium fact, mg/kg
780941875942917Transparent yellow-brown solution

The lack of sediments in the autoclave
78717421680948845Transparent yellow-brown solution

The lack of sediments in the autoclave
78526242560937871Transparent yellow-brown solution

The lack of sediments in the autoclave
7881489214040103249421Transparent yellow-brown solution

The lack of sediments in the autoclave

1. Method for continuous production of acetic acid and/or methyl acetate, including consistent implementation of the following steps:

a) the beginning of the initial continuous process for the carbonylation of methanol or a derivative of methanol that can be carbonyliron, acetic acid and/or methyl acetate in homogeneous liquid f is ze and under pressure of carbon monoxide in the presence of a catalytic system, includes homogeneous catalyst based on rhodium and halogenated promoter and in the presence of water in the reaction medium in a quantity greater than or equal to 14%,

moreover, the specified source process is carried out in a setting that includes the reaction zone I, where the temperature of the support from 150 to 250°and the total pressure is in the range from 5·105up to 200·105PA; zone effervescence II, where the products leaving the reaction zone I, is partially evaporated at a pressure less than the pressure in the reaction zone I; while not evaporated fraction out of the zone effervescence II, recycle to the reaction zone I, and evaporated fraction is subjected to cleaning in the separation zone III through separation and/or distillation, and/or purification of the formed acetic acid and/or methyl acetate,

b) the continuation of the continuous production process with incremental additions over time compounds of iridium, in order to gradually transform the composition of the homogeneous catalyst used in stage (a), with a catalytic system containing a predetermined atomic ratio of rhodium to iridium, transforming thus the composition of the catalyst without stopping the process,

in continuation of the continuous production process of acetic acid and/or methyl acetate in support is to maintain the composition of the catalytic system such how he became the result of the conversion in step (b), by adding compounds of rhodium, or iridium compounds, or both.

2. The method according to claim 1, wherein the concentration of rhodium and iridium in the reaction medium support simultaneous addition of rhodium and iridium by a catalytic solution containing dissolved rhodium and iridium.

3. The method according to claim 1 or 2, characterized in that the compounds of iridium added in the form of pre-dissolved compounds of iridium.

4. The method according to claim 3, characterized in that the used operating mode of dissolution of the added compounds of iridium, compatible with the production facilities and production process, carried out by conventional methods carbonylation for dissolution of rhodium compounds used in these methods as catalysts.

5. The method according to claim 1 or 2, characterized in that the compounds of iridium added in the form of a solid derivative of iridium, which dissolves in situ in the reaction medium.

6. The method according to claim 1 or 2, characterized in that the compounds of iridium added continuously or discretely.

7. The method according to claim 1 or 2, characterized in that the reaction medium support the molar concentration of rhodium in the range between 0.1 and 50 mmol/l and the molar concentration of iridium in the range between 0.1 and 25 mmol/L.

8. The method according to claim 7, characterized in that the compounds of iridium add thus to compensate for the loss of rhodium, replacing lose rhodium iridium and thus supporting the concentration of the catalytic metal.

9. The method according to claim 1 or 2, characterized in that the atomic ratio of iridium/rhodium supported in is from 1/99 to 99/1.

10. The method according to claim 1 or 2, characterized in that the compounds of iridium add to the state when iridium is the only metal in the homogeneous catalytic system, but such a predetermined atomic ratio is 0/100.

11. The method according to claim 1 or 2, characterized in that the compounds of iridium add through their introduction into the reaction medium in the reaction zone I.

12. The method according to claim 1 or 2, characterized in that the compounds of iridium added by introducing a flow recirculation zone II or III to the reaction zone I.

13. The method according to claim 1 or 2, characterized in that exercise control over the concentration of metals corrosion in the reaction medium so that it is maintained in a value less than or equal to 5000 mg/kg

14. The method according to claim 1 or 2, characterized in that it further includes an additional stage in which the water content of the reaction medium is reduced to a value less 14% relative to the weight of the reality in the operating environment.

15. The method according to 14, wherein the specified additional phase water concentration in the reaction medium to maintain the value of < 5% relative to the weight of the reaction medium.

