Method of reducing concentration of aldehyde in target stream

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of reducing concentration of aldehyde in the crude stream of a carbonylation process, involving feeding a crude stream containing a carbonylatable agent selected from a group consisting of methanol, methyl acetate, methyl formate and dimethyl ether or mixture thereof, having primary concentration of aldehydes; and reaction thereof in gaseous phase with a deposited catalyst which contains at least one metal from group 8 to 11, in conditions which facilitate reduction of primary concentration of aldehydes to secondary concentration of aldehydes.

EFFECT: method improves degree of reduction of aldehyde.

28 cl, 3 tbl, 3 ex

 

The technical field to which the invention relates.

This invention relates to a method of reducing the concentration of aldehyde in the target stream. The invention particularly relates to a method for reducing the concentration of aldehyde in the target stream way carbonylation. The invention also relates to a method for reducing the concentration of aldehyde in the target stream containing carbonyliron reagent. More specifically, the invention relates to a method for reducing the concentration of aldehyde in the feed stream to the carbonylation reactor method carbonylation.

The level of technology

Among the currently used methods for the synthesis of acetic acid one of the most commercially suitable is catalyzed carbonylation carbonyliron reagent(s), in particular methanol, carbon monoxide, as described in US. Patent No. 3769329, publ. in Paulik et al. in October 30, 1973. Typically, the carbonylation catalyst contains rhodium as dissolved, or otherwise dispersed in a liquid reaction medium or deposited on an inert solid, together with a halogenated promoter catalyst, an example of which is methyliodide. Rhodium can be introduced into the reaction system in any form. The nature of the halide promoter is in General not critical. The patentees disclose a very large R the d of suitable promoters, most of which are organic iodides. The most typical and effectively, the reaction is carried out at a constant bubbling gas of carbon monoxide through the liquid reaction medium in which is dissolved catalyst.

The improvement in the method of prior art for the carbonylation of an alcohol, to obtain the carboxylic acid containing one carbon atom more than the alcohol, in the presence of a rhodium catalyst, reveal in aseparating U.S. patents 5001259, publ. on March 19, 1991; 5026908, published on June 25, 1991; and 5144068, publ. September 1, 1992; and European patent EP 0 161 874 B2, publ. July 1, 1992. As here disclosed, acetic acid is produced from methanol in a reaction medium containing acetate, metalhalide, mainly methyliodide, and the presence of rhodium in a catalytically effective concentration. These patents disclose that the stability of the catalyst and the efficiency of the carbonylation reactor can be supported at a staggeringly high levels, even at very low water concentrations, namely 4 weight percent or less in the reaction medium (despite the common industry practice of maintaining approximately 14-15 wt.% water) by maintaining in the reaction medium, along with a catalytically effective amount of rhodium and at least limit the concentration of water, set the authorized concentration of iodide ions in addition to the iodide ion, which is in the form of moduledata. The iodide ion is a simple salt, preferably a lithium iodide. Patents have reported that the concentration of acetate and salts of iodide is an important parameter in influencing the rate of carbonylation of methanol to obtain acetic acid, especially at low concentrations in water reactor. When using relatively high concentrations of acetate and salts of iodide receive a surprising degree of stability of the catalyst and the efficiency of the reactor, even when the liquid reaction medium contains water in concentrations as low as about 0.1 wt.%, so low that it can be widely defined simply as "the maximum concentration of water. Moreover, the used, the reaction medium improves the stability of the rhodium catalyst, namely resistance to deposition of the catalyst, especially during the stages of the recovery process of the product. At these stages distillation to recover the product acetic acid tends to remove from the catalyst, the carbon monoxide, which in a production environment maintained in the reaction vessel, is a ligand with a stabilizing effect on the rhodium. U.S. patents 5001259, 5026908 and 5144068 incorporated herein by reference.

It was found that shallow way carbonylation get in ssnoi acid reduces the amount of such by-products as carbon dioxide, hydrogen and propionic acid, the amount of other impurities normally present in trace quantities may be increased in the dry method, carbonylation, and sometimes quality suffers acetic acid, when trying to increase productivity by improving the catalyst or modification of the reaction conditions.

These trace impurities affect the quality of acetic acid, especially when they recycle in the production process, which, among other things, may lead to accumulation of these contaminants over time. Unsaturated aldehydes, namely, CROTONALDEHYDE and atolkachova aldehyde, which receive aldol reaction of acetaldehyde, it is the impurities that reduce the permanganate index of acetic acid, qualitative test, widely used in the production of acetic acid. Used here, the term "aldehyde" is intended to denote compounds that contain aldehyde functional groups, these compounds can include or not to include unsaturation (see Catalysis of Organic Reaction, 75, 369-380 (1998)for further details on the impurities in the carbonylation process. These aldehyde compounds may be found in any set of threads of the carbonyl process. As disclosed, such aldehyde compounds may be the way the van in the process. In this regard, aldehyde compounds can be found in any set of internal threads of the process. Such aldehyde compounds are also often found in raw materials widely used in the method of carbonylation. The usual industry sources carbonyliron reagents can include aldehyde compounds that may be present in undesirable concentrations. For this reason, aldehyde compounds can be detected in the feed stream fed to the carbonylation reactor. Similar threads for example technological and commodity flows, Carboniferous method will contain at least one carbonyliron reagent.

The present invention is directed to reducing the concentration of aldehyde, which can be represented in the form of compounds such as acetaldehyde, Butyraldehyde, CROTONALDEHYDE, 2-atolkachova aldehyde and 2-ethylbutyraldehyde and the like, especially in the target stream containing carbonyliron reagent, or the target thread's method carbonylation.

The above aldehyde compounds such as acetaldehyde, are sources for any set of other undesirable by-products that can be formed in Carboniferous the way. Acetaldehyde, in particular, is a source of propionic acid. By smart is the solution concentration of aldehyde present invention may also reduce or remove such unwanted by-products. Thus, the main goal is to reduce the content of aldehydic compounds, particularly acetaldehyde.

