Oxidation method of producing carboxylic acids and alkenes and optionally alkenylcarboxylate or alkylcarboxylate

FIELD: chemistry.

SUBSTANCE: proposed is a method of oxidising alkane from C2 to C4, obtaining the corresponding alkene and carboxylic acid and/or oxidising alkene from C2 to C4, obtaining the corresponding carboxylic acid. The method involves addition into the reaction zone of the above mentioned alkane and/or alkene, containing molecular oxygen gas, carbon monoxide and optionally water, in the presence of a catalyst, effective for oxidising the alkane to the corresponding alkene and carboxylic acid and/or effective for oxidising the alkene to the corresponding carboxylic acid at temperature between 100 and 400 °C. Concentration of carbon monoxide is kept between 1 and 20% of the total volume of the initial material added to the oxidation reaction zone. The method can optionally involve further reaction in a second reaction zone.

EFFECT: new oxidation method for producing carboxylic acids and alkenes.

30 cl, 3 ex, 1 tbl, 2 dwg

 

The present invention relates to a method for oxidation of alkane and/or alkene with2C4the corresponding alkene and/or carboxylic acids, in particular to a method for oxidation of ethane to ethylene and acetic acid. The present invention relates also to the United ways in which the said alkene and carboxylic acid are used as reagents to obtain alkenylboronic or alkylcarboxylic.

Catalytic gas-phase oxidation of ethane to ethylene and acetic acid are known. In 1978 the company Union Carbide Corporation in the Journal of Catalysis, published a report describing the oxidation of ethane to ethylene in a fixed bed. In addition, several US patents (4250346, 4524236, 4568790, 4899003 and 4596787) described low-temperature oxidative dehydrogenation of ethane to ethylene. In the US 4899003 describes how oxidative dehydrogenation of ethane, in which the product stream contains ethylene, acetic acid, carbon oxides and unreacted ethane. Before returning to the process of unreacted ethane co and CO2removed. Carbon monoxide can be removed, for example, by oxidation to carbon dioxide and subsequent adsorption.

In EP-A-0546677 described by way of the oxidation of ethane to acetic acid in a reactor with a fluidized bed. In the method described in EP-A-0546677, most of the waste from reacto is and the recycle stream into the reactor, with the aim of maintaining in the reactor a high concentration of carbon oxides as diluents. (These diluents help regulate the temperature.) However, in order to prevent continuous accumulation in the reactor of carbon oxides from the exhaust of the reactor flow select the purified stream. For example, in EP-A-0546677 directed into the reactor, the source material contains 25% and 40% CO2. One drawback of high concentrations of co and CO2the source material is that the lowering of the partial pressure of ethane and ethylene, which may reduce the speed of the oxidation reaction.

As in WO 01/90042 and WO 01/90043 described a combined method of producing vinyl acetate, the first stage of which is the oxidation of ethane to acetic acid and ethylene with subsequent conversion of acetic acid and ethylene in the vinyl acetate. At the stage of conversion to vinyl acetate as a by-product can be obtained monoxide. WITH can be returned to the oxidation reactor, however, the carbon monoxide concentration in the recycled source material is relatively low. Specifically, WO 01/90042 and WO 01/90043 write that on stage (stages) of receipt of acetic acid and ethylene are usually formed by small amounts of carbon monoxide (<100 ppm million) and that, if carbon monoxide is get in Bo is her significant quantities (up to 5%), then you may want stage of removal. In WO 01/90042 and WO 01/90043 says nothing about any advantages of saving in sent into the reactor source material number.

In EP-A-0877727 described the United way of getting acetic acid and/or vinyl acetate in a variety of pre-defined variables and proportions of the gaseous source material containing ethylene and/or ethane. This combined method comprises a first stage in which ethylene and/or ethane catalytically oxidized in the first reaction zone to obtain a first product stream containing acetic acid, water, ethylene, and optionally ethane, carbon monoxide and/or carbon dioxide. Next, acetic acid and ethylene obtained in this first reaction zone, the second reaction zone is introduced into contact with the containing molecular oxygen gas in the presence of a catalyst to obtain a second stream of products containing vinyl acetate, water, acetic acid and optionally ethylene.

It was found that the oxidation of the alkane with2With4the corresponding alkene and carboxylic acid, in particular the oxidation of ethane to ethylene and acetic acid, and/or oxidation of the alkene with2With4obtaining the appropriate carboxylic acids, in particular the oxidation of ethylene to acetic acid is you, can be successfully carried out by maintaining at a certain interval the amount of carbon monoxide in the source material.

Accordingly, a first object of the present invention proposes a method of alkane oxidation with2With4the corresponding alkene and carboxylic acid and/or oxidation of the alkene with2With4obtaining the appropriate carboxylic acid, and this method involves feeding in the oxidation reaction zone mentioned alkane and/or alkene containing molecular oxygen gas, carbon monoxide, and optionally water, in the presence of a catalyst effective for the oxidation of the alkane to the corresponding alkene and carboxylic acid and/or effective for the oxidation of the alkene to the corresponding carboxylic acid, to obtain a first product stream containing alkene and carboxylic acid, characterized in that the concentration of the above-mentioned carbon monoxide is maintained within the range of from 1 to 20% of the total volume of the original material submitted to the oxidation reaction zone.

The second object of the present invention is a combined method of obtaining alkenylboronic. Thus, the present invention also proposed a combined method of obtaining alkenylboronic of the alkane with2/sub> With4and/or alkene with2With4moreover , this method includes the following stages:

(a) filing in the oxidation reaction zone mentioned alkane and/or alkene containing molecular oxygen gas, carbon monoxide, and optionally water, in the presence of a catalyst effective for the oxidation of the alkane to the corresponding alkene and carboxylic acid and/or effective for the oxidation of the alkene to the corresponding carboxylic acid, to obtain a first product stream containing alkene and carboxylic acid, where the carbon monoxide concentration maintained within the range of from 1 to 20% of the total volume of the original material submitted to the oxidation reaction zone, and (b) contacting in a second reaction zone at least part mentioned alkene, at least part of the mentioned carboxylic acids obtained from the oxidation reaction zone, and contains the molecular oxygen gas in the presence of at least one catalyst effective upon receipt of alkenylacyl, obtaining a second product stream containing alkenylboronic.

The third object of the present invention is a combined method of obtaining alkylcarboxylic. Thus, the present invention also proposed a combined method of producing alkylcarboxylic the and of the alkane with

With2With4and/or alkene with2With4moreover , this method includes the following stages:

(a) filing in the oxidation reaction zone mentioned alkane and/or alkene containing molecular oxygen gas, carbon monoxide, and optionally water, in the presence of a catalyst effective for the oxidation of the alkane to the corresponding alkene and carboxylic acid and/or effective for the oxidation of the alkene to the corresponding carboxylic acid, to obtain a first product stream containing alkene and carboxylic acid, where the carbon monoxide concentration maintained within the range of from 1 to 20% of the total volume of the original material submitted to the oxidation reaction zone, and

(b) contacting in a second reaction zone at least part of said alkene, at least part of the mentioned carboxylic acids obtained from the oxidation reaction zone, and optionally water, in the presence of at least one catalyst effective upon receipt of alkylcarboxylic, obtaining a second product stream containing alkylcarboxylic.

It was found that the presence of carbon monoxide (CO) in the source material in the oxidation of alkanes and/or alkenes with2With4inhibits the formation of additional carbon monoxide and reduces common with lectively in relation to carbon oxides (CO x). In addition, increases the selectivity for the target alkene and/or carboxylic acid product or products. For example, it was found that with the use of the method according to the present invention in the oxidation of ethane to ethylene and acetic acid can be enhanced selectivity for acetic acid as product. As an additional advantage of reducing the formation of COx(which is vysokoekonomichny process) allows improved control over the heat, which creates the opportunity for carrying out oxidation reactions with higher performance.