16. The method according to item 15, wherein the specified additional stage in the reaction medium was injected methylformate, at the same time carried out the carbonylation reaction of methanol or derived methanol, giving in to carbonyliron, and isomerization of methylformate under pressure of carbon monoxide.

17. The method according to item 16, wherein the gradually stop filing methanol or derived methanol, giving in to carbonyliron, in a reaction medium in order to get into the system isomerization of methylformate under pressure of carbon monoxide.

18. The method according to claim 1 or 2, characterized in that it additionally includes the stage of gradual transformation of the composition of the homogeneous catalyst by adding over time, platinum compounds, and the concentration of platinum supported in the range from 1 to 25 mmol/l of reaction medium.



 

Same patents:

FIELD: petrochemical processes.

SUBSTANCE: invention relates to improved C2-C4-alkane oxidation process to produce corresponding alkene and carboxylic acid, which process comprises bringing indicated alkane in oxidation reaction zone into contact with molecular oxygen-containing gas and corresponding alkene and optionally with water in presence of at least one catalyst efficient for oxidation of alkane into corresponding alkene and carboxylic acid. Resulting product contains alkene, carboxylic acid, and water, wherein alkene-to-carboxylic acid molar ratio in oxidation reaction zone is controlled or maintained at desired level by way of controlling alkene and optional water concentrations in oxidation reaction zone and also, optionally, controlling one or several from following parameters: pressure, temperature, and residence time in oxidation reaction zone. Invention also relates to integrated process of producing alkyl carboxylate including above-indicated stage of producing alkene and carboxylic acid in first reaction zone and stage of bringing, in second reaction zone, at least part of each of alkene and carboxylic acid obtained in first reaction zone in contact with each other in presence of at least one catalyst effective in production of alkyl carboxylate to produce the same. Invention further relates to production of alkenyl carboxylate including above-indicated stage of producing alkene and carboxylic acid in first reaction zone and stage of bringing, in second reaction zone, at least part of each of alkene and carboxylic acid obtained in first reaction zone plus molecular oxygen-containing gas into contact with each other in presence of at least one catalyst effective in production of alkenyl carboxylate to produce the same.

EFFECT: enhanced process efficiency.

55 cl, 1 dwg, 7 tbl, 22 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to technology for manufacturing acetic acid by the carbonylation reaction of methanol with carbon monoxide. Method is carried out in the continuous regimen in the carbonylation reactor wherein methanol and carbon monoxide are fed and catalytically active rhodium-comprising catalyst medium is maintained wherein this medium comprises the following components: water, 0.1-14 wt.-%; methyliodide, 1-20%; alkaline metal iodide salt, 2-20%; methyl acetate and acetic acid, 0.5-30%. The total pressure value in reactor is 15-40 atm. Flow of the reaction products is subjected for rapid evaporation and fed to the distillation stage comprising up to two distillation columns wherein purified acetic acid is separated and some flows recirculating into reactor. Removal of iodide impurities from the final product is carried out by contacting the flow with anion-exchange resin at temperature 100°C, not less, followed by purification stage with sulfocation-exchange resin in form of silver or mercury salt comprising 1% of active sites, not less, at temperature 50°C, not less. The level of aldehyde impurities in the flow recirculating into reactor is regulated by the distillation off method. The content of iodides in acetic acid is less 10 parts/billion. Method provides decrease of energy consumption and preparing acetic acid of high purity degree.

EFFECT: improved producing method.

28 cl, 3 tbl, 7 dwg, 12 ex

FIELD: analytical methods.

SUBSTANCE: invention relates to assessing acetic acid vapors in working zone air of linoleum, acetylcellulose, and alkyl acetate manufacture enterprises. Method comprises sampling air, detecting and recording analytical signal followed by calculation of acetic acid concentration. Sample is placed in detection cell with piezoquartz resonator whose electrodes are preliminarily modified with acetone solution of polyethylene glycol adipate sorbent such that mass of sorbent after removal of solvent were 10-30 μg. Recording of analytical signal is accomplished in the form of response of modified electrodes of piezoquartz resonator 15 sec after introduction of sample into detection cell. Calculation of acetic acid concentration is performed according to equation of calibration curve: ΔF = 1.4CM, where ΔF is response of modified electrodes of piezoquartz resonator, Hz, and CM is acetic acid concentration is air sample, mg/m3. Advantages of method are following: excluded sample preparation stage; reduced assessment time from 7-9 h to 0-45 min (taking into account time used for modifying electrodes and subsequent regeneration of detection cell); increased number of assessments without replacement of sorbent; reduced sorbent restoration time; and reduced assessment error.