Traditional methods for the removal of such aldehyde impurities include processing flow of the product acetic acid oxidants, ozone, water, methanol, activated carbon, amines and the like. Such processing can be combined or not combined with a distillation of acetic acid. The most typical treatment includes a series of distillations of the final product. Also known removing aldehyde impurities from organic streams by processing organic streams by aminoguanidinium, such as hydroxylamine, which interacts with the aldehyde components with the formation of Asimov, followed by distillation to separate the purified organic product from oxomnik reaction products. However, additional processing of the final product increases the cost method, and distillation of the treated product, acetic acid and can lead to the formation of additional impurities.

Thus, it became important to determine the most cost-effective ways to reduce the concentration of aldehyde compounds in Carboniferous process, including technological and commodity flows containing carbonyliron reagent, without contamination of the final product or add the extra cost. Accordingly, there remains a need for alternative methods to improve the degree of recovery of the aldehyde. The present invention provides one such alternative solution.

The invention

This invention relates to a method of reducing the concentration of aldehydes in the target stream. The invention in particular relates to a method for reducing the concentration of aldehydes in the target stream Carboniferous process. The invention also relates to a method for reducing the concentration of aldehydes in the target stream, including carbonyliron reagent. More specifically, the invention relates to a method for reducing the concentration of aldehyde in the feed stream to the carbonylation reactor Carboniferous process.

In one aspect, the invention provides a method, comprising: providing a target thread, which contains carbonyliron reagent and the initial concentration of aldehydes; and the provision of the interaction of the target thread and the deposited catalyst that includes at least one metal from 8 to 11 group, under conditions sufficient to reduce the initial concentration of aldehydes to secondary concentration of aldehydes.

In another aspect, the invention provides a method, comprising: providing a target flow Carboniferous process, servicei concentration of aldehydes; introduction the target flow in the reaction vessel containing the deposited catalyst comprising at least one metal from 8 to 11 groups; finding the target thread in conditions that reduce the initial concentration of aldehydes; and removing from the reaction vessel treated stream with a secondary concentration of the aldehydes which is less than the initial concentration of aldehydes.

In another aspect, the invention provides a method, comprising: providing a supply current to Carboniferous process containing carbonyliron reagent with the primary concentration of aldehydes; the introduction of the target flow in the reaction vessel containing the deposited catalyst comprising at least one metal from 8 to 11 groups; finding the raw stream in conditions that reduce the initial concentration of aldehydes; and removing from the reaction vessel treated stream with a secondary concentration of the aldehydes which is less than the initial concentration of aldehydes.

While the invention may be subjected to various modifications and implement alternative forms, specific embodiments of have been shown in the examples and will be described here in detail. However, it should be understood that the invention is not limited to the embodiments described herein. Preferably sabreena covers all modifications, equivalents and alternatives falling within the scope of invention which is defined in the attached claims.

Description of illustrative embodiments

This invention relates to a method of reducing the concentration of aldehyde in the target stream. The invention in particular relates to a method for reducing the concentration of aldehyde in the target stream of the carbonyl process. The invention also relates to a method for reducing the concentration of aldehyde in the target stream containing carbonyliron reagent. More specifically, the invention relates to a method for reducing the concentration of aldehyde in the feed stream to the reactor carbonylation carbonylation process.

Illustrative variants of the embodiment of the present invention

In the interest of clarity, not all features of the modern implementations described in this description. It should, of course, be understood that the development of any such modern variant implementation, numerous specific solutions of the embodiments should be taken to achieve the specific goals of researchers, such as compliance with system-and business constraints, which will vary from one embodiment to another. Moreover, it should be understood that such a program of experimental work can be long and complicated, but in spite of this, will be serial is Ino to run for specialists in this field of technology owning the details of this description.

In various embodiments, implementation of the present invention provides a method of reducing the concentration of aldehydes in the target stream that contains at least one aldehyde compound, the primary concentration of aldehydes. In certain embodiments of the implementation used by the target process thread carbonyl which may contain or not contain carbonyliron reagent. In some embodiments, the implementation provides a method of reducing the concentration of aldehyde in the feed stream of the carbonyl process, which contains at least one carbonyliron reagent and at least one aldehyde compound in the primary concentration of aldehydes.

In various embodiments, the implementation of the target thread with primary concentration of aldehydes are subjected to interaction of the target thread is coated with a catalyst that contains at least one metal from 8 to 11 group, under conditions that reduce the initial concentration of aldehydes to secondary concentration of the aldehydes. In the result, the method can be achieved the desired reduction of the concentration of aldehyde compounds and can be separated treated stream with a secondary concentration of the aldehydes. The treated stream can be successfully and is used in subsequent processes or stages of the process, where it is desirable to have a reduced concentration of aldehydes.

In General, the invention is not limited by the concentration of aldehyde compounds, comprising an initial concentration of aldehydes. The preferred modes of carrying out the process may vary depending on the concentration of the aldehyde compounds constituting the primary concentration of aldehydes in the target stream.

As disclosed previously, "aldehyde compound" means a compound or compounds that contain functional groups, such compounds can include or not to include unsaturation. Aldehyde compound whose concentration in the stream may be reduced by the application of the present invention includes acetaldehyde, Butyraldehyde, CROTONALDEHYDE, 2-atolkachova aldehyde and 2-ethylbutyraldehyde and the like. A particularly desirable application of the present invention is to reduce the concentration of acetaldehyde.

Aldehyde compound in the target stream is present in the primary concentration of aldehydes, which can be the concentration of a single aldehyde compounds, if the target thread there is only one aldehyde compound, or the total concentration of two or more aldehyde compounds, if the target thread is more than one aldehyde compounds. Similarly, secondary conc the Oia aldehydes, which can be detected in the treated stream may be the concentration of a single aldehyde compounds, if there is only one aldehyde compound, or the total concentration of two or more aldehyde compounds, if present more than one aldehyde compounds. The decrease in the concentration of aldehydes may be due to a decrease in the concentration of one or more individual aldehyde compounds.