The preferred starting material alkane contains from2With4. Alkanolamide source material may also include the corresponding alkene. When the corresponding alkene is sent to the oxidation reaction zone together with alkanol, the oxidation reaction can be carried out with a more significant amount of alkene in the source material. Usually supply greater amounts of alkene leads to increased formation of COx. However, when implementing the method according to the present invention the formation of COxfor larger allocated quantities (concentrations) alkene is at least partially suppressed feeding from 1 to 20 vol.% WITH. Therefore, the additional advantage of the present invention is its implementation allows you to feed in the oxidation reaction zone is more increased amount of alkene, leading to improved performance. For example, it was found that the oxidation of ethane and ethylene to acetic acid and ethylene in the reactor is possible to deliver large quantities of ethylene with achievement of high performance.

In a preferred variant of the original material support such a number of carbon monoxide, whereby the selectivity for carbon monoxide in the oxidation reaction zone is low, constituting, for example, less than 1%. Thus, the amount of carbon monoxide in the first product stream leaving the oxidation reaction zone is slightly higher than the amount of carbon monoxide in the original material submitted to the oxidation reaction zone. Contained in the first product stream, the carbon monoxide can be separated from alkene and carboxylic acids as components of the first product stream and return in the process. In a preferred embodiment, carbon monoxide is fed into the oxidation reaction zone comprises at least part of these recycled carbon monoxide. In a more preferred embodiment, the process may be returned essentially all of the carbon monoxide, the content is present in the first product stream, in particular 90% or more, more preferably 95% or more. In the oxidation reaction zone typically produces a small amount of carbon monoxide, which can be balanced, for example, losses in the stages of cleaning and/or purified stream. Although it is theoretically possible to carry out the process with virtually no education in the oxidation reaction zone carbon monoxide (zero selectivity for carbon monoxide), in practice, to prevent the accumulation of inert materials that are in any of the source materials may be contained as impurities, usually need a small clean stream. This is the preferred number of carbon monoxide (counter number) usually depends on the specific reactions of the oxidation catalyst and the reaction conditions such as temperature. When the process is carried out while balancing amount, the method according to the present invention has the additional advantage that it can be done without any special stages removal of carbon monoxide (other than any treatment), thereby decreasing capital and technological costs associated with these stages.

In the oxidation reaction zone may also be sent fresh monoxide angle of the ode. For example, when the process in the oxidation reaction zone must be conducted so that the carbon monoxide in the source material were spent with the formation of carbon dioxide at a rate greater than the rate of formation of carbon monoxide, in addition to recycled WITH, in the oxidation reaction zone can be served WITH fresh.

When the oxidation reaction zone is part of an integrated process, such as obtaining alkenylacyl, carbon monoxide is fed into the oxidation reaction zone may include carbon monoxide is returned to the process with the other stages of the United way, such as, for example, carbon monoxide is recycled after separation from the second product stream leaving the second reaction zone to obtain alkenylboronic.

In the beginning of the process in the source material for the reaction in order to achieve the target amount of carbon monoxide in the source material as a whole can be introduced fresh monoxide. According to another variant of the original amount of carbon monoxide in the original material submitted to the oxidation reaction zone, in the beginning of the process may be less than the amount that you want to keep, but he usually builds up to the quantity required is about to keep the original material back into the process generated in the process of carbon monoxide.

In a preferred embodiment, the amount of carbon monoxide in the source material (in the form of fresh and/or recirculated component) supported at the level of more than 2.5% of the total volume of the source material, in particular more than 5% of the total volume of the source material, for example from more than 5 to 20 vol.% or from more than 5 to 15% of the total volume of the source material.

In a preferred embodiment, the amount of carbon monoxide in the source material (in the form of fresh and/or recirculated component) supported at the level of less than 15% of the total volume of the source material, in particular in the range from more than 5 to less than 15% of the total volume of the source material, for example from more than 5 to 10% of the total volume of the source material.

In a preferred embodiment, the oxidation of the alkene with2With4obtaining the appropriate carboxylic acid is a process of obtaining acetic acid from ethylene.

In a preferred embodiment, the process of oxidation of the alkane with2With4the corresponding alkene and carboxylic acid is a process of producing ethylene and acetic acid from ethane. In a preferred embodiment, ethylene is served in a reaction zone with ethane.

Solid catalysts are effective in the oxidation of alkane and/or alkene with2With4can be used in the form of podviznogo or fluidized bed. In a preferred embodiment, the oxidation reaction is carried out in heterogeneous conditions with solid catalysts and reagents in the liquid phase.

Catalysts effective for the oxidation of the alkane to alkene and carboxylic acid may include any acceptable catalysts known in the art, such as those used for the oxidation of ethane to ethylene and acetic acid, are described in the following patents and applications: US 4596787, EP-A 0407091, DE 19620542, WO 99/20592, DE 19630832, WO 98/47850, WO 99/51339, EP-A 1043064, WO 99/13980, US 5300682 and US 5300684, the contents of which are incorporated into this description by reference.

Patent US 4596787 relates to a method of low-temperature oxidative dehydrogenation of ethane to ethylene using a catalyst, corresponding to the empirical formula MoaVbNbcSbdXeas it is presented in the mentioned patent, and these elements are combined with oxygen.

EP-A 0407091 relates to a method and catalyst for producing ethylene and/or acetic acid by the oxidation of ethane and/or ethylene in the presence of an oxidation catalyst comprising molybdenum, rhenium and tungsten.

DE 19620542 relates to oxidation catalysts based on molybdenum, palladium and rhenium for obtaining acetic acid from ethane and/or ethylene.

WO 99/20592 relates to a method for selective receipt of acetic acid is from ethane, ethylene or mixtures thereof and oxygen at high temperature in the presence of a catalyst corresponding to the formula MoaPdbXcYdin which X represents one or more of the following elements: Cr, Mn, Nb, TA, Ti, V, Te and W; Y represents one or more of the following elements: B, Al, Ga, In, Pt, Zn, Cd, Bi, Ce, Co, Rh, Ir, Cu, Ag, Au, Fe, Ru, Os, K, Rb, Cs, Mg, Ca, Sr, Ba, Nb, Zr, Hf, Ni, P, Pb, Sb, Si, Sn, Tl, and U, and represents 1, b represents from 0.0001 to 0.01, with means from 0.4 to 1, and d denotes 0.005 to 1.

DE-A1 19630832 belongs to the similar catalytic composition, and which denotes 1, b>0, C>0, d denotes from 0 to 2. In the preferred embodiment, and represents 1, b represents from 0.0001 to 0.5, with means ranging from 0.1 to 1.0, and d denotes from 0 to 1.0.

WO 98/47850 relates to a method for producing acetic acid from ethane, ethylene or mixtures thereof in the presence of a catalyst corresponding to the formula WaXbYcZdin which X represents one or more of the following elements: Pd, Pt, Ag and Au, Y represents one or more of the following elements: V, Nb, Cr, Mn, Fe, Sn, Sb, Cu, Zn, U, Ni and Bi, a, Z denotes one or more of the following elements: Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ti, Zr, Hf, Ru, Os, Co, Rh, Ir, B, Al, Ga, In, Tl, Si, Ge, Pb, P, As, and Te, and 1 denotes that b>0, C>0, and d denotes from 0 to 2.

WO 99/51339 relates to catalytic compositions for the selective oxidation of ethane and/or ethylene to acetic acid; this composition sod is RIT in combination with oxygen the elements Mo aWbAgcIrdXeYfwhere X denotes the elements Nb and V; Y represents one or more elements selected from the group including Cr, Mn, TA, Ti, In, Al, Ga, In, Pt, Zn, Cd, Bi, CE, Co, Rh, Cu, Au, Fe, Ru, Os, K, Rb, Cs, Mg, Ca, Sr, Ba, Zr, Hf, Ni, P, Pb, Sb, Si, Sn, Tl, U, Re and Pd; and a , b, C, d, e, and f denotes the gram-atom ratios of the elements, in which 0<a≤1; 0≤b < 1 and a+b=1; 0<(c+d)≤0,1; 0<e≤2 and 0≤f≤2.