EFFECT: accelerated assessment and increased assessment accuracy.

2 tbl, 7 ex

FIELD: chemical engineering.

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EFFECT: enabled storage of aqueous acetic acid solutions during winter period without need of warming.

1 dwg, 2 ex

FIELD: organic chemistry, chemical technology.

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EFFECT: improved method for preparing.

2 tbl, 1 dwg, 4 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for removing higher organic iodides from organic media. Method for removing organic iodides containing 10-16 carbon atoms from non-aqueous organic media containing organic iodides with 10-16 carbon atoms is carried out by contacting indicated organic media with silver- or mercury-exchange cationic, ion-exchange substrate at temperature from 50°C to 150°C. Invention proposes a method for removing iodides having 10-16 carbon atoms from acetic acid or acetic anhydride by providing flow of acetic acid or acetic anhydride containing organic iodide having 10-16 carbon atoms. Indicated flow is contacted with macroporous strong acid ion-exchange resin wherein at least 1% of active sites acquire form of silver or mercury at temperature in the range 50°C - 150°C. Indicated silver- or mercury-exchange ion-exchange resin removes effectively at least 90 wt.-% of indicated organic iodides from indicated flow of ready acetic acid or acetic anhydride. Also, invention proposes a method for removing organic iodides containing 10-16 carbon atoms from acetic acid or acetic anhydride involving contact of acetic acid or acetic anhydride comprising dodecyl iodide with silver- or mercury-exchange cationic ion-exchange substrate at temperature in the range 50°C - 150°C. Method provides the complete removing higher organic iodides from flow of acetic acid and/or acetic anhydride.

EFFECT: improved method for removing.

29 cl, 5 dwg, 13 ex

FIELD: chemical industry; production of synthesis gas, methanol and acetic acid on its base.

SUBSTANCE: the invention is dealt with the methods of production of synthesis gas, production of methanol and acetic acid on its base. The method of upgrading of the existing installation for production of methanol or methanol/ ammonia provides for simultaneous use of the installation also for production of acetic acid or its derivatives. The existing installation contains a reformer, to which a natural gas or other hydrocarbon and a steam (water), from which a synthesis gas is formed. All the volume of the synthesis gas or its part is processed for separation of carbon dioxide, carbon monoxide and hydrogen. The separated carbon dioxide is fed into an existing circuit of synthesis of methanol for production of methanol or is returned to the inlet of the reformer to increase the share of carbon monoxide in the synthesis gas. The whole volume of the remained synthesis gas and carbon, which has not been fed into the separator of dioxide, may be transformed into methanol in the existing circuit of a synthesis of methanol together with carbon dioxide from the separator and-or carbon dioxide delivered from an external source, and hydrogen from the separator. Then the separated carbon monoxide is subjected to reactions with methanol for production of acetic acid or an intermediate compound of acetic acid according to the routine technology. A part of the acetic acid comes into reaction with oxygen and ethylene with formation of monomer of vinyl acetate. With the help of the new installation for air separation nitrogen is produced for production of additional amount of ammonia by the upgraded initial installation for production of ammonia, where the separated hydrogen interacts with nitrogen with the help of the routine technology. As the finished product contains acetic acid then they in addition install the device for production of a monomer of vinyl acetate using reaction of a part of the acetic acid with ethylene and oxygen. With the purpose of production of the oxygen necessary for production of a monomer of vinyl acetate they additionally install a device for separation of air. At that the amount of nitrogen produced by the device of separation of air corresponds to nitrogen demand for production of additional amount of ammonia. The upgraded installation ensures increased production of additional amount of ammonia as compared with the initial installation for production of methanol. The invention also provides for a method of production of hydrogen and a product chosen from a group consisting of acetic acid, acetic anhydride, methyl formate, methyl acetate and their combinations, from hydrocarbon through methanol and carbon monoxide. For this purpose execute catalytic reforming of hydrocarbon with steam in presence of a relatively small amount of carbon dioxide with formation of the synthesis gas containing hydrogen, carbon monoxide and carbon dioxide, in which synthesis gas is characterized by magnitude of the molar ratio R = ((H2-CO2)/(CO+CO2)) from 2.0 up to 2.9. The reaction mixture contains carbon monoxide, water -up to 20 mass %, a dissolvent and a catalytic system containing at least one halogenated promoter and at least one rhodium compound, iridium compound or their combination. The technical result provides, that reconstruction of operating installations increases their productivity and expands assortment of produced industrial products.

