Method for continuous producing acetic acid (variants) and method for treatment of acetic acid flow

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

 

The SCOPE of the INVENTION

This invention generally relates to methods for the production of acetic acid; and, in particular, to low-energy (i.e. low power) modes of production of acetic acid by carbonyliron methanol and carbon monoxide and the use of at most two distillation columns in the primary treatment system.

BACKGROUND of INVENTION

Among the currently used methods for the synthesis of acetic acid one of the most commercially applicable is catalyzed by a rhodium carbonylation of methanol with carbon monoxide, as described in U.S. patent No. 3769329 Paulik and other carbonylation Catalyst contains rhodium, dissolved or otherwise dispersed in a liquid reaction medium along with the halogen-containing promoter and a catalyst, such as methyliodide. Usually the reaction is performed with the catalyst dissolved in the liquid reaction medium through which continuously pass gaseous carbon monoxide. Paulik et al. found that in order to provide a beneficial effect on the reaction rate to the reaction mixture can be added to water. Usually use a water concentration of more than about 14 wt.%. This so-called "deep" way carbonylation.

Alternatively, a "deep" way CT is arilirovaniya in U.S. patent No. 5001259, 5026908 and 5144068 proposed "dry" method of carbonylation. In the "dry" method carbonylation can be used water concentration below 14 wt.% and even below 10 wt.%. The use of low concentration of water simplifies production of the desired carboxylic acid in its ice form.

In the way carbonylation to acetic acid, it is desirable to minimize the number of operations of distillation, in order to minimize the energy consumption in the way. In the given ratio in U.S. patent No. 5416237 Aubigne and others proposed a method for the production of acetic acid by carbonyliron methanol in the presence of a rhodium catalyst, under the conditions and salt-iodide as a stabilizer. The improvement according to patent '237 is to maintain a final concentration of water in the liquid reaction composition to about 10 wt.%, and the concentration of acetate, at least 2 wt.%, and the selection of product - acetic acid - passing the liquid reaction composition through an area of rapid evaporation with vapor fraction which is served on a single distillation column, from which secrete the product is acetic acid. The disadvantage of eliminating the stage of distillation is that it suffers from a degree of purity of the product. In particular, distillation columns tend to remove wysockis the s iodides, and aldehyde polluting products. Both these impurities are detrimental to the commercial desirability of the end product.

State of the art well-known variety of tools for removing iodides. Hilton was found that the macroporous strongly acidic cation-exchange resin, at least 1% of the active centers, converted into silver or mercury form, provide high efficiency removal of iodide impurities from acetic acid or other organic environment. The amount of silver or mercury associated with resin, can be from less than about 1% of the active centers to above 100%. Preferably, from about 25% to about 75% of the active centers were converted to the silver or mercury form and, most preferably, about 50%. In U.S. patent No. 4615806 a method for removing various iodide from acetic acid. In particular, it is shown in the examples of removal under the conditions, HI, I2and hexylidene.

Various embodiments of the basic invention disclosed in U.S. patent No. 4615806, subsequently appeared in the literature. In U.S. patent No. 5139981 Kurland shows the method of removing iodides from a liquid contaminated with impurities halogen free carboxylic acid by contacting a liquid contaminated by halogen acid with silver(I)-exchange macroporous resin. The halogen reacts with silver is m, associated with resin, and is removed from the stream carboxylic acid. More specifically the invention of the '981 relates to an improved method of manufacturing silver-exchange macroporous resins suitable for use in the removal of iodide from acetic acid.

U.S. patent No. 5227524 Jones discloses a method of removing iodides using silver exchange macrostate strongly acidic ion-exchange resin. The resin has from about 4 to about 12% cross-linking, surface area protonotariou form less than 10 m2/g after drying the water from the wet state and surface area of more than 10 m2/g after drying of the wet state, in which water was replaced by methanol. The resin has at least one percent of the active centers, converted into silver form and, preferably, from about 30 to about 70% of its active sites converted to the silver form.

In U.S. patent No. 5801279 Miura and other method steps of a layer of silver exchange macrostate strongly acidic ion-exchange resin for removing iodides from a stream of acetic acid type Monsanto. The mode of action includes an action layer silver-exchange resin with a gradual rise of temperature, and the contacting acetic acid and/or acetic anhydride containing iodide compounds from the resin. As an example, the patent describes UD the other hexylidene of acetic acid at temperatures from about 25° With up to about 45°C.

In addition, for the removal of iodide impurities from acetic acid and/or acetic anhydride can be used other ion-exchange resin. In U.S. patent No. 5220058 Fish et al. have shown the use of ion exchange resins, having exchanged for metal tirinya functional group, to remove impurities iodide from acetic acid and/or acetic anhydride. Usually Tilney functional group ion-exchange resin was exchanged for silver, palladium or mercury.

Additionally, in European patent publications No. 0685445 A1, a method for removing iodide compounds from acetic acid. The method involves contacting the stream of acetic acid containing iodides, with polyvinylpyridine at elevated temperatures to remove iodides. Usually acetic acid according to the publication '445 served on the resin layer at a temperature above 100°C.

Under the influence of increasing costs and higher energy prices increases the motivation to simplify methods of chemical production and, in particular, to reduce the number of production stages. In this regard, it is noted that in U.S. patent No. 5416237 Aubigne and others proposed the only area of the refining process for the manufacture of acetic acid. These modifications of the method, while desirable from the point of view of energy costs, have a tendency that set high requirements to the cleaning system. In particular, fewer recyclo leads to the fact that you enter a larger number (or worse delete) iodide in product flow and, in particular, more iodides with high molecular weight. For example, in the product flow can be octreotid, deciided and domiciliated, as well as hexadecanolide; they all trudnoudaljaemye using conventional technologies.

In addition, other impurities in the acetic acid produced by carbonyliron methanol catalyzed by rhodium, namely aldehydes and propionic acid. In article Watson, The CativaTMProcess for the Production of Acetic Acid, Chem. Ind. (Dekker) (1998) 75 Catalysis of Organic Reactions, pp. 369-380, suggest that acetaldehyde undergoes reduction by hydrogen catalyzed by rhodium system with the formation of ethanol, which then gives propionic acid. Postulate that improved rhodium catalytic system increases constant levels rhodium-acyl particles with higher speed form free acetaldehyde.

The exact chemical path in the way that the carbonylation of methanol, which leads to the formation of crotonic aldehyde, 2-atolkachova aldehyde and other reducing permanganate compounds are not well understood. One of the prominent theories of education premastication aldehyde and 2-atolkachova aldehyde in the way carbonylation of methanol is they are the result of reactions Alderney and cross-Alderney condensations involving acetaldehyde. The main efforts should be directed at removing acetaldehyde.

Conventional technologies used for the removal of acetaldehyde and other carbonyl impurities include treatment with acetic acid oxidants, ozone, water, methanol, amines and the like. In addition, each of these technologies can be combined or not combined with a distillation of acetic acid. The most typical cleaning processing includes a series of distillations product - acetic acid. In addition, it is known that carbonyl impurities can be removed from organic streams by processing organic threads amine compound such as hydroxylamine, which reacts with the carbonyl compounds with the formation of Asimov, followed by distillation to separate the purified organic product from oxomnik reaction products. However, this method of processing product - acetic acid - increases the cost of the process.

In U.S. patent No. 5625095 Miura and others, and international PCT application no PCT/US97/18711, the publication number WO 98/17619 proposed various methods for removing acetaldehyde, and other impurities in the process catalyzed by rhodium to obtain acetic acid. Usually these methods provide the more the removal of undesirable impurities from a stream of recycle to reduce the concentration of acetaldehyde in the system.

SUMMARY of the INVENTION

In accordance with this invention provides a low-energy way carbonylation using on stage primary treatment at most two distillation columns. In accordance with the method of the invention, the amount of aldehydes in the product flow, preferably regulate the removal of aldehydes from the system or process so that the generated low levels of impurities aldehydes and their derivatives, such as organic iodides. In addition, high-boiling iodides can be removed by using high temperature ion-exchange resin, and the product shows a high degree of purity.