EP-A 1043064 relates to catalytic compositions for the oxidation of ethane to ethylene and/or acetic acid and/or for the oxidation of ethylene to acetic acid; the composition comprises in combination with oxygen the elements molybdenum, vanadium, niobium and gold in the absence of palladium according to the empirical formula MOaWbAucVdNbeYfin which Y represents one or more elements selected from the group including Cr, Mn, TA, Ti, In, Al, Ga, In, Pt, Zn, Cd, Bi, CE, Co, Rh, Ir, Cu, Ag, Fe, Ru, Os, K, Rb, Cs, Mg, Ca, Sr, Ba, Zr, Hf, Ni, P, Pb, Sb, Si, Sn, Tl, U, Re, Te and La; and b, C, d, e, and f denotes the gram-atom ratios of the elements, in which 0<a≤1; 0≤b < 1 and a+b=1; 10-5<C≤0,02; 0<d≤2; 0<e≤1 and 0≤f≤2.

WO 99/13980 relates to a catalyst for selective oxidation of ethane to acetic acid corresponding to the formula MoaVbNbcXdin which X denotes at least one promoter element selected from the group comprising P, B, Hf, Te and As; and denotes the Chi is lo in the range of from about 1 to about 5; b is 1; C represents a number in the range from about 0.01 to about 0.5; and d denotes a number in the range from greater than 0 to about 0.1.

US 5300682 relates to the application of oxidation catalyst of the empirical formula VPaMbOxwhere M denotes one or more elements of a number of Co, Cu, Re, Fe, Ni, Nb, Cr, W, U, TA, Ti, Zr, Hf, Mn, Pt, Pd, Sn, Sb, Bi, Ce, As, Ag and Au, and represents from 0.5 to 3, b is from 0 to 1, and x corresponds to the valence requirements.

US 5300684 refers to the oxidation reaction in the fluidized bed using, for example, a catalyst of the formula

Mo0,37Reof 0.25V0,26Nb0,07Sb0,03Ca0,02Ox.

Other acceptable for use in the present invention, the oxidation catalysts presented in the application WO 99/13980, which refers to the use of catalysts with elements in combination with oxygen in the relative gram-atom ratios of MoaVbNbcXdwhere X denotes P, b, Hf, Te, or As; patent US 6030920, which refers to the use of catalysts with elements in combination with oxygen in the relative gram-atom ratios of MoaVbNbcPdd; application WO 00/00284, which refers to the use of catalysts with elements in combination with oxygen in the relative gram-atom ratios of MoaVbNbcPddand/or MoaV LacPdd; patent US 6087297, which refers to the use of catalysts with elements in combination with oxygen in the relative gram-atom ratios of MoaVbPdcLad; application WO 00/09260, which refers to the use of catalysts with elements in combination with oxygen in the relative gram-atom ratios of MoaVbLacPddNbeXfwhere X denotes a Cu or Cr, and each of e and f may denote zero; applications WO 00/29106 and WO 00/29105 that relate to the use of catalysts with elements in combination with oxygen in the relative gram-atom ratios of MoaVbGacPddNbeXfwhere X denotes the La, Te, Ge, Zn, Si, In or W; and the application WO 00/38833, which refers to the use of catalysts with elements in combination with oxygen in the relative gram-atom ratios of MoaVbLawithPddNbeXfwhere X represents Al, Ga, Ge or Si, the content of which is incorporated into this description by reference.

Solid catalysts are effective in the oxidation of alkane and/or alkene with C2C4may be native or not be printed on the media. Examples of acceptable carriers include silica, diatomaceous earth, montmorillonite, aluminum oxide, silicon dioxide/aluminum oxide, dioxide, zircon is, titanium dioxide, silicon carbide, activated carbon and mixtures thereof.

Each of the components, namely: alkane containing molecular oxygen gas, alkene and water can be introduced into the oxidation reaction zone as a fresh source material and/or recycled component.

Containing molecular oxygen gas used in the oxidation reaction zone, may be air or a gas richer or poorer in molecular oxygen than air. Acceptable gas can represent, for example, oxygen diluted with an appropriate diluent, such as nitrogen or carbon dioxide. Preferred containing molecular oxygen gas is oxygen. In a preferred embodiment, at least a number containing molecular oxygen gas is directed to the oxidation reaction zone, regardless of alkane and an optional alkenovich source materials and all recycled threads.

Alkane and/or alkene, directed to the oxidation reaction zone in the process according to the present invention can be practically pure or can be mixed, for example, with one or more materials such as nitrogen, methane, carbon dioxide, carbon monoxide, hydrogen and low concentrations of alkenes/alkanes With3/S4.

<> In a preferred embodiment, the total number of inert impurities such as methane, nitrogen, carbon dioxide and argon contained in Allenova and/or albanova the source material is in the range from 0 to 3 vol.%, and more preferably in the range from 0 to 2.5%vol., in particular from 0 to 2.14%vol.

In a preferred embodiment, the total number of reactive impurities such as propane and other hydrocarbons contained in Allenova and/or albanova the source material is in the range from 0 to 10 vol.%, and more preferably in the range from 0 to 5%vol.

Fresh monoxide, if used, may be essentially pure or may include impurities such as carbon dioxide, hydrogen, nitrogen, noble gases and water.

Suitable alkane concentration (in the form of fresh raw materials and recycled component) is from greater than 0 to 90 mol%, inclusive of all materials sent to the oxidation reaction zone, including recycled materials, preferably from 10 to 80 mol %, more preferably from 40 to 80 mol %.

Suitable concentration of alkene (in the form of fresh raw materials and recycled component) is from greater than 0 to 50 mol%, inclusive of all materials sent to the oxidation reaction zone, including recycled materials, preferably the t 1 to 30 mol %, more preferably from 2 to 20 mol %.

It is advisable to take an optional water (in the form of fresh raw materials and/or recycled component) is from 0 to 50 mol%, inclusive of all materials sent to the oxidation reaction zone, including recycled materials, preferably from 0 to 25 mol %, more preferably from 2 to 15 mol %.

The preferred starting material sent to the oxidation reaction zone for oxidation of ethane and ethylene to acetic acid and ethylene, containing (in mol %) from 40 to 80% ethane, from 2 to 20% of ethylene, from 2 to 15% of water, from 5 to 15% of carbon monoxide and from 5 to 20% oxygen, and the rest is inert gases such as argon, carbon dioxide and/or nitrogen. In a preferred embodiment, oxygen is added directly into the fluidized bed.

When in the oxidation reaction zone use solid catalysts, alkane and/or alkene containing molecular oxygen gas and all of the recycled gases in the preferred embodiment, is passed through the oxidation reaction zone with length of stay in it corresponding to the aggregate average hourly rate of gas supply (SPG) from 500 to 10000 h-1and SSPG defined as the amount of [calculated at standard temperature and pressure (CTD)] of the gas passing through the react is R, divided by the bulk volume of the precipitated catalyst.

The oxidation reaction of the present invention can be effectively carried out at a temperature in the range from 100 to 400°C., typically in the range from 200 to 380°C., preferably from 250 to 350°C.

The oxidation reaction of the present invention can be effectively carried out under atmospheric or elevated pressure, for example under a gauge pressure in the range from 80 to 400 psi.

During the oxidation reaction of the present invention typically can be achieved in the conversion of alkane in the interval from 1 to 99%.

During the oxidation reaction of the present invention typically can be achieved in the conversion of oxygen in the range from 30 to 100%.

Acceptable performance of the catalyst during the oxidation reaction of the present invention is in the range from 10 to 10,000 g of carboxylic acid, such as acetic acid, per hour per kilogram of catalyst.