EFFECT: the invention ensures, that reconstruction of operating installations increases their productivity and expands assortment of produced industrial products.

44 cl, 3 ex, 6 dwg

FIELD: vinyl acetate production by ethane catalytic acetoxylation with acetic acid obtained as intermediate.

SUBSTANCE: claimed method includes: a) bringing gaseous raw material, containing ethane as a main component, into contact in the first reaction zone with molecular oxygen-containing gas in presence of catalyst to obtain the first product stream including acetic acid and ethylene; b) bringing the said first product stream in second reaction zone with molecular oxygen-containing gas in presence of catalyst to obtain the second product stream including vinyl acetate; c) separation the second product stream from stage b) to recovery of vinyl acetate. In the first reaction zone catalyst of general formula MOaPdbXcYd is used, wherein X is at least one element selected from Ti, V, and W; Y is at least one element selected from Al, Bi, Cu, Ag, Au, K, Rb, Cs, Mg, Ca, Sr, Ba, Nb, Sb, Si, and Sn; a, b, c, and d are gram-atom ratio, and a = 1; b = 0.0001-0.01, preferably 0.0001-0.005; c = 0.4-1, preferably 0.5-0.8; and d = 0.005-1, preferably 0.01-0.3. Gaseous raw material from step a) preferably includes ethane and molecular oxygen-containing gas in volume ratio of ethane/oxygen between 1:1 and 10:1, and 0-50 % of vapor as calculated to total volume of starting raw material. Ratio of selectivity to ethylene and selectivity to acetic acid in the first product stream is 0:95-95:0.

EFFECT: integrated technological cycle with controllable product yield while changing technological parameters of the process.

6 cl, 11 ex, 2 tbl, 1 dwg

FIELD: industrial inorganic synthesis.

SUBSTANCE: process is accomplished by continuously feeding methanol and/or reactive derivative thereof and carbon monoxide into carbonylation reactor filled with reaction mixture containing iridium carbonylation catalyst, methyl iodide cocatalyst, water in limited concentration, acetic acid, and methyl acetate, liquid reaction mixture further including at least one promoter selected from ruthenium, osmium, rhenium, and tungsten. Carbonylation of methanol to produce acetic acid involves reaction with carbon monoxide in liquid reaction mixture. When recovering acetic acid from liquid reaction mixture, concentration of water is maintained therein not exceeding 4.5%. During reaction, partial pressure of carbon monoxide in reactor is maintained within a range between 0 and 6 bar.

EFFECT: accelerated carbonylation reaction, diminished by-product formation, and simplified acetic acid recovery operation.

6 dwg, 3 tbl

FIELD: organic chemistry, chemical technology, catalysts.

SUBSTANCE: invention relates to a method for preparing acetic acid by gas-phase oxidation of ethane and/or ethylene with oxygen using catalyst comprising molybdenum and palladium. For realization of method gaseous feeding comprising ethane, ethylene or their mixture and oxygen also are contacted at enhanced temperature with catalyst that comprises elements Mo, Pd, X and Y in combination with oxygen of the formula (I): MoaPdbXcYd wherein X and Y have the following values: X means V and one or some elements optionally taken among the following group: Ta, Te and W; Y means Nb, Ca and Sb and one or some elements optionally taken among the following group: Bi, Cu, Ag, Au, Li, K, Rb, Cs, Mg, Sr, Ba, Zr and Hf; indices a, b, c and d mean gram-atom ratios of corresponding elements wherein a = 1; b = 0.0001-0.01; c = 0.4-1, and d = 0.005-1. Niobium is added to the catalyst structure using niobium ammonium salt. Preferably, niobium ammonium salt is used as the niobium source. The continuance of contact time and composite values of the parent gaseous mixture are so that taken to provide output value by acetic acid to be above 470 kg/(m3 x h). The selectivity of oxidation reaction of ethane and/or ethylene to acetic acid is above 70 mole %. Invention provides enhancing stability and output of catalyst.

