Method for carbonylation of dimethyl ether

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

 

The present invention is a method of producing methyl acetate by the reaction of dimethyl ether with carbon monoxide in the presence of zeolite catalyst.

The acetate is used in industry in petrochemical processes, specifically as a raw material for producing acetic acid and/or acetic anhydride.

Industrial production of acetic acid works as a homogeneous liquid-phase process in which the catalysts for carbonylation reactions are the noble metals of group VIII, such as rhodium or iridium, and alkylated, such as methyliodide. The main disadvantage of this method is the use of iodide, which can lead to corrosion of equipment and difficulties associated with the separation of product and catalyst components in the same phase. Both of these problems could be avoided if it would be possible to develop a heterogeneous gas-phase process using does not contain iodide solid catalyst.

In EP-A-0596632 describes how a vapor-phase carbonylation of methanol to obtain acetic acid in the presence of the modified mordenite catalyst at high temperatures and pressures.

In WO 01/07393 describes a method of catalytic conversion of raw materials containing carbon monoxide and hydrogen, to obtain the at least one alcohol is, simple ether and their mixtures, and the reaction of carbon monoxide with at least one of the following substances: alcohol, simple ester and mixtures thereof in the presence of a catalyst selected from solid superacids, heteropolyacids, clays, zeolites and molecular sieves, in the absence of a halide promoter, at these temperatures and pressures, which provide at least one of the following substances: ester, acid, acid anhydride and mixtures thereof. However, the use of zeolites as catalysts for the carbonylation reaction is not described.

In WO 2005/105720 described a method of obtaining a carboxylic acid and/or its complex ester or anhydride with carbonyliron aliphatic alcohol or a reactive derivative of such an alcohol with carbon monoxide in the practical absence of halogen in the presence of the modified mordenite catalyst when temperature of from 250 to 600°C and a pressure of from 10 to 200 bar. The use of dimethyl ether as raw materials is not described.

In WO 2006/121778 described a method of obtaining a lower alkyl complex ester of a lower aliphatic carboxylic acid carbonyliron in the practical absence of water, lower alkyl simple ether, carbon monoxide in the presence of mordenite or ferrierite catalyst. In accordance with annoyances application the carbonylation process is carried out at temperatures of 250°C or below, and preferably from about 150 to about 180°C, in order to minimize the formation of by-product.

In a publication in Angewandte Chemie, Int. Ed. (2006), 45(10), 1617-1620, is devoted to the description catalyzed by zeolite carbonylation of dimethyl ether, it is shown that at 165°C. increasing the concentration of dimethyl ether has no effect on output in one pass methylacetate product.

Whereas the above-described state of the art, there remains a need in heterogeneous gas-phase process of obtaining acetate of dimethyl ether in practically anhydrous conditions using a zeolite catalyst, which would be better in comparison with other processes, in which the raw material used is capable of carbonyliron reagents.

Now it was found that the high catalytic activity can be achieved in the case when the carbonyl process at a temperature of from more than 250 to 350°C., in the presence of hydrogen and at a concentration of dimethyl ether comprising at least 1 mol%. calculated on the total composition of raw materials.

Accordingly, the present invention provides a method of producing methyl acetate, comprising carbonylation feedstock based on DIMET the gross air of carbon monoxide under practically anhydrous conditions in the presence of hydrogen at a temperature component from more than 250 to 350°C. and in the presence of zeolite catalyst effective in the specified carbonyliron, and the concentration of dimethyl ether is at least 1 mol%. calculated on the total supply of raw materials.

To ensure that the method was cost-effective, the yield of the desired product in a single pass per unit of time must be kept to acceptable levels. In carbonylation processes for the carbonylation reagent such as methanol or dimethyl ether, is usually used carbon monoxide. It was found that during carbonylation using methanol, carbon monoxide and zeolite catalyst increasing methanol concentration leads to a decrease of the product yield in a single pass per unit time. However, now unexpectedly been found that in carbonylation processes involving dimethyl ether, carbon monoxide and zeolite catalyst increasing the concentration of dimethyl ether leads to a corresponding increase of the magnitude of the output product in a single pass per unit time (flow rate).