The first product stream from the oxidation process can be addressed directly in the subsequent process, but in the preferred embodiment, it is sent to the subsequent process indirectly after one or more stages of separation, such as the removal of carbon monoxide separation or reaction. Therefore, the second object of the present image is etenia at least part of alkene and at least part of the carboxylic acid, obtained from the oxidation reaction zone, is introduced into contact with the containing molecular oxygen gas with obtaining alkenylacyl, such as vinyl acetate. The third object of the present invention at least part of alkene and at least part of the carboxylic acid obtained from the oxidation reaction zone, is introduced into contact with a suitable catalyst to obtain alkylcarboxylic, such as ethyl acetate. In a preferred embodiment, alkane oxidize in the presence of a suitable oxidation catalyst in the first oxidation reaction zone with getting alkene and carboxylic acid in a ratio of approximately 1:1 for use in subsequent reactions receipt of alkenylboronic or alkylcarboxylic. However, alkene or carboxylic acid can be added to the first product stream (or delete) needs to obtain the desired starting material for the second reaction zone. Therefore, before the second reaction zone, you can add optional alkene and/or optional additional carboxylic acid or from the first product stream can be selected carboxylic acid and/or alkene.

As an additional alkene can be used fresh alkene and/or recycled alkene from the second reaction zone.

Additional the alkene, introduced into the second reaction zone to obtain alkenylboronic or alkylcarboxylic may be essentially pure or may be mixed, for example, with one or more components, such as nitrogen, argon, methane, carbon dioxide, carbon monoxide, hydrogen and low concentrations of alkenes/alkanes With3/S4.

The second object of the present invention in a suitable embodiment, the second reaction zone alkene injected in high concentrations, as in the oxidation reaction zone alkene is administered in low concentrations. Low concentrations (less than 20 mol % of the total amount of starting material) alkene introduced into the oxidation reaction zone, provide an opportunity to obtain the required equimolar or near equimolar mixture of alkene and carboxylic acid. High concentrations of alkene (more than 50 mol % of the total amount of starting material)is introduced into the second reaction zone, maximize selectivity for alkenylsilanes product, such as vinyl acetate.

Suitable concentration of alkene, such as ethylene, directed to the second reaction zone under second object of the invention is at least 50 mol % of the total amount of starting material directed to the second reaction zone, preferably less is th least 55 mol %, more preferably at least 60 mol %. It is advisable to alkene of up to 85 mol % of the total amount of starting material introduced into the second reaction zone, preferably in the range from at least 50 to 80 mol %, in particular at least 55 to 80 mole %.

The third object of the present invention in a suitable embodiment, the second reaction zone alkene enter in optimal concentrations, and in the oxidation reaction zone alkene is administered in low concentrations. Low concentrations (less than 20 mol % of the total amount of starting material) alkene introduced into the oxidation reaction zone, provide an opportunity to obtain the required equimolar or near equimolar mixture of alkene and carboxylic acid. The alkene can be introduced into the second reaction zone in the optimal concentrations to maximize selectivity for alkenylsilanes product, such as ethyl acetate.

In the second embodiment of the method according to the present invention can be applied is known in the art catalysts receiving alkenylbenzenes. Thus, the catalyst, effective upon receipt of vinyl acetate, which, when executing the present invention can be used in the second reaction zone may, in luceti, in particular, the catalysts presented in patents and applications GB 1559540, US 5185308 and EP-A 0672453, the contents of which are incorporated into this description by reference.

In GB 1559540 described catalyst, effective upon receipt of vinyl acetate by reaction of ethylene, acetic acid and oxygen, and the catalyst essentially comprises (1) a catalyst carrier particle diameter is from 3 to 7 mm, and the specific pore volume is equal to from 0.2 to 1.5 ml/g, and the pH value of the suspension of this catalyst carrier in water concentration of 10 wt.% is from 3.0 to 9.0, (2) paradiishotel alloy distributed in a surface layer of a catalyst carrier, and this surface layer is at a distance of less than 0.5 mm above the surface of the carrier, palladium in the alloy is contained in an amount of from 1.5 to 5.0 g/l of catalyst, and the gold is contained in an amount of from 0.5 to 2.25 g/l of catalyst, and (3) from 5 to 60 g of the alkali metal acetate per liter of catalyst. In the US 5185308 described catalyst impregnated with sheath, effective upon receipt of vinyl acetate from ethylene, acetic acid and oxygen-containing gas, and the catalyst essentially comprises (1) a catalyst carrier particle diameter which is from about 3 to about 7 mm, and the specific pore volume is equal to from 0.2 to 1.5 ml/g, (2) palladium, and gold, distributed in the EXT is eating the layer thickness of 1.0 mm particles of the catalyst carrier, and (3) from about 3.5 to about 9.5 wt.% potassium acetate, where the value of the mass ratio between gold and palladium in the above-mentioned catalyst is in the range of from 0.6 to 1.25.

In EP-A 0672453 described palladium catalysts for the conduct of processes of production of vinyl acetate in the fluidized bed and cooking.

According to a third object in the method according to the present invention it is possible to use the catalysts known in the art to obtain alkylcarboxylic. Catalysts, effective upon receipt of alkylcarboxylic that can be used in the second reaction zone may include, for example, catalysts that are described in the application EP-A-0926126, the contents of which are incorporated into this description by reference.

In EP-A-0926126 describes a method for esters placed sequentially in several reactors reaction of ethylene, propylene or mixtures thereof with a saturated aliphatic C1-C4monocarboxylic acid in the presence heteropolyanions catalyst.

The process of obtaining alkenylacyl, such as vinyl acetate, or alkylcarboxylic, such as ethyl acetate, in the second reaction zone is generally carried out in heterogeneous conditions, and the reactants are in the gas phase.

Containing molecular oxygen gas, using the method in the second reaction zone to obtain alkenylacyl, may include a gas containing unreacted molecular oxygen from the oxidation reaction zone and/or additional containing molecular oxygen gas.

Additional containing molecular oxygen gas, if used, may be air or a gas richer or poorer in molecular oxygen than air. Acceptable additional containing molecular oxygen gas may represent, for example oxygen, diluted with a suitable diluent, such as nitrogen, argon or carbon dioxide. Preferred additional containing molecular oxygen gas is oxygen. In a preferred embodiment, at least some part containing molecular oxygen gas is directed to the second reaction zone, regardless of the submission as reagents alkene and carboxylic acid.

The third object of the present invention in a second reaction zone to obtain alkylcarboxylic you that it is not necessary to add water. In case of presence of water in a suitable embodiment are in the form of water vapor and number in the range from 1 to 10 mol % of the total amount of starting material directed to the second reaction zone.

Additional carboxylic acid supplied to the second reaction zone for the teachings of alkenylboronic or alkylcarboxylic, may include fresh acid and/or recycled acid. In a preferred embodiment, at least part of the carboxylic acid introduced into the second reaction zone contains a carboxylic acid derived from the oxidation reaction zone.

Fresh and return in the process carboxylic acid can be injected into the second reaction zone either as separate streams of source materials, either in the form of a single stream of starting materials containing both fresh and recirculated acid.

Recycled carboxylic acid supplied to the second reaction zone to obtain alkenylboronic or alkylcarboxylic may include at least part of the acid obtained in the subsequent processes, in particular in the process of separating the unreacted acid from the second product stream.

At least part of the carboxylic acid, which is directed to the second reaction zone, can be fluid. When the second reaction zone to obtain alkenylboronic use of solid catalysts, alkene, carboxylic acid, all additional alkene or carboxylic acid as reagents, all recycled streams containing molecular oxygen gas in the preferred embodiment, is passed through a second reaction zone at a compound average hourly feed rate g is for (SPG) from 500 to 10000 h -1.

The process of obtaining alkenylboronic in the second reaction zone can be effectively carried out at a temperature in the range from 140 to 200°C.

The process of obtaining alkenylboronic in the second reaction zone can be effectively carried out under a gauge pressure in the range of 50 to 300 psi.

The process of obtaining alkenylboronic in the second reaction zone can be effectively conducted either in a fixed or fluidized bed.

