The way to improve the performance carboniferous catalyst solution by removing metal corrosion

 

(57) Abstract:

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 to remove corrosion products of the metal. The method involves contacting the catalyst solution with ion exchange resin, preferably in the lithium form, and sufficient to reduce the concentration of alkali metal ions with water in order to optimize the removal of corrosion products of the metal. The technical result - the destruction of the catalyst solution carbonyl products of metal corrosion. 3 S. and 12 C.p. f-crystals, 1 Il., table 2.

The scope of the invention

The invention relates in General to improvements in the carbonylation of methanol to acetic acid in the presence of registeruser catalyst. More specifically the invention relates to an improved method of regeneration of the catalyst solution used in the reaction of the carbonyl process with low water content.

The basis of the invention

As pointed Paulik et. al. in U.S. patent 3.769.329 from 30.10.1973, among primenyaetsa catalytic carbonylation of methanol with carbon monoxide. The carbonylation catalyst contains rhodium, which is either dissolved or otherwise dispersed in a liquid reaction medium, or supported on an inert solid material, together with halide catalytic promoter, an example of which is methyl iodide. Rhodium can be introduced into the reaction system in one of many forms, and here is inappropriate, even if it were possible, to determine accurately the nature of the rhodium group in the active catalyst complex. Likewise is not critical and the nature of the halide promoter. U.S. patent 3.769.329 discloses a number of suitable promoters, most of which is organic iodides. The most common method of carrying out the reaction with the catalyst dissolved in the liquid reaction medium under continuous bubbling of gaseous carbon monoxide.

Improvement of the previously known process for the carbonylation of an alcohol to obtain carboxylic acid having one carbon atom more than the alcohol, in the presence of a rhodium catalyst disclosed in U.S. patent 5.001.259 and in the European patent 161.874 B2. As described there, acetic acid (HAc) is obtained from methanol (MeOH) in a reaction medium containing acetate (MeOAc), methylguanosine ivalsa on the discovery of the fact, the stability of the catalyst and the performance of the carbonylation reactor can be maintained at a surprisingly high level even at very low concentrations in water, i.e. 4% of the mass. or less, in the reaction medium (despite the usual industry practice to maintain about 14 or 15% of the mass. of water). As described in U.S. patent 5.001.259, the carbonylation reaction proceeds while maintaining in the reaction medium of a catalytically effective amount of rhodium, at least a finite concentration of water, methyl acetate and methyl iodide, and a given concentration of iodide ions in excess of the amount of iodine, which contains iodide in the stands or other organic iodide. Ideny ion is present as a salt, and lithium iodide is preferred. U.S. patent 5.001.259 and European patent 161.874 B2 indicate that the concentration of acetate and Yudenich salts are important parameters to ensure the rate of carbonylation of methanol to acetic acid, particularly at low concentrations of water in the reactor. Through the use of relatively high concentrations of acetate and Yudenich salts get surprisingly high degree of catalytic activity and performance reaks., that is, when the concentration is so low that it can be called simply "the end" by the water concentration. In addition, the reaction medium improves the stability of the rhodium catalyst. This stability of the catalyst is improved due to the resistance to the deposition of the catalyst, especially at those stages of the process where the product is extracted, where the distillation used to highlight the product acetic acid, has a tendency to removal of the catalyst by carbon monoxide, which in an environment that is supported in the reactor, is a ligand, the stabilizing effect of rhodium. U.S. patent 5.001.259 attached this link.

In a continuous process for the carbonylation of methanol to acetic acid solution containing a soluble catalyst complex is separated from the reactor product and returned to the reactor. However, for a long period of time, the corrosion is caused by the dissolution included in metallurgical alloys apparatus of metals, such as iron, Nickel, molybdenum, chromium, etc., and their accumulation in recirculating stream of catalyst. It is known that these other metals if they are present in sufficient quantity to affect the reaction of the carbon dioxide and hydrogen and methane. Thus the presence of contamination due to corrosion of the metal exerts a harmful influence on the process, resulting, in particular, to the reduction of output in the calculation of the carbon monoxide. Additionally, other metals can react with iodine ion, which makes this component catalytic system incapable of reaction with rhodium and causes instability of the catalytic system. Given the high cost registeruser catalyst replacement cost spent catalyst may be available. Therefore, the method of regeneration of the catalyst is not only desirable, but necessary.