More specifically, in accordance with this invention features a continuous method for the production of acetic acid, including:

(a) reaction of methanol with the raw material - carbon monoxide in the carbonylation reactor containing a catalytic reaction medium while maintaining the specified reaction medium, at least a finite concentration of water, from about 0.1 wt.% to less than 14 wt.%, along with (i) salt, soluble in the reaction medium at the reaction temperature, in a quantity sufficient to maintain the concentration of iodide ions in the range of from about 2 to about 20 wt.%, effective as a stabilizer cat who lyst and copromotor; (ii) from about 1 to about 20% under the conditions; (iii) from about 0.5 to about 30 wt.% methyl acetate; (iv) a rhodium catalyst; and (v) acetic acid. A portion of the reaction medium is extracted from the reactor and evaporated at a stage of rapid evaporation. The evaporated vapors distilled to form a liquid stream, a product of acetic acid with the use of up to two distillation columns, giving at the same time, one or more threads of recycling to the reactor. The amount of aldehyde in the liquid product flow - acetic acid can optionally be adjusted in one of three ways or a combination of these methods, which include: (i) action in the reactor total pressure from about 15 to about 40 atmospheres, while maintaining the partial pressure of hydrogen of less than 6 psia (absolute pressure in pounds per square inch); (ii) maintaining in the reaction medium concentration under the conditions of less than about 5 wt.%; and (iii) removing aldehyde impurities, at least one stream recycling.

Especially preferred iodide salts are iodide salts of alkali metals such as lithium iodide. Salt can be formed in situ, for example, by adding to the reactor lithium acetate or a salt-forming phosphines, including the pentavalent phosphine oxide. If only iodide ions can be titrated with silver, minimizing the deposition of p is Diya and provide operation while maintaining most or at least 50% of the rhodium in the oxidized state, Rh(I) at a concentration of water of less than 14%, it is "Sol", corresponding to the definition given here. Salt can be used individually or in combination to maintain the required level of iodide ions. Compare U.S. patent No. 5817869 with U.S. patent No. 6013129, the contents of which are listed as references.

The iodides are removed from the residual liquid stream of acetic acid so that the product had an iodide content of less than about 10 h/billion (ppb). The iodides are removed in one of two ways:

(a) the first method involves contacting a liquid residual product flow - acetic acid - anionic ion exchange resin at a temperature of at least about 100°C, followed by contacting the liquid residual product flow - acetic acid with silver or mercury-exchange substrate, in which at least 1% of the active centers (for example, sulfonic groups) resin converted to the silver or mercury form;

(b) the second method involves contacting a liquid residual product flow - acetic acid with silver or mercury-exchange ion exchange substrate at a temperature of at least about 50°in which at least 1% of the active sites of the resin converted to the silver or mercury form.

When using anionic resin, in particular, the preferred resins are polyvinylpyridine resin and polyvinylpyrrolidone resin. Anionic resin is usually used at a temperature of at least about 150°C.

If you use silver or mercury-exchange substrate, it is usually macrostate strong acid cation resin. The temperature can be from about 60 to about 100°C. Sometimes use a minimum temperature of 60°With, however, in some executions, the preferred minimum temperature of 70°C.

In General, if you use silver or mercury-exchange strongly acidic cationic resin, usually from about 25% to about 75% of the active centers transform into the silver or mercury form. Most typically, when turn thus about 50% of the active centers.

Aldehydes in the system may, optionally, be regulated by the removal of aldehydes from recycling to the reactor, for example, by distillation from the condensed stream recycling.

Alternatively, the level of aldehyde impurities in the system may be regulated to minimize the partial pressure of hydrogen or level under the conditions in the reactor. In particular, when the total pressure in the reactor of from 15 to 40 atmospheres can be used the absolute partial pressure of from about 0.1 to 4 psia. The partial pressure in Dorada from about 1 to about 4 psia may be preferable. The relatively low level under the conditions in the reactor may be about 5 wt.% or less. In addition, there may be used a level under the conditions of from about 1 to about 5 wt.%.

In another aspect of the invention is provided (receipt) of acetic acid by the method described here, when the product has a content of propionic acid is less than approximately 500 h/million Usually product - the acid has a content of propionic acid is less than about 250 ppm, preferably less than about 150 h/million

Particularly preferred methods are those in which use silver-cation exchange substrate to remove iodides and relatively low partial pressure of hydrogen in the reactor to regulate the aldehyde impurities. The flow of product in many cases contains organic iodides with aliphatic chain C10 or more, which must be removed. Sometimes there are more than 25% of iodides or even 50%with the length of the organic chain more than 10 carbon atoms.

In the absence of devices end cleaning limit and other factions especially dominated by deciided and dodecylamide that are difficult to remove from the product stream, as will be clear based on the data below. Silver exchange cationic substrates of the present invention typically remove more than 90% of these iodides; often the flow of product is that it contains from 10 to 1000 h/bn all iodides before treatment, what makes the product unsuitable for use in sensitive iodides applications.

To some extent the typical content is from about 20 hours per billion to about 750 h/bn iodide to processing for removing iodides, while the processing for removing iodides, preferably, is used to remove at least about 99% of the total present iodide. In a typical embodiment, for processing for removing iodides are in contact of the product with silver exchange macrostate ion exchange resins, functionalized with acid, where the product contains more than 100 h/bn organic iodide before treatment, after treatment contains less than 10 h/bn organic iodide.

The following related applications related to the objective of the present invention, shown here as a reference, the appropriate parts of which are described below.

U.S. patent No. 09/386708, registered on August 31, 1999, Mark O. Scates and others, entitled "Rhodium/Inorganic Iodide Catalyst System for Methanol Carbonylation Process with Improved Impurity Profile"; U.S. patent No. 09/386561, registered on August 31, 1999, Hung-Cheung Cheun and others, entitled "Rhodium/Inorganic Iodide Catalyst System for Methanol Carbonylation Process with Improved Impurity Profile"; and U.S. patent No. 09/534868 registered 21 March 2000, George A. Blay and others, entitled "Method of Remouving Organic Iodides from Organic Media.

The above and additional special the spine of this invention will be further evaluated in the subsequent discussion.

If not defined in the context or explicitly used here,"%", "percent" or similar refer to mass percent (wt.%). Similarly, the term "ppm"is "parts per million" and the like, and "h/bn" refers to mass ppm and mass ppb, respectively, unless otherwise specified. The term "active centers" ion exchange resin refers to the centers of the specified resin capable of exchanging ions. For example, in Cotonou ion-exchange resin having a cation exchange capacity of 2 millieu./g, 2 millieu./g be 100% active centers, 1 millisv./g is 50% of the active centers and so on.

Description of the DRAWINGS

The invention is described below with reference to various drawings. In the drawings:

Figure 1 is a schematic diagram of the first device, applicable in the practice of the present invention;

Figure 2 is a schematic diagram of a second apparatus, applicable in the practice of the present invention;

Figure 3 is a graph of the concentration of iodide in the treated acetic acid depending on the time for commercial samples of materials from the remainder of the drying columns, where processing produced under normal conditions;

Figure 4 is a graph of iodide in a solvent for elution solvent of acetic acid depending on the time for dodecylamide and hexylidene after treatment with RA is personal temperatures;

Figure 5 is a graph iodide depending on the time in the eluent solvent for acetic acid after treatment for hexylidene and neopentylene;

6 is a graph of various isotherms elution with 25°to 100°for alkylated removed from acetic acid; and

7 is a graph of the concentration of iodide in a solvent for elution solvent of acetic acid depending on the time for commercial samples of material treated at 25°and 50°in accordance with this invention.