EFFECT: improved preparing method.

14 cl, 1 tbl, 6 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to technology for manufacturing acetic acid by the carbonylation reaction of methanol with carbon monoxide. Method is carried out in the continuous regimen in the carbonylation reactor wherein methanol and carbon monoxide are fed and catalytically active rhodium-comprising catalyst medium is maintained wherein this medium comprises the following components: water, 0.1-14 wt.-%; methyliodide, 1-20%; alkaline metal iodide salt, 2-20%; methyl acetate and acetic acid, 0.5-30%. The total pressure value in reactor is 15-40 atm. Flow of the reaction products is subjected for rapid evaporation and fed to the distillation stage comprising up to two distillation columns wherein purified acetic acid is separated and some flows recirculating into reactor. Removal of iodide impurities from the final product is carried out by contacting the flow with anion-exchange resin at temperature 100°C, not less, followed by purification stage with sulfocation-exchange resin in form of silver or mercury salt comprising 1% of active sites, not less, at temperature 50°C, not less. The level of aldehyde impurities in the flow recirculating into reactor is regulated by the distillation off method. The content of iodides in acetic acid is less 10 parts/billion. Method provides decrease of energy consumption and preparing acetic acid of high purity degree.

EFFECT: improved producing method.

28 cl, 3 tbl, 7 dwg, 12 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for removing higher organic iodides from organic media. Method for removing organic iodides containing 10-16 carbon atoms from non-aqueous organic media containing organic iodides with 10-16 carbon atoms is carried out by contacting indicated organic media with silver- or mercury-exchange cationic, ion-exchange substrate at temperature from 50°C to 150°C. Invention proposes a method for removing iodides having 10-16 carbon atoms from acetic acid or acetic anhydride by providing flow of acetic acid or acetic anhydride containing organic iodide having 10-16 carbon atoms. Indicated flow is contacted with macroporous strong acid ion-exchange resin wherein at least 1% of active sites acquire form of silver or mercury at temperature in the range 50°C - 150°C. Indicated silver- or mercury-exchange ion-exchange resin removes effectively at least 90 wt.-% of indicated organic iodides from indicated flow of ready acetic acid or acetic anhydride. Also, invention proposes a method for removing organic iodides containing 10-16 carbon atoms from acetic acid or acetic anhydride involving contact of acetic acid or acetic anhydride comprising dodecyl iodide with silver- or mercury-exchange cationic ion-exchange substrate at temperature in the range 50°C - 150°C. Method provides the complete removing higher organic iodides from flow of acetic acid and/or acetic anhydride.

EFFECT: improved method for removing.

29 cl, 5 dwg, 13 ex

FIELD: chemical industry; production of synthesis gas, methanol and acetic acid on its base.