In accordance with U.S. patent 4.007.130 catalyst solution containing a complex reaction product of rhodium or iridievogo component, the halide component and carbon monoxide, which contains the products of corrosion of metal in close contact with the ion exchange resin in its hydrogen form and get the catalyst solution, free from corrosion products of the metal. As described in U.S. patent 4.007.130, the contacting is carried out, omitting the catalyst solution contaminated undesirable corrosion products of metal, through the layer of ion exchange resin, and receiving output from the catalyst layer of restvracii, are adsorbed and removed by the resin. After saturation, as evidenced by leakage of the products of corrosion of the metal in the output stream, the resin is regenerated by treatment with mineral acid, such as hydrochloric, sulphuric, phosphoric or uudistoodetena acid, and re-used.

However, the U.S. patent 4.007.130 does not consider the use of the catalyst solutions, such as proposed in the previously mentioned U.S. patent 5.001.259. Thus, in the improved catalyst solutions, as discussed above, there is a specified concentration Yudenich ions in excess of the amount of iodine, which is present as methyl iodide or other organic iodide. This extension of ideny ion is present as a salt, and most preferably in the form of lithium iodide. It was found that the regeneration of the catalyst solution to remove metal impurities by passing the catalyst solution through the layer of cation exchange resin in hydrogen form as described in U.S. patent 4.007.130, ion of an alkali metal catalyst solution mainly is removed. The removal of the alkali metal ion of the catalyst solution greatly reduces reactivity and stapostol regeneration of the catalyst solutions carbonyl containing alkali metal ions, in particular lithium, which could be removed from the catalyst solution contamination by metals corrosion, while avoiding removal from solutions of the required components. Therefore, the object of the present invention is to develop a method of processing litiisoderzhashchego catalyst solutions carbonylation to the removal of corrosion products of the metal and the selection of the catalyst solution in a form suitable for return to the process in the form of active catalyst without the need of excessive replacement of its components.

U.S. patent 4.894.477 attached this link suggests using a strongly acidic ion-exchange resin in ion form for the removal of metals corrosion (for example, iron, Nickel, molybdenum, chromium, etc.,) from the reaction system carbonylation. The method described in U.S. patent 4.894.477, particularly applicable to those processes that are used for carbonylation of methanol to acetic acid at low concentrations in water, as proposed in U.S. patent 5.001.259. The process of isolation and purification of acetic acid is improved in conditions of low water content. However, since the concentration of lithium in the reactor carborane water in the reaction system is lowered, capacity cycle ion exchange process for removal of metals corrosion is reduced. In other words, during low water content is manifested a strong tendency for accumulation of metals corrosion in the catalyst solution carbonylation. In conditions with low water content are difficult to remove metals corrosion of the carbonylation reaction. This issue was not addressed in U.S. patent 4.894.477. Accordingly, it is desirable to provide a method of recycling catalyst solution carbonylation to remove the metal corrosion products in the carbonylation process with low water content.

Brief description of the invention

The present invention relates to a method of regeneration or improve the performance of the catalyst solution carbonylation at low water content. The catalytic solution contains soluble complexes of rhodium and contamination by metals corrosion. The improved method comprises closely contacting the catalyst solution with ion exchange resin (IOS) in the form of alkali metal, preferably lithium form, and with a sufficient quantity of water to improve the removal of metals corrosion of the catalyst solution and get produce iron, Nickel, chromium, molybdenum, etc.

Usually the catalyst solution has a water content of from about 0.25 to about 50 wt. -%, preferably from about 5 to about 30 wt. -%, and most preferably from about 5 to about 15% of the mass. for improved removal of metal corrosion.

In accordance with the present invention the catalyst solution containing rhodium and at least a finite concentration of ions of an alkali metal, preferably lithium ions, which is contaminated with metals corrosion and has a given concentration of water is introduced into contact with ion exchange resins, where the additional amount of water introduced into the resin in a quantity sufficient to increase the concentration of water (or reduce the concentration of ions of an alkali metal) in the catalyst solution, and get the catalyst solution without additives metals or significantly reduced their contents.

Typically, the contacting is carried out, omitting the catalyst solution containing impurities of metals through the layer of ion exchange resin in the form of alkali metal, preferably Li-form, and receiving output from layer catalyst solution which contains rhodium component and lithium componey resin layer of the resin may be regenerated by treating the salt of lithium, such as lithium acetate, and reused. Sources of water for the layer ion-exchange resins include, but are not limited to, fresh water added to the layer of resin, or water flows through the reaction system, where the water may be the only or predominant component of the system carbonylation reaction.

The method according to the invention solves the problem associated with systems carbonylation reaction at low water content. The method described here with reference to the carbonylation process using ion-exchange resin in its ion form. However, ion associated with the resin, can be a cation of any known alkaline metal such as lithium, sodium, potassium, etc., provided that the corresponding ion is used as the iodide promoter in the reaction system.

Brief description of drawings

Figure 1 is a schematic diagram showing a flow chart of a process used catalytic carbonyliron methanol in acetic acid and the removal of corrosion products of the metal of the threads of the process.

Detailed description of the invention

One implementation of the present invention relates to the improvement of the Strait is passed through the reaction medium, contained in the reactor, and representing the solution of acetic acid with a low content of water containing rhodium, metallogeny promoter, methyl acetate and lithium iodide. The product acetic acid is recovered from the effluent from the reactor flow pressure drops of the solution to separate the product from the catalyst solution in the form of steam, and then return the catalyst solution to the reactor. During the reaction and during the various stages of the process due to corrosion of metal tanks and columns go into solution and will appear in different threads of a process. Therefore, these streams may contain contamination by metals corrosion and are the threads that need to come into contact with ion exchange resin to remove contaminants metals corrosion. The improvement of this invention includes increasing the water content is preferred for process threads passed through the ion exchange resin until the amount is sufficient to enhance removal of contaminants metals corrosion and receiving streams of the process with substantially reduced content of impurities of metals corrosion.

Another implementation of the present invention relates to a method for improving performance of catalepsia metals, selected from the group comprising iron, Nickel, chromium, molybdenum, and mixtures thereof, where the method comprises contacting the catalyst solution with ion exchange resin in the form of alkali metal, preferably lithium form, and an aqueous medium, preferably water, in a quantity sufficient to reduce the concentration of ions of the alkali metal in the catalyst solution, and obtaining a catalyst solution with a lower content of impurities of metals corrosion.

The method according to the present invention is applicable to regeneration or to improve performance catalyst solutions with low water content, containing a metal salt, a soluble rhodium complexes and mixtures of metals.

The regeneration method according to the invention is particularly applicable to catalyst solutions used for carbonylation of methanol to acetic acid at low water content, as proposed in U.S. patent 5.001.259. Therefore, catalyst solutions, which should be improved by the method of the invention will be mainly contain rhodium catalyst and lithium ion, which is present in the form of salt is lithium iodide.

Although the present invention to isogenopak other products of the carbonylation. For example, proposed in the present invention, the technology can be applied in the process of producing acetic anhydride or in the process of joint production of acetic acid and acetic anhydride. Usually the carbonyl process for acetic anhydride or the joint production of acetic acid and acetic anhydride are in anhydrous conditions. In accordance with the present invention for obtaining acetic anhydride or the joint production of acetic acid and acetic anhydride aqueous medium, preferably water, may be added to the layer ion-exchange resin, to improve the removal of metals corrosion and thereby increase the productivity of the catalyst solution. Other processes which can be used in the present invention include the carbonylation of alcohols, complex or simple esters to the corresponding acids, anhydrides, or mixtures thereof. Usually these alcohols, esters or ethers contain from 1 to 20 carbon atoms.

When carbonyliron methanol in acetic acid with a low water content is shown in U.S. patent 5.001.259 used catalyst includes rhodium component and a halide promoter, in which the halogen precicesly system is present in the form coordination compounds of rhodium with a halide component, forming at least one of the ligands of such coordination compounds. It is also believed that in addition to the coordination of rhodium and halogen ligands are carbon monoxide to form coordination compounds or complexes with rhodium. The presence of a rhodium component of the catalyst system can be provided by introducing into the reaction zone of rhodium in the form of metallic rhodium, salts and oxides of rhodium, organic rhodium compounds, coordination compounds of rhodium, etc.

Halide promoting component catalytic system represents a halide compound comprising an organic halide. So, there can be used alkyl-, aryl - substituted alkyl - or aryl halides. Preferably the halide promoter is present in the form of alkylhalogenide, in which the alkyl radical corresponds to the alkyl radical of raw alcohol, which carbanilide. For example, when carbonyliron methanol in acetic acid halide promoter will consist of methylglucamide, and more preferably from methyl iodide.

Used the liquid reaction medium may include any solvent compatible with the catalyst system, and may include pure alcohols is the first solvent and liquid reaction medium for the process of carbonylation at low water content is the product carboxylic acid. So, for carbonylation of methanol to acetic acid is the preferred solvent is acetic acid.

Water is also introduced into the reaction environment, but in concentrations that are much lower than those previously considered to be useful to achieve a satisfactory reaction rate. It is known that in the reactions catalyzed by rhodium carbonyl addition of water has a beneficial effect on the reaction rate (U.S. patent 3.769.329). So industrial operations are carried out at concentrations in water of at least 14% of the mass. Referring to U.S. patent 5.001.259 is completely unexpected that the reaction rate substantially close to the speed of the reaction at such high levels of concentration of water or exceeding them, can be reached at water concentrations below 14% of the mass. and as low as 0.1% of the mass.

In accordance with the carbonyl process is described in U.S. patent 4.894.477, the desired reaction rate is achieved even at low water concentrations by introducing into the reaction medium of ester, which corresponds carbonyliron alcohol and obtained by the reaction of carbonyl acid, and the extension of iodide ion in excess of iodine, which is present in the form to the methanol in acetic acid ester is an acetate, and incremental iodine promoter is jodido salt, such as lithium iodide. It was found that at low concentrations in water methyl acetate and lithium iodide act as promoters speed only when both components are present in relatively high concentrations, and that the promotion is higher when both components are present simultaneously. It was not known previously. It is believed that the concentration of lithium iodide used in the reaction medium described in U.S. patent 4.894.477 is quite high compared to that in the earlier practice was used when the use of halide salts in the reaction systems of this type.

As mentioned above, the catalyst solutions carbonylation with low water content are used carbonyliron alcohols. The materials used, which can Carboniferous include alkanols having 1-20 carbon atoms. Preferred raw materials are alkanols containing 1 to 10 carbon atoms, and most preferred alkanols with 1 to 6 carbon atoms. Methanol is especially preferred raw material and converted into acetic acid.

The carbonylation reaction may conducts the and, barotraumas through the liquid reaction medium comprising rhodium catalyst, halogenated promoterwise component, alkyl ether and additional soluble promoter - jodido salt, at a temperature and pressure suitable for the formation of the product of the carbonylation. So, if the feedstock is methanol, the halogenated promoter will represent methyl iodide and alkyl ether will be a acetate. It is generally accepted that the concentration of iodide ion in the catalytic system, and not the cation associated with the iodide, and that at a given molar concentration of iodide nature of the cation is not as important as the effect of the concentration of iodide. Can be used iodide salt of any metal or any iodide salt of any organic cation, unless the salt is sufficiently soluble in the reaction medium to provide the desired level of concentration of iodide. Iodide salt may be a Quaternary salt of an organic cation or iodide salt of an inorganic cation, preferably it is iodide salt of a member of the group consisting of metals of groups 1 and 2 of the periodic table (on view in "Handbook of Chemistry and Physics, CRC Press, Cleveland, Ohio, 1995-96 (76th edition)). In h the Oia. The use of lithium iodide and its deadweight loss when removing metal impurities from the catalyst solution by ion exchange, however, create a problem that is directly authorized by way of regeneration of the catalyst according to the invention.

Typically, the temperature of the carbonylation reaction may be approximately 150-250oC, and the temperature range of about 180-220oC is preferred. The partial pressure of carbon monoxide in the reactor can vary widely, but typically is about 2 to 30 atmospheres and preferably is about 4 to 15 atmospheres. Because the partial pressure of by-products and the pressure of the vapors contained in the reactor liquids, the total pressure in the reactor is in the range of from about 15 to 40 atmospheres.

Fig. 1 shows a reaction system which can be used in the process of regeneration of the catalyst according to the present invention. The reaction system includes a liquid-phase carbonylation reactor, evaporator, column separation of methyl acetate and acetic acid (hereinafter "separation column"), a decanter, a drying column and ion-exchange resin. For illustration in Fig. 1 shows one of IOS. It is clear that the process Carboniferous an autoclave with stirring, which is automatically maintained at a constant level of the reaction liquid. In this reactor is continuously injected carbon monoxide, fresh methanol, sufficient water to maintain at least a finite concentration of water in the reaction medium, recycle catalyst solution from the cube evaporator and recycle methyl iodide and methyl acetate from the top of the separation column. Can be applied and other water distillation systems if they provide a way to extract the crude acetic acid and recycled to the reactor catalyst solution, methyl iodide and methyl acetate. In a preferred process, the original carbon monoxide is continuously introduced into the carbonylation reactor directly below the mixer. Gaseous raw materials are thoroughly dispersed in the reaction liquid by stirring. The gaseous stream is discharged from the Stripping reactor, to prevent the accumulation of gaseous by-products and to maintain a given partial pressure of carbon monoxide at a given total reactor pressure. The temperature in the reactor is maintained automatically, and the source of the carbon monoxide is introduced at a rate sufficient to maintain the desired total pressure in reacto is of constant liquid level, and is introduced at a point midway between the helmet and the bottom of the evaporator. From the evaporator catalyst solution is displayed as blue stream (mainly acetic acid containing rhodium and jodido salt along with lesser quantities of methyl acetate, methyl iodide and water), while chlebowy flow evaporator contains mainly the product of acetic acid with iodine stands, acetate and water. Part of the carbon monoxide together with gaseous byproducts, such as methane, hydrogen and carbon dioxide goes from the top of the evaporator.

The product acetic acid is derived from a cube of the separation column (it can also output in the form of a side selection), then assigned to the desired final purification by methods which are obvious to a person and which are not included in the subject of the present invention. The use of the drying column is a means of purification of the product acetic acid. Chlebowy flow separation column containing predominantly methyl iodide and methyl acetate, returns to recycling in the carbonylation reactor together with fresh iodine stands, with fresh methyl iodide is introduced at a rate, dostatochno the reaction medium. Fresh methyl iodide is necessary to compensate for small losses of methyl iodide in the evaporator and Stripping from the carbonylation reactor. Part shlamovogo stream from the separation column is introduced into the decanter, which divides the streams of methyl iodide and methyl acetate in the heavy water phase methyl iodide and methyl acetate and a light phase containing aqueous acetic acid. Any flow of water from the cleanup phase, which will contain a small amount of acetic acid may be combined with a light phase aqueous acetic acid of the decanter for return to the reactor.

It was found that the impurity metals, in particular iron, Nickel, chromium and molybdenum may be present in any of the threads above process. The accumulation of these metal impurities adversely affecting the rate of formation of acetic acid and the stability of the process as a whole. Therefore, the ion-exchange resin is introduced into the process to remove these impurities of metals from process threads. In Fig. 1 ion-exchange resin used to remove contaminants from metal corrosion of the catalyst solution is recycled from the cube evaporator to the reactor. It should be understood that any of the threads of the process moeran is what this thread should be at this temperature when not deactivated resin. In the General case, the processed threads in the process will have the final concentration of the rhodium catalyst and/or lithium cation of the additional salt is lithium iodide, which added to the catalyst promoter. In Fig. 1 the flow of the cube of the separation column is processed to remove metals corrosion, and water from a stream of dilute acetic acid, is directed to an ion-exchange resin.

The sources of water to be added to the resin include fresh water, from the reaction system, or the water from the reaction system, which eventually is returned to the reactor. Preferably, the water from the reaction system was applied to the resin for use in an improved process for the removal of metals corrosion. The balance on the water then remains closed in the system carbonylation reaction. Examples of sources of water include (but are not limited to) the water contained in the recycle streams of dilute acetic acid, water from the light phase, or water from the combined streams (for example, the United streams of the heavy and light phases, or combined light phase and flows razbalovani water from any point within the reaction system.

The amount of water added to the ion-exchange resin, can vary to optimize the removal of metals corrosion. When conditions in the carbonylation reactor, using 14% of the mass. or 15% of the mass. water, one would expect only a small increase in the number of metal corrosion, remove the for loop saturation ion-exchange resin. However, under conditions of low water content in the reactor the need should the concentration of water in IOS-the process of removing corrosion is important. In General, the water content of the catalyst solution contains about 0.25 to about 50 wt%. water. However, the preferred interval is from about 5 to about 30 wt. -%, and the most preferred range from about 5 to about 15 wt. -%

The resin used for the regeneration of the catalyst solution according to the invention are cation-exchange resins either strongly acidic or weakly acidic type. As mentioned above, any cation is acceptable provided that the corresponding cation used in iodide the promoter. For the purposes of illustrating the present invention used cation exchange resin in the lithium form. Resin strongly and weakly acidic type readily available as the industry is new or methacrylic acid, or esters, or the corresponding NITRILES, and only a few available on the market are phenolic resins. Strongly acidic cation-exchange resins, which are preferred for use in the present invention, represented mainly sulfonated styrene-divinylbenzene copolymers, although some of the available resins of this type are the phenol-formaldehyde condensation polymers. Appropriate is a gel type resin or macrostate type of resin, but the latter is preferred, because to be processed catalyst solution contains organic components.

Macrostate resins are widely used in the practice of catalysis. They require a minimum amount of water to maintain them in the swelled state. The present invention partly unexpectedly, as experts on the use of resins macrosector type believe that very little water is required for their use. These problems, as such, are not expected to pitches with changing concentrations of water in the carbonyl process from high to low. However, it was found that as the concentration of water in the reaction process was reduced, it was the years of macromycetes resin.

The contacting metal contaminated catalyst solution and the resin can be carried out in the apparatus with stirrer, where the resin is suspended in catalyst solution with intensive stirring, and then the catalyst solution allocate by decantation, filtration, centrifugation, etc., However, the processing of the catalyst solutions are usually carried out by passing contaminated with metals solution through the column with a porous layer of resin. Regeneration of the catalyst can be conducted as batch, semi-continuous or continuous operation with manual or automatic control with the use of well-known in the practice of ion exchange methods and procedures.

Ion-exchange treatment may be conducted at temperatures in the range of from about 0oC to about 120oC, although lower or higher temperatures limited only by the stability of the applied resin. Preferred temperatures are temperatures in the range of from about 20oC to about 90oC, chromium is removed more efficiently at higher temperatures. At higher temperatures the desired purging with nitrogen or CO. If the temperature above the boiling point of primeco phase. However, pressure is not a critical variable. Usually applied atmospheric pressure or the pressure of the weakly above atmospheric, but, if required, can be used high or low blood pressure.

The flow rate of the catalyst solution through the resin in the process of removing metal corrosion will generally those recommended by the manufacturer of the resin and usually will be from about 1 to about 20 volumes of a layer in an hour. Preferably the flow rate is from about 1 to about 12 volumes of the layer in an hour. After contacting the layer containing rhodium flow process to remove all of the rhodium layer of resin is necessary to rinse or wash the layer of the resin with water or carbonylation product of the process, from which was taken the catalyst for processing, such as acetic acid. Washing or rinsing is carried out under the same flow rates that stage and remove the dirt.

After the resin has become saturated, i.e. when started leakage of metallic impurities in the output stream, the resin may be regenerated by passing through it a solution of organic salts, for illustration purposes, preferably lithium salts. Usually salt of lithium, used ESCWA and methods are those which are well known in practice and recommended by the manufacturer of the resin. Preferred as the regenerating agent is lithium acetate, because the acetate anion is present in the reaction system and is readily available for use. An additional advantage is that its use eliminates the stage of flushing, usually required after the regeneration process, if applicable other regenerating substances.

To maximize the regeneration capacity of metal corrosion and to improve the performance of the column with the resin layer at relatively high concentrations of lithium acetate, regeneration solution of lithium acetate must contain a certain amount of acetic acid or of obtained product, in order to avoid the formation of any insoluble compounds of metals corrosion during the regeneration cycle. The precipitation of these compounds during the regeneration cycle may reduce the regenerative capacity of the column and also lead to clogging layer resin. Usually, you can use the acetic acid concentration is from about 0.1 to about 95 wt. -%, moreover, the acetic acid concentration is from about 0.1 to about 20% of the mass. are preferred.

the sustained fashion the type of operation is a continuous operation. In a continuous process outlet stream from the catalyst solution, which should be returned to the reactor for the production of acids, assign, pass through the layer of ion exchange resin with water recycle stream to provide a sufficient concentration of water to increase the quantity of adsorbed thereon corrosion products, and purified from these corrosion products output stream, along with United water recycling back into the flow of the circulating catalyst and then into the reactor. The operation of ion exchange can be cyclic (when more than one ion exchanger is available for use). After the resin becomes saturated one ion exchanger outlet flow of the catalyst solution switch on a fresh layer, while the saturated layer is subjected to regeneration.

The invention is illustrated in non-limiting examples, are given in table. 1 and 2.

1. The way to improve the performance of the catalyst solution carbonylation at low concentrations in water containing rhodium and an alkaline metal and an additional impurity metals corrosion, comprising contacting the catalyst solution carbonylation with ion exchange resins, in Cotati water in the catalyst solution in the range of from about 0.25 wt. % to about 50 wt.%, that allows you to remove from the catalyst solution carbonyl impurity metals corrosion.

2. The method according to p. 1, wherein the resin is a strongly acidic cation exchange resin.

3. The method according to p. 1, characterized in that said contacting is performed by passing the catalyst solution through the column with a fixed layer of the specified resin.

4. The method according to p. 1, characterized in that the specified resin regenerate after saturation by flushing salt of an alkali metal.

5. The method according to p. 1, characterized in that the concentration of water in the catalyst solution passing through the cycle of contacting is in the range of from about 5 wt.% to about 30 wt.%.

6. The method according to p. 5, characterized in that the concentration of water in the catalyst solution passing through the cycle of contacting is in the range of from about 5 wt.% to about 15 wt.%.

7. The method according to p. 4, characterized in that the specified alkali metal salt is lithium acetate.

8. The method according to p. 4, characterized in that the alkali metal is potassium.

9. The method according to p. 4, wherein the alkaline metal is nottruly water and alkali metal and contamination by metals corrosion, selected from the group comprising iron, Nickel, chromium, molybdenum, and mixtures thereof, comprising contacting the specified catalyst solution with a cation exchange resin in a cycle of contact with the cation exchange resin, in which an additional quantity of water sufficient to maintain the concentration of water in the catalyst solution passing through the cycle of engagement, from about 0.25 wt.% to about 50 wt. % that allows to remove from the catalyst solution carbonyl impurity metals corrosion.

11. The method according to p. 10, characterized in that the concentration of water in the catalyst solution passing through the cycle of contacting is in the range of from about 5 wt.% to about 30 wt.%.

12. The method according to p. 11, characterized in that the concentration of water in the catalyst solution passing through the cycle of contacting is in the range of from about 5 wt.% to about 15 wt.%.

13. The way to improve the performance of the catalyst solution carbonylation at low water content, containing rhodium and an alkaline metal and an additional impurity metals corrosion, comprising the contacting of the catalyst solution with jonoob is to maintain the water concentration in the catalyst solution, passing through the loop of the probe in the range of from about 0.25 wt.% to about 50 wt.%, that allows you to remove from the catalyst solution carbonyl impurity metals corrosion.

14. The method according to p. 13, characterized in that the concentration of water in the catalyst solution passing through the cycle of contacting is in the range of from about 5 wt.% to about 30 wt.%.

15. The method according to p. 14, characterized in that the concentration of water in the catalyst solution passing through the cycle of contacting is in the range of from about 5 wt.% to about 15 wt.%.

 

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The invention relates to a new method of regenerating catalyst alkylation, which contains a sulfone component and method of removal mechanisms of alkylation catalyst, and the specified sulfon is sulfolane, and KRM-absorbent material selected from the group consisting of aluminum oxide, carbon and mixtures thereof

FIELD: processes catalyzed by metal-phosphoro-organic ligand complexes when target product may be selectively extracted and separated from liquid product.

SUBSTANCE: Specification gives description of methods of separation of one or several products of decomposition of phosphoro-organic ligand, one or several reaction byproducts and one or several products from liquid reaction product synthesized continuously and containing one or several non-consumed reagents, catalyst in form of complex of metal-phosphoro-organic ligands, not obligatory free phosphoro-organic ligand, one or several said decomposition products of phosphoro-organic ligand, one or several said reaction byproducts, one or several said products, one or several non-polar solvents and one or several polar solvents by separation of phases where (i) is selectivity of non-polar phase for phosphoro-organic ligand relative to one or several products expressed by ratio of distribution coefficient Ef1 whose magnitudes exceeds about 2.5; (ii)is selectivity of non-polar phase for phosphoro-organic ligand relative to one or several decomposition products expressed by ratio of distribution coefficients Ef2 whose magnitude exceeds proximately 2.5; and (iii) is selectivity of non-polar phase for phosphoro-organic ligand relative to one or several reaction byproducts expressed by ratio of distribution coefficients Ef3 whose magnitude exceeds approximately 2.5 (versions). Description is also given of continuous methods of obtaining one or several products (versions) and reaction mixture containing one or several aldehyde products.

EFFECT: increased conversion of initial materials and selectivity by product; avoidance or exclusion of deactivation of catalyst.

20 cl, 2 tbl

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to regeneration of basic anionite catalysts for process of production of alkylene glycols via hydration of corresponding alkylene oxides. Method according to invention consists in treatment of spent catalyst with aqueous solution of inorganic salts of iodine and inorganic acids or with hydroiodic acid aqueous solution.

EFFECT: achieved complete restoration of initial volume and selectivity of catalyst and thereby prolonged lifetime of expensive anionite catalyst.

1 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: method involves, for example: (a) evaporation of said oxidised discharge stream, containing terephthalic acid, metallic catalyst, impurities, water and solvent, in the first zone of an evaporator to obtain a vapour stream and a concentrated suspension of the discharge stream; and (b) evaporation of the said concentrated suspension of the discharge stream in the second zone of the evaporator to obtain a stream rich in solvent and a high-concentration suspension of the discharge stream, where the said second zone of the evaporator has an evaporator operating at temperature ranging from 20C to 70C, where from 75 to 99 wt % of the said solvent and water is removed by evaporation from the said oxidised discharge stream at step (a) and (b); (c) the said high-concentration suspension of the discharge stream is filtered in a zone for separating solid products and liquid to form a filtered product and a mother liquid; (d) washing the said filtered product using washing substances fed into the said zone for separating solid products and liquid to form a washed filtered product and washing filtrate; and dehydration of the said filtered product in the said zone for separating solid products and liquid to form a dehydrated filtered product; where the said zone for separating solid products and liquid has at least one pressure filtration device, where the said pressure filtration device works at pressure ranging from 1 atmosphere to 50 atmospheres; (e) mixing water and optionally extractive solvent with the said mother liquid and with all of the said washing filtrate or its portion in the mixing zone to form an aqueous mixture; (f) bringing the extractive solvent into contact with the said aqueous mixture in the extraction zone to form a stream of extract and a purified stream, where the said metallic catalyst is extracted from the said purified stream.

EFFECT: improved method of extracting metallic catalyst from an oxidised discharge stream obtained during production of terephthalic acid.

36 cl, 3 dwg, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention describes method for extraction of homogeneous ruthenium catalyst from glycolic acid hydrogenation reaction product, glycolic acid esters and/or glycolic acid oligomers under action of extractant containing hydrophobic solvent and optional hydrophilic solvent. Ruthenium catalyst, which may include 1,1,1-tris(diaryl- or dialkylfosfinomethyl)alkane ligands, can be extracted from hydrophobic extract phase as result of extraction under action of hydrophilic solvent and sent for recycling in process of producing ethylene glycol as result of glycolic acid and glycolic acid derivatives hydrogenation.

EFFECT: technical result is effective method of ruthenium-1,1,1-tris(diaryl- or dialkylfosfinomethyl)alkane catalyst compositions extracting from glycolic acid hydrogenation waste product till maximum extraction of catalyst system at minimal costs in combined method, taking into account stages of both reaction and separation for producing ethylene glycol.

29 cl, 7 dwg, 26 tbl, 17 ex

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