DETAILED DESCRIPTION

It should be noted that catalyzed by rhodium way to obtain acetic acid is well known. Therefore, the invention will be described in terms of differences from the earlier methods, such as described in U.S. patent No. 5001259, 5026908, 5144068, the contents of which are hereby incorporated by reference. There are two criteria that should be satisfied to maintain the optimum performance of the reaction system catalyzed by rhodium carbonylation of methanol to acetic acid. These criteria are put forward in addition to the need to maintain a stable state of the catalytic system, from which during the selection of the product is not precipitated rhodium catalyst. First, it is desirable to maintain high performance in the reactor ka is bonierbale, what is measured by the number of the formed acetic acid per unit time per unit volume or mass of liquid reaction medium contained in the reactor. It can be defined as "the performance of the reactor or volumetric capacity of the reactor, also denoted "STY". Secondly, the improved method involves maintaining optimal performance, measured by the final allocation of glacial acetic acid in the combined system, including carbonylation and purification system. Specialists in this field recognize that water is an undesirable component of the crude acetic acid and that the more water present in the product flow, the greater the cost of the process and requirements of the investment in cleaning system allocated product. Therefore, the system performance must be considered along with the performance of the reaction, the system performance depends on the extent to which it is not allowed the water in the remainder of the stream of raw product. The drier the flow, the higher the system performance, unless the performance of the reaction of the support with a suitable degree of purity.

For the purposes of this invention used catalyst contains rhodium component and a halogen promoter, in which the halogen is usually what I iodine. As is well known, the catalytic system is preferably generally homogeneous. Guess rhodium component of the catalyst system of this invention must be present in the form coordination compounds of rhodium and halogen component, providing at least one of the ligands of the specified coordination compounds. In addition to the coordination of rhodium and halogen, believed to be the carbon monoxide and the ligands form coordination compounds or complexes with rhodium. The rhodium component of the catalyst system in this invention can be provided by introducing into the reaction zone of rhodium in the form of a metallic rhodium, salts and oxides of rhodium, organic rhodium compounds, coordination compounds of rhodium, and the like. Halogen promoting component of the system consists of compounds of halogen containing organic halide. So there may be used alkyl-, aryl - substituted alkyl - or aryl halides. Preferably, halogen promoters are present in the form of alkylhalogenide, in which the alkyl radical corresponds to the alkyl radical of the free alcohol, which carbonyliron. For example, when carbonyliron of methanol to acetic acid, the halogen promoter may contain methylguanosine and, most preferably, methyliodide. Used, the reaction medium can with erati any solvent, compatible with the catalytic system, and may contain pure alcohol or alcohol mixture of raw materials, and/or the desired carboxylic acid and/or esters of these two compounds. The preferred solvent and reaction medium for the method of the present invention contain acetic acid.

The water content in the reaction medium also support, but in relatively low concentrations; its concentration is below about 14%. Shown (U.S. patent No. 5001259, 5026908 and 5144068)that the reaction rate is essentially equal to and greater than the rate of reaction obtained at water concentrations above about 14%, can be achieved at water concentrations below 14% and up to 0.1 wt.%. In accordance with this invention, the desired reaction rate gain at low water concentrations by maintaining a presence in the reaction medium of ester, which corresponds to the alcohol, which should be carbonyliron, and the acid is the reaction product of a carbonyl - and, most preferably, an additional iodide ion, moreover iodide, which is present in the catalyst promoter, such as methyliodide or other organic iodide. So, in reaction, carbonylation of methanol to acetic acid complex ester is methyl acetate, and an additional iodide by copromotion is a salt of iodide and lithium iodide is the most preferred.

It was found that at low concentrations in water methyl acetate and iodide ion act as promoters in terms of speed of response, if present in relatively high concentrations of each of these components, and that the promotion of stronger if both component are present simultaneously, as shown in U.S. patent No. 5001259, 5026908, 5144068.

In addition, it is shown that in the reaction media, having a concentration of acetate above 2 wt.%, ion iodide is necessary not only to increase the reaction rate, but also to stabilizirovannye rhodium catalyst, the stability of which is adversely affected by high concentrations of acetate even at high concentrations of water.

Table 1 gives the appropriate intervals of some of the various components in the reactor used in the method of this invention.

The amount of water, ion iodide, methyl acetate and under the conditions as shown in the broad and preferred or optimal intervals to achieve the stabilization of the catalyst and increase the rate of reaction. The preferred spacing is such that preferred from the viewpoint of optimal operation of the entire system, including the allocation system of the primary product, as explained above. You can see that the recommended concentration is then basically the same as for stabilizirovannye, and to increase speed.

Suitable stable ion exchange resins used in accordance with this invention to obtain a silver or mercury-exchange resin to remove iodides are usually resin type "RSO3H", classified as "strong acid", that is sulfosalicylate cation exchange resin macroporous type. In particular, a suitable ion exchange substrate is a resin Amberlyst® 15 (Rohm and Haas), which is suitable for use at elevated temperatures. Can be used other stable ion exchange substrates, such as zeolites, if the material is stable in an organic medium under interesting circumstances, that is not decomposed chemically or does not release the silver or mercury in unacceptable quantities. Zeolite cation exchange substrate is proposed, for example, in U.S. patent No. 5962735 Kulprathipanja and others, the contents of which are hereby incorporated by reference.

At temperatures above about 50°With silver or mercury-cation exchange substrate may seek to release a small amount of silver of about 500 h/billion or less, and, therefore, the silver or mercury-exchange substrate is chemically stable in interest conditions. More preferably, the loss of silver is less than about 100 h/bn in the organic environment and, more preferably, Maine is e about 20 h/bn in the organic environment. Loss of silver may be a little higher in the beginning or if the process is conducted in the light, as the iodide of silver is light sensitive and can form soluble complexes in contact with the light. Anyway, if it is desirable, after the silver or mercury-exchange material of this invention can be located layer of cationic material in non-form to capture the silver or mercury released from the cationic ion exchange resin.

The method of this invention can be carried out in any suitable configuration. In particular, the preferred configuration is to use a layer of microporous material (called here "protective layer"), since this configuration is especially convenient. A typical flow rate, such as is used in the purification of acetic acid is from about 0.5 to about 20 volumes of the layer per hour (BV/h). Layer volume is simply the volume filled with the resin in the layer. Just take that to a 100 ml resin layer volume should be 100 ml. Typical flow rate is typically from about 6 to about 10 BV/hour, preferably 8 BV/h in many cases implementation.

Same flow rate used in the application of anionic protective layer pyridine or pyrrolidone resin. The term "pyridine resin", "is OLIMAR, containing the pyridine ring and the pyridine polymer" and the like used here to refer to polymers containing substituted or unsubstituted pyridine ring or a substituted or unsubstituted pyridine containing polycondensation rings such as quinoline ring. The substituents include those which are inert to the process conditions of the carbonylation of methanol, such as an alkyl group or alkoxygroup. Typical examples of insoluble polymers containing pyridine ring, are obtained by the reaction of vinylpyridine with devicelevel monomer or reaction vinylpyridine vinyl monomer containing divinely monomer, such as copolymers of 4-vinylpyridine) - derivatives and divinylbenzene, copolymers of 2-vinylpyridine) - derivatives and divinylbenzene, copolymers of styrene, vinylbenzene and divinylbenzene, copolymers of vinylpyrrolidone and polystyrene and copolymers of vinylpyridine, methyl acrylate and atelierista. Particularly preferred polymers are described in U.S. patent No. 5334755 Yoneda and others, the contents of which are hereby incorporated by reference. The preferred relatively high degree of cross-linkage in the polymer.

The terms "pyrrolidone resin, polymer containing pyrrolidone ring", "pyrrolidinone polymer" and the like used here is relative to the polymer containing nesennye or unsubstituted pyrrolidone rings. Substituents can be any inert to the environment carbonylation of methanol, such as alkyl groups or alkoxygroup. Typical examples of insoluble polymers containing pyrrolidone ring, are obtained by the reaction of vinylpyrrolidone with vinyl monomer containing divinely monomer, such as a copolymer of vinylpyrrolidone with divinylbenzene. Pyrrolidone polymers are discussed in U.S. patent No. 5466874 Scates and others, as well as in U.S. patent No. 5286826, 4786699 and 4139688, the contents of which are hereby incorporated by reference. The preferred polymer pyrrolidinyl substrate available under the trademark Reillex® Reilley Tar and Chemical Corporation of Indianapolis, IND.

