Carbonylation method for producing methyl acetate

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of reducing formation of byproducts when producing methyl acetate, which involves carbonylation of dimethyl ether with carbon monoxide in one or more carbonylation reaction zones in the presence of a mordenite catalyst to obtain a methyl acetate product, characterised by that at least one of methyl acetate and acetic acid is fed into at least one of said reaction zones.

EFFECT: improved method of reducing formation of byproducts when producing methyl acetate.

17 cl, 5 dwg, 1 tbl, 4 ex

 

The present invention relates to a method for carbonylation of receipt of acetate by the reaction of dimethyl ether (DME) with carbon monoxide in the presence of added acetate and/or acetic acid and mordenite catalyst.

In industry use of liquid-phase methods carbonyl, such as the carbonylation of methanol and/or its reactive derivatives in the presence of homogeneous catalysts with obtaining acetic acid. Also known gas-phase methods carbonylation using methanol and dimethyl ether using heterogeneous catalysts.

In EP-A-0596632 described headspace method carbonylation of methanol to obtain acetic acid at high temperatures and pressures in the presence of mordenite catalyst which contains copper, Nickel, iridium, rhodium or cobalt.

In WO 01/07393 describes a method of catalytic conversion of raw materials containing carbon monoxide and hydrogen, to obtain the at least one of the following: alcohol, simple ester and mixtures thereof, and the reaction of carbon monoxide with at least one of the following: alcohol, simple ester and mixtures thereof, in the presence of a catalyst selected from the group comprising solid superacids, heteroalicyclic, clay, zeolites and molecular sieves, in the absence of halogenating the promotion is RA, at a temperature and pressure sufficient to obtain at least one of the following: an ester, acid, acid anhydride and mixtures thereof.

In WO 2005/105720 described a method of obtaining a carboxylic acid and/or its ester or anhydride by carbonylation of aliphatic alcohol or its reactive derivative with carbon monoxide practically in the absence of a halogen at a temperature in the range varying between 250 and 600°C and a pressure in the range from 10 to 200 bar in the presence of mordenite catalyst modified with copper, Nickel, iridium, rhodium or cobalt as frame elements contains silicon, aluminum and at least one of the following: gallium, boron and iron.

In WO 2006/121778 describes a method for NISS. Olkiluoto ether ness. aliphatic carboxylic acids by carbonylation mainly anhydrous environment NISS. Olkiluoto simple ether such as dimethyl ether, carbon monoxide in the presence of mordenite or ferrierite catalyst.

The disadvantage of conducting the carbonylation reactions in the presence of a zeolite catalyst, such as mordenites, is that the selectivity of the carbonylation product, methyl acetate, decreases due to the formation of by-products and, in particular, the formation of by-products methane and C2+-hydrocarbons. With2+-Hydrocarbons are typically With 2-C6-aliphatic hydrocarbons, such as ethane and propane, With2-C6-alkenes, such as ethylene and propylene. Can also produce aromatic hydrocarbons, such as methylated benzenes, for example, xylenes.

Thus, it would be helpful if you could reduce the formation of such by-product in ways to obtain the acetate carbonyliron during the catalysis of the mordenite.

According to the invention it was found that, if the carbonylation reaction carried out in the presence of added acetate (i.e. acetate, which is added in addition to that, which is formed as a product of the carbonylation reaction between dimethyl ether and carbon monoxide) and/or acetic acid, decreases the formation of by-products.

In accordance with this present invention relates to a method for production of acetate, which comprises the carbonylation of dimethyl ether and carbon monoxide in one or more areas of the carbonylation reaction in the presence of mordenite catalyst with getting acetate, wherein at least one of these zones reactions add at least one of the following: methyl acetate and acetic acid.

According to the invention it was found that, if the way carbonyliron which I load at least one of the following: methyl acetate and acetic acid, it reduces the formation of by-products and, in particular, reduces the formation of by-products methane and C2+-hydrocarbons.

In addition, if the acetate is contained in the downloadable dimethyl ether introduced into the reaction zone at the start of the carbonylation reaction, it was found that significantly reduces the formation of hydrocarbon and thereby provides improved starting the reaction.

Thus, the present invention also relates to the use of at least one of the following: methyl acetate and acetic acid in the method carbonylation reduce the formation of by-products, the method comprises the carbonylation of dimethyl ether and carbon monoxide in one or more areas of the carbonylation reaction in the presence of mordenite catalyst with getting acetate, wherein at least one of these zones reactions add at least one of the following: methyl acetate and acetic acid.

The method proposed in the present invention, is a method of carbonylation in which dimethyl ether carbonylic carbon monoxide with getting acetate. Dimethyl ether can be substantially pure or may contain small amounts of inert impurities. In industry demeti the new ether is produced by the catalytic conversion of synthesis gas (mixtures of hydrogen and carbon monoxide) over catalysts for methanol synthesis and dehydration of methanol. This catalytic transformation leads to a product which mainly contains dimethyl ether, but can contain some amount of methanol. In the method proposed in the present invention, downloadable dimethyl ether may optionally contain a small amount of methanol, provided that the amount of methanol contained in the download, not so large as to inhibit the carbonylation reaction, leading to the formation of acetate. According to the invention it was found that in the downloadable dimethyl ether valid methanol content of 5 wt.% or less, such as 1 wt.% or less.