Dimethyl ether is used as a raw material in the method in accordance with the present invention, can be an almost pure dimethyl ether. In industrial practice, dimethyl ether catalytic get to the version of the synthesis gas (mixture of hydrogen and carbon monoxide) over catalysts for methanol synthesis and dehydration of methanol. Such catalytic conversion yields a product that contains mainly dimethyl ether, but may also contain some methanol. In the method according to the present invention, the raw materials based on the dimethyl ether may include a small amount of methanol, and the methanol content in the raw material is not so large as to impede the carbonylation of dimethyl ether to a product - acetate. It was found that a valid presence in raw materials on the basis of dimethyl ether 5% of the mass. or less, for example 1% of the mass. or less of methanol.

The carbon monoxide can be an almost pure carbon monoxide, for example carbon monoxide, which is usually supplied by suppliers of industrial gases, or it may contain impurities that do not affect a conversion of dimethyl ether to methyl acetate, for example nitrogen, helium, argon, methane and/or carbon dioxide.

In the method in accordance with the present invention alone or together with carbon monoxide can be submitted hydrogen. A mixture of hydrogen and carbon monoxide produced in industrial scale steam reforming of hydrocarbons and partial oxidation of hydrocarbons. Such mixtures are commonly referred to as synthesis gas. The synthesis gas consists mainly of carbon monoxide and hydrogen, but may also contain small amounts of deoxidised.

Suitably the molar ratio of carbon monoxide to hydrogen can be from 1:3 to 15:1, for example from 1:1 to 10:1, for example from 1:1 to 4:1.

In the method in accordance with the present invention, the concentration of dimethyl ether in the raw material is at least 1 mol%. calculated on the total composition of the gaseous raw material. The feed stream of raw materials may only include dimethyl ether, hydrogen and carbon monoxide. However, as described above, the industrial sources of carbon monoxide typically contain inert gases such as argon. Inert gases such as nitrogen and helium, may also be present in raw materials.

If the process is carried out as a continuous process, the raw materials will also include any threads in the process, returned to the reactor, for example, unreacted carbon monoxide and/or unreacted dimethyl ether.

Appropriately dimethyl ether present in the raw material at a concentration factor of 1 to 20 mol%, for example from 1.5 to 10 mol%, for example, from 1 to 5 mol%, or from 1.5 to 5 mol%, calculated on the total feed (including recycled amount).

The molar ratio of dimethyl ether to carbon monoxide suitably ranges from 1:1 to 1:99, for example from 1:2 to 1:60.

The zeolite catalyst may be any zeolite which is able to catalyze the carbonylation of dimate the new ether carbon monoxide with getting acetate.

Zeolites are available from commercial sources, mainly in Na, NH4or H-form. NH4the form can be transformed into the acid (H-form) by known methods, for example by calcination at high temperature. Na-form can be converted into the acid (H-form) the first transformation in NH4-form ion exchange with ammonium salts, such as ammonium nitrate. Alternatively, the zeolite can be synthesized by known methods.

Zeolites include a system of channels that can be interconnected with other systems of channels or cavities, such as nests or cells. Ring structures are typically 12-membered rings, 10-membered ring or 8-membered ring. Zeolites can contain rings of various sizes. Zeolites for use in the present invention preferably contain at least one channel, which is set to 8-membered ring. Most preferably the channel formed by 8-membered rings, interconnected with at least one channel formed by the rings 10 and/or 12 members. The window size of the canal system should be such that the reagent, dimethyl ether and molecules of carbon monoxide could freely diffuse inside the zeolite cage and out. Appropriate window size of the channel formed by 8-membered rings may be at the ore of 2.5×3.6 angstroms. In Atlas of Zeolite Framework Types (.Baerlocher, W.M.Meier, D.H.Olson, 5ethe edition. Elsevier, Amsterdam, 2001) in combination with the online version (http://www.iza-structure.org/databases/) a brief summary of the topological and structural details of the structures of zeolites, including the types of ring structures present in the zeolite, and the dimensions of the channels defined for each type of rings. Examples of zeolites suitable for use in the present invention include zeolites MOR framework type, such as mordenite, FER, for example ferrierite, OFF, such as offretite, and GME, such as Gmelina.