Catalysts that may be used in accordance with the invention, are applied catalysts that include at least one metal from 8 to 11 group. The nature of media that can be used with this invention, in General, not limited and in General it is expected that these media finds applicability in the General industrial chemical methods can probably be used in accordance with the present invention. Suitable carrier materials include both organic and inorganic media. Acceptable organic or carbon carriers include, but are not limited to, carriers, based on coconut fatty coal, charcoal and other hydrocarbons. Acceptable inorganic or carbon carriers include, but are not limited to, carriers, based on metal oxides, such as alumina, oxide to Omnia, the titanium oxide, zirconium oxide and magnesium oxide, mixed metal oxides, alumina, and silicon carbide. Similarly, the physical properties of media that can be used when applying the present invention is basically not limited properties, is widely used to describe media, including, but not limited to, pore size, surface area, water absorption and other properties.

As noted earlier, the catalysts which can be used in accordance with the present invention is applied catalysts that include at least one metal from 8 to 11 group. Preferably, the catalyst contains at least one metal from 8 to 10 groups. Even more preferably, the catalyst contains only one metal 10 groups. Preferred catalysts include ruthenium, palladium and/or platinum, preferably palladium and/or platinum and even more preferably palladium. Although the catalyst may contain a single metal from 8 to 11 groups can be used catalysts comprising more than one metal from 8 to 11 group.

The concentration of the metal, which can be used in implementing the present invention is basically not limited. Applied catalysts of different metals at various concentrations and at various wear the s, which can be used in accordance with the present invention, for the most part available from various commercial sources. Desirable catalysts can contain more than 0.01 mass% of the metal, more than 0.1 weight percent of the metal, greater than 0.25 mass% of metal or even of more than 0.5 weight percent of the metal. Desirable catalysts may contain less than 5.0 mass% of metal, less than 2.5 weight percent metal, and even less than 1.0 weight percent of the metal.

The catalysts that were used in the present invention include commercial catalysts, 0.5 wt.% Pd pellet coal (Engelhard Co., product no. C3880), 0.5 wt.% Pt pellet coal (Engelhard Co., product no. C3757) and 1.0 wt.% EN pellet coal (Catalyst C, 5.5 g, Engelhard Co., product no. C4023).

Although it is preferable to use one type of media with one metal catalyst is one or a combination of metals of the catalyst, the usage of composite media types and/or compound of metals of the catalyst and is not outside the scope of the claims of the invention. Preferred catalysts include catalysts containing palladium or platinum on a carbon carrier.

In various embodiments, implementation of the present invention, the target stream is subjected to interaction of the target thread is coated with a catalyst, which contains at least one metal from 8 to 11 group, under conditions that reduce the initial concentration of aldehydes to secondary concentration of the aldehydes. The conditions under which it can be done way to get the desired result within two main modes: the mode of oxidation and decomposition. In the mode of oxidation reaction is carried out in the presence of oxygen. Oxygen can be present in the form of pure oxygen, air or a combination of pure oxygen and air. Can also be used compounds which serve as sources of oxygen. Preferably the oxygen present in the air. When the mode of oxidation reaction, leading to the decrease of the concentration of aldehyde, may be at any concentration of available oxygen, even at the limiting oxygen concentration. Thus, in addition to oxygen can be used an inert carrier, such as nitrogen.

Specialist in the art that owns the information for this description, recognizes that the process can be carried out under milder conditions, namely temperature and pressure, if you use a higher concentration of oxygen. It is possible to conduct the process in terms of ignition. Preferably, the concentration of oxygen and the temperature is set and/or support to t the th, to achieve the desired reduction in the concentration of aldehyde. Specialist in the art will recognize that the oxygen concentration and temperature can affect even have a significant impact on the operation time and the action of the catalyst. The concentration of oxygen and the temperature is preferably chosen such that the conversion was at the desired level, and the lifetime of the catalyst increased with decreasing decay carbonyliron reagents and other components that may be present, and reduce the formation of unwanted side products.

In the mode of oxidation in the reaction of introducing the molar ratio of oxygen concentration, i.e. the oxygen source, the primary concentration of the aldehydes preferably more than 0.1, more preferably more than 0.5, more preferably more than 1, even more preferably more than 5 and even more preferably more than 7.5. The maximum molar ratio of concentration of the oxygen source to the primary concentration of the aldehyde, as a rule, is not limited; however, in some embodiments, the implementation may be desirable to limit the amount of the oxygen source on the basis of a desire to remain with the ignition limit or minimize the formation of undesirable by-products.

Mode decomposition method is carried out in the absence of oxygen. In the mode of Razlog is of the target thread may be diluted with an inert gas or gases. Alternatively, the target thread may be subjected to the process without the use of an inert carrier gas.

As in the oxidation mode, and the mode of decomposition, the target stream is preferably fed into the vessel containing the catalyst at conditions, namely temperature and pressure at which the target thread is in the gas phase, namely above the dew point of the target thread. In some embodiments, the implementation of the target thread may be one stripped off in a separate apparatus before submitting to the process of the present invention. Preferably the target thread overheat to the desired temperature. When carrying out the method of the present invention in accordance with the variations in implementation of the flux of any gas method in the reactor, including any inert carrier gas, is preferably introduced first. If the system is at a temperature above the dew point of the target thread, the target thread, containing an initial concentration of aldehydes, served in the reactor. The target thread, which is now mixed with any of the gases in accordance with the method, result in interaction with the catalyst at the desired conditions, including temperature, pressure and flow level. To reduce the content of aldehydes. The treated stream containing secondary concentration of the aldehydes which is less than the initial concentration of aldehyde is, withdrawn from the reactor.

Temperature and pressure, which can be used for the method, otherwise basically not limited. Depending on other conditions of the method the method can be carried out at temperatures below 150°C, below 125°C below 100°C and even below 50°C., depending on other conditions of the method the method can be carried out at temperatures above 150°C, above 175°C above 200°C and even above 250°C. Preferably the temperature should be selected to control not only the decrease of the concentration of aldehyde, but also to prevent non-selective oxidation reactions, which increase with increasing temperature. In some embodiments, the implementation will be desirable to keep the temperature at 225°C, more preferably at 200°C to prevent decomposition of any of carbonyliron reagents, including, but not limited to, methyl acetate and methanol, which may be present in the target stream.