Upon receipt of alkenylboronic in the second reaction zone can be achieved, the degree of conversion of carboxylic acids in the range of from 5 to 80%.

Upon receipt of alkenylboronic in the second reaction zone can be achieved, the degree of conversion of the oxygen in the range from 20 to 100%.

Upon receipt of alkenylboronic in the second reaction zone can be achieved, the degree of conversion of the alkene in the range of from 3 to 100%.

In a suitable embodiment, the second reaction zone can be achieved selectivity in terms of alkene against alkenylsilanes product, such as vinyl acetate, at least 85%, particularly at least 90%.

Acceptable performance of the catalyst upon receipt of alkenylboronic in the second reaction zone is in the range from 10 to 10000 g alkenylboronic/h/is g catalyst.

When the method according to the second object of the present invention use ethane, the product stream withdrawn from the second reaction zone to obtain alkenylacyl, may include vinyl acetate, water and acetic acid, and optionally unreacted ethylene, ethane, oxygen, acetic aldehyde, nitrogen, argon, carbon monoxide and carbon dioxide. This product stream can be divided azeotropic distillation in the upper fraction containing vinyl acetate and water, and the bottom fraction containing acetic acid and water. The bottom fraction away from the base of the distillation column as a liquid bottoms. In addition, one or more steps above the base of the column, you can also take steam. Before this stage distillation from the second product stream can be removed ethylene, ethane, acetaldehyde, carbon monoxide and carbon dioxide if they are reasonable in view of the upper gaseous fraction scrubbing column, from the base of which divert the liquid fraction containing vinyl acetate, water and acetic acid. Carbon monoxide, if present, may be returned to the reaction zone of oxidation. Ethylene and/or ethane can be returned to the oxidation reaction zone and/or the second reaction zone.

The vinyl acetate is recovered from the top of the fraction, for example of appropriate decant the Oia. The selected vinyl acetate can be optionally purified by a known method.

The bottom fraction containing acetic acid and water, after further purification, preferably without treatment, you can return to the second reaction zone. According to another variant of the bottom fraction produce acetic acid, which optionally can be subjected to further purification by a known method, for example by distillation.

When the method according to the second object of the present invention use ethane, in the preferred embodiment, from a stream containing carbon monoxide, exhaust from the oxidation reaction zone (reactor oxidation of ethane) before the reaction of acetic acid and ethylene in the second reaction zone (reactor obtain MVA) produce acetic acid and ethylene. The remaining exhaust stream may, if desired, be processed, for example to remove at least some amount received FROM the2, and returned to the oxidation reaction zone to maintain the amount of carbon monoxide in the original material sent in the above-mentioned reaction zone. The implementation of the method according to the present invention avoids the need for any technological stages of removal of carbon monoxide or decrease required for their implementation mA the staff (for example, as required in the method described in WO01/90042).

In another embodiment, the second object of the present invention at least some amount of carbon monoxide in the exhaust stream from the oxidation reaction zone may be allocated to the second reaction zone to maintain a reasonable amount of carbon monoxide in the original material sent to the second reaction zone. Carbon monoxide, including all the additional carbon monoxide, which can be obtained in the second reaction zone, may be further separated from the second product stream and returned to the oxidation reaction zone to maintain the desired amount of carbon monoxide in the original material submitted to the oxidation reaction zone.

The method according to the present invention is further illustrated by considering the drawings and the examples.

Figure 1 presents a schematic representation of the method of oxidation of ethane and ethylene to acetic acid and ethylene.

Figure 2 presents a schematic representation of the combined method of producing vinyl acetate from ethane and ethylene in accordance with the second object of the present invention.

If we turn to figure 1, the stream (1) raw materials containing fresh ethane and oxygen and optionally water and ethylene, and a recycled stream(2), containing unreacted ethane and carbon monoxide, is fed into the reactor for the oxidation of ethane fluidized bed with acceptable layer of catalyst (3) oxidation to obtain acetic acid and ethylene. The source material contains from 1 to 20 vol.% of carbon monoxide. As a result of the oxidation reaction produces a stream (4) products containing acetic acid, ethane, ethylene, carbon monoxide, carbon dioxide, water and all inert gas, which is contained in the source material and/or recirculated flows. Water and acetic acid to produce acceptable in the first separation means (5), for example in the scrubber, obtaining a gaseous stream (6), containing mainly ethane, ethylene, carbon monoxide and carbon dioxide. Water can be, optionally, removed from acetic acid using a suitable separation means such as distillation. At least some carbon dioxide from a gaseous stream (6) can be deleted in the system (7) removal of CO2for example, using potassium carbonate. Division within an acceptable second separation means (8) of the thread (6) can be allocated at least some amount contained inert gas and a quantity of ethylene, in consequence of which remains in the stream (2)containing the non-is reacting ethane, the carbon monoxide and the remaining inert materials, CO2or ethylene, which is returned to the reactor (3) oxidation of ethane to maintain the required amount of carbon monoxide. In order to prevent the accumulation of inert materials from this recycled flow or from somewhere else can be selected material for cleaning.

2 is in General similar to figure 1, which are therefore used, where appropriate, the same numbering. According to figure 2, in further isolated from the first separation means (5) stream of acetic acid and water and separated from the second separation means (8) stream of ethylene together with oxygen, optional additional acetic acid and/or ethylene demand is sent to the reactor (9) receipt of vinyl acetate, in which they come into contact with a suitable catalyst with the formation of the second product stream containing vinyl acetate. Before the flow of acetic acid and water from the first separation means into the reactor (9) receipt of vinyl acetate with at least part of the above-mentioned stream of acetic acid and water can, optionally, be sent to an acceptable separation means for removing at least part of the contained water, for example in the distillation column. The whole is contained in the second of photocartoon carbon monoxide can be extracted and combined with the recirculated flow (2) for return to the reactor (3) oxidation of ethane fluidized bed. All is contained in the second product stream of unreacted ethylene and acetic acid can be extracted and returned to the reactor (9) receipt of vinyl acetate.

Examples

In guided into the reactor starting material for the oxidation of ethane to acetic acid in various amounts of added carbon monoxide. The source material consisted of 60% vol. ethane, 5% vol. ethylene, 5% vol. water, 6,6% vol. oxygen, the required amount of carbon monoxide, and the rest was accounted for by nitrogen. The source material was passed over a catalyst for the oxidation of ethane at temperatures of about 302, 293 283°C. the Results are presented in the table.

Table
WITH the source material (mol %)Conversion (%)The selectivity (S·mol %)
OxygenEthyleneCOCO2COxAsón
098,0 55,99,9the 3.813,730,4
2,596,852,48,74,413,134,5
597,451,25,06,111,137,6
1096,952,80,77,78,438,8
302°C, gauge pressure 16 bar, 3200/4, 60% ethane, 5% ethylene, 5% water, to 6.6% oxygen, the rest is nitrogen
WITH the source material (mol %) Conversion (%)The selectivity (S·mol %)
OxygenEthyleneCOCO2COxAsón
082,655,39,8the 3.813,631,2
2,579,551,68,34,212,535,8
582,850,3a 4.96,111,0 38,7
1081,554,2-1,38,37,138,8
293°C., a gauge pressure of 16 bar, 3200/4, 60% ethane, 5% ethylene, 5% water, to 6.6% oxygen, the rest is nitrogen
WITH the source material (mol %)Conversion (%)The selectivity (S·mol %)
OxygenEthyleneCOCO2COxAsón
064,550,710,44,114,5 34,8
2,560,153,18,74,112,834,1
563,847,75,06,211,241,1
1061,451,8-2,98,15,243,0
283°C., a gauge pressure of 16 bar, 3200/4, 60% ethane, 5% ethylene, 5% water, to 6.6% oxygen, the rest is nitrogen

These results show that when increasing the amount of CO in the sent into the reactor source material decreases as a result of suppression of the resulting number. Suppression of education is not compensated by an equivalent increase in the formation of CO2x), and improving the selectivity in respect of acetic acid.

These results also show that the point at which education WITH fully suppressed (actually not formed), depends on the temperature oxidation reaction zone. Thus, for complete inhibition of education WITH at a higher temperature requires a higher concentration of carbon monoxide in the original material submitted to the oxidation reaction zone.

1. The method of alkane oxidation with2With4the corresponding alkene and carboxylic acid and/or oxidation of the alkene with2With4obtaining the appropriate carboxylic acid, which involves feeding in the oxidation reaction zone mentioned alkane and/or alkene containing molecular oxygen gas, carbon monoxide, and optionally water, in the presence of a catalyst effective for the oxidation of the alkane to the corresponding alkene and carboxylic acid and/or effective for the oxidation of the alkene to the corresponding carboxylic acid, to obtain a first product stream containing alkene and carboxylic acid, and the oxidation reaction is carried out at a temperature in the range from 100 to 400°C, different t is m, the concentration of the above-mentioned carbon monoxide is maintained within the range of from 1 to 20% of the total volume of the original material submitted to the oxidation reaction zone, in which the method optionally further comprises contacting in a second reaction zone at least part of said alkene and at least part of the mentioned carboxylic acids obtained from the oxidation reaction zone, and contains the molecular oxygen gas in the presence of at least one catalyst effective upon receipt of alkenylacyl, obtaining a second product stream containing alkenylboronic or optional further includes contacting in a second reaction zone at least part of said alkene, at least part of the mentioned carboxylic acids obtained from the oxidation reaction zone, and optionally water, in the presence of at least one catalyst effective upon receipt of alkylcarboxylic, obtaining a second product stream containing alkylcarboxylic.

2. The method according to claim 1, in which carbon monoxide is sent to the oxidation reaction zone in the form of fresh gas and/or recycle gas.

3. The method according to claim 1, wherein the first product stream contains carbon monoxide.

4. The method according to claim 3, in which at least 90% is onoxide carbon contained in the first product stream, a recycle to the oxidation reaction zone.

5. The method according to claim 1, wherein the second product stream contains alkenylacyl and carbon monoxide.

6. The method according to claim 5, in which the carbon monoxide is separated from the second product stream and recycled to the oxidation reaction zone.

7. The method according to claim 1, in which the number of carbon monoxide in the source material (in the form of fresh and/or recycle gas) support at the level of more than 2.5% of the total volume of the source material.

8. The method according to claim 7, in which the number of carbon monoxide is maintained at the level of more than 5% of the total volume of the source material.

9. The method according to claim 7, in which the number of carbon monoxide support in the range of from more than 5 to 20% of the total volume of the source material.

10. The method according to claim 7, in which the number of carbon monoxide support in the range of from more than 5 to 15% of the total volume of the source material.

11. The method according to claim 1, in which the number of carbon monoxide in the source material (in the form of fresh and/or recycle gas) support at the level of less than 15% of the total volume of the source material.

12. The method according to claim 11, in which the number of carbon monoxide support in the range of from more than 5 to less than 15% of the total volume of the source material.

13. The method according to claim 11, in to the m number of carbon monoxide support in the range of from more than 5 to 10% of the total volume of the source material.

14. The method according to claim 1, in which2-C4alkane is a ethane, alkene with C2C4represents ethylene and the carboxylic acid is an acetic acid.

15. The method according to claim 1, wherein in the oxidation reaction zone serves ethane and ethylene.

16. The method according to claim 1, in which each of alkane and alkene sent to the oxidation reaction zone in the form of fresh source material and/or recycled component.

17. The method according to claim 1, in which the concentration of the alkane (in the form of fresh source material and the recycled component) is from 0 to 90 mol.% of the total amount of starting material sent to the oxidation reaction zone.

18. The method according to claim 1, in which the concentration of alkene (in the form of fresh source material and the recycled component) is from 0 to 50 mol.% of the total amount of starting material sent to the oxidation reaction zone.

19. The method according to claim 1, in which the water is directed to the oxidation zone in the form of fresh source material and/or recycled component in a concentration in the range of from more than 0 to 50 mol.% of the total amount of starting material.

20. The method according to claim 1, in which the molar ratio of alkene to carboxylic acid in the first product stream is approximately 1:1.

21. The method according to claim 1, in kotorayarabotaet is a vinyl acetate.

22. The method according to claim 1, wherein the second reaction zone send additional alkene and/or additional carboxylic acid.

23. The method according to claim 1, in which the concentration of alkene sent to the oxidation reaction zone is less than 20 mol.% of the total amount of starting material and/or the concentration of alkene directed to the second reaction zone is more than 50 mol.% of the total amount of starting material.

24. The method according to claim 1, in which the concentration of alkene directed to the second reaction zone to produce in her alkenylboronic is at least 60 mol.% of the total amount of starting material.

25. The method according to item 23 or 24, in which the alkene is an ethylene.

26. The method according to claim 1, wherein the second reaction zone to produce in her alkenylboronic is a reactor with a fixed bed or fluidized bed.

27. The method according to claim 1, in which alkylcarboxylic represents the ethyl acetate.

28. The method according to claim 1 or 27, in which the water is directed to the second reaction zone in an amount in the range from 1 to 10 mol.% of the total amount of starting material.

29. The method according to claim 1, in which the total amount of inert impurities contained in the alkene and/or alkane sent to the oxidation reactor is in the range from 0 to 3%vol.

30. The method according to claim 1, in which oterom the total number of reactive impurities, contained in the alkene and/or alkane sent to the oxidation reactor is in the range from 0 to 10 vol.%.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to improved method of producing methanol, acetic acid and optionally vinyl acetate, which includes integrated stages: separation of hydrocarbons source into first and second hydrocarbons flows; vapour reforming of first hydrocarbons flow with vapour in order to obtain subjected to reforming flow; autothermal reforming of mixture of subjected to reforming flow and second hydrocarbons flow with oxygen and carbon dioxide in order to obtain synthesis-gas flow; separation of smaller part of synthesis-gas flow into flow with higher carbon dioxide content, flow with higher hydrogen content and flow with higher content of carbon oxide; recirculation of flow with higher carbon dioxide content to autothermal reforming; compression of remaining part of synthesis-gas flow, CO2 flow, not necessarily from associated process, and at least part of flow with higher hydrogen content for supplying feeding flow to circuit of methanol synthesis in order to obtain methanol product, whose stoichiometric coefficient is determined as [(H2-CO2)/(CO+CO2)], and stoichiometric coefficient of feeding flow constitutes from 2.0 to 2.1; acetic acid synthesis from at least part pf methanol product and flow with higher content of carbon oxide, and optionally synthesis of vinyl acetate from at least part of synthesised acetic acid.

EFFECT: elaboration of improved method of producing methanol, acetic acid, characterised by highly economical indices and low intensity of CO2 emission.

23 cl, 2 ex, 2 dwg

FIELD: chemistry.

SUBSTANCE: reaction of alkene with molecular oxygen is carried out in reactor with pseudoliquefied layer in presence of catalytically active pseudoliquefied layer of solid particles, which lies in the following: gas, containing molecular oxygen, concentration of oxygen in which exceeds its concentration in air, is introduced into pseudoliquefied layer simultaneously supporting turbulent mode in pseudoliquefied layer. Invention also relates to method of obtaining vinylacetate by reaction of ethylene and acetic acid with molecular oxygen in reactor with pseudoliquefied layer in presence of catalytically active pseudoliquefied layer of solid particles, which have diameter in range from 20 to 300 mcm, distribution according to particle diameter constitutes at least 20 mcm; at to method of carrying out reaction of molecular oxygen with ethane, ethylene or their mixture obtaining acetic acid and optionally ethylene in reactor with pseudoliquefied layer in presence of catalytically active pseudoliquefied layer of solid particles.

EFFECT: elaboration of safer method of carrying out reaction.

45 cl, 2 tbl, 3 ex,4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to method of oxidising alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acids. The method includes the following stages: (a) contact in the oxidation reaction zone of the alkane, which contains molecular oxygen gas, not necessarily corresponding to the alkene and not necessarily water in the presence of at least one catalyst, effective with the oxidation of the alkane to the corresponding alkene and carboxylic acid, alkane, oxygen and water; (b) separation in the first separating agent at least part of the first stream of products in a gaseous stream, which includes alkene, alkane and oxygen, and a liquid stream, which includes carboxylic acid; (c) contact of the mentioned gaseous stream with the solution of a salt of metal, capable of selectively chemically absorbing alkene, with the formation of a liquid stream rich in chemically absorbed alkene; (d) isolation from the flow of the solution of salt of the metal. The invention also relates to combined methods of obtaining alkyl-carboxylate or alkenyl-carboxylate (for example vinyl acetate), moreover these methods include oxidising of alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acid, isolation of alkene from the mixture of alkene, alkane and oxygen by absorption using the solution of the salt of metal and extraction of the stream rich in alkene from the solution of the salt from metal for using when obtaining alkyl-carboxylate and alkenyl-carboxylate.

EFFECT: improved method of oxidising alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acids.

46 cl, 1 dwg

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to a process for production of C2-C4-alkane into alkene and carboxylic acid and immediately using them in ester synthesis stage. According to invention, to produce alkyl carboxylate, in particular ethyl acetate, or alkenyl carboxylate, in particular vinyl acetate, stage wherein alkane is oxidized to corresponding alkene and carboxylic acid is combined with alkenyl carboxylate or alkyl carboxylate production stage. Process comprises contacting of alkane- and alkene-containing gas raw material with molecular oxygen and catalyst in the first oxidation reaction zone, catalyst being efficient in oxidation of alkane into corresponding alkene and carboxylic acid. In the second reaction zone, part of streams isolated in separation stage and enriched with alkene and carboxylic acid is brought into contact with at least one catalyst efficient to produce either alkyl carboxylate or alkenyl carboxylate in presence of oxygen-containing gas. For example, first product stream consists of ethylene and acetic acid with water admixture. In the second reaction zone, stream enriched with alkene and carboxylic acid comes into contact with oxygen, optionally in presence of additional amount of ethylene and/or acetic acid from the first product stream. As a result, second product stream comprising vinyl acetate, water, acetic acid, and optionally small amounts of carbon oxides is obtained. Second product stream is separated into fractions containing vinyl acetate and acetic acid, which are subjected to further purification. In a cycle wherein acetic acid from main fraction is regenerated, the latter is recycled to vinyl acetate stage in the second reaction zone.

EFFECT: improved economical efficiency of process.

36 cl, 1 dwg

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for oxidation of (C2-C4)-alkane and preparing the corresponding alkene and carboxylic acid. Method involves addition of this alkane to contact with molecular oxygen-containing gas in oxidative reaction zone and optionally at least one corresponding alkene and water in the presence of at least two catalysts with different selectivity. Each catalyst is effective in oxidation of alkane to corresponding alkene and carboxylic acid resulting to formation of product comprising alkene, carboxylic acid and water wherein the molar ratio between alkene and carboxylic acid synthesized in the reaction zone is regulated or maintained at the required level by regulation the relative amounts of at least two catalyst in the oxidative reaction zone. Also, invention relates to the combined method for preparing alkyl carboxylate comprising abovementioned stage in preparing alkene and carboxylic acid in the first reaction zone. Then method involves the stage for addition of at least part of each alkene and carboxylic acid prepared in the first reaction zone to the inter-contacting in the second reaction zone the presence of at least one catalyst that is effective in preparing alkyl carboxylate to yield this alkyl carboxylate. Also, invention relates to a method for preparing alkenyl carboxylate comprising the abovementioned stage for preparing alkene and carboxylic acid in the first reaction zone and stage for inter-contacting in the second reaction zone of at least part of each alkene and carboxylic acid synthesized in the first reaction zone and molecular oxygen-containing gas in the presence of at least one catalyst that is effective in preparing alkenyl carboxylate and resulting to preparing this alkenyl carboxylate.

EFFECT: improved method for oxidation.

30 cl, 1 dwg, 5 tbl, 14 ex

FIELD: petrochemical processes.

SUBSTANCE: invention relates to improved C2-C4-alkane oxidation process to produce corresponding alkene and carboxylic acid, which process comprises bringing indicated alkane in oxidation reaction zone into contact with molecular oxygen-containing gas and corresponding alkene and optionally with water in presence of at least one catalyst efficient for oxidation of alkane into corresponding alkene and carboxylic acid. Resulting product contains alkene, carboxylic acid, and water, wherein alkene-to-carboxylic acid molar ratio in oxidation reaction zone is controlled or maintained at desired level by way of controlling alkene and optional water concentrations in oxidation reaction zone and also, optionally, controlling one or several from following parameters: pressure, temperature, and residence time in oxidation reaction zone. Invention also relates to integrated process of producing alkyl carboxylate including above-indicated stage of producing alkene and carboxylic acid in first reaction zone and stage of bringing, in second reaction zone, at least part of each of alkene and carboxylic acid obtained in first reaction zone in contact with each other in presence of at least one catalyst effective in production of alkyl carboxylate to produce the same. Invention further relates to production of alkenyl carboxylate including above-indicated stage of producing alkene and carboxylic acid in first reaction zone and stage of bringing, in second reaction zone, at least part of each of alkene and carboxylic acid obtained in first reaction zone plus molecular oxygen-containing gas into contact with each other in presence of at least one catalyst effective in production of alkenyl carboxylate to produce the same.

EFFECT: enhanced process efficiency.

55 cl, 1 dwg, 7 tbl, 22 ex

FIELD: vinyl acetate production by ethane catalytic acetoxylation with acetic acid obtained as intermediate.

SUBSTANCE: claimed method includes: a) bringing gaseous raw material, containing ethane as a main component, into contact in the first reaction zone with molecular oxygen-containing gas in presence of catalyst to obtain the first product stream including acetic acid and ethylene; b) bringing the said first product stream in second reaction zone with molecular oxygen-containing gas in presence of catalyst to obtain the second product stream including vinyl acetate; c) separation the second product stream from stage b) to recovery of vinyl acetate. In the first reaction zone catalyst of general formula MOaPdbXcYd is used, wherein X is at least one element selected from Ti, V, and W; Y is at least one element selected from Al, Bi, Cu, Ag, Au, K, Rb, Cs, Mg, Ca, Sr, Ba, Nb, Sb, Si, and Sn; a, b, c, and d are gram-atom ratio, and a = 1; b = 0.0001-0.01, preferably 0.0001-0.005; c = 0.4-1, preferably 0.5-0.8; and d = 0.005-1, preferably 0.01-0.3. Gaseous raw material from step a) preferably includes ethane and molecular oxygen-containing gas in volume ratio of ethane/oxygen between 1:1 and 10:1, and 0-50 % of vapor as calculated to total volume of starting raw material. Ratio of selectivity to ethylene and selectivity to acetic acid in the first product stream is 0:95-95:0.

EFFECT: integrated technological cycle with controllable product yield while changing technological parameters of the process.

6 cl, 11 ex, 2 tbl, 1 dwg

The invention relates to a method for the synthesis of vinyl acetate in industrial scale

The invention relates to a catalyst for the receipt of vinyl acetate in the fluidized bed

The invention relates to the production of acetic acid

FIELD: chemistry.

SUBSTANCE: invention relates to improved method of producing methanol, acetic acid and optionally vinyl acetate, which includes integrated stages: separation of hydrocarbons source into first and second hydrocarbons flows; vapour reforming of first hydrocarbons flow with vapour in order to obtain subjected to reforming flow; autothermal reforming of mixture of subjected to reforming flow and second hydrocarbons flow with oxygen and carbon dioxide in order to obtain synthesis-gas flow; separation of smaller part of synthesis-gas flow into flow with higher carbon dioxide content, flow with higher hydrogen content and flow with higher content of carbon oxide; recirculation of flow with higher carbon dioxide content to autothermal reforming; compression of remaining part of synthesis-gas flow, CO2 flow, not necessarily from associated process, and at least part of flow with higher hydrogen content for supplying feeding flow to circuit of methanol synthesis in order to obtain methanol product, whose stoichiometric coefficient is determined as [(H2-CO2)/(CO+CO2)], and stoichiometric coefficient of feeding flow constitutes from 2.0 to 2.1; acetic acid synthesis from at least part pf methanol product and flow with higher content of carbon oxide, and optionally synthesis of vinyl acetate from at least part of synthesised acetic acid.

EFFECT: elaboration of improved method of producing methanol, acetic acid, characterised by highly economical indices and low intensity of CO2 emission.

23 cl, 2 ex, 2 dwg

FIELD: chemistry.

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

EFFECT: enhanced carbonylation speed and selectivity.

36 cl, 6 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention claims method of preparation of catalytic composition applied onto a carrier and acceptable for ethane and/or ethylene oxidation to acetic acid, where catalytic composition applied onto carrier includes catalyst of one or more metal components, on a carrier with aluminium alpha-oxide. Method involves the following stages: (a) preparation of suspension of one or more metal components and aluminium alpha-oxide carrier or carrier precedent particles, (b) dispersion drying of suspension, and optionally (c) calcination of dispersion-dried suspension to obtain catalytic composition applied onto carrier. Invention also claims catalytic composition applied onto carrier and obtained by the claimed method, and method of selective ethane and/or ethylene oxidation to acetic acid using the catalytic composition applied onto carrier.

EFFECT: high selectivity of target products and reduced COX generation.

44 cl, 2 tbl, 1 dwg, 3 ex

FIELD: chemistry.

SUBSTANCE: reaction of alkene with molecular oxygen is carried out in reactor with pseudoliquefied layer in presence of catalytically active pseudoliquefied layer of solid particles, which lies in the following: gas, containing molecular oxygen, concentration of oxygen in which exceeds its concentration in air, is introduced into pseudoliquefied layer simultaneously supporting turbulent mode in pseudoliquefied layer. Invention also relates to method of obtaining vinylacetate by reaction of ethylene and acetic acid with molecular oxygen in reactor with pseudoliquefied layer in presence of catalytically active pseudoliquefied layer of solid particles, which have diameter in range from 20 to 300 mcm, distribution according to particle diameter constitutes at least 20 mcm; at to method of carrying out reaction of molecular oxygen with ethane, ethylene or their mixture obtaining acetic acid and optionally ethylene in reactor with pseudoliquefied layer in presence of catalytically active pseudoliquefied layer of solid particles.

EFFECT: elaboration of safer method of carrying out reaction.

45 cl, 2 tbl, 3 ex,4 dwg

FIELD: chemistry.

SUBSTANCE: improved is method of obtaining acetic acid by means of carbonilation of methanol and/or its reaction-able derivative with carbon monoxide in carbonilation reaction zone, which contains liquid reaction medium, including iridium carbonilation catalyst, methyliodide co-catalyst, amount of water within range from 0.1 to 20 wt %, acetic acid, methylacetate, at least one promoter - ruthenium, and stabilising compound, selected from group, which consists of alkali metal iodides, alkali-earth metal iodides, metal complexes, able to generate ions I-, salts, able to generate I-, and mixtures of two or more such compounds, molar ratio of promoter to iridium being more than 2 up to 15:1, and molar ratio of stabilising compound to iridium is within range (from more than 0 to 5):1, and where method includes additional stages: a) from said carbonilation reaction zone liquid reaction medium with dissolved and/or carried along carbon monoxide and other gases is drained; b) said drained liquid reaction medium is not obligatory passed through one or several additional reaction zones in order to convert at least part of dissolved and/or carried along carbon monoxide; c) said liquid reaction medium from stage (a) and stage (b) is passed in one or several stages of fast evaporation, in order to form (i) vapour fraction, including condensing components and waste low pressure gas, condensing components contain obtained acetic acid and waste low pressure gas, which contains carbon monoxide and other gases, dissolved and/or carried along with drained liquid reaction medium, and (ii) liquid fraction, including iridium carbonilation catalyst, promoter and acetic acid as solvent; d) from waste low pressure gas condensing components are separated; and e) liquid fraction from stage of fast evaporation is recirculated into carbonilation reactor.

EFFECT: method allows to prevent or reduce loss of catalyst and promoter.

14 cl, 7 tbl, 2 dwg, 32 ex

FIELD: chemistry.

SUBSTANCE: catalytic system for obtaining acetic acid includes iridium carbonilation catalyst, methyliodide co-catalyst, non-obligatory, at least one of the following elements: ruthenium, osmium, rhenium, zinc, gallium, tungsten, cadmium, mercury and indium, ant, at least, one promoter - non-halogenohydrogen acid. Non-halogenohydrogen acid can represent oxo-acid, superacid and/or hateropolyacid. Method of obtaining acetic acid by reaction of carbon monoxide with methanol and/or its reaction-able derivative in liquid reaction composition, which includes methylacetate, water in limited concentration, acetic acid and said catalytic system, is described. Application of catalytic system for obtaining acetic acid is described.

EFFECT: increasing rate of carbonilation.

27 cl, 5 tbl, 20 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of oxidising alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acids. The method includes the following stages: (a) contact in the oxidation reaction zone of the alkane, which contains molecular oxygen gas, not necessarily corresponding to the alkene and not necessarily water in the presence of at least one catalyst, effective with the oxidation of the alkane to the corresponding alkene and carboxylic acid, alkane, oxygen and water; (b) separation in the first separating agent at least part of the first stream of products in a gaseous stream, which includes alkene, alkane and oxygen, and a liquid stream, which includes carboxylic acid; (c) contact of the mentioned gaseous stream with the solution of a salt of metal, capable of selectively chemically absorbing alkene, with the formation of a liquid stream rich in chemically absorbed alkene; (d) isolation from the flow of the solution of salt of the metal. The invention also relates to combined methods of obtaining alkyl-carboxylate or alkenyl-carboxylate (for example vinyl acetate), moreover these methods include oxidising of alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acid, isolation of alkene from the mixture of alkene, alkane and oxygen by absorption using the solution of the salt of metal and extraction of the stream rich in alkene from the solution of the salt from metal for using when obtaining alkyl-carboxylate and alkenyl-carboxylate.

EFFECT: improved method of oxidising alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acids.

46 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention pertains to perfection of the method of obtaining acetic acid with rate of volume flow of at least 15g-mol/l/h, a catalytic carbonylation reaction, involving reaction of a compound, chosen from a group containing methanol, methyliodide, methylacetate, dimethyl ether, or their combination, in the presence of carbon monoxide and a catalyst system based on rhodium in a reaction mixture, where the reaction mixture consists of not less than 2.0% mass, water, metal, in concentration of at least 1000 h/million, chosen from a group containing rhodium and a combination of rhodium and iridium, iodide ion in concentration from 2 to 20% weight, and a halogen promoter, chosen from a group, containing halogen-hydrogen, alkyliodide, iodine salt or acetate salt of a group IA metal, group II metal, quatanary ammonium salt, phosphoric acid salt, or their combination in concentration from 2.0% mass to 30.0% mass. The method is used for attaining reaction speed of at least 15 g-mol/l/h. The invention also pertains to the method of obtaining acetic acid from a carbonylation reaction in a system, consisting of a reaction zone and a cleaning zone, and involves the following stages: (a) reaction of methanol, methyliodide, metylacetate, dimethyl ether or their combination with carbon monoxide in the presence of a catalyst system based on rhodium in a reaction mixture, with water content from 0.1% mass to 5.0% mass, iodide ion in concentration from 2 to 20% mass, and a halogen promoter, chosen from a group, containing halogen-hydrogen, alkyliodide, iodine salt or an acetate salt of a group IA metal, group IIA metal, quaternary salt of ammonia, phosphoric