SUBSTANCE: the invention is dealt with the methods of production of synthesis gas, production of methanol and acetic acid on its base. The method of upgrading of the existing installation for production of methanol or methanol/ ammonia provides for simultaneous use of the installation also for production of acetic acid or its derivatives. The existing installation contains a reformer, to which a natural gas or other hydrocarbon and a steam (water), from which a synthesis gas is formed. All the volume of the synthesis gas or its part is processed for separation of carbon dioxide, carbon monoxide and hydrogen. The separated carbon dioxide is fed into an existing circuit of synthesis of methanol for production of methanol or is returned to the inlet of the reformer to increase the share of carbon monoxide in the synthesis gas. The whole volume of the remained synthesis gas and carbon, which has not been fed into the separator of dioxide, may be transformed into methanol in the existing circuit of a synthesis of methanol together with carbon dioxide from the separator and-or carbon dioxide delivered from an external source, and hydrogen from the separator. Then the separated carbon monoxide is subjected to reactions with methanol for production of acetic acid or an intermediate compound of acetic acid according to the routine technology. A part of the acetic acid comes into reaction with oxygen and ethylene with formation of monomer of vinyl acetate. With the help of the new installation for air separation nitrogen is produced for production of additional amount of ammonia by the upgraded initial installation for production of ammonia, where the separated hydrogen interacts with nitrogen with the help of the routine technology. As the finished product contains acetic acid then they in addition install the device for production of a monomer of vinyl acetate using reaction of a part of the acetic acid with ethylene and oxygen. With the purpose of production of the oxygen necessary for production of a monomer of vinyl acetate they additionally install a device for separation of air. At that the amount of nitrogen produced by the device of separation of air corresponds to nitrogen demand for production of additional amount of ammonia. The upgraded installation ensures increased production of additional amount of ammonia as compared with the initial installation for production of methanol. The invention also provides for a method of production of hydrogen and a product chosen from a group consisting of acetic acid, acetic anhydride, methyl formate, methyl acetate and their combinations, from hydrocarbon through methanol and carbon monoxide. For this purpose execute catalytic reforming of hydrocarbon with steam in presence of a relatively small amount of carbon dioxide with formation of the synthesis gas containing hydrogen, carbon monoxide and carbon dioxide, in which synthesis gas is characterized by magnitude of the molar ratio R = ((H2-CO2)/(CO+CO2)) from 2.0 up to 2.9. The reaction mixture contains carbon monoxide, water -up to 20 mass %, a dissolvent and a catalytic system containing at least one halogenated promoter and at least one rhodium compound, iridium compound or their combination. The technical result provides, that reconstruction of operating installations increases their productivity and expands assortment of produced industrial products.

EFFECT: the invention ensures, that reconstruction of operating installations increases their productivity and expands assortment of produced industrial products.

44 cl, 3 ex, 6 dwg

FIELD: industrial inorganic synthesis.

SUBSTANCE: process is accomplished by continuously feeding methanol and/or reactive derivative thereof and carbon monoxide into carbonylation reactor filled with reaction mixture containing iridium carbonylation catalyst, methyl iodide cocatalyst, water in limited concentration, acetic acid, and methyl acetate, liquid reaction mixture further including at least one promoter selected from ruthenium, osmium, rhenium, and tungsten. Carbonylation of methanol to produce acetic acid involves reaction with carbon monoxide in liquid reaction mixture. When recovering acetic acid from liquid reaction mixture, concentration of water is maintained therein not exceeding 4.5%. During reaction, partial pressure of carbon monoxide in reactor is maintained within a range between 0 and 6 bar.

EFFECT: accelerated carbonylation reaction, diminished by-product formation, and simplified acetic acid recovery operation.

6 dwg, 3 tbl

The invention relates to the production of acetic acid by carbonyliron methanol using a rhodium catalyst in the carbonylation reactor

The invention relates to equipment for carrying out the catalytic oxidation of gas-vapor mixtures in stationary conditions, preferably for formic acid, which finds application in chemical, metallurgical, leather and other industries

The invention relates to the continuous receipt of acetic acid by feeding methanol and/or its reactive derivative and carbon monoxide in a carbonylation reactor for

The invention relates to the production of acetic acid and/or methyl acetate

FIELD: industrial inorganic synthesis.

SUBSTANCE: process is accomplished by continuously feeding methanol and/or reactive derivative thereof and carbon monoxide into carbonylation reactor filled with reaction mixture containing iridium carbonylation catalyst, methyl iodide cocatalyst, water in limited concentration, acetic acid, and methyl acetate, liquid reaction mixture further including at least one promoter selected from ruthenium, osmium, rhenium, and tungsten. Carbonylation of methanol to produce acetic acid involves reaction with carbon monoxide in liquid reaction mixture. When recovering acetic acid from liquid reaction mixture, concentration of water is maintained therein not exceeding 4.5%. During reaction, partial pressure of carbon monoxide in reactor is maintained within a range between 0 and 6 bar.

EFFECT: accelerated carbonylation reaction, diminished by-product formation, and simplified acetic acid recovery operation.

6 dwg, 3 tbl

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