Method for carbonylation of dimethyl ether

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

 

The 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, just what about the ether and mixtures thereof, 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 this patent application process is carbonyliron carried out at temperatures of 250°C or lower, and preferably from about 150 to about 180°C, in order to minimize the formation of by-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 increased productivity and/or selectivity of the catalyst can be achieved by performing the carbonyl process at a temperature of from 250 to 350°C and pressures greater than 10 bar (excess.).

In accordance with this present invention provides a method of producing methyl acetate, comprising carbonylation feedstock on the basis of dimethyl ether and carbon monoxide under practically anhydrous conditions in the presence of zeolite catalyst effective in the specified carbonyliron, and the reaction is carried out at a temperature of from more than 250 to 350°C and a pressure of from more than 10 to 100 barg.).

The present invention solves the above problem by the fact that the process is carried out at high temperature and high pressure to get good is electively and/or performance in relation to methylacetate product. The discovery of the fact that these goals can be achieved at high temperatures and high pressure, was unexpected, because of the data described in the application WO 2006/121778 described above, one would expect that the effect of increasing the temperature of the reaction catalyzed by zeolite carbonylation of dimethyl ether to reduce the rate of formation of acetate, as well as the selectivity in respect of this product. In addition, the carbonylation of methanol in the presence of zeolite catalyst usually requires that the reaction temperature was more than 250°C, so it was expected that productivity and/or selectivity achieved by carbonyliron dimethyl ether under the same conditions as the carbonylation of methanol, will be lower.

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 produced by the catalytic conversion of 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 Syrena the basis of dimethyl ether may include a small amount of methanol, moreover, 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% by weight. or less, for example, 1% wt. or less of methanol.

Appropriately dimethyl ether present in the raw materials in concentrations that constitutes from 0.1 to 20 mol.%, for example from 1 to 20 mol%, for example from 1.5 to 10 mol.%, for example, from 1.5 to 5 mol.%, calculated on the total feed (including recycled amount).

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.

Raw materials on the basis of carbon monoxide may contain 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 include small amounts of carbon dioxide.

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

The molar ratio of carbon monoxide to dimethyl ether in a suitable manner is from 1:1 to 99:1, such as from 2:1 to 60:1.

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

Zeolites are available from commercial sources, mainly in Na, NH4or H-form. MN4form can be converted to the acid form (H-form) by known methods, for example, by annealing 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, vzaimosvjazi is 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 least 2.5 x 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 X2About3where 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 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 of the zeolite such as 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.%=(the 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 40 to 120 mol%, 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 mordini is maybe in addition to the 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 molar percent of 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 in almost no 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 EPE is in the 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. Appropriate raw materials based on the dimethyl ether can contain water in an amount of 2.5 wt.%. or less, for example of 0.5% wt. or less.

The process in accordance with the present invention is carried out at a temperature of from more than 250 to 350°C and a pressure of from more than 10 to 100 barg.). Appropriately, the temperature may range from 275 to 350°C., for example from 300 to 350°C or from 275 to 325°C.

Appropriate pressure may be from more than 10 up to 80 barg.), for example, from more than 10 to 50 barg.), from 15 to 80 barg.), from 15 to 50 barg.), from 30 to 80 barg.) and from 30 to 100 barg.), for example from 50 to 100 barg.).

Appropriate process can be performed at a temperature of from 275 to 350°C., for example from 300 to 350°C and at a pressure of from more than 10 to 100 barg.), for example, from more than 10 up to 80 barg.), for example, 15 is about 50 barg.) and from 30 to 80 barg.).

Volumetric hourly rate of gas (OCSG) appropriately ranges from 500 to 40000 h-1for example from 1000 to 20000 h-1for example , from 2000 to 20000-1.

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, which support the desired temperature and pressure.

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 ppm million, preferably less than 100 ppm million

The primary product of the process is the acetate, but you can also get a 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, some to icesto 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

The mordenite in which the ratio of silicon oxide to aluminum oxide was 20 (former production company Süd Chemie), 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 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 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 the anchor is Esaki. 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 90°C for 12 hours. Then the mordenite was progulivali in a muffle furnace (furnace volume 18 l) in air (without purging) using the following temperature program. 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 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

Catalyst D was prepared in the same way as catalyst B, except that they used silver nitrate (99+%, ACS) (7,16 g to 50 g of the mordenite) instead of propantheline nitrate copper (II) (98% ACS). In the resulting mordenite silver content was 55%mole. with respect to aluminum.

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

Catalyst D was prepared in the same way as catalyst B, except that use is whether the 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%mole. with respect to aluminum.