Dimethyl ether can also be formed from dimethylcarbonate, for example, in the interaction of liquid dimethylcarbonate with gamma-aluminum oxide by decomposition of dimethylcarbonate with the formation of dimethyl ether and carbon dioxide.

Dimethyl ether is preferably introduced into the reaction zone at a concentration in the range from not less than 1.0 to 20 mol.%, for example, from 1.5 to 10 mol.%, such as from 2.5 to 5 mol.%, in terms of the total number of downloadable gases (including recycled products) in the reaction zone. If you use more than one reaction zone, the concentration of dimethyl ether is introduced into each reaction zone may be the same or different. Dimethyl ether, introduced in C is well reaction can be a fresh and/or recycled dimethyl ether.

In addition to dimethyl ether and carbon monoxide, gases loaded in the reaction zone may include methyl acetate, acetic acid, hydrogen and inert gases such as nitrogen, helium and argon.

In the method proposed in the present invention, at least one reaction zone add at least one of the following: methyl acetate and acetic acid. If you use more than one zone of the reaction, the acetate and/or acetic acid can be added to some but not necessarily all used the reaction zone.

If in the reaction zone to add the acetate, the molar ratio of acetate to the amount of dimethyl ether is preferably in the range from 1:100 to 5:1, such as from 1:10 to 3:1.

The acetate preferably can be added to the reaction zone in the amount of 5 mol.% or less, in terms of the total number of downloadable gases (including recycled products). The acetate is preferably added in amounts in the range from 0.05 to 5 mol.%, such as from 0.5 to 5 mol.% in terms of the total number of downloadable gases (including recycled products).

When dimethyl ether is introduced into the reaction zone in the amount of 5 mol.%, the acetate, preferred the nutrient contained in the number, constituting from 0.5 to 2.5 mol.% in terms of the total number of downloadable gases (including recycled products).

If you add acetic acid, it interacts with dimethyl ether contained in the reaction zone, with the formation of methyl acetate and methanol. The amount of added acetic acid is preferably in the range from more than 0 up to 1 mol.% in terms of the total number of downloadable gases (including recycled products), for example, in the range from 0.1 to 0.8 mol.%.

Components method carbonylation can be loaded into the reaction zone separately or can be downloaded in the form of mixtures of 2 or more components. Thus, the acetate and/or acetic acid can be downloaded into the reaction zone separately or together with dimethyl ether.

The acetate can be introduced into the reaction zone in the form of fresh acetate and/or recycled methyl acetate.

Alternative or additionally obtained the acetate of one of the reaction zone can be added in the next reaction zone.

Methyl acetate and acetic acid can be downloaded into the reaction zone in the form of steam or you can download it in liquid form in the pre-evaporation, which in turn couples to interact with the catalyst.

In the preferred embodiment, uses the t at least 2 consecutive reaction zone, for example from 2 to 30 reaction zones, and dimethyl ether is injected into one or more of these zones reactions in the form of fresh dimethyl ether together with at least one of the following: fresh and/or recycled methyl acetate and acetic acid.

The carbon monoxide can be a mostly pure carbon monoxide, for example, carbon monoxide is usually purchased from suppliers of industrial gases, or it may contain impurities that do not interfere with the conversion of dimethyl ether to methyl acetate, such as nitrogen, helium, argon, methane and/or carbon dioxide.

The method proposed in the present invention, can be carried out in the presence of hydrogen. Carbon monoxide and hydrogen preferably can be loaded into the reaction zone in the form of a mixture. A mixture of hydrogen and carbon monoxide getting into the industry by steam reforming of hydrocarbons by partial oxidation of hydrocarbons. Such mixtures are commonly referred to as synthesis gas. The synthesis gas contains mainly carbon monoxide and hydrogen, but may also contain smaller amounts of carbon dioxide.

The molar ratio of carbon monoxide: hydrogen may preferably be in the range of from 1:3 to 15:1, such as from 1:1 to 10:1, e.g. from 1:1 to 4:1.

If the method is used the hydrogen, it can be a gauge of parts the social pressure, equal not below 0.1 bar, such as from 1 to 30 bar.

The molar ratio of carbon monoxide to the amount of dimethyl ether is preferably in the range from 1:1 to 99:1, such as from 2:1 to 60:1.

The catalyst used in the method proposed in the present invention is a zeolite of the mordenite. The structure of mordenite are well known and described, for example, in the publication of The Atlas of Zeolite Framework Types (C.Baerlocher, W.M.Meier, D.H.Olson, 5thed. Elsevier, Amsterdam, 2001). See online version (http://www.iza-structure.org/databases/) is a summary of topological and structural characteristics of zeolites including mordenite.