The method in General is not limited by the pressure inside the reactor. Conditions, including pressure, should be selected so that carbonyliron reagent or other dialdehydes connection, it is desirable to maintain without oxidation or decomposition prior to any significant degree. Depending on other conditions, in preferred embodiments of implementing the method is mainly carried out at Yes is the thoughts, changing from 0 to 150 pounds per square inch. As a specialist in the art that owns the information for this description, it is clear that the temperature, pressure, oxygen concentration (if you use oxygen, and other parameters will vary depending on such factors as the volumetric rate and the desired conversion, and will also vary depending on the target thread, namely, does the flow carbonyliron reagent as a main component. For example, you can change the temperature or the concentration of oxygen in order to maintain the desired degree of conversion. Indeed, throughout the shelf-life of the catalyst can be expected that it would be desirable to control the temperature range. Although it is clear that the choice of conditions for the various embodiments of the present invention to achieve the desired result in decreased concentrations of aldehydes target flow from the primary concentration of aldehydes to secondary concentration of aldehydes, can be somewhat complicated and lengthy, such work will be consistently carried out to specialists in the art that owns the information for this description.

Stage of exposure to the interaction of the target stream can be conducted in any number of vessels, p is osposobljenih to maintain conditions suitable for achieving a reduction in the concentration of aldehyde. Preferably the vessel or reactor allows control in the continuous mode of operation as, for example, the target thread with the primary concentration of the aldehydes may be subjected to the process together with the processed stream with a secondary concentration of aldehydes, lower than the initial concentration of aldehydes. Suggest that different reactor designs, widely used in heterogeneous catalysis, can be used in combination with different variants of implementation of the present invention. Thus, it is expected that the implementation of the present invention can be used in gas-phase reactors, suspension, fixed bed, with irrigated layer and fluidized bed. The preferred gas-phase reactors and fixed bed.

The method of the present invention reduces the concentration of aldehyde compounds from the primary concentration of aldehydes to secondary concentration of the aldehydes. It can be assumed that the desired decrease in the concentration of aldehydes depends on certain factors, which are unique to each embodiment of the method. For example, in the preferred embodiment, where the method is used to process the commodity flow method carbonyl desired mind is nisene the concentration of aldehydes will be mainly determined by the quality requirements of the product acetic acid by the method of carbonylation. The embodiment of the method can be controlled to achieve reductions in the concentration of aldehydes in a wide range. The decrease in the concentration of aldehydes from primary concentration of aldehydes to secondary concentration of the aldehydes can be conventionally defined as (initial concentration of aldehydes - secondary concentration of aldehydes)/initial concentration of aldehydes × 100%. Depending on conditions, method and specific targets for each implementation can be achieved by reducing the concentration of aldehydes up to 25%, even up to 75% and up to 99.9%.

As disclosed in some embodiments, the implementation of the target thread may also contain one or more carbonyliron reagents. Carbonyliron reagents are compounds that can be introduced into the reaction in Carboniferous method for acetic acid. Such carbonyliron reagents include, but are not limited to, methanol, methyl acetate, methylformate, dimethyl ether or mixtures thereof. Particularly preferred application of the present invention includes processing of target streams containing methyl acetate, methanol, or a combination of methyl acetate and methanol.

In the variants of implementation, in which the target thread also contains carbonyliron reagent, the reduction of the concentration of aldehyde compounds, preferably reach without knowledge is sustained fashion the reduction of the concentration carbonyliron reagent, originally located in the target stream. The concentration carbonyliron reagent in the treated stream in the result, the method is not significantly reduced in comparison with the concentration carbonyliron reagent in the target stream.

According to different variants of implementation of the present invention the method is used for processing the target flow Carboniferous process. Such target flows Carboniferous process can contain or not contain carbonyliron reagent, and, if carbonyliron reagent is present, the concentration carbonyliron reagent in the target stream can vary within wide limits.

Target flows Carboniferous process, which can be attributed to the method of the present invention include technological(s) thread(s) inside Carboniferous process and raw material(s) thread(s)supplied(s) in carbonyloxy reactor.

Inward technology flows, ie, process flows, Carboniferous process, containing at least one aldehyde compound, and which can optionally include or not to include carbonyliron reagent, which can be subjected to the method of the present invention include, but are not limited to, light fraction in distant parts of the column, light fractions in the desorption column, light coat, the AI in the column drying and/or other process streams.

A more desirable application of the present invention is to process the raw stream Carboniferous process, which contains at least one carbonyliron reagent and is characterized by the initial concentration of aldehydes, which must be reduced before the raw stream will be served in carbonyloxy reactor Carboniferous process. Suitable raw material flows, which can be subjected to the method of the present invention include carbonyliron reagent or mixture carbonyliron reagents as a main component. Suitable raw streams contain methyl acetate, methanol or combinations of acetate and methanol. Even more appropriate commodity flows contain methyl acetate, methanol or combinations of acetate and methanol as the main component of the raw stream.

Specialist in the art that owns the information for this description, it will be clear that the catalysts which can be used when implementing the present invention, can over time lose activity because of the conditions, which may be permanent, reversible or partially reversible. Deactivation may occur when the management method of the present invention under oxidative conditions or conditions of decomposition. If deactivation is caused by, or exclusively, or despair is t invertible, or partially reversible mechanisms, it is desirable to regenerate the catalyst. Regeneration may lead to full or partial recovery of the activity of the catalyst. Regeneration is an aspect of the invention.

According to different variants of implementation of the present invention, the regeneration can be achieved in several ways. One acceptable method is the exposure of the catalyst to oxidizing conditions, preferably in the absence of the target stream, and preferably at elevated temperatures. A certain degree of reduction can also be achieved when carrying out the method of the present invention, i.e. in the presence of the target stream, at high concentrations of oxygen, preferably more than 1 mol.% oxygen, more preferably greater than 2 mol.% oxygen, even more preferably greater than 3 mol.% the oxygen. Suitable for the regeneration of the oxygen concentration will depend largely on the limitations of the method and temperature of the layer, which can be achieved. A typical set of conditions for the regeneration will include the operating mode with 3 mol.% oxygen and 150°C. with higher concentrations of oxygen may lead to the regeneration of the catalyst in a shorter period of time or at a lower temperature. In various embodiments, the implementation of the regeneration of the catalyst may the be facilitated by the use of fluidized beds of the reactor, in which part of the catalyst is constantly restored, or the use of a reactor with many layers, with layers that are recovered when inactive are used in the process.

As disclosed, the preferred implementation of the present invention is a processing target thread Carboniferous process, characterized by the initial concentration of aldehydes, which may optionally include or not carbonyliron reagent. In such embodiments, the implementation of the target thread with primary concentration of aldehydes served in the reaction vessel containing the deposited catalyst comprising at least one metal from 8 to 11 group. In the reaction vessel of the target thread is in the conditions required to reduce the initial concentration of aldehydes. The treated stream with a secondary concentration of the aldehydes which is less than the initial concentration of aldehydes, is removed from the reaction vessel. In the variants of implementation, in which the target thread further comprises carbonyliron reagent, the treated stream will also contain carbonyliron reagent.

As disclosed in accordance with other preferred variants of the implementation of the target thread is the primary thread Carboniferous way. In such embodiments, the implementation syreveport Carboniferous way containing carbonyliron reagent with the primary concentration of aldehydes, served in the reaction vessel containing the deposited catalyst comprising at least one metal from 8 to 11 group. In the reaction vessel of the target thread is in the conditions required to reduce the initial concentration of aldehydes. The treated stream containing carbonyliron reagent with a secondary concentration of the aldehydes which is less than the initial concentration of aldehydes, is removed from the reaction vessel, and then served or sent, or indirectly, which may include combinations with other source materials, in the carbonylation reactor.

To provide a better understanding of the present invention, the following examples of certain aspects of some embodiments. Any way, the following examples should not be interpreted to limit or define the scope of invention.

Examples

Example 1. The experiments were conducted in the laboratory gas-phase tubular reactor of ideal displacement from the fixed layer. For each experiment the catalyst (8 cubic inches) was placed in a stainless steel tube size 0.5 inch inner diameter × 48 inch length. Applied catalysts contained 0.5 wt.% Pd pellet coal (Catalyst A, 3,41 g, Engelhard Co., product no. C3880), 0.5 mA is from.% Pt on granulated coal (Catalyst, of 3.32 g, Engelhard Co., product no. C3757) and 1.0 wt.% EN pellet coal (Catalyst C, 5.5 g, Engelhard Co., product no. C4023). The temperature in the reactor was controlled by a heater. The upper part of the reactor was Packed with quartz and served as pre-heating/blending. Liquid raw material containing aldehyde, was pumped into the reactor at a flow rate of 0.75-1.1 cm3/min and one stripped off in the upper part of the reactor tube. 3 mol % O2in the nitrogen carrier was filed at a speed of 305 standard cubic centimeters per minute (SKSM) and added to the liquid raw material prior to feeding into the reactor. Flow rate and reaction temperature were chosen in such a way as to maintain the vapor mixture is outside the explosive limits. The off-stream reactor was cooled, and the condensed products were weighed and analyzed on the outgoing line GC. Non-condensable gas stream containing unreacted raw materials and products, was passed through a back pressure regulator. The reactor was run at a pressure of 50 psig. Liquid raw material contained 76 wt.% methyl acetate (Meoac), 24 wt.% methanol (Meon), about 840 ppm of acetaldehyde (Ach), 104 ppm ethyl acetate, 18 ppm of dimethylacetal and other trace components. Only minor amounts of impurities detected in the product, including ppm of methylformate, acetic acid is islote, dimethylcarbonate and water. The results for the three modes a, b and C shown below (table 1). CASE is hourly space velocity of the liquid.

Table 1
ModeCASE (h-1)% reduction of the concentration of AcH
Temperature→150°C175°C200°C
And9,0795,496,299,7
Inof 6.6898,598,6of 99.1
of 7.2326,645,876,5

Example 2. The experiments were carried out as described in Example 1, except that as a carrier gas was used nitrogen (N2). The results for the three modes a, b and C shown below (table 2).

Table 2
ModeCASE (h-1)% reduction of the concentration of AcH
Temperature→150°C175°C200°C
And9,0762,484,0to 97.1
In7,1420,251,180,3
7,4738,243,854,6

Example 3. The experiments were conducted in the laboratory gas-phase tubular reactor of ideal displacement from the fixed layer. For each experiment the catalyst (200 cubic centimeters, 0.5 wt.% Pd on charcoal, Engelhard Co., product no. C3880) was placed in a stainless steel tube size 1.6 inch inner diameter × 60 inch length. The temperature in the reactor was controlled by a heating tape and dvuhkamernyi heater. The upper part of the reactor was Packed with quartz. Liquid raw material containing acetaldehyde, was what acano tube pre-heating/blending, Packed with quartz, 6,2 to 15.1 cm3/min carrier Gas comprising nitrogen containing from 0 to 6 mol % O2as shown in the table. 3, was fed at a speed of 450-810 SKSM. Flow rate and temperature of pre-heating/blending were chosen in such a way as to maintain the vapor mixture is outside the explosive limits. The reactor was run at a pressure of 50 psig and a liquid raw material contained 76 wt.% methyl acetate (Meoac), 24 wt.% methanol (Meon), about 840 ppm of acetaldehyde (Ach), 104 ppm ethyl acetate, 18 ppm of dimethylacetal and other trace components. The off-stream reactor was cooled, condensed products were weighed and analyzed by GC out of line. Non-condensable gas stream containing unreacted raw materials and products, was passed through a back pressure regulator. Autonomous GHI flow noncondensable gas product showed that the reaction had formed a small amount of CO, CO2and CH4. In the absence of oxygen was not formed significant amounts of CO2. Only minor amounts of impurities detected in the product, including ppm of methylformate (F), acetic acid (SPLA), water and dimethylcarbonate. The results are shown below (table 3).

Table 3
ModeTemperature (°C)Mol % O2in GazaGas consumption (SKSM)CASE (h-1)% reduction of the concentration of AcHMeFO (ppm)HOAc (ppm)
115238105,077,638660
21733810a 4.986,9128130
320238105,098,313283
414668104,892,91343 57
517768105,095,0349189
61986810a 4.999,375295
715234502,189,7219178
817734502,198,131311
920034502,1100,00528
101516 4502,095,8848233
1117664502,199,947452
1220064502,0100,031680
1315004502,169,80124
1417604502,198,61255
1519904502,1100,00 409

Thus, the present invention is well adapted to implement and achieve the objectives and advantages, also noted as those that are inherent. Although the invention has been presented and described by reference to examples of embodiment of the invention, such reference does not imply limitation of the invention and does not imply any restrictions. The invention allows various modifications, changes and equivalents in form and function, as will be clear to experts in the fields of technology and with the information of this disclosure. Presented and described embodiments of the invention just described and do not exhaust the scope of the invention. Thus, it is understood that the invention is restricted only by the nature and scope of the attached claims, giving full understanding equivalents in all respects.

1. A method of reducing the concentration of aldehyde in the feed stream of a carbonylation process comprising feeding raw stream containing carbonyliron agent selected from the group consisting of methanol, methyl acetate, methylformate and dimethyl ether or mixtures thereof,
having an initial concentration of aldehydes;
and its interaction in the gas phase coated with a catalyst that contains at least one metal 8 is a group of up to 11 groups, in conditions that reduce the initial concentration of aldehydes to secondary concentration of aldehydes.

2. The method of claim 1, in which the raw stream includes the process stream of the carbonyl process.

3. The method of claim 1, wherein the carrier includes coal.

4. The method of claim 1, wherein the carrier includes charcoal from coconut.

5. The method of claim 1, wherein the metal includes at least one metal from the 8 group 10 group.

6. The method of claim 1, wherein the metal includes at least one metal 10 group.

7. The method of claim 1, wherein the metal includes at least palladium.

8. The method of claim 1, wherein the metal includes at least platinum.

9. The method of claim 1, wherein the conditions include oxidative mode.

10. The method of claim 1, wherein the conditions include the mode of decomposition.

11. The method of claim 1, wherein the conditions include a molar ratio of concentration of the oxygen source to the primary concentration of aldehydes than 0.5.

12. The method of claim 1, wherein the conditions include a molar ratio of concentration of the oxygen source to the primary concentration of aldehydes more than 1.

13. The method of claim 1, additionally including the regeneration of the deposited catalyst in the presence of commodity flow, or in the absence of commodity flow when oxygen concentrations greater than 1 mol.% oxygen, at a temperature and time sufficient d is I the regeneration of the catalyst.

14. The method of claim 1, additionally including the regeneration of the deposited catalyst in the presence of the raw stream or in the absence of commodity flow when oxygen concentrations greater than 3 mol.% oxygen, at a temperature and time sufficient to regenerate the catalyst.

15. A method of reducing the concentration of aldehyde in the feed stream of a carbonylation process, including
summarizing the raw stream, including carbonyliron reagent selected from the group consisting of methanol, methyl acetate, methylformate and dimethyl ether and mixtures thereof having a primary blood levels of aldehydes,
to the reaction vessel containing the deposited catalyst comprising at least one metal from the 8 groups of up to 11 groups, and the interaction of flow in the gas phase under conditions that reduce the initial concentration of aldehydes to secondary concentration of aldehydes, and
removal from the reaction vessel treated stream with a secondary concentration of the aldehydes, which is less than the initial concentration of aldehydes.

16. The method of clause 15, in which the raw stream includes the process stream of the carbonyl process.

17. The method of clause 15, in which the carrier includes coal.

18. The method of clause 15, in which the carrier includes charcoal from coconut.

19. The method of clause 15, in which the metal includes, IU the greater extent, one metal from the 8 group 10 group.

20. The method of clause 15, in which the metal comprises at least one metal 10 group.

21. The method of clause 15, in which the metal includes at least palladium.

22. The method of clause 15, in which the metal includes at least platinum.

23. The method of clause 15, wherein the conditions include oxidative mode.

24. The method of clause 15, wherein the conditions include the mode of decomposition.

25. The method of clause 15, wherein the conditions include a molar ratio of concentration of the oxygen source to the primary concentration of aldehydes than 0.5.

26. The method of clause 15, wherein the conditions include a molar ratio of concentration of the oxygen source to the primary concentration of aldehydes more than 1.

27. The method of clause 15, further comprising regeneration of deposited catalyst in the presence of commodity flow, or in the absence of commodity flow when oxygen concentrations greater than 1 mol.% oxygen, at a temperature and time sufficient to regenerate the catalyst.

28. The method of clause 15, further comprising regeneration of deposited catalyst in the presence of the raw stream or in the absence of commodity flow when oxygen concentrations greater than 3 mol.% oxygen, at a temperature and time sufficient to regenerate the catalyst.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to an improved carbonylation method intended for producing a carbonylation product through reaction of carbon monoxide with raw material which contains alcohol and/or reactive derivative thereof, in vapour phase using a heterogeneous catalyst in form heteropoly acid which undergoes ion exchange with one or more metals selected from a group comprising rhodium, iridium, copper and palladium, and a group IA metal selected from lithium, sodium, potassium and rubidium, or in which these metals are included, where the heteropoly acid has formula H3M12XO40, where M denotes tungsten, molybdenum, chromium, vanadium, tantalum or niobium and X denotes phosphorus or silicon.

EFFECT: method provides high conversion of the methanol reagent and longer service life of the catalyst.

28 cl, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to synthesis of esters from the alcohol fraction of caprolactam. The method of producing esters from caprolactam production wastes is realised via esterification of organic acid and alcohol in autocatalytic heat release conditions which support the esterification reaction at temperature 40-130°C using a catalyst in form of cation-exchange resin which is pre-treated with sulphuric acid in amount of 0.4-2 wt % of the weight of the loaded material with cooling down of the reaction mixture before separating the two phases.

EFFECT: high efficiency of the method.

2 cl, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: method relates to production of acetic acid ether (methyl acetate) via carbonylation of dimethyl ether in gas phase in presence of catalyst and may be used in chemical industry. Invention covers catalyst for carbonylation of dimethyl ether that comprises acid cesium salt of phosphor-tungsten heteropoly acid CsxHyPW12O40, where 1.3≤x≤2.2, y=3-x with platinum additive in amount of 0.25-1.0 wt %. Catalyst in prepared on adding cesium soluble salt to mix of solutions of phosphor-tungsten heteropoly acid and platinum-hydrochloric acid, both taken in required ratio, evaporating, drying, tabletting and grinding to required size. Invention covers also production of methyl acetate in presence of above described catalyst.

EFFECT: higher catalytic activity.

5 cl, 9 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to novel compounds of general formula (I)

, in which X denotes a CHO, CH2OH or CH2OC(O)R group, where R denotes a straight of branched C1-C5 alkyl chain; as well as to a synthesis method, particularly synthesis of 6,8-dimethylnon-7-enal (1) through hydroformylation of 5,7-dimethylocta-1,6-diene. The invention also relates to fragrant compositions containing formula (I) compounds. Owing to their fragrant properties, these compounds are of great interest in perfumery, particularly cosmetic products and household chemicals.

EFFECT: obtaining novel fragrant compositions.

12 cl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to novel compounds of general formula (I)

, in which X denotes a CHO, CH2OH or CH2OC(O)R group, where R denotes a straight of branched C1-C5 alkyl chain; as well as to a synthesis method, particularly synthesis of 6,8-dimethylnon-7-enal (1) through hydroformylation of 5,7-dimethylocta-1,6-diene. The invention also relates to fragrant compositions containing formula (I) compounds. Owing to their fragrant properties, these compounds are of great interest in perfumery, particularly cosmetic products and household chemicals.

EFFECT: obtaining novel fragrant compositions.

12 cl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing lower alkyl ether of lower aliphatic alcohol having formula R1-COO-R2, involving reaction of a pre-dried lower alkyl ether having formula R1-O-R2, in which R1 and R2 independently denote C1-C6alkyl groups, provided that the total number of carbon atoms in groups R1 and R2 ranges from 2 to 12, or R1 and R2 together form a C2-C6 alkenyl group, with material which contains carbon monoxide, in the presence of a catalyst which contains mordenite and/or ferrierites in anhydrous conditions. The invention also relates to a method of producing carboxylic acids through hydrolysis of esters obtained using the method given above.

EFFECT: high output and selectivity of end product.

29 cl, 3 tbl, 9 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method for synthesis of an ester through reaction of 1-olefin with a monobasic carboxylic acid and water in vapour phase in the presence of a heteropolyacid catalyst on silica gel, in which the silica gel support is in from of granules treated with water vapour at temperature between 100 and 300°C for a period of time between 0.1 to 200 hours, before or simultaneously with application of the heteropolyacid onto the support. The invention also relates to a heteropolyacid catalyst deposited on silica gel and to a method of preparing the catalyst, where the support is obtained by treating silica gel granules with water vapour at temperature between 100 and 300°C for a period of time between 0.1 and 200 hours, before or simultaneously with application of the heteropolyacid onto the support.

EFFECT: use of the said catalyst in the ester synthesis method through reaction of 1-olefin with a monobasic carboxylic acid and water in vapour phase enables to reduce content of methyl ethyl ketone in products.

43 cl, 1 ex

FIELD: chemistry.

SUBSTANCE: method of producing acetic acid and its ester or anhydride involves bringing methanol and/or its reactive derivative selected from methyl acetate and dimethyl ether into contact with carbon monoxide in the presence of a catalyst at temperature ranging from 250 to 600°C and pressure ranging from 10 to 200 bars, and where content of iodide in the methanol and/or its reactive derivative, carbon monoxide and catalyst is less than 500 parts/million, where the catalyst essentially consists of mordenite which contains skeleton elements in form of silicon, aluminium and one or more of other elements selected from gallium and boron, and in which copper, nickel, iridium, rhodium or cobalt is added through ion exchange or some other method.

EFFECT: high selectivity with respect to the end product and high catalyst stability.

22 cl, 3 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: described is a carbonylation method for producing a carbonylation product by bringing carbon monoxide into contact with initial material containing alcohol and/or its reactive derivative, in vapour phase using a heterogeneous heteropolyacid catalyst containing one or more metal cations selected from Cu, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and Pt. The initial material contains 0.5-20 wt % water and water in the initial material is fresh and/or recycled.

EFFECT: increased catalyst activity, increased degree of convertion of methanol into the desired product.

35 cl, 5 ex, 3 tbl

FIELD: chemistry.

SUBSTANCE: method includes carbonylation of the alcohol and/or of its reactive derivative with carbon monooxide in liquid reaction mixture carried out in carbonylation reactor. The said liquid reaction mixture contains the said alcohol and/or its reactive derivative, carbonylation catalyst, alkyl halide cocatalyst whereat the said catalyst includes at least one metal selected from rhodium or iridium coordinated with polydentate ligand whereat the said polydentate ligand has the bite angle at least 145° or forms the "hard" Rh or Ir metal-ligand complex; the said polydentate ligand includes at least two coordination groups; at least two of them independently contain P, N, As or Sb as coordination atoms. The hydrogen/carbon monooxide mole ratio is supported in the range at least 1:100 and/or carbon monooxide directed to carbonylation reactor contains at least 1 mole % of hydrogen; catalyst flexibility range is less 40°. The method is tolerable to hydrogen presence i.e. liquid side-products are formed in small amounts or are not formed at all.

EFFECT: improvement of the method of carboxylic acid and its ester obtaining.

49 cl, 3 tbl, 13 ex

FIELD: chemistry.

SUBSTANCE: invention refers to advanced process of diacerein production with aloe-emodin and it mono-, di - and triacetylate derivatives within 0 to 5 parts per million containing water-organic solution of weak-base diacerein salt is extracted with solvent miscible or practically immiscible with water. Method allows for product containing diacerein and up to 5 parts per million of aloe-emodin, i.e. enables product with low aloe-emodin content, and is characterised with simplicity of implementation.

EFFECT: product with low aloe-emodin content and simplicity of implementation.

10 cl, 6 ex

FIELD: industrial organic synthesis.

SUBSTANCE: method comprises contacting vapor-phase mixture at 150-205°C with alkali and/or alkali-earth metal carboxylate dispersed on activated carbon resulting in conversion of alkyl iodides into corresponding carboxylic acid esters, while iodine becomes bound in the form of inorganic iodide.

EFFECT: facilitated freeing of carboxylic acid product from organic iodine compounds.

4 cl, 2 tbl, 32 ex

The invention relates to methods for complex diesters of terephthalic acid and diodes of polyesters

The invention relates to an improved process for the preparation of ethyl acetate, widely used mainly in organic synthesis

FIELD: chemistry.

SUBSTANCE: invention relates to an improved carbonylation method intended for producing a carbonylation product through reaction of carbon monoxide with raw material which contains alcohol and/or reactive derivative thereof, in vapour phase using a heterogeneous catalyst in form heteropoly acid which undergoes ion exchange with one or more metals selected from a group comprising rhodium, iridium, copper and palladium, and a group IA metal selected from lithium, sodium, potassium and rubidium, or in which these metals are included, where the heteropoly acid has formula H3M12XO40, where M denotes tungsten, molybdenum, chromium, vanadium, tantalum or niobium and X denotes phosphorus or silicon.

EFFECT: method provides high conversion of the methanol reagent and longer service life of the catalyst.

28 cl, 1 tbl

FIELD: chemistry.

SUBSTANCE: method relates to production of acetic acid ether (methyl acetate) via carbonylation of dimethyl ether in gas phase in presence of catalyst and may be used in chemical industry. Invention covers catalyst for carbonylation of dimethyl ether that comprises acid cesium salt of phosphor-tungsten heteropoly acid CsxHyPW12O40, where 1.3≤x≤2.2, y=3-x with platinum additive in amount of 0.25-1.0 wt %. Catalyst in prepared on adding cesium soluble salt to mix of solutions of phosphor-tungsten heteropoly acid and platinum-hydrochloric acid, both taken in required ratio, evaporating, drying, tabletting and grinding to required size. Invention covers also production of methyl acetate in presence of above described catalyst.

EFFECT: higher catalytic activity.

5 cl, 9 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing dialkyl ether of naphthalene dicarboxylic acid used in production of different polymer materials such as polyesters or polyamides from a liquid-phase reaction mixture containing low-molecular alcohol, naphthalene dicarboxylic acid, and material which contains polyethylene naphthalate, in mass ratio of alcohol to acid between 1:1 and 10:1, at temperature between 260°C and 370°C and pressure between 5 and 250 absolute atmospheres.

EFFECT: method enables production of highly pure NDC.

6 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: method of producing acetic acid and its ester or anhydride involves bringing methanol and/or its reactive derivative selected from methyl acetate and dimethyl ether into contact with carbon monoxide in the presence of a catalyst at temperature ranging from 250 to 600°C and pressure ranging from 10 to 200 bars, and where content of iodide in the methanol and/or its reactive derivative, carbon monoxide and catalyst is less than 500 parts/million, where the catalyst essentially consists of mordenite which contains skeleton elements in form of silicon, aluminium and one or more of other elements selected from gallium and boron, and in which copper, nickel, iridium, rhodium or cobalt is added through ion exchange or some other method.

EFFECT: high selectivity with respect to the end product and high catalyst stability.

22 cl, 3 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: described is a carbonylation method for producing a carbonylation product by bringing carbon monoxide into contact with initial material containing alcohol and/or its reactive derivative, in vapour phase using a heterogeneous heteropolyacid catalyst containing one or more metal cations selected from Cu, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and Pt. The initial material contains 0.5-20 wt % water and water in the initial material is fresh and/or recycled.

EFFECT: increased catalyst activity, increased degree of convertion of methanol into the desired product.

35 cl, 5 ex, 3 tbl

FIELD: chemistry.

SUBSTANCE: method includes carbonylation of the alcohol and/or of its reactive derivative with carbon monooxide in liquid reaction mixture carried out in carbonylation reactor. The said liquid reaction mixture contains the said alcohol and/or its reactive derivative, carbonylation catalyst, alkyl halide cocatalyst whereat the said catalyst includes at least one metal selected from rhodium or iridium coordinated with polydentate ligand whereat the said polydentate ligand has the bite angle at least 145° or forms the "hard" Rh or Ir metal-ligand complex; the said polydentate ligand includes at least two coordination groups; at least two of them independently contain P, N, As or Sb as coordination atoms. The hydrogen/carbon monooxide mole ratio is supported in the range at least 1:100 and/or carbon monooxide directed to carbonylation reactor contains at least 1 mole % of hydrogen; catalyst flexibility range is less 40°. The method is tolerable to hydrogen presence i.e. liquid side-products are formed in small amounts or are not formed at all.

EFFECT: improvement of the method of carboxylic acid and its ester obtaining.

49 cl, 3 tbl, 13 ex

FIELD: chemistry.

SUBSTANCE: invention concerns improved method of obtaining carboxylic acid and/or complex alcohol ether and carboxylic acid, involving carbonylation of C1-C8 aliphatic alcohol and/or its reactive derivative by carbon monoxide in liquid reaction mix in carbonylation reactor. Liquid reaction mix includes indicated alcohol and/or its reactive derivative, carbonylation catalyst, alkylhalide co-catalyst and optionally water in limited concentration, the catalyst including cobalt, rhodium or iridium coordinated with tridentate ligand, or their mix. Also invention concerns application of carbolylation catalyst including cobalt, rhodium or iridium coordinated with tridentate ligand, or their mix, in carbonylation method of obtaining carboxylic acid and/or complex alcohol ether and carboxylic acid.

EFFECT: enhanced carbonylation speed and selectivity.

36 cl, 6 tbl, 3 ex

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