Example 1: Carbonylation of dimethyl ether

Dimethyl ether was carbonyliron carbon monoxide in the presence of zeolite catalysts a, B and C, at a temperature of from 220 to 350°C. and a pressure of from 10 to 50 bar (Rel.). The experiments were conducted 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 with 50, 100 or 200 ál zeolite catalyst (so that hourly space velocity of gas was $ 4000, 2000 and 1000 h, respectively), the catalyst was placed on a sintered metal mesh, pore size which was 20 μm. All samples zeolite catalyst was heated at 5°C °C/min to 100°C in a stream of gas containing 98.6% of the mol. nitrogen and 1.4 mol%. helium at atmospheric pressure, and flow rate of 3.4 ml/min and kept at this temperature for 1 hour. Then the reactor was created pressure 10 bar (Rel.) and the system was kept under these conditions for 1 hour. Then the reactor was started to apply the mixture containing the 63,1 mol.% carbon monoxide, 15.8% of mol. hydrogen, 19,7 mol.% nitrogen and 1.4 the ol.% helium at a flow rate of 3.4 ml/min, and the system was heated at 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 to values of 220, 250, 300 and 250°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, to 15.8 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 continued for about 78,6 hours under these conditions, and then the pressure was increased from 10 to 30 barg.), and the system was allowed to stabilize for 30 minutes. These conditions were maintained for about 28 hours, and then the pressure was increased from 30 to 50 barg.). The system was again allowed to stabilize for 30 minutes and then maintained under these conditions for another 28 hours. Coming 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. 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. The data obtained as the average Majesty the us in the period from 50,1 to 78,6 h process, formed results for pressure 10 bar (g.); the data obtained in the period from 78,6 to 107,1 h, formed results for pressure 30 bar (g.); and the data obtained in the period from 107,1 to 135.6 h of reaction, formed results for a pressure of 50 barg.).

The performance and selectivity of reactions, carbonylation of dimethyl ether represented in figure 1-6. Performance, as the output of acetylon in one pass, defined as the sum of the output of the Asón in one pass and exit Meoac multiplied by MWAcOH/MWMeOAc. Selectivity was calculated as ([Meoac] output+[Asón] output)/([DME] - [DME] output - 0,5*[Meon] output - 0,5*[Meoac] output)*100.

Figure 1 shows the performance that was achieved by the pressure of the reaction of 50 barg.), at each of the temperatures of the reaction components 220, 250, 300 and 350°C. figure 2 presents the selectivity of formation of products of carbonylation of methyl acetate and acetic acid is achieved when the pressure of the reaction 50 barg.), at each of the temperatures of the reaction components 220, 250, 300 and 350°C. figure 3 presents the performance achieved when the pressure of the reaction of 30 barg.), at each of the temperatures of the reaction components 220, 250, 300 and 350°C. figure 4 presents the selectivity of formation of products of carbonyl mutilate the ATA and acetic acid, achieved when the pressure of the reaction of 30 bar (Rel.), at each of the temperatures of the reaction components 220, 250, 300 and 350°C. figure 5 and 6 shows the performance and selectivity, respectively, achieved when the pressure in the reactor of 10, 30 or 50 barg.) and at a temperature of 300°C.

As can be seen from figures 1 to 4, higher productivity and selectivity achieved when working in the process anhydrous carbonylation of dimethyl ether at temperatures above 250°C and pressures above 10 bar (g.).

Experiment A: Carbonylation of methanol

Methanol was carbonyliron carbon monoxide in the presence of zeolite catalysts a, B, C, and the Experiments were conducted 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 with 50, 100 or 200 ál zeolite catalyst (so that hourly space velocity of gas was $ 4000, 2000 and 1000 h, respectively), the catalyst was placed on a sintered metal mesh, pore size which was 20 μm. All samples zeolite catalyst was heated at 5°C°C/min to 100°C in a stream of gas, terasawa 98,8% mol. nitrogen and 1.2 mol%. helium at atmospheric pressure, and flow rate of 3.4 ml/min, and held at this temperature for 1 hour. Then the reactor was creating the desired pressure (30, 50 or 80 barg.)) and kept the system at the desired pressure for 1 hour. Then the reactor was started to serve a new mixture involving 63,2% mol. carbon monoxide, to 15.8 mol.% hydrogen, 19,8 mol.% nitrogen and 1.2 mol.% helium at a flow rate of 3.33 ml/min, and the system was heated at 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 9.9 mol.% nitrogen is 1.2 mol.% helium and 9.9 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, as a result, the composition of the gas took the values described above. The reaction was continued for at least 56,5 hours under the above conditions. Coming 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 P-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. For each of the experiments took averages over a period of 28.5 hours, from 27,8 to 56.3 hours of reaction.