For the method according to the present invention it is preferable that the ratio of silica to alumina in the zeolite was at least 5, preferably 100 or less, for example from 7 to 40, for example from 10 to 30. If aluminum atoms replaced by elements modifiers frame, for example gallium, preferably, the ratio of silicon oxide to X2O3where X is a trivalent element, such as aluminum, gallium, iron and/or boron, was, at least 5, preferably 100 or less, for example from 7 to 40, for example from 10 to 30.

In one of the preferred variants of the present invention the zeolite catalyst is a zeolite of the mordenite. The mordenite can be used in the acid form (H-mordenite), or he may not necessarily be subjected to the ut ion exchange or otherwise may be subject to one or more of the following metals: copper, silver, Nickel, iridium, rhodium, platinum, palladium or cobalt.

The metal content in the zeolite mordenite can be expressed as the relative amount of metal in gram-atoms of metal per gram-atom of aluminium in the mordenite. The metal content can also be expressed in molar percent of deposited material relative to aluminium in the mordenite, as the ratio of:

Metal, mol%. = (number of gram-atoms of Metal/number of gram-atoms of aluminum)×100.

For example, the copper content in the mordenite average of 0.55 gram-atoms of copper per aluminum, corresponds to the copper content of 55 mol%. in relation to the content of aluminium in the mordenite.

Suitably, the metal content can be from 1 to 200 mol%. with respect to aluminum, for example from 50 to 120 mol%, for example, from 50 to 110 mol%, or from 55 to 120 mol%, for example, from 55 to 110 mol%.

Frame structure of mordenite may, in addition to silicon atoms and aluminium, contain more trivalent elements, such as boron, gallium and/or iron.

If the mordenite contains at least one or more trivalent elements in the frame structure, the metal content in the mordenite can be expressed as the relative metal content in gram-atoms of metal per gram atom of the total content of trivalent elements in the mordenite. The metal content can also be expressed in mole is x percent metal content relative to the total content of trivalent elements in the mordenite in accordance with the following formula:

Metal, mol%. = (gram-atoms of metal/gram-atoms total content of trivalent elements)×100.

Since the carbonylation reaction is conducted almost in the absence of water, it is preferable that the zeolite catalyst was dried before use. The zeolite can be dried, for example, by heating to a temperature of from 400 to 500°C.

It is preferable to activate the zeolite catalyst immediately before use by heating the zeolite at elevated temperature for at least one hour in a stream of nitrogen, carbon monoxide, hydrogen or mixtures thereof.

The process runs under practically anhydrous conditions, i.e. with little or no water. When carbonyliron dimethyl ether to methyl acetate water in-situ is not formed. Water was found to inhibit the reaction of the carbonylation of dimethyl ether to obtain methyl acetate. Thus, in the method according to the present invention, the water content support as low as possible. To avoid adding water to the system, the reagent is dimethyl ether and carbon monoxide (and catalyst) is preferably dried prior to introduction into the process. However, the presence of small quantities of water allowed in the process without negative impact on the formation of acetate. Appropriately dimethyl ether can contain water in a quantity which as 2.5% of the mass. or less, for example 0.5% mass. or less.

The process in accordance with the present invention is carried out at a temperature of from more than 250 to 350°C. suitably, the temperature may range from 275 to 350°C., for example from 275 to 325°C.

The process in accordance with the present invention can be implemented with a total pressure of from 1 to 100 bar (excess.), for example from 10 to 100 barg.), for example from 30 to 100 barg.).

Volumetric hourly rate of gas (OCSG) appropriately ranges from 500 to 40000 h-1for example , from 2000 to 20000 h-1.

The process in accordance with the present invention is suitably carried out by passing vapors of dimethyl ether and gaseous carbon monoxide through a fixed bed or a fluidized bed of zeolite catalyst, in which to maintain the required temperature.

Preferably the process in accordance with the present invention is carried out practically in the absence of halides such as iodide. The phrase "virtual absence" understand that the content of the halide, such as iodide content in the reacting gases (dimethyl ether and carbon monoxide) in the catalyst is less than 500 hours/million, preferably less than 100 hours/million

The primary product of the process is the acetate, but you can also get the small amount of acetic acid. The acetate obtained by the method in accordance with the present invention, it is possible to allocate in the form of steam and then condense it into a liquid.

The acetate can be extracted and sold as such, or it can be used in other chemical processes. If methyl acetate is recovered from the reaction products of the carbonylation, a certain amount or all of the methyl acetate can hydrolyze with obtaining acetic acid. Alternatively, the entire reaction product of the carbonylation can be directed to stage hydrolysis and highlight the acetic acid from the products of this stage. The hydrolysis can be conducted by known methods, for example by reactive distillation in the presence of an acid catalyst.

The process may be continuous or periodic, preferably as a continuous process.

Hereinafter the invention will be illustrated with reference to the following examples.

Obtaining catalyst

Catalyst: H-mordenite

H-Mordenite (H-MOR), in which the ratio of silicon oxide to aluminum oxide was 20 (former production company Süd-chemie)was progulivali in the air without blowing in a muffle furnace (furnace volume 18 l). The temperature was raised from room temperature up to 500°C at 5°C/min and held at this temperature for 24 hours. Then the mordenite extruded with the force is 12 tonnes using 33 mm molds using Specac press, and then crushed and sieved, received a fraction with a particle size of from 212 to 335 mm.

Catalyst B: Cu-mordenite, Cu(55)-MOR

Weighed H-mordenite (40 g), in which the ratio of silicon oxide to aluminum oxide was 20 (former company Süd Chemie), was placed in a round bottom flask with a volume of 500 ml, were also placed there to 6.43 g propantheline nitrate copper (II) (98% ACS) and an anchor stirrer. Then the flask was added a sufficient amount of deionized water (approximately 100 ml) until a thick suspension. Then the upper part of the flask is tightly closed and the contents of the flask was stirred over night. Then impregnated with copper mordenite was dried under reduced pressure on a rotary evaporator, and then in an oven at 100°C for 12 hours. Then the zeolite was progulivali in a muffle furnace (furnace volume 18 l) in air (without purging). The temperature was raised from room temperature up to 500°C at 5°C/min and held at this temperature for 24 hours. Then the zeolite was pressed with a force of 12 tons using 33 mm molds using Specac press, and then crushed and sieved, received a fraction with a particle size of from 212 to 335 microns. The copper content in the mordenite was 55 mol%. with respect to aluminum contained in the mordenite.

The catalyst: Ag-mordenite, Ag(55)-MOR

Zeolite was prepared as catalyst B, except that used either the rat silver (99+%, ACS) (7,16 g to 50 g of the mordenite) instead of propantheline nitrate copper (II) (98% ACS). In the resulting mordenite content of silver was equal to 55 mol%. with respect to aluminum.

Catalyst G: Ag-mordenite, Ag(70)-MOR

Zeolite was prepared as catalyst B, except that they used silver nitrate (99+%, ACS) (1,82 g to 10 g of the mordenite) instead of propantheline nitrate copper (II) (98% ACS). In the resulting mordenite silver content was 70 mol%. with respect to aluminum.

Experiment 1: Carbonylation of methanol

Methanol was carbonyliron carbon monoxide in the presence of catalysts a, B, C and D and hydrogen. The carbonylation reaction was carried out in a flow reactor pressurized device, comprising 60 identical parallel isothermal flow tubular reactor as described, for example, in WO 2006107187. The reactors were placed in 4 blocks of 15 reactors, the temperature in each of the blocks is regulated independently. To each tube was loaded 25, 50 or 100 μl of the catalyst (to watch the volumetric rate of gas was $ 8000, 4000 and 2000 h-1, respectively), the catalyst was placed on a sintered metal mesh, pore size which was 20 μm. All samples zeolite catalyst was heated at a speed of 5°C/min to 100°C in a stream of gas containing 98,8% mol. nitrogen and 1.2 mol%. helium at atmospheric pressure, and flow rate of 3.4 ml/min, and kept at this temperature T. the value of 1 hour. Then the reactor was created pressure 30 bar (g.), feeding a mixture of 98.8% of the mol. nitrogen and 1.2 mol%. helium, and the system was kept under these conditions for 1 hour. Then feed the mixture of nitrogen and helium were off and began to apply a new mixture involving 63,2% mol. carbon monoxide, 15.8% of mol. hydrogen, 19.8% of mol. nitrogen and 1.2 mol%. helium at a flow rate of 3.4 ml/min, and the reactor was heated with a rate of 3°C/min to 300°C. the System was kept under these conditions for 3 hours. After this temperature units 1 through 4 were brought up to value 275, 300, 325 and 350°C, respectively, and gave the system to stabilize for 10 minutes. At this point, the activation of the catalyst is considered completed, and the system began to apply a new mixture of gases containing 63,2% mol. carbon monoxide, 15.8% of mol. hydrogen, of 14.8 mol%. nitrogen, and 1.2 mol%. helium and 4.9 mol%. methanol with a rate of 3.4 ml/min Methanol was supplied in liquid form at the entrance to each reactor, where it evaporates, resulting in the composition of the gas took the values described above. Then the experiment continued, using the following compositions of the gas mixtures.

CO, mol%.H2, mol%.N2, mol%.Meon, mol%.Not, mol%.The beginning of the lo feed hThe end of the submission, h
63,215,814,8a 4.91,2037,3
63,215,89,909,91,237,365,5
63,215,814,8a 4.91,265,5to 92.1
63,215,816,831,2to 92.1119,5
63,215,814,8a 4.91,2119,5136,1
63,215,89,99,91,2136,1Coming out of the reactor system flow directed in two gas chromatograph. One of them was microchromatography Varian 4900 containing three columns (molecular sieve 5A, Porapak® Q and CP-Wax-52), each of which is equipped with a heat conductivity detector. The other was a device Interscience Trace with two columns (CP-Sil 5 and CP-Wax 52), each of which is equipped with a detector ionization in the flame.

Average results for volumetric performance for a period of time to 92.1 to 152.5 h shown in figure 1. Volumetric performance acetyll was defined as the sum of the volumetric productivity of obtaining Asón and receipt of Meoac multiplied by MWAcOH/MWMeOAc.

From figure 1 it is clear that the increase in methanol concentration leads to decrease in volumetric productivity.

Example 1: Carbonylation of dimethyl ether

Dimethyl ether was carbonyliron carbon monoxide in the presence of catalysts a, B, C and D in the presence of hydrogen. The carbonylation reaction was carried out in a flow reactor under pressure, comprising 60 identical parallel isothermal flow tubular reactor as described, for example, in WO 2006107187. The reactors were placed in 4 blocks of 15 reactors, the temperature in each of the blocks is regulated independently. To each tube was loaded 25, Il 100 µl of the zeolite catalyst (for example, to watch the volumetric rate of gas was $ 8000, 4000 and 2000 h-1, respectively), the catalyst was placed on a sintered metal mesh, pore size which was 20 μm. All catalyst samples were heated at 5°C/min to 100°C at atmospheric pressure in a stream of gas containing 98.6% of the mol. nitrogen and 1.4 mol%. helium, at a flow rate of 3.4 ml/min, and held at this temperature for 1 hour. Then the reactor was created a pressure of 30 barg.) using a gas containing 98.6% of the mol. nitrogen and 1.4 mol%. helium, and the system was kept under these conditions for 1 hour. Then into the reactor instead of a mixture of nitrogen and helium began to apply the mixture containing the 63,1% mol. carbon monoxide, 15.8% of mol. hydrogen, 19,7% mol. nitrogen and 1.4 mol%. helium, at a flow rate of 3.4 ml/min, and the reactor was heated with a rate of 3°C/min to 300°C. the System was kept under these conditions for 3 hours. Then the temperature units 1 through 4 were brought up to value 275, 300, 325 and 350°C, respectively, and gave the system to stabilize for 10 minutes. At this point, the activation of the catalyst is considered completed, and the system began to apply a new mixture of gases containing 63,1% mol. carbon monoxide, 15.8% of mol. hydrogen, of 14.8 mol%. nitrogen and 1.4 mol%. helium and 4.9 mol%. dimethyl ether, with a rate of 3.4 ml/min. and the Reaction continued for approximately 93 hours. Leaving react the nuclear biological chemical (NBC system stream is directed in two gas chromatograph. One of them was microchromatography Varian 4900 containing three columns (molecular sieve 5A, Porapak® Q and CP-Wax-52), each of which is equipped with a heat conductivity detector. Another chromatograph was a device Interscience Trace with two columns (CP-Sil 5 and CP-Wax 52), each of which is equipped with a detector ionization in the flame. Were averaged results for volumetric productivity and selectivity for a period of time with a duration of 27 hours, from 65 to 93 hours response.

Example 2: Carbonylation of dimethyl ether

Repeating the method of example 1 using 50, 100, or 200 μl of catalysts a, B, C, G and the flow of gas mixture of 6.8 ml/min For reactions of carbonyl temperature units 1 through 4 were 220, 250, 300 and 350°C, respectively. After 154,4 hours the reaction was conducted the following experiment designed to determine the effect of changes in the concentration of DME. At this stage, the gas stream was switched to 63.1 mol%. carbon monoxide, 15.8% of mol. hydrogen, of 14.8 mol%. nitrogen and 1.4 mol%. helium and 4.9 mol%. dimethyl ether. The reaction was continued using this mixture in the course of 21.5 hours, and then the gas flow was changed, began to apply the mixture containing the 63,1% mol. carbon monoxide, 15.8% of mol. hydrogen, a 17.3 mol%. nitrogen and 1.4 mol%. helium and 2.5 mol%. dimethyl ether. The reaction continued for another 28 hours in these conditions, and then changed the gas flow encinal to apply the mixture, including 63,1% mol. carbon monoxide, 15.8% of mol. hydrogen, 18.2% in mol. nitrogen and 1.4 mol%. helium and 1.5 mol%. dimethyl ether. Under these conditions, the reaction was continued for 28,5 hours. Performance data for one pass was averaged over a significant period of time to obtain results for each of the following concentrations DME: 5, 2.5 and 1.5 mol%. Performance data in a single pass below in tables 1 through 3. Volumetric performance acetyll was defined as the sum of the volumetric productivity of obtaining Asón and receipt of Meoac multiplied by MWAcOH/MWMeOAc.

Table 1
250°CVolumetric performance aceticum, g/lcathVolumetric performance aceticum, g/lcathVolumetric performance aceticum, g/lcath
1.5% of DME2.5% of DME5% DME
H-MOR - 50 ál2,92,83,5
H-MOR - 100 ál2,9 2,7a 3.9
H-MOR - 200 ál2,72,83,5
Cu(55) MOR - 50 ál7,18,211,7
Cu(55) MOR - 100 ál9,910,214.4V
1.5% of DME2.5% of DME5% DME
Cu(55) MOR - 200 ál10,411,317,9
Ag(55) MOR - 50 ál11,912,916,6
Ag(55) MOR - 100 ál11,312,215,7
Ag(55) MOR - 200 álto 12.012,9the 17.3

Table 2
300°CVolumetric performance aceticum, g/lka is hVolumetric performance aceticum, g/lcathVolumetric performance aceticum, g/lcath
1.5% of DME2.5% of DME5% DME
H-MOR - 50 ál10,813,318,0
H-MOR - 100 ál14,915,320,0
H-MOR - 200 ál15,217,6to 19.9
Cu(55) MOR - 50 ál30,031,547,5
Cu(55) MOR - 100 ál42,248,967,0
Cu(55) MOR - 200 ál45,156,081,2
Ag(55) MOR - 50 ál43,7to 43.156,7
Ag(55) MOR - 100 ál33,257,3
Ag(55) MOR - 200 ál29,039,654,4

Table 3
350°CVolumetric performance aceticum, g/lcathVolumetric performance aceticum, g/lcathVolumetric performance aceticum, g/lcath
1.5% of DME2.5% of DME5% DME
H-MOR - 50 ál12,815,119,3
H-MOR - 100 ál14,817,622,5
1.5% of DME2.5% of DME5% DME
H-MOR - 200 ál12,315,020,2
Cu(55) MOR - 50 álto 59.6 72,590,1
Cu(55) MOR - 100 ál58,571,0101,3
Cu(55) MOR - 200 ál---
Ag(55) MOR - 50 ál32,4to 38.352,0
Ag(55) MOR - 100 álto 38.350,665,0
Ag(55) MOR - 200 ál34,746,362,7

From tables 1 to 3 shows that increasing the concentration of dimethyl ether leads to higher volumetric productivity.

Example 3

In experiment 1 and example 1 of the carbonylation reaction was carried out at 300°C using 5 mol%. methanol and 5 mol%. dimethyl ether, respectively. Data volume performance in a single pass and selectivity of these reactions during the period from 65 92 h of reaction are presented in figure 2, and the selectivity is shown in figure 3.

Volumetric performance acetyll was defined as the sum of the volumetric productivity of obtaining Asón and the floor is placed Meoac, multiplied by MWAcOH/MWMeOAc.

For carbonylation of methanol:

Selectivity = ([Meoac]output + [Asón] output)/([MeOH] input [MeOH] output - 2*[Me2O] output [Meoac] output)*100.

For the carbonylation of dimethyl ether:

Selectivity = ([Meoac] output + [Asón]output)/([DME] - [DME] output - 0,5*[Meon] output - 0,5*[Meoac] output)*100.

From figure 2 and 3 you can see that the carbonylation mixture containing 5 mol%. dimethyl ether, provides the best results in volumetric productivity and selectivity in comparison with the process of carbonylation of a mixture containing an equivalent concentration of methanol.

Example 4

Preparation of catalyst

Catalyst D - N-ferrierite

NH4-ferrierite, in which the ratio of silicon oxide to aluminum oxide is 55 (produced by the former company Zeolyst) was progulivali in a muffle furnace in air without blowing. The temperature was raised from room temperature up to 110°C at 5°C/min and kept catalyst at this temperature for 2 hours. Then the temperature was raised to 450°C at 5°C/min and kept catalyst at this temperature for 12 hours. Then N-ferrierite extruded with a force of 12 tons using 33 mm molds using Specac press, and then crushed and sieved, received a fraction of the particle size from 212 to 335 mm.

Catalyst E: Cu-offretite, Cu(55)-offretite

To 0.3 g NH4-offretite, in which the ratio of silicon oxide to aluminum oxide is 10 (the production of the former Sintef) was added 430 μl of a solution containing 0.3 g of propantheline nitrate copper (II) (98% ACS) per ml of water. At the same time added an additional amount of water (to bring the total number of added solution to about 700 μl) and the resulting suspension was intensively mixed on a roller table for at least 1 hour to ensure thorough mixing. Then, the zeolite was dried at 50°C for at least 16 hours, then at 110°C for 4 hours and then progulivali in a muffle furnace in air without blowing. The temperature of annealing was increased from room temperature up to 500°C at a rate of 2°C/min and then progulivali the catalyst at this temperature for 2 hours. Then offretite containing copper, extruded with a force of 12 tons using 33 mm molds using Specac press, and then crushed and sieved, received a fraction with a particle size of from 212 to 335 microns. The content of Cu in Cu-offretite was about 55 mol%. with respect to the aluminum content.

Carbonylation of dimethyl ether

The procedure of example 1 was repeated, using 50 μl of catalysts D and E in the reactor (designed so that OCSG was 400 h -1at a pressure of 70 barg.). After keeping the reactor temperature at 300°C for 3 hours the temperature was set at 180°C and the system was allowed to stabilize for 10 minutes, and then started feeding the gas mixture composition of 63.1 mol%. carbon monoxide, 15.8% of mol. hydrogen, of 14.8 mol%. nitrogen and 1.4 mol%. helium and 4.9 mol%. dimethyl ether with a rate of 3.4 ml/min. the Reaction was carried out under these conditions for 32,2 h, and then increased the temperature to 300°C. the Reaction was carried out for another 88 hours. The results of measuring the volumetric productivity is presented in figure 4.

1. The way to increase catalytic activity upon receipt of acetate, comprising carbonylation feedstock on the basis of dimethyl ether with carbon monoxide in the presence of hydrogen under practically anhydrous conditions at a temperature of from more than 250 to 350°C., in the presence of zeolite catalyst effective in the specified carbonyliron, and the concentration of dimethyl ether is at least 1 mol.%, in the calculation of the total number of raw materials.

2. The method according to claim 1, wherein the concentration of dimethyl ether is from 1.5 to 10 mol.%, in the calculation of the total number of raw materials.

3. The method according to claim 2, in which the concentration of dimethyl ether is from 1.5 to 5 mol.%, in the calculation of the total number of raw materials.

4. The method according to p., in which the zeolite contains at least one channel, which is set to 8-membered ring.

5. The method according to claim 4, in which the specified 8-membered ring channel interconnected with at least one channel, which is set to 10 and/or 12-membered ring.

6. The method according to claim 1, wherein the zeolite is selected from the group including mordenite, ferrierite, offretite and gmelinite.

7. The method according to claim 6, in which the mordenite is chosen from H-mordenite or mordenite, which is subjected to ion exchange or other means applied to at least one metal selected from the group comprising copper, Nickel, iridium, silver, rhodium, platinum, palladium and cobalt.

8. The method according to claim 7, in which the mordenite caused by metal selected from copper, silver and mixtures thereof.

9. The method according to claim 7 or 8, in which the content of metal in the mordenite is from 55 to 120 mol.% with respect to aluminum.

10. The method according to claim 1, in which the process is carried out at a pressure of from 10 to 100 barg.).

11. The method according to claim 1, in which the molar ratio of carbon monoxide: hydrogen is from 1:3 to 15:1.

12. The method according to claim 1, in which at least part methylacetate product hydrolyzing with obtaining acetic acid.

13. The method according to claim 1, in which the process is carried out at a temperature of from 275 to 350°C in the presence of a zeolite of mordenite and the concentration of dimethyl ether is from 1.5 to 5 mol.%, in the calculation of the total number of raw materials.



 

Same patents:

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 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 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: invention relates to an improved method for selective production of acetic acid and/or methyl acetate, with formation of small amounts of hydrocarbon by-products, involving bringing methanol and/or reactive derivative thereof, selected from dimethyl ether and methyl acetate, into contact with carbon monoxide in aqueous conditions in the presence of a ferrierite catalyst.

EFFECT: improved method for selective production of acetic acid and/or methyl acetate.

23 cl, 1 tbl, 15 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: 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: invention relates to an improved method of increasing rate of reaction without a ruthenium promoter and reducing toxicity of the catalyst system when producing acetic acid via carbonylation of methanol and/or reactive derivative thereof with carbon monoxide in at least one carbonylation reaction zone, containing a liquid reaction composition which contains an iridium carbonylation catalyst, a methyl iodide cocatalyst, water in an a limited concentration, acetic acid, methyl acetate and indium and rhenium as promoters.

EFFECT: high efficiency of the method.

16 cl, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of preventing precipitation of a catalyst system when producing acetic acid via carbonylation of methanol and/or reactive derivative thereof with carbon monoxide in at least one carbonylation reaction zone, containing a liquid reaction composition containing an iridium carbonylation catalyst, a methyl iodide cocatalyst, water in an a limited concentration, acetic acid, methyl acetate and boron and gallium as promoters.

EFFECT: combination of boron and gallium as promoters enables to avoid problems with precipitation which are observed in ruthenium-promoted reactions, and the rate of reaction also remains the same compared with conventional ruthenium promoters.

15 cl, 2 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing acetic acid through carbonylation of methanol and/or reactive derivative selected from methyl acetate, methyl iodide, dimethyl ether and mixtures thereof, carbon monoxide in the presence of a catalyst in a liquid reaction mixture containing methyl iodide and water in concentration of 0.1-30 wt %, wherein the catalyst includes a complex of a metal with a chelate-like ligand of general formula (I), wherein Z represents carbon, each of L1 and L2 represents a coordination group containing a donor P atom or a donor N atom; each R3 is independently selected from hydrogen, or a C1-C6 alkyl group, and M is selected from Rh and Ir; or general formula (II), wherein Z represents carbon, each of L3 and L4 represents a coordination group containing a donor P atom or a donor N atom, and M is selected from Rh and Ir.

EFFECT: method provides high selectivity of formation of acetic acid.

14 cl, 2 tbl, 6 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 producing acetic acid via carbonylation of methanol and/or reactive derivative thereof with carbon monoxide in at least one carbonylation reaction zone, containing a liquid reaction composition containing a iridium carbonylation catalyst, a methyl iodide cocatalyst, water in an a limited concentration, acetic acid, methyl acetate and ruthenium and at least one of niobium salt or tantalum salt as promoters.

EFFECT: method enables to conduct carbonylation with considerably smaller amounts of by-products while simultaneously maintaining an acceptable rate of reaction.

16 cl, 2 tbl, 2 ex

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