The mordenite is available as Na-mordenite, NH4-mordenite or H-mordenite. For use as a catalyst in the way carbonylation proposed in the present invention, the mordenite is preferably used in the H form or subjected to ion exchange or otherwise include one or more metals.

The ammonium form of mordenite can be transformed into H-form by well known techniques, such as annealing at high temperature. The sodium form of mordenite can be converted into acid form (H-form) held by first turning in the ammonium form by ion exchange with ammonium salts, such as ammonium nitrate.

Alternative is, in the mordenite can include at least one metal, preferably chosen from the group including copper, silver, gold, Nickel, iridium, rhodium, platinum, palladium or cobalt, more preferably at least one metal selected from the group including copper and silver.

The inclusion of metals in the mordenite can be performed by any known method, such as the well-known methods of ion exchange, wet impregnation and the so called "impregnation by capacity". If the mordenite should be subjected to ion exchange, then to 100% capable of exchanging cations centers of mordenite can be exchanged for metal ions by well known methods, Preferably, all the cations remaining in subject to the exchange mordenite, was the protons, therefore, currency is convenient to begin with ammonium or hydrogen form.

Alternatively, ion exchange, ammonium or hydrogen form of mordenite can be impregnated with a solution of metal salts and then dried. When using ammonium form, the mordenite is preferably ignited after the inclusion of metal or ion exchange with the metal.

The inclusion of metals in the mordenite can be expressed using the partial inclusion of metal in the form of a number of gram-atoms of metal per 1 gram-atom of aluminum contained in the mordenite. The inclusion of metals also exp is down in the form of a percentage molar content in terms of the content of aluminium in the mordenite with the formula: mol.% metal = (number of gram-atoms of metal/number of gram-atoms of aluminum)×100.

For example, the content of the mordenite average of 0.55 gram-atom of copper per 1 gram-atom of aluminum equivalent equal to 55 mol.% the copper content in terms of the content of aluminium in the mordenite.

The metal can be included in the amount in the range from 1 to 200 mol.% in terms of aluminum content, for example, from 50 to 120 mol.%, such as from 50 to 110 mol.% in terms of the content of aluminium in the mordenite.

Preferably, if mordantly catalyst designed for use in the present invention, selected from the group including H-mordenite containing copper mordenite containing silver mordenite.

For use in the method proposed in the present invention, preferably, the mordenite had a ratio of silicon dioxide to aluminum oxide, at least 5, but preferably less than or equal to 100, for example in the range from 6 to 90, for example, from 10 to 40.

The method proposed in the present invention, preferably in the mostly arid environment, i.e. mainly in the absence of water. Carbonylation of dimethyl ether with the formation of acetate leads to the formation of water in situ. It is established that water suppresses the carbonylation of dimethyl ether with the formation of acetate. Therefore, in the method proposed in the present invention, the support as you lower the water content. Reagents dimethyl ether and carbon monoxide (and modenity catalyst) is preferably dried before introduction into the reaction. However, a small amount of water can be tolerated without harmful effects on the formation of acetate. Water may preferably be contained in the downloadable dimethyl ether in the amount of 2.5 wt.% or less, such as 0.5 wt.% or less.

The method proposed in the present invention preferably can be performed at a temperature in the range from 100 to 350°C.

The method proposed in the present invention, can be carried out at a gauge pressure in the range from 1 to 100 bar, such as from 10 to 100 bar.

Hourly space velocity of gas (COG) preferably is in the range from 500 to 40000 h-1such as from 4000 to 10000 h-1. Since the method proposed in the present invention, it is preferable to carry out practically in the absence of water, preferably mordantly the catalyst was dried before use. The catalyst can be dried, for example, by heating to a temperature equal to 400 to 500°C.

Preferably, mordantly the catalyst was activated prior to use by heating the catalyst at an elevated temperature for at least 1 h in a flow of nitrogen, carbon monoxide, is odorata or mixtures thereof.

The method proposed in the present invention, it is preferable to carry out practically in the absence of halides such as iodide. The term "almost" means that the content of the halide, such as iodide in the reacting gases and the catalyst is less than 500 ppm million, preferably less than 100 ppm million

The method proposed in the present invention, it is preferable to carry out using fixed layer, fluidized bed or moveable mordenite catalyst.

The method proposed in the present invention, can be performed in a single reaction zone or in at least 2 successive reaction zones, for example from 2 to 30 zones of the reaction. One or more reaction zones can be in the same reaction vessel. If necessary, between the reaction zones, you can install additional heating or cooling devices.

The primary product of the method proposed in the present invention, is the acetate, but may be formed and a small amount of acetic acid. The formed acetate can be extracted in the form of steam and then condense into a liquid.