Performance and selectivity results from carbonyliron at 325°C and pressures of 10, 30 and 50 barg.) shown in Fig.7 and 8. Performance, as the output of acetylon in one pass, defined as the sum of the output of the Asón in one pass and exit Msoas multiplied by MWAcOH/MWMeOAc. Selectivity was calculated as ([Meoac] output+[Asón] output)/([DME] - [DME] output - 0,5*[Meon] output - 0,5*[Meoac] output)*100.

As can be seen from Fig.7 and 8, the productivity and selectivity of the reactions, carbonylation of methanol decreases with increasing pressure. These results are opposite to the results obtained in the determination of the dependence of productivity and selectivity of the reactions with dimethyl ether, presented on figure 5 and 6 from the pressure: in this case, the productivity and selectivity increased with increasing pressure.

Example 2: Carbonylation of dimethyl ether

Repeating the procedure of example 1 using 25, 50 and 100 µl of the catalysts a, B, C and D in the reactor (constructed is so, that OCSG was 8000, 4000 and 2000 h-1, respectively). In reactors has created a pressure of 30 barg.), and temperature units 1 through 4 were regulated so that it was 275, 300, 325 and 350°C. the Reaction was carried out in the gas composition of 63.1 mol.% carbon monoxide, to 15.8 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 for 93 hours. Data on productivity and selectivity were averaged over a period of 27 hours, taken from 65 to 93 hours of reaction. Figure 9 and 10 shows the success of the process performance and selectivity, respectively.

Experiment B: Carbonylation of methanol

Repeated the experiment And the pressure was 30 bar, and the composition supplied to the reaction gas was as follows: 63,25 mol.% carbon monoxide, to 15.8 mol.% hydrogen, of 14.8 mol%. nitrogen is 1.2 mol.% helium and 4.95 mol.% the methanol flow rate was 3.4 ml/min. the Reaction was conducted for 92 hours. Performance and selectivity was calculated as average of the period from 65,5 up to 92.1 h of reaction. Figure 9 and 10 shows the achieved performance and selectivity, respectively.

Carbonylation of methanol in the presence of zeolite catalyst usually requires a reaction temperature above 250°C in order to achieve an acceptable reaction rate. There were m is the group of what carbonylation of dimethyl ether in the presence of zeolite catalyst requires a reverse, that is, the reaction temperature should be kept below 250°C. However, from figures 9 and 10 clearly shows that the implementation of the carbonylation of dimethyl ether in the presence of a zeolite catalyst to be used and elevated temperature and pressure not just to achieve high productivity and selectivity, but these performance and higher selectivity compared with the results obtained by carbonyliron of methanol on the same catalyst under the same reaction conditions.

Example 3

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 with a particle size of 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 4000 h-1at a pressure of 70 barg.). After the shock is Rivonia temperature in the reactor 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, to 15.8 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 performance results presented figure 11.

1. The way to improve the performance and selectivity upon receipt of acetate, comprising carbonylation feedstock on the basis of dimethyl ether and carbon monoxide under practically anhydrous conditions in the presence of zeolite catalyst effective in the specified carbonyliron, and the reaction is carried out at a temperature of from more than 250 to 350°C. and at a pressure of from more than 10 to 100 barg.).

2. The method in accordance with claim 1, in which the temperature ranges from 275 to 350°C.

3. The method in accordance with claim 2, in which the temperature is from 300 to 350°C.

4. The method in accordance with claim 1, wherein the pressure is from more than 10 up to 80 barg.).

5. The method in accordance with claim 4, in which the pressure is from 15 to 80 barg.).

6. The method in accordance with claim 5, in which the pressure is from 30 to 80 barg.).

7. The method in accordance with claim 1, wherein the carbonylation is carried out in the presence of hydrogen.

8. The way in is accordance with claim 1, in which the zeolite contains at least one channel specified 8-membered ring.

9. The method in accordance with claim 8, in which the zeolite is chosen from the group comprising mordenite, ferrierite, offretite and gmelinite.

10. The method in accordance with claim 9, in which the mordenite is a H-mordenite, or it 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.

11. The method in accordance with claim 10, in which the mordenite is subjected to ion exchange or otherwise deposited metal selected from copper, silver and mixtures thereof.

12. The method in accordance with claim 11 in which the metal content is from 50 to 120 mol.% with respect to aluminum.

13. The method in accordance with claim 1, in which at least some amount of methylacetate product hydrolyzing with obtaining acetic acid.

14. The method in accordance with claim 1, in which dimethyl ether is present in the raw materials in concentrations that constitutes from 0.1 to 20 mol.%, calculated on the total composition of raw materials (including recycled products).

15. The method in accordance with claim 1, wherein the carbonylation is carried out in the presence of a zeolite of mordenite at a temperature of from 275 to 350°C., at a pressure of from 10 to 50 barg.).