It is desirable that the above-mentioned polymers containing nitrogen heterocyclic rings were cross stitched, at least 10%, preferably at least 15% or 20% and up to 75%. The degree of cross-linkage is less than 10% is undesirable because the mechanical strength of the polymer may degrade during use. If the degree of cross-linking increases, may be unduly restricted the availability of the polymer surface. Therefore, the preferred maximum degree of cross-linkage 50 or 60%. It is assumed that used here, the term "degree of cross-linkage" refers to the content in terms of mass%, for example deviceloop monomer.

Pyridine or pyrrolidone insoluble polymer may be in free base form, or N-oxide or Quaternary derivative, as noted above. Insoluble polymer containing pyridine or pyrolidine ring, preferably, is in the form of beads or granules, more preferably a spherical shape having a particle diameter of 0.01-2 mm, preferably 0.1 to 1 mm, more preferably from 0.25 to 0.7 mm For the objectives of this invention can be used commercially available pyridine containing polymers, such as Reillex-425 (product Reilly Tar and Chemical Corporation) and KEH-316, KEH-501 and KEH-212 (products Koei Chemical Co., Ltd.). As noted above, pyrrolidone also available from Reilly Tar and the preferred degree of crosslinking of at least about 20%.

The invention hereinafter described in connection with figures 1 and 2, where similar numbers indicate similar parts. Figure 1 shows the first installation 10 applicable for implementing the method of the present invention. The installation 10 includes a reactor 12, the instantaneous evaporator, the separation column 16, and the optional high-temperature resin layer 20, the heat exchanger 22 and the resin layer 24. Additionally provided with a capacitor 30 for collecting light fractions from the separation column. Figure 1 is a column 16 at the same time works as a distillation column for light fractions and how dehydratases the distillation column.

Acetic acid produced by liquid-phase reaction is usually at about 150°s-200°in the reactor 12 under pressure of from about 30 to about 60 bar. Carbon monoxide and methanol is continuously injected into the reactor with back-mixing, where the mass transfer of carbon monoxide in the liquid phase increases maximally adequate mixing, designated 32, at high partial pressure of carbon monoxide. Non-condensable by-products are removed by blowing from the reactor to maintain an optimum partial pressure of carbon monoxide in the reactor, as shown at 34. Exhaust gases from the reactor is treated for separation of condensed substances, for example under the conditions before burning.

The catalyst solution containing the product is acetic acid, and the various components of the reaction mixture, such as complexes of rhodium and iodide salts, assign and send in a quick evaporator 14 through line 36. In quick evaporator 14 product - acetic acid - and most of the light fractions (methyliodide, methyl acetate, water) is separated from the solution of the catalyst from the reactor and served with dissolved gases in the cleaning section by adiabatic rapid evaporation in a single phase. The specified preliminary division also performs the function of removing the heat of reaction. The solution of catalyst recycling is in the reactor 12 through recycling of the catalyst 38.

The vaporous product of the speed evaporator 14 flows through the line 40 to the separator (light fractions) of the column 16. Methyliodide, methyl acetate and water are condensed in the head part 30 with the formation of two phases (organic and aqueous). One or both phases may be treated for removal of aldehydes and aldehyde impurities before returning to the reactor through lines 42, 44, 46, as shown in figure 1. As noted previously, the preferred ways of handling these phases are described in U.S. patent No. 5625075 and in WIPO publication WO 98/17619, the contents of which are hereby incorporated by reference. The upper part of the shoulder strap, for example aqueous phase, can be recyclebank in column 16 as a reverse flow through the line 48, while the rest of the columns 16 are returned to the reactor through line 50, 46.

The product acetic acid is extracted from the side of the stream 52 and serves on the resin layer 20 at elevated temperature and pressure. The lateral flow is located near the bottom of the column and can be extracted in the form of vapor or liquid side stream. If this is the lateral flow in the form of vapor, it condenses to feed on the layer 20. Typically, the layer 20 operates at a temperature above approximately 170°and consists of anionic ion-exchange resin from polymer containing heterocyclic ring. Most preferably, the resin layer 20 is a layer of particles pyridine resin or pyrrolidino smo is s, as described above, appropriately cross stitched so that it can withstand operation at elevated temperatures and pressure.

The product leaves the high temperature resin layer 20 through the line 54 and enters the heat exchanger 22, where the product is cooled to a temperature of about 100°With or below.

For the subsequent removal of iodides using a layer of silver-cation exchange macroporous resin 24.

Product - acetic acid leaves the system through line 56.

Figure 2 shows an alternative system 10 where it can be carried out a method of the invention. Parts in figure 2 are numbered and work in essentially the same manner as in figure 1, except that there is additionally provided a separating column dehydration 18 to capture the flow of the product acetic acid from the column 16 through line 52, as well as differences in the system of removal of iodide, as described below. Head fraction from the tank 18 condense 58 and receive two phases, aqueous and organic, which both recyclist in the reactor 12. Water flow thus return back flow into the column 18 through line 62. Dry crude acetic acid released from the column 18 as a residual stream 64 and flows into the heat exchanger 22, which cools the product in such a way that the average temperature in the layer of the resin 24 is supported, preferably, between when the Arno 50 and 70° C. If it is desired to operate in layer 24 at a higher temperature, it is convenient to place the heat exchanger in front of the layer 24. After cooling, the flow process on the resin layer 24 and again cooled in the heat exchanger 26 before serving resin layer 28. The resin layer 28 is a layer of silver or mercury-exchange cation exchange environment and typically operates at an average temperature of the product from about 35°With up to about 20°C.

Used here, the term "primary treatment system" and similar terms refer to cleaning equipment, working on the flow of the primary product from the quick evaporator, excluding extraction equipment, scrubbers, and removal of alkanes and so on. So, in relation to figure 1, the primary treatment system consists of a column of light fractions and dehydration 16, high temperature resin layer 20, the resin layer 24 and connecting pipelines. It should be noted that the rapid evaporator is not considered part of the primary treatment system, as scrubbers and the like. Therefore, in relation to figure 2, the primary treatment system includes a column of light fractions 16, the dehydration column 18 and the resin layers 24 and 28.

Specific preferred modes of operation of the resin layers, especially layer 24 described below. Next, you can see that the aldehyde impurities regulate optimisation of the conditions in the reactor 12, as described below.

the reamers

In the following examples 1-5 and comparative examples a to F used the procedure described below. If not indicated otherwise, remove iodides was carried out using silver-exchange resin Amberlyst® 15. The resin (100 ml wet) were loaded into a glass column with an outside diameter of 22 mm and suirable acetic acid containing iodides, with a flow rate of 13.3 ml/min Level of iodide in the eluate was measured every two (2) hours. The total iodide was measured in the eluate any suitable way. One appropriate method is neutron activation analysis (NAA), well known in modern technology. We measured the levels of iodide in specific varieties. The preferred method in this latter aspect is gas chromatography using electron-capture detector.

Comparative examples a and b

Samples of residue from the drying column standard type Monsanto installation for the production of acetic acid containing 540 h/bn total iodide and 238 h/bn total iodide were processed at room temperature, using a silver-exchange resin Amberlyst® 15, and the total iodides in the eluate was measured as a function of time, as shown in figure 3. As can be seen from figure 3, the removal of total iodide typically less than about 90% at the beginning of the test and gradually subsides over a period of time of 10 hours before the value is positive lower removal efficiency.

Identified in the original supplied raw materials of different iodide components were:

methyliodide

ethyliodide

2-iodine-2-methylpropan

propyliodide

2-butylated

butylated

iodine

pentolite

hexalite

actilite

deciided

domiciliated

hexadecenoic.

The predominant identified organic iodide components with high molecular weight were deciided and domiciliated.

Comparative examples C and D and example 1

Following the procedure described above, was measured the temperature dependence of the performance of the protective layer for relatively high (ppm) level of organic iodides in acetic acid. Results for dodecylamide (example) and mexilitine (example D) at 25°and for dodecylamide at 100°shown in figure 4. The results show that the performance of the protective layer significantly increased at 100°compared with 25°With, in particular, for dodecylamide. Improved performance includes both the removal efficiency and the service life of the layer.

Comparative examples E, F

Following the procedure described above, we studied the effect of branching chains on the performance of the protective layer by comparing removal hexylidene removing neopentylene (example F). The results are shown in figure 5.