The acetate can be extracted and sold without processing or it can be used in other chemical processes. After removal of acetate from the reaction product ka is boilerhouse part or whole can hydrolyze with obtaining acetic acid. Alternatively, the entire reaction product of the carbonylation can be directed to stage hydrolysis and then to separate the acetic acid. The hydrolysis can be conducted by known techniques, such as reactive distillation in the presence of an acid catalyst.

The method can be carried out in a continuous or periodic manner, preferably in a continuous way.

The drawings show the following:

Figure 1 shows the time dependence of methane release in g/l/h in a single pass per unit of time (the website of altar servers) in the stream to the carbonylation conducted using 0 mol.%, of 0.05 mol.%, of 0.625 mol.% and 2.5 mol.% methyl acetate.

Figure 2 shows the time dependence of methane release in g/l/h in a single pass per unit of time (the website of altar servers) in the stream to the carbonylation conducted using 0 mol.% and 1 mol.% methyl acetate and 2.5 mol.% dimethyl ether.

Figure 3 shows the time dependence of the selectivity of formation of acetate in the stream to the carbonylation conducted using 0 mol.% and 1 mol.% methyl acetate and 2.5 mol.% dimethyl ether.

Figure 4 shows the dependence on time of the output With2+hydrocarbons in g/l/h in a single pass per unit of time (the website of altar servers) in the stream to the carbonylation conducted using 0 mol.% and 1 mol.% methyl acetate and 2.5 mol.% dimethyl ether.

Figure 5 Pref is dena time dependence of methane release in g/l/h in a single pass per unit of time (the website of altar servers) in the stream to the carbonylation, carried out with the addition of 0 mol.%, to 0.3 mol.% and of 0.625 mol.% acetic acid.

Below the present invention is illustrated by the following examples.

Example 1

Carbonylation of dimethyl ether

This example demonstrates the effect of using 0 mol.%, of 0.05 mol.%, of 0.625 mol.% and 2.5 mol.% methyl acetate in the load on the carbonylation of dimethyl ether with carbon monoxide in the presence of hydrogen.

Each carbonylation reaction was carried out in the installation of flow-through reactor pressure vessels containing one reactor, made of alloy Hastelloy. The reactor contains 55 ml of glass beads, 10 ml of gamma-aluminum oxide and 5 ml of catalyst, all separated by glass wool.

The catalyst consists of mordenite (Zeolyst CBV21A) with the inclusion of 55 mol.% copper. Before use, the catalyst was condensed under a pressure of 12 tons in the mold size 26 mm using a pneumatic press, crushed and sieved to obtain the fraction of pellets the size of 500-1000 μm. Using helium at a flow rate equal to 13.2 l/h, over a catalyst created a pressure of 30 bar, required for the reaction, and then was heated to 100°C and at this temperature was kept for 17 hours and Then the temperature linearly, powisle up to 300°C at 3°C/min, then injected helium, carbon monoxide and hydrogen in a molar ratio, composing the m 1:

4:1 (Not: FROM: H2to maintain CASH equal to 4000/h, within 2 hours After 2 hours the reactor was injected amount of liquid dimethylcarbonate required to obtain 5 mol.% dimethyl ether. In the case of acetate required quantity of solution in dimethylcarbonate also introduced into the reactor together with the quantity of liquid loading required to maintain equal to 5 mol.% the content of dimethyl ether. Flow rate of helium, carbon monoxide, hydrogen, dimethyl ether and methyl acetate were sufficient to maintain CASH equal to 4000/h In the case of acetate, the helium flow was reduced to maintain CASH equal to 4000/h Output stream from the reactor is sent to a receptacle for collecting fluid, the temperature of which was maintained equal to 20°C and condensed liquid products. These products via regular intervals was analyzed using gas chromatography (GC) and determined the concentration of liquid reactants and liquid products of the carbonylation reaction. The remaining steam flow was analyzed using GC in real time and determine the concentrations of the reactants and products of the carbonylation reaction. The reaction was carried out for up to 160 hours at a temperature of 300°C., a pressure of 30 bar and hourly volume rate of gas (COG)equal to 4000/h

The value of the website of altar servers (output per aisle is in a unit of time) for a by-product of methane is shown in figure 1. Figure 1 clearly shows that the presence of acetate in the raw material is introduced into the reaction significantly reduces the formation of methane.

Example 2

Carbonylation of dimethyl ether using 1 mol.% the acetate

Carbonylation of dimethyl ether in the presence of a catalyst containing mordenite (Zeolyst CBV21A) with the inclusion of 55 mol.% copper held in the system flow reactors high pressure, consisting of 16 identical reactors of the type described in WO 2005063372. Used reactors with an internal diameter of 9.2 mm In the center of each reactor was placed inner tube with a diameter of 3.2 mm, which were placed thermocouple. Prior to the introduction of catalyst in each reactor in the holder of the catalyst was placed a layer of corundum sieve fraction 125-160 μm thickness of about 10 cm on Top of the layer of oxide was placed 1,948 g of catalyst (size pellets from 125 to 160 microns) in terms of weight in the dry state (determined by loss of the catalyst during calcination by heating the catalyst from room temperature to 600°C at a constant rate, equal to approximately 30°C/min), diluted with 3 ml of corundum (the size of the pellets from 125 to 160 microns). Each of the above areas to summarize, hitting or shaking, and have a stable layer and the zone of catalyst a certain initial height. On a diluted catalyst layer applied particle cor the NDA size 125-160 μm thickness of about 13 see Using a mixture of 2:1 WITH:

H2at a flow rate of 12 l/h, over a catalyst created a pressure of 70 bar, required for the reaction. Then the catalyst was heated up to 220°C at a rate of 0.5°C/min and this temperature was kept for 3 hours Then the temperature was linearly increased up to 300°C at a rate of 0.5°C/min, then kept for 3 hours Then download containing carbon monoxide and hydrogen was replaced with a mixture of carbon monoxide, hydrogen, dimethyl ether, methyl acetate, argon and nitrogen in a molar ratio of CO/H2/dimethyl ether/Ar/acetate/N2average 54/29/2,5/5/1/8,5, at a flow rate of 12 l/h, and dimethyl ether with a velocity of 0.30 l/h, and methyl acetate with a rate of 0.12 l/h was downloaded in the form of steam, and at full load, provided the molar ratio of CO/H2/acetate/dimethyl ether comprising 54/29/1/2,5. In addition, variable speed equal 0-150 ml/min, injected nitrogen for equalization of pressure fluctuations in the output channels 16 reactors. From the test reactor output stream was passed through a gas chromatograph to determine the concentration of the reactants and products of the carbonylation. The reaction was carried out for 150 hours at a temperature of 300°C., a pressure of 70 bar, hour flow rate of gas (COG) over the catalyst equal to 4000/4, when the molar relationship is WITH/N 2/Dimethyl ether/Ar/acetate/N2at full load, comprising 54/29/2,5/5/1/8,5.

Experiment A - Carbonylation of dimethyl ether in the absence of acetate in loading

Repeated the procedure used in example 2, except that the load for the carbonylation reaction is not contained acetate. Raw materials for the carbonylation contained a mixture of carbon monoxide, hydrogen, dimethyl ether, argon and nitrogen in a molar ratio of CO/H2/DME/Ar/N2average 54/29/2,5/5/9,5, at a flow rate of 12 l/h

The results of studies on the reactions of carbonyl conducted in example 2 and the experiment As shown in Fig.2-4. The outputs of the by-products of methane and C2+hydrocarbons in a single pass per unit of time (the website of altar servers) is shown in figure 2, and 4, respectively. The selectivity of the formation of acetate is presented in figure 3.

From the data presented in figure 2 and 4, one can clearly see that the presence of acetate in the download for the carbonylation reaction reduces the amount of generated methane and C2+hydrocarbons compared to the amount formed in the absence of acetate in the download for the reaction.

From the data shown in figure 3, it can be seen that the presence of acetate in the download for the carbonylation reaction leads to an increase in selectivity education m is tracedata compared with those observed in the absence of acetate in the download for the reaction.

Example 3

Carbonylation of dimethyl ether with the addition of 5 mol.% the acetate

Carbonylation of dimethyl ether in the presence of a catalyst containing mordenite (Zeolyst CBV21A) with the inclusion of 55 mol.% copper held in the system flow reactors high pressure, consisting of 16 identical reactors of the type described in WO 2005063372. Each reactor had an inner diameter of 3.6 mm Before the introduction of the catalyst into the reactor in the appropriate holder of the catalyst was placed a layer of steatite sieve fractions of 100-350 μm thickness of about 5 cm Top layer of steatite were placed area corundum sieve fraction 125-160 μm thickness of about 5 cm on Top of the layer of oxide was placed 0.625 g of catalyst (size pellets from 125 to 160 microns) in terms of weight in the dry state (determined by loss of the catalyst during calcination by heating the catalyst from room temperature to 600°C at a constant rate, equal to approximately 30°C/min), diluted with by using 3 ml of corundum (the size of the pellets from 125 to 160 microns). The catalyst was covered with a layer of oxide with a thickness of approximately 5 cm with particle size 125-160 μm. On top of the layer of oxide was placed area of steatite sieve fractions of 100-350 μm thickness of about 5 cm Each of the above areas to summarize, hitting or shaking, and have a stable layer and the area of the catalyst particular initial the height. Using a mixture of 4:1 FROM: N2at a flow rate equal to 4,275 l/h, over a catalyst created a pressure of 70 bar, required for the reaction. Then the catalyst was heated to a constant temperature equal to 220°C at a rate of 0.5°C/min and this temperature was kept for 3 hours Then the temperature was linearly increased up to 300°C at a rate of 0.5°C/min, then kept for 3 hours Then download containing carbon monoxide and hydrogen, substituted for downloading WITH/N2/dimethyl ether in a molar ratio of average 72/18/10, at a flow rate equal to 4,275 l/h, and the download speed vapors of dimethyl ether was equal 0,4275 l/H. in Addition, variable rate equal to 0-50 ml/min, injected nitrogen for equalization of pressure fluctuations in the output channels 16 reactors. From the test reactor output stream was passed through a gas chromatograph to determine the concentration of the reactants and products of the carbonylation. The reaction was carried out for 148 hours at a temperature of 300°C., a pressure of 70 bar, hour flow rate of gas (COG)equal 4275/4 when the molar ratio of CO/H2/dimethyl ether at full load, comprising 72/18/10. After the reaction just for 148 h load was replaced by a mixture of CO/H2/dimethyl ether in a molar ratio of average 76/19/5, and the reaction was carried out for e is e 49 PM

After the reaction all over 197 hours in the reactor for carbonylation has introduced additional loading acetate, eventually, into the reactor was introduced boot/H2/dimethyl ether/methyl acetate in a molar ratio of average 72/18/5/5, at a temperature of 300°C, a pressure of 70 bar and hourly volume rate of gas (COG)equal 4275/4. The reaction was carried out for a further 45 hours After the reaction just for 242 h acetate introduction of additional loading was stopped and the loading in the reactor was replaced by a mixture of CO/H2/dimethyl ether in a molar ratio of average 76/19/5, at a temperature of 300°C, a pressure of 70 bar and hourly volume rate of gas (COG)equal 4275/4. The reaction was carried out for a further 74 including research Results of the carbonylation reaction is shown below in table 1.

Table 1
Time/hDownload DME/mol.%Download Meoac/mol.%The website of altar servers for methane/G.-1B-1
194506
22355 <2
28850b

Table 1 shows the results on the impact of the presence or absence of an additional load of acetate in the formation of by-product methane. Clearly you can see that the presence of acetate in the download for carbonylation suppresses the formation of methane and that in the absence of acetate in the download for carbonylation increases the formation of methane.

Example 4

This example demonstrates the effect of using 0 mol.%, to 0.3 mol.% and of 0.625 mol.% acetic acid by carbonylation of dimethyl ether. Repeated the procedure used in example 1, except that the acetate was replaced by 0.3 mol.% 0.625 mol.% acetic acid.

The value of the website of altar servers (output in one pass per unit time) for a by-product of methane is shown in figure 5. Data in figure 5 clearly show that the addition of acetic acid to the reaction mixture leads to a significant reduction in the formation of methane.

1. A method of reducing the formation of by-products upon receipt of acetate, which comprises the carbonylation of dimethyl ether and carbon monoxide in one or more areas of the carbonylation reaction in the presence of mordenite catalyst to obtain a product which methyl acetate, characterized in that at least one of these zones reactions add at least one of the following: methyl acetate and acetic acid.

2. The method according to claim 1, which is carried out in the presence of hydrogen.

3. The method according to claim 1 or 2, in which the molar ratio of acetate to the amount of dimethyl ether is in the range from 1:100 to 5:1.

4. The method according to claim 3, in which the molar ratio of acetate to the amount of dimethyl ether is in the range from 1:10 to 3:1.

5. The method according to claim 1 or 2, in which acetate is added to the reaction zone in an amount in the range from 0.05 to 5 mol.% in terms of the total number of downloadable gases (including recycled products).

6. The method according to claim 5, in which acetate is added to the reaction zone in an amount in the range from 0.5 to 5 mol.% in terms of the total number of downloadable gases (including recycled products).

7. The method according to claim 1 or 2, in which acetate is added to the reaction zone in the form of fresh and/or recycled methyl acetate and/or the formed product of acetate.

8. The method according to claim 1 or 2, in which the acetate is introduced into the reaction zone at the start of the method carbonylation.

9. The method according to claim 1 or 2, in which acetic acid is added to the reaction zone in amounts that are in di the range from more than 0 up to 1 mol.% in terms of the total number of downloadable gases (including recycled products).

10. The method according to claim 9, in which acetic acid is added to the reaction zone in an amount in the range from 0.1 to 0.8 mol.% in terms of the total number of downloadable gases (including recycled products).

11. The method according to claim 1 or 2, in which mordantly catalyst selected from the group including H-mordenite containing copper mordenite containing silver mordenite.

12. The method according to claim 1 or 2, which is carried out in 2-30 sequential reaction zones.

13. The method according to item 12, in which dimethyl ether is introduced into the reaction zone in the form of fresh and/or recycled dimethyl ether.

14. The method according to item 13, in which dimethyl ether is introduced into the reaction zone in the form of fresh dimethyl ether together with at least one of the following: fresh and/or recycled methyl acetate and acetic acid.

15. The method according to claim 1 or 2, in which the formed product methyl acetate hydrolyzing with obtaining acetic acid.

16. The method according to claim 1 or 2, in which the carbon monoxide is introduced into the reaction zone in the form of a mixture with hydrogen.

17. The method according to claim 1 or 2, in which carbon monoxide and hydrogen present in the mixture in a molar ratio of from 1:3 to 15:1.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to improved method of increasing catalytic activity and/or selectivity in the process of obtaining product of methylacetate and/or acetic acid, which includes contact of carbonylated reagent, selected from dimethyl ether and methanol, with carbon monoxide in presence of catalyst, representing H-mordenite, bound with mesoporous binding agent, selected from silicon oxides, aluminium oxides, silicon oxides-aluminium oxides, magnesium silicates and magnesium-alumosilicates.

EFFECT: increased catalytic activity and/or selectivity.

15 cl, 6 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of obtaining acylated alkoxylate of secondary alcohol of formula R1-C(O)-(OA)n-OR2(I), in which R1 is linear or branched alkyl group, including from 1 to 30 carbon atoms, optionally substituted cycloalkyl group, which includes from 5 to 30 carbon atoms, or optionally substituted aryl group, including from 6 to 30 carbon atoms, OA stands for one or several oxyalkylene fragments, which can be similar or different, n stands for integer number in the range from 0 to 70, and R2 is linear or branched alkyl group, including from 4 to 32 carbon atoms, optionally substituted cycloalkyl group, including from 5 to 32 carbon atoms, or optionally substituted bicycloalkyl group, including from 7 to 32 carbon atoms, where claimed method includes: (i) interaction of one or several olefins with internal double bond with one or several carboxylic acids in presence of catalytic composition with obtaining one or several ethers of carboxylic acid; (ii) interaction of one or several ethers of carboxylic acid, obtained at stage (i), with one or several alkylene oxide reagents in presence of catalytically efficient quantity of catalytic composition, which includes: (a) one or several salts of alkali earth metals and carboxylic acids and/or hydroxycarboxylic acids, which include 1-18 carbon atoms, and/or hydrates of the former; (b) oxygen-containing acid, selected from sulfuric acid and orthophosphoric acid; (c) alcohol, containing from 2 to 39 carbon atoms; and/or products of (a), (b) and/or (c) interactions with obtaining one or several acylated alkoxylates of secondary alcohols.

EFFECT: invention also relates to methods of obtaining alkoxylates of secondary alcohols and alkoxy sulfates of secondary alcohols, including the claimed method.

10 cl, 4 ex, 1 dwg, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a method of increasing efficiency and catalyst stability when producing methyl acetate, involving carbonylation of dimethyl ether based material with carbon monoxide in virtually anhydrous conditions in the presence of a zeolite catalyst which is efficient in said carbonylation, wherein the reaction is carried out at temperature ranging from 275°C to 350°C, and in the presence of hydrogen.

EFFECT: high efficiency and catalyst stability.

14 cl, 9 ex, 4 dwg, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a method of increasing efficiency and selectivity when producing methyl acetate, involving carbonylation of material based on dimethyl ether with carbon monoxide in virtually anhydrous conditions in the presence of a zeolite catalyst which is efficient in said carbonylation, wherein the reaction is carried out at temperature ranging from higher than 250 to 350°C, and at pressure ranging from higher than 10 to 100 bar (isobar).

EFFECT: high efficiency and selectivity when producing methyl acetate.

15 cl, 11 dwg, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to chemical engineering and specifically to processing fusel oil, which is a large-tonnage waste in the alcohol industry. Fusel oil from production of ethyl alcohol is processed by esterification with glacial acetic acid in the presence of a sulphuric acid catalyst, and neutralisation, wherein esterification is carried out while boiling the reaction mixture and continuously separating water using a separating flask. The obtained product is separated from the catalyst under a vacuum at temperature not higher than 110°C. The obtained product and the catalyst are separately neutralised and the obtained product is additionally dried.

EFFECT: method enables to process fusel oil into a highly efficient component of mixed solvents of high quality with low cost of production and high output of the product.

4 cl

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of increasing catalytic activity when producing methyl acetate, involving carbonylation of dimethyl ether-based material with carbon monoxide in the presence of hydrogen in virtually anhydrous conditions at temperature ranging from more than 250°C to 350°C, in the presence of a zeolite catalyst which is efficient in said carbonylation, wherein concentration of dimethyl ether is at least 1 mol % with respect to the total amount of material.

EFFECT: improved method of increasing catalytic activity when producing methyl acetate.

13 cl, 4 ex, 3 tbl, 4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing C1-C3 aliphatic carboxylic acid and/or the corresponding ester, by carbonylating the corresponding C1-C3 aliphatic alcohol and/or an ester or ether derivative thereof with carbon monoxide material containing hydrogen, in the presence of a catalyst containing a zeolite having at least one 8-member ring channel, said 8-member ring channel being connected with a channel formed by a ring with greater than or equal to 8 members, said 8-member ring having a window size of at least 2.5 Å × at least 3.6 Å and at least one Bronsted acid site and that zeolite has a silicon dioxide: X2O3 molar ratio of not less than 5, where X is selected from aluminium, boron, iron, gallium and mixtures thereof with the condition that the zeolite is not mordenite or ferrierite. The catalysts demonstrate considerable carbonylation activity compared to other zeolite catalysts.

EFFECT: improved method of producing C1-C3 aliphatic carboxylic acid.

41 cl, 2 tbl, 18 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts for producing methyl acetate and a method of producing methyl acetate. Described is a method of producing methyl acetate, involving carbonylation of dimethyl ether-based material with carbon monoxide with almost no water in the presence of a mordenite catalyst in which at least one of the following elements is introduced using an ion exchange or some other method: silver and copper, and in which platinum is also introduced into the mordenite via an ion exchange or some other method in amount of 0.05-10 mol % with respect to aluminium. Described is a catalyst for producing methyl acetate via carbonylation of dimethyl ether-based material with carbon monoxide in virtually anhydrous conditions, which is prepared via simultaneous ion exchange or saturation of the ammonium or hydrogen form of mordenite with platinum and at least one of the metals - silver and copper, drying and/or calcination of the mordenite which has been saturated or subjected to ion exchange, wherein the catalyst contains platinum in amount of 0.05-10 mol % with respect to aluminium and a catalyst prepared via ion exchange or saturation of the ammonium or hydrogen form of mordenite with at least one of the metals - silver and copper, drying and/or calcination of the mordenite which has been saturated or subjected to ion exchange to obtain copper- and/or silver-containing mordenite, followed by ion exchange or saturation of the copper- and/or silver-containing mordenite with platinum, wherein the catalyst contains platinum in amount of 0.05-10 mol % with respect to aluminium.

EFFECT: high catalytic activity.

15 cl, 1 tbl, 2 dwg, 2 ex

FIELD: chemistry.

SUBSTANCE: catalyst further contains chromium oxide in amount of 5.0-20.0 wt % of the total amount of catalyst. Ethanol with water content of up to 15 wt % is used in the process. Use of the method enables to increase ethanol conversion to 58%, ethyl acetate selectivity to 95%, and use ethanol with water concentration of up to 15 wt %.

EFFECT: method does not require feeding an additional amount of hydrogen into the process.

2 cl, 10 ex, 1 tbl

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

FIELD: chemistry.

SUBSTANCE: invention relates to field of catalysis. Described is method of selective dealumination of zeolites of structure type MOR, which includes introduction of monovalent metal and processing with water vapour into zeolite. Application of obtained zeolites as catalysts of carbonylation is described.

EFFECT: increased activity.

15 cl, 5 dwg, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing (13C2-carbonyl)dimethyl phthalate which can be used to produce (13C2-carboxy)phthalic acid. Both compounds can be used to produce a range of agents for tumour diagnosis and therapy. The disclosed method involves carbonylation of 1,2-dibromobenzene with carbon monoxide 13CO in methanol at temperature of 100-150°C, pressure of not more than 1.0 MPa, in the presence of a catalyst system containing palladium acetate and a phosphine ligand, taken in molar ratio of 1:0.5-1:10, in the presence of triethylamine or sodium acetate. The method enables to obtain a product with output of up to 94.5% with isotopic purity of up to 99.3%. Catalyst efficiency reaches 9.9 mol/mol-h. (13C2-carboxy)phthalic acid with isotopic purity of 99% can be obtained from the obtained product via acid hydrolysis.

EFFECT: high output of the end product.

2 cl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing C1-C3 aliphatic carboxylic acid and/or the corresponding ester, by carbonylating the corresponding C1-C3 aliphatic alcohol and/or an ester or ether derivative thereof with carbon monoxide material containing hydrogen, in the presence of a catalyst containing a zeolite having at least one 8-member ring channel, said 8-member ring channel being connected with a channel formed by a ring with greater than or equal to 8 members, said 8-member ring having a window size of at least 2.5 Å × at least 3.6 Å and at least one Bronsted acid site and that zeolite has a silicon dioxide: X2O3 molar ratio of not less than 5, where X is selected from aluminium, boron, iron, gallium and mixtures thereof with the condition that the zeolite is not mordenite or ferrierite. The catalysts demonstrate considerable carbonylation activity compared to other zeolite catalysts.

EFFECT: improved method of producing C1-C3 aliphatic carboxylic acid.

41 cl, 2 tbl, 18 ex

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

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 relates to improved method of increasing catalytic activity and/or selectivity in the process of obtaining product of methylacetate and/or acetic acid, which includes contact of carbonylated reagent, selected from dimethyl ether and methanol, with carbon monoxide in presence of catalyst, representing H-mordenite, bound with mesoporous binding agent, selected from silicon oxides, aluminium oxides, silicon oxides-aluminium oxides, magnesium silicates and magnesium-alumosilicates.

EFFECT: increased catalytic activity and/or selectivity.

15 cl, 6 tbl, 4 ex

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