 

Same patents:

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 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 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: 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 improved carbonylation methods for producing acetic acid, one of which involves: (a) carbonylation of methanol or reactive derivative thereof in the presence of water, a catalyst selected from rhodium catalysts, iridium catalysts and mixtures thereof, a promoter from methyl iodide to form a reaction mixture with acetic acid in a reactor; (b) separating the stream of the reaction mixture with acetic acid into a liquid recirculation stream and a first stream of the crude product which contains acetic acid; (c) feeding the first stream of crude product into a column for distillation of light fractions; (d) distillation of the stream of crude product to remove low-boiling components as the overhead product and form a first stream of the purified product in form of a side stream and a liquid residual stream, the liquid residual stream primarily consisting of acetic acid, where the first stream of purified product is fed into a dehydration column, after which the dried product is fed into a column for distillation of heavy fractions, and acetic acid is collected in form of an overhead product from the column for distillation of heavy fractions; (e) evaporating at least a portion of the liquid residual stream to obtain a second product stream; and (f) feeding the second product stream after condensation or compression thereof for further processing after merging with the first stream of purified product into said dehydration column. The invention also relates to an apparatus for producing acetic acid, comprising: (a) a reactor for carbonylation of methanol or reactive derivatives thereof in the presence of water, a catalyst selected from rhodium catalysts, iridium catalysts and mixtures thereof, and a promoter from methyl iodide to form a reaction mixture with acetic acid in the reactor; (b) a flash evaporation apparatus connected to the reactor and configured for inlet of the stream of the reaction mixture and separation thereof into (i) a liquid recirculating stream and (ii) a crude first product stream containing acetic acid; (c) a column for distillation of light fractions, which is connected to the flash evaporation apparatus which is configured for separation of low-boiling components in form of an overhead product from the first product stream and formation of a first stream of purified product in form of a side stream, and a liquid residual stream; (d) a dehydration column connected to the column for distillation of light fractions; (e) a column for distillation of heavy fractions connected to the dehydration column; and (f) an evaporation reservoir, also connected to the column for distillation of light fractions, for evaporation of at least a portion of the liquid residual stream and configured to feed a second product stream into the dehydration column; or a column for distillation of the liquid residual stream to form a stream of the purified product and meant for feeding it into the dehydration column or into the column for distillation of heavy fractions, where the column for distillation of the liquid residual stream is a stripping column. The apparatus and methods of producing acetic acid thus involve extraction of the product from the residue of light fractions in a stripping column and feeding the extracted acid for further processing in order to increase efficiency of the system.

EFFECT: reduced load on the column for distillation of light fractions; the load on the dehydration column can also be reduced in the embodiment, wherein further removal of water from the extracted acid is not necessary.

15 cl, 4 dwg, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to methods of removing acetaldehyde from a mixture of methyl acetate, methanol and acetaldehyde, one of which involves: (a) feeding the mixture of methyl acetate, methanol and acetaldehyde into a rectification column; (b) rectification of the mixture of methyl acetate, methanol and acetaldehyde at pressure of 68.95 kPa (10 pounds/square inch) or higher to form a vapour stream output from the top of the column which is rich in acetaldehyde compared to the mixture, and a bottom residue poor in acetaldehyde compared to the mixture; (c) returning as reflux a portion of the vapour stream which is output from the top of the column into the rectification column; and (d) removing a stream of the bottom residue poor in acetaldehyde from the rectification column, where temperature of the vapour stream from the top of the column ranges from 85°C to 115°C. The invention also relates to a method of producing acetic acid, involving: (a) cleaning the mixture of methyl acetate, methanol and acetaldehyde with removal of acetaldehyde by: (i) feeding the mixture of methyl acetate, methanol and acetaldehyde into a rectification column; (ii) rectification of the mixture of methyl acetate, methanol and acetaldehyde at pressure of 68.95 kPa (10 pounds/square inch) or higher to form a vapour stream which is output from the top of the column which is rich in acetaldehyde compared to the mixture, and a bottom residue poor in acetaldehyde compared to the mixture; (iii) returning as reflux a portion of the vapour stream output from the top of the column into the rectification column; and (iv) removing a stream of the bottom residue poor in acetaldehyde from the rectification column; (b) feeding the cleaned stream of bottom residue into the reaction mixture for carbonylation together with carbon oxide, where the reaction mixture for carbonylation contains water, a catalyst selected from rhodium catalysts, iridium catalysts or mixtures thereof, a promoter from methyl iodide and acetic acid; and (c) extracting acetic acid from the carbonylation mixture, where temperature of the stream which is output from the top of the column ranges from 85°C to 115°C.

EFFECT: improved methods.

15 cl, 8 dwg, 6 tbl, 16 ex

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 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

Up!