Examples 24

Following the procedure described above was evaluated the performance of the protective layer of the silver exchange Amberlyst® 15 to remove dodecylamide at 25°S, 50°, 75°and 100°and removal of hexylidene at 25°C. the Results are shown in Fig.6, where for comparison, also the results of examples C and D. in this case, you can see that the removal efficiency with acceptable capacity layer significantly increases at temperatures above about 50°C.

Example 5

Following the procedure described above, the investigated samples of acetic acid (the remainder of the drying columns) of the installation (production) acetic acid type Monsanto, containing, respectively, 540 h/bn total iodide (example A), 238 h/bn total iodide (example) and 259 h/bn total iodide (example 5). The acid was processed as described above using a protective layer of silver exchange Amberlyst® 15 at 25°s and 50°C. As can be seen from Fig.7, the performance at 50°With far exceeded the removal efficiency at 25°C. in fact, the protective layer was removed more than 99% (close to the quantitative removal) of the total iodide at 50°C.

As part of this invention, it is desirable to adjust the amount of acetaldehyde carbonyl impurities included in the product flow. Some methods include processing the UKS the red acid oxidizers ozone, water, methanol, amines and the like. These methods may include, for example, removing carbonyl impurities from organic streams by processing the organic flow of amine compound such as hydroxylamine, which reacts with the carbonyl compounds with the formation of Asimov, followed by distillation to separate the purified organic product from oxomnik reaction products. As noted above, this method increases the cost of the process.

In U.S. patent No. 5625095 Miura and others, and in international application number PCT/US 97/18711, publication no WO 98/17619 proposed various methods to remove aldehydes and other impurities from catalyzed by rhodium method for the production of acetic acid. Typically, these methods include the extraction of impurities from streams of recycling to reduce the concentration of acetaldehyde in the system. The description of the patent '095 and international application no PCT/US 97/18711 given here as a reference, and these techniques can be used to regulate the concentration of acetaldehyde in the system of the present invention.

Another method of regulating the concentration of acetaldehyde in the product flow is to minimize the formation of by-products. It was found that it is advantageous to maintain the partial pressure of hydrogen at levels previously known given in the second area, or at lower levels. The formation of aldehyde acid and its derivatives, in particular, crotonic aldehyde and 2-atolkachova aldehyde, can be significantly reduced. The following examples illustrate this peculiarity, which may be used in connection with this invention.

The reaction system, which is used to demonstrate the present invention contains (a) liquid-phase reactor homogeneous carbonylation, (b) the so-called "quick evaporator, and (C) dividing the column for separation under the conditions and acetic acid. The carbonylation reactor is usually an autoclave with a stirrer, the inside of which is automatically at a constant level support reactive liquid components. In the specified reactor continuously introduce fresh methanol, sufficient water to maintain at least a finite concentration of water in the reaction medium, recyclebank solution of catalyst from the bottom of the quick evaporator and recyclebank methyliodide and methyl acetate from the top of the separation column to separate under the conditions and acetic acid. Can be used an alternative distillation system, unless they provide a means for separation of the crude acetic acid and recyclization in the reactor solution of the catalyst, under the conditions and Metalac the Tata. In the process continuously introduced into the carbonylation reactor mixed stream of carbon monoxide/hydrogen below the mixer used for mixing the contents. Mixed flow of gases, of course, fully dispersed in the reaction liquid specified means. Gaseous blown divert flow from the reactor to prevent the accumulation of gaseous by-products and to maintain the partial pressure of carbon monoxide in the installation at a given total reactor pressure. Regulation of the outflow of gases can also regulate the partial pressure of hydrogen in the reactor. The temperature of the reactor is adjusted automatically, and the supply of carbon monoxide/hydrogen is produced at a rate sufficient to maintain the desired total pressure in the reactor.

Liquid product away from the carbonylation reactor at a rate sufficient to maintain a constant level, and served in a quick evaporator at a point intermediate between its top and bottom. In quick evaporator solution of the catalyst to divert as the main thread (mainly acetic acid containing rhodium and iodide salt along with lesser quantities of methyl acetate, iodotope bromide and water), while the upper shoulder strap quick evaporator contains mainly product - acetic acid - addition is methyliodide, the acetate and water. Part of carbon monoxide and hydrogen with gaseous byproducts, such as methane, hydrogen and carbon dioxide, is released from the head part quick evaporator.

The product acetic acid is released from the base of the column, separating methyliodide and acetic acid (it can also go as a side stream near the bottom), and then selected for the final cleaning, as necessary, by methods well known at the present level of technology that is beyond the scope of this invention. Head stream from the separator under the conditions and acetic acid containing mainly methyliodide and methyl acetate, recyclist in the carbonylation reactor.

The method of regulating the primary reaction involves ongoing analysis of the liquid contents of the reactor, and the contents of carbon monoxide and hydrogen in the gas otodrom channel of the reactor and, on the basis of this analysis, the regulation of flows of carbon monoxide, hydrogen, water, methanol and under the conditions to maintain the specific composition of the reaction medium. Additionally, you should specify that the addition of methanol in a carbonylation reactor is not based on the analysis of the content of methanol, and the analysis of the content of acetate. Most methanol is almost immediately converted into acetate by the Les admission to the carbonylation reactor.

In the continuous method described above, the catalytic support system in a certain state, and the reagents are continuously served in a reaction zone containing a catalytic system at the desired temperature and pressure. Products are continuously selected, as described above, the selection of the solution containing the catalytic system, unreacted feedstock, the equilibrium components and the desired product. The desired product is then separated from the specified solution to allow retalitate containing the catalyst solution, which contains unreacted feedstock and equilibrium components.

The following examples are provided to demonstrate ways of regulating the level of aldehyde impurities in accordance with this invention. Specialists in the art will understand that the methods described in the examples represent ways proposed by the inventors for good functioning in the practical implementation of the invention, and can be considered as preferable for practical use. However, such experts shall, in the light of the present invention, to understand what can be done many changes in specific embodiments, the implementation of which are disclosed here, and get similar or the same results without derogating from su and and scope of the invention.

Examples 6-9

Continuous pilot plant, equipped as described above, 4-liter reactor, operating with 1.5 l reaction volume was used to study the effect of partial pressure of hydrogen on the formation of by-products when carbonyliron methanol. Process conditions and results are shown in table 2 below. "Impurities at the outlet of the column" refers to the impurities in the crude product is acetic acid, and "NR" refers to the absolute partial pressure of hydrogen in the reaction vessel in pounds per square inch.

tr>
Table 2

The data in the partial pressure of hydrogen
Examples6789
The pressure in the reactor NRR (psia)2,03,39,414,6
The flow of methanol (g/min)14,915,015,015,0
The composition of the reaction mixture in the reactor
Methyliodide, wt.%10,611,010,810,9
Methyl acetate, wt.%2,62,52,52,5
Water, wt.%4,04,04,14,3
Rh, ppm632652657651
LiI, wt.%6,68,28,48,7
Boiling point, °195,2194,0191,8192,3
Impurities at the outlet of the column
Propionic acid, ppm140197363500
CROTONALDEHYDE, h/million1468
2-atolkachova aldehyde, h/million1368
Butyl acetate, ppm361316

As you can see, the impurity profile is improving at a lower partial pressure of hydrogen in the reactor.

Although the preceding examples show a decrease in the content of crotonic aldehyde and the like, the experts in this field will understand that the impurities and side products catalyzed by the rhodium carbonylation system include butane, butanol, butylated is t, butylated, ethanol, ethyl acetate, ethyliodide, hexalite and high-boiling impurities. This invention apparently minimizes the formation of these impurities.

Another method of regulation of aldehydes acids includes a process at relatively low concentrations under the conditions.

Typical homogeneous reaction system, which is used for the following examples, generally similar to that described above and includes (a) a liquid-phase carbonylation reactor, (b) rapid evaporator and (C) dividing the column for separation under the conditions and acetic acid. The carbonylation reactor is usually an autoclave with a stirrer, in which the components of the reacting liquid content is automatically maintained at a constant level. In the specified reactor continuously introduce fresh methanol, sufficient water to maintain at least the final (>50 ppm and at least about 0.1 wt.%) the water concentration in the reaction medium, recyclebank solution of catalyst from the bottom of the quick evaporator and retalitory methyliodide, acetate and water from the upper part of the separation column to separate under the conditions and acetic acid. For further condensation process upstream speed evaporator can be used distillation system. The remainder of the C speed evaporator return to the reactor. Carbon monoxide is continuously injected and thoroughly dispersed in the carbonylation reactor. Gaseous purge stream away from the head part of the reactor to prevent the formation of gaseous by-products and maintain the partial pressure of carbon monoxide in the installation at a given total reactor pressure. The temperature and pressure in the reactor regulating means, known in modern technology.

The crude liquid product away from the carbonylation reactor at a rate sufficient to maintain a constant level, and type in a quick evaporator at a point intermediate between its top and bottom. In quick evaporator solution of a catalyst selected as the main thread with the prevailing acetic acid containing rhodium catalyst and an iodide salt along with lesser quantities of methyl acetate, and water under the conditions, while the condensed head flow speed evaporator contains mainly the crude product, acetic acid, along with methyliodide, acetate and water. Part of carbon monoxide together with gaseous byproducts, such as methane, hydrogen and carbon dioxide, leaving the head part quick evaporator.

Dry acetic acid (<1500 ppm of water) is removed from the base of the separation column to separate METI the iodide and acetic acid (it can also output in the form of a side stream near the base) for the final cleaning, if desired, in ways that are obvious to experts in the art and which are not included in the scope of this invention. Top zipper from separating columns for separation under the conditions and acetic acid containing mainly methyliodide, acetate and water, returned to the carbonylation reactor.

The following specific examples are for purposes of better illustrating the invention. These examples, however, in no way limit the scope of the invention and do not imply that in the practice of this invention should be applied exclusively to the above conditions, parameters, or values.

Examples 10-12

Continuous carbonylation of methanol was carried out in the reaction system, as described above, which contained the reactor with a stirrer, a quick evaporator and separation column for separation under the conditions and acetic acid. With the exception of varying the concentration under the conditions, reaction conditions were repeated in each of the following examples to demonstrate the effect of reducing the content under the conditions on acetaldehyde.

Each experience has reached steady state before collecting data about the contamination, continuous operation of the reactor while maintaining a constant target composition and the reaction conditions as shown in table 3. Then, at least 12 hours when Bireli data and build a graph showing that the carbonylation reaction takes place in a stationary mode.

The results of examples 10-12 are shown in table 3. With regard to table 3, the values are the data of mass balance over a 12-hour period of stable conditions. The results of each of examples 10 and 12 represent the mass balance in the course of individual experience. The results of example 11 are average for the mass balances in the two working periods.

As you can see, the concentration of acetaldehyde in the reactor decreases with decreasing content of MeI.

In another aspect of the invention features a method of reducing the intensity of the color (Pt-Co) acetic acid, hereinafter called the "color intensity according to American public health Association (ARNA)". Typically, this method involves treatment with acetic acid to achieve a low confidence level below about 5 color units ARNA. For illustration 10 samples of acetic acid were tested at different levels of iodide and ferrous impurities. Only one sample, which was produced from a material having a color index ARNA 65 shows a value greater than 5 color units ARNA after treatment. This aspect of the present invention better estimate of the examples.

Examples 13-22

There was prepared a resin with what emeniem macroporous resin Rohn & Haas Amberlyst® 15 with 10% of the centers, converted into silver (Ag+) form. Acetic acid was obtained from a remainder of the drying column type installation Monsanto (for example, line 64 figure 2) and from the residual stream end of column fractions from unit production of acetic acid type Monsanto. As is well known to specialists in this field of technology, end fraction has a higher concentration of iodide and non-ferrous contaminants are usually of the same type as present in the remainder of the drying column containing deciided and domiciliated. The remainder of the drying column and the remainder of the drying columns, supplemented with 0.1% of the balance end of the fractions were treated with compound resin obtained as described above, at 50°With most of the detail shown in table 4 below. Used here, the terms "intensity of the color, color units Pt-Co color units" and the like refer to ARNA, sometimes refer to colour Hazen units Pt-Co, determined in accordance with ASTM (American standard test method), marking D1209-62 "Standard Method of Test for Color of Clear Liquids Platinum-Cobalt Standards, preferably using a suitable spectrometer.

The layer of resin = Rohm & Haas Amberlyst® 15 c 10% of the seats in the form of Ag+.

Conditions continuous reaction:

feed rate = 4 to 5 volumes of layer/hour

the temperature of the Loya = 75° C.

The addition of 0.1% of end fractions of the material of the remainder of the drying column was used to accelerate the release of resin by increasing the concentration of the same iodide and non-ferrous components to those already present in the stream.

As you can see, the processing of the resin, in particular, at elevated temperatures, is effective to maintain the intensity of staining at the level of less than 10 and usually less than 5 color units Pt-Co. This treatment is particularly useful in connection with a continuous process for the production of acetic acid comprising: (a) the interaction of methanol with the feed stream of carbon monoxide in a carbonylation reactor containing a catalytic reaction medium while maintaining the specified reaction medium during this reaction, at least a finite concentration of water is from about 0.1 wt.% to less than 14 wt.%; (b) the abstraction of flow of the reaction medium from the reactor and the evaporation part of the allotted environment at the stage of rapid evaporation; (C) distillation quickly evaporated vapor to form a liquid stream of acetic acid, using in the primary purification of two distillation columns, while providing one or more recyclebank flows in the specified reactor; and (d) removing iodides from the specified liquid flow - acetic acid with simultaneous regulate the increased intensity of the color specified stream of acetic acid so that so the product had an iodide content of less than about 10 h/bn and the colour intensity is less than about 10, preferably less than about 5, where this stage of removal of iodides and regulation of the intensity of the color of the specified product stream consists essentially of contacting the specified liquid flow product of acetic acid with silver or mercury-exchange ion exchange substrate at a temperature of at least 50°where at least 1% of the active centers of the specified resin converted to the silver or mercury form.

A method of processing a stream of acetic acid is usually applied to flow with the colour intensity of more than about 5, and provides for the contacting of the liquid product flow - acetic acid with silver or mercury-exchange ion exchange substrate at a temperature of at least about 50°where at least one percent of the active centers of the specified resin converted to the silver or mercury form, so that the treated acetic acid has the intensity of staining after processing is less than approximately 5. Sometimes acetic acid has the colour intensity of more than about 10 to contacting the stream with the specified silver or mercury-exchange ion exchange substrate. Typically, the stream of acetic acid contains deciided and dodecylamide before processing the specified sulfur is ro - or mercury-exchange ion exchange substrate.

Although the invention has been described above, various modifications of the specific implementation options within the essence and scope of the present invention are obvious to experts in this field. This invention defined in the attached claims.

1. Continuous method for the production of acetic acid, including:

(a) interaction of methanol with the feed stream of carbon monoxide in a carbonylation reactor containing a catalytic reaction medium while maintaining the specified reaction medium during this reaction, at least a finite concentration of water is from about 0.1 to less than 14 wt.%, along with (i) iodide salt of an alkali metal, soluble in the reaction medium at the reaction temperature in quantity, allowing to maintain the concentration of iodide ions in the range of from about 2 to about 20 wt.%, effective as a stabilizer, catalyst and copromotor, (ii) from about 1 to about 20 wt.% under the conditions, (iii) from about 0.5 to about 30 wt.% methyl acetate; (iv) a rhodium catalyst, and (v) acetic acid;

(b) the flow diverting the specified reaction medium from the specified reactor and the evaporation part of the allotted environment at the stage of rapid evaporation;

(c) distillation quickly evaporated vapor to form a liquid stream of acetic acid, using the primary treatment system to two distillation columns, providing one or more streams of recycling in the specified reactor; and

(d) removing iodides from the specified liquid flow - acetic acid and simultaneous regulation of the intensity of the color specified stream of acetic acid so that the product had an iodide content of less than about 10 h/bn iodide and the colour intensity is less than about 10, where this stage of removal of iodides and regulation of the intensity of the color of the specified product stream consists essentially in contacting the specified liquid flow - acetic acid with silver or mercury-exchange ion exchange substrate at a temperature of at least 50°where at least 1% of the active centers of the specified resin converted to the silver or mercury form.

2. A method of processing a stream of acetic acid, having the colour intensity is more than 10 obtained by carbonyliron methanol in a homogeneous catalytic system based on rhodium catalyst, and the specified catalytic system contains iodide ions, comprising contacting the specified liquid flow - acetic acid with silver or mercury-exchange ion exchange substrate at a temperature of at least about 50°where at least 1% of the active centers of the specified resin converted to the silver or mercury form, so that the product, i.e. the treated acetic acid, had an iodide content of less than about 10 h/bn iodide and the intensity of staining after processing is less than approximately 10.

3. The method according to claim 2, where the specified acetic acid has the colour intensity of more than about 5 to contact the specified stream with the specified silver or mercury-exchange ion exchange substrate and the color intensity is less than about 5 after this treatment.

4. The method according to claim 3, where the specified thread acetic acid contains deciided and dodecylamide to contact the specified stream with the specified silver or mercury-exchange ion exchange substrate.

5. Continuous method for the production of acetic acid, including:

(a) the interaction of methanol with the feed stream of carbon monoxide in a carbonylation reactor containing a catalytic reaction medium while maintaining the specified reaction medium during this reaction, at least a finite concentration of water is from about 0.1 to less than 14 wt.%, along with (i) iodide salt of an alkali metal, soluble in the reaction medium at the reaction temperature in quantity, allowing to maintain the concentration of iodide ions in the range of from about 2 to about 20 wt.%, effective the th as a stabilizer, catalyst and copromotor, (ii) from about 1 to about 20 wt.% under the conditions, (iii) from about 0.5 to about 30 wt.% methyl acetate; (iv) a rhodium catalyst, and (v) acetic acid;

(b) the flow diverting the specified reaction medium from the specified reactor and the evaporation part of the allotted environment at the stage of rapid evaporation;

(c) distillation quickly evaporated vapor to form a liquid flow - acetic acid, using the primary treatment system to two distillation columns, providing one or more recycletech flows in the specified reactor; and

(d) removing iodides from the specified liquid flow - acetic acid, so that the product had an iodide content of less than about 10 h/bn iodide, where the specified stage of removing iodides from the stream of product - acetic acid chosen from the group consisting of (i) contacting the specified liquid flow - acetic acid with an anionic ion exchange resin at a temperature of at least 100°followed by contacting the specified liquid flow - acetic acid with silver or mercury-exchange ion exchange substrate, where at least 1% of the active centers of the specified resin converted to the silver or mercury form, or (ii) contacting the specified liquid flow - acetic acid with Cerebro - or mercury-exchange ion exchange substrate at a temperature, at least about 50°where at least 1% of the active centers of the specified resin converted to the silver or mercury form, and, in addition, includes the regulation of the level of aldehyde impurities in the specified flow of product through the removal of aldehydes from the specified stream recycling.

6. The method according to claim 5, where these aldehydes are removed from the stream recycling by distillation.

7. The method according to claim 5, where the specified stage of removing iodides from the specified liquid flow - acetic acid includes contacting the specified liquid flow - acetic acid with polyvinylpyridine resin.

8. The method according to claim 7, where the specified stage of contacting the specified stream product - acetic acid with the specified polyvinylpyridine resin is carried out at a temperature of at least about 150°C.

9. The method according to claim 5, where the specified stage of removing iodides from the specified liquid flow - acetic acid includes contacting the specified liquid flow - acetic acid with polyvinylpyrrolidone resin.

10. The method according to claim 9, where the specified stage of contacting the specified stream product - acetic acid with the specified polyvinylpyrrolidone resin is carried out at a temperature of at least about 150°C.

11. The method according to claim 5, where the specified stage of removing iodides from the data of the liquid product stream is acetic acid includes contacting the specified stream product with macroporous, silver or mercury-exchange ion-exchange resin, where at least 1% of active sites converted to the silver or mercury form, at a temperature of at least about 50°C.

12. The method according to claim 5, where the specified stage of removing iodides from the specified liquid flow - acetic acid involves contacting the specified stream product with macroporous, silver or mercury-exchange ion-exchange resin, where at least 1% of active sites converted to the silver or mercury form, at a temperature of at least about 60°C.

13. The method according to item 12, where a specified liquid product flow - acetic acid is brought into contact with the specified silver or mercury-exchange macroporous resin at a temperature of at least about 70°C.

14. The method according to claim 11, where from about 25 to about 75% of the active centers of the specified macroporous resin converted to the silver form.

15. The method according to 14, where about 50% of the active centers of the specified macroporous resin converted to the silver form.

16. Continuous method for the production of acetic acid, including:

(a) the interaction of methanol with the feed stream of carbon monoxide in a carbonylation reactor containing a catalytic reaction among the u, while maintaining the specified reaction medium during this reaction, at least a finite concentration of water is from about 0.1 to less than 14 wt.%, along with (i) iodide salt of an alkali metal, soluble in the reaction medium at the reaction temperature in quantity, allowing to maintain the concentration of iodide ions in the range of from about 2 to about 20 wt.%, effective as a stabilizer, catalyst and copromotor, (ii) from about 1 to about 20 wt.% under the conditions, (iii) from about 0.5 to about 30 wt.% methyl acetate; (iv) a rhodium catalyst, and (v) acetic acid;

(b) the flow diverting the specified reaction medium from the specified reactor and the evaporation part of the allotted environment at the stage of rapid evaporation;

(c) distillation quickly evaporated vapor to form a liquid flow - acetic acid, using the primary treatment system to two distillation columns, providing one or more recycletech flows in the specified reactor; and

(d) removing iodides from the specified liquid flow - acetic acid, so that the product had an iodide content of less than about 10 h/bn iodide, where the specified stage of removing iodides from the stream of product - acetic acid chosen from the group consisting of (i) contacting the specified liquid is about the flow of the product - acetic acid with an anionic ion exchange resin at a temperature of at least 100°followed by contacting the specified liquid flow - acetic acid with silver or mercury-exchange ion exchange substrate, where at least 1% of the active centers of the specified resin converted to the silver or mercury form, or (ii) contacting the specified liquid flow - acetic acid with silver or mercury-exchange ion exchange substrate at a temperature of at least about 50°where at least that 1% of the active centers of the specified resin converted to the silver or mercury form, and, in addition, includes the regulation of the level of aldehyde impurities in the specified stream of product by maintaining the specified reactor concentration under the conditions of about 5 wt.% or less.

17. The method according to clause 16, where the content under the conditions specified in the reactor is maintained at a level of from about 1 to about 5 wt.%.

18. Continuous method for the production of acetic acid, including:

(a) interaction of methanol with the feed stream of carbon monoxide in a carbonylation reactor containing a catalytic reaction medium while maintaining the specified reaction medium during this reaction, at least a finite concentration of water is from about 0.1 to less than 14 m is from.%, along with (i) iodide salt of an alkali metal, soluble in the reaction medium at the reaction temperature in quantity, allowing to maintain the concentration of iodide ions in the range of from about 2 to about 20 wt.%, effective as a stabilizer, catalyst and copromotor, (ii) from about 1 to 20 wt.% under the conditions, (iii) from about 0.5 to about 30 wt.% methyl acetate; (iv) a rhodium catalyst, and (v) acetic acid;

(b) the flow diverting the specified reaction medium from the specified reactor and the evaporation part of the allotted environment at the stage of rapid evaporation;

(c) distillation quickly evaporated vapor to form a liquid flow - acetic acid, using up to two distillation columns, providing one or more streams of recycling in the specified reactor;

(d) the regulation of the level of impurity iodides in the specified stream of product by maintaining the partial pressure of hydrogen in the reactor below about 6 psia when the total pressure in the reactor from about 15 to 40 atmospheres; and

(e) removing iodides from the specified liquid flow - acetic acid so that the product had an iodide content of less than about 10 h/bn iodide, by contacting the specified liquid flow - acetic acid with silver or mercury-exchange ion-exchange with what stratum when the flow temperature of the product above 50° With, and where the specified product stream contains organic iodide with long aliphatic chains of C10 or greater.

19. The method according to p, where the specified product stream contains at least about 25% of organic iodides with long aliphatic chains of C10 or greater.

20. The method according to claim 19, where at least about 50% organic iodide in the specified organic environment, are organic iodides having the length of the aliphatic chain C10 or greater.

21. The method according to p, where these organic iodides contain iodides selected from the group consisting of deciided (C10) and dodecylamine (C12).

22. The method according to item 21, where this treatment is effective to remove at least about 90% decyl(C10)and dodecyl(C12)-iodides from the organic environment.

23. The method according to p, where the specified product stream contains from about 10 to about 1000 h/bn all iodides before processing the specified silver or mercury-exchange cation exchange substrate.

24. The method according to item 23, where this non-aqueous organic medium contains from about 20 to about 750 h/bn all iodides before processing the specified silver or mercury-exchange cation exchange substrate.

25. The method according to paragraph 24, where the specified processing by contacting a specified organic environment with the specified silver or mercury-exchange cation exchange substrate at a temperature above 50°With the effect of the VNA for deletion at least about 99% of all iodide present in the specified organic environment.

26. The method according to p where the specified ion exchange substrate is a resin functionalized with acid.

27. The method according to p, where the specified stream prior to contacting with the specified ion exchange substrate has an iodide content of more than about 100 h/bn organic iodide.

28. The method according to item 27, where the specified stream after contact with the specified ion exchange substrate has a content of organic iodide less than 10 h/bn



 

Same patents:

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.

SUBSTANCE: objective of invention is how to store inflammable 60-80% aqueous acetic acid solutions under winter conditions. Problem is solved by adjusting concentration of acetic acid solution to a value at which crystallization temperature of solution is the same as average temperature in storehouse for a given winter month, for which purpose aqueous acid solution is circulated through a circuit, whereupon volume, temperature, concentration of solution, and amount of acetic acid in natural form and 100% form are determined. When indicated concentration is exceeded in storehouse, required amount of water is added while circulating solution to achieve desired concentration. Further, aqueous acetic acid solution is pumped out into transportation container. After transportation, solution is pumped into shop container, wherein above-listed parameters are redetermined and presence or absence of solid phase in the storehouse is checked. In case of equality of concentrations in shop container and in storehouse, there is lack of solid phase in the storehouse. When concentration in shop container is less than in storehouse, solid phase is available in storehouse and then, for next admittance, calculated amount of water is introduced into storehouse with circulation through circuit to obtain average acid concentration in storehouse, at which crystallization temperature of solution is the same as average temperature in storehouse for a given winter month. At subsequent withdrawal of aqueous acetic acid solution from storehouse all the operations are repeated.

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1 dwg, 2 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing acetic acid solution. Method involves the following procedures. Capacity with the parent raw is filled with water in the amount providing preparing acetic acid semihydrate and then water is poured in another capacity in the amount providing preparing 72-80% of acetic acid solution from semihydrate prepared in the first capacity. Then semihydrate is pumped off from the first capacity to the second one in the amount to obtain 17-50% acetic acid solution and prepared solution is stirred for 5-7 min. Sample is taken for control of mass part of acetic acid in the range 17-50%. Semihydrate is pumped off from the first capacity in the second one again under layer of liquid up to its filling and bottom layer of solution is stirred for 1-5 min. Sample is taken from the top layer for control of mass part of acetic acid in the range 17-50% and from the bottom layer in the range 72-80%. Then the bottom layer is pumped off in the amount equal to the amount of semihydrate charged at the second step. Method provides reducing fire hazard of technological process and diminishing concentration of acetic acid vapors in air of working zone.

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

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

The invention relates to the production of acetic acid by carbonyliron of methanol with carbon monoxide, in particular to the purification method of the circulating flow boiling components at the stage of distillation of acetic acid

FIELD: chemical technology.

SUBSTANCE: invention relates to the improved method for extraction of carbonyl and (or) acid compounds from the complex multicomponent organic liquid mixtures. Method involves treatment of organic liquid mixtures with sodium sulfite an aqueous solution at intensity of mechanical stirring providing formation of uniform emulsion. The content of carbonyl compounds and acids in the parent mixture to be treated is determined and treatment is carried out with 4.16-26% aqueous solution of sodium sulfite as measured 1.05-1.1 mole of sodium sulfite per 1 g-equiv. of carbonyl compound, and in exceeding of the content of acids (g-equiv.) in the parent mixture over the content of carbonyl compounds - with 1 mole sodium sulfite per 1 g-equiv. of acids and in the mass ratio of sodium sulfite aqueous solution to organic mixture = (1-2.5):(2-1) at temperature 15-30°C; if the content of acids in the parent mixture (g-equiv.) is less the content of carbonyl compounds (g-equiv.) then under control of pH value change in an aqueous phase method involves additional addition of mineral or organic acid in the amount as a difference in the content of carbonyl compounds (g-equiv.) and the content of acids (g-equiv.) in the parent charge of organic mixture per treatment at such rate that pH value of aqueous would decrease constantly but not less 6.5. This simple method provides removing both carbonyl compounds and acids being without significant limitations for the content of carbonyl compounds and acids in the parent mixture. Invention can be used in different branches of industry for treatment of compositions or for utilization of carbonyl compounds and (or) acids.

EFFECT: improved method for extraction.

5 cl, 3 tbl, 26 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to the improved method for treatment of organic mixtures from carbonyl compounds and acids by their treatment with sodium sulfite. Method involves using organic mixtures comprising carbonyl compounds and carboxylic acids in the ratio = 1 g-equiv. : 1 g-equiv. or with excess of acids, or with excess of carbonyl compounds. In this case before treatment with sodium sulfite carboxylic acid is added to the parent mixture in the amount to obtain the ratio of carbonyl compounds to acids as 1 g-equiv. per 1 g-equiv. and treatment is carried out with solid sodium sulfite in beaded mill with the mass ratio of the composition charge to glass beads as a grinding agent = 1:(1-2) at the rate of mechanical mixer rotation 1440 rev/min, not less, and in dosing sodium sulfite 1.2-1.5 mole per 1 g-equiv. of carbonyl compounds or excess of acid in the presence of stimulating additive up to practically complete consumption of carbonyl compounds, or carbonyl compounds and acids. Process is carried out in the presence of sodium and potassium hydroxide and acetate and sodium nitrate also as a stimulating additive taken in the amount 1-4% of mass sodium sulfite to be added up to practically complete consumption of carbonyl compounds and acids in composition to be treated. This simple method provides high degree of purification being even in small parent content of carbonyl compounds and acids.

EFFECT: improved method for treatment.

4 cl, 3 tbl, 19 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for preparing biologically active sum of triterpene acids from fir wood greens. Method for preparing biologically active sum of triterpene acids from dried and milled fir wood green involves double extraction with organic solvent - isopropyl alcohol by infusion with raw in the definite conditions followed by treatment of extract with alkali agent an aqueous solution, acidification of an aqueous-alkaline extract and isolation the end product from its. Method provides effective enhancing the yield of biologically active sum of triterpene acids and to simplify the technological process.

EFFECT: improved method for preparing.

1 tbl, 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

The invention relates to an improved method of allocation of ketones and/or acids from hydrocarbon mixtures such as crude oils, petroleum products, dispersed organic matter of rocks, etc
The invention relates to a new process for the preparation of fluorinated acids emulsifiers of waste water for the purpose of regeneration, namely, that first from waste water of polymerization of fluorinated monomers remove interfering components selected from finely dispersed solids and transferred to the solid component, and then connect the fluorinated acid emulsifiers on anion exchange resin and elute from it these fluorinated acid emulsifiers

The invention relates to an improved method for producing crystals of adipic acid used in the production of polymers, for example, to obtain a polyamide or polyurethanes

The invention relates to a method of separation of carboxylic acids or their methyl esters of high purity and can be used in various cleaning processes, the division and separation of carboxylic acids from different colored hydrocarbon mediums: oil, oil products, the dispersed organic matter of rocks, etc

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

The invention relates to biotechnology, in particular to a method for producing a biologically active amount of triterpene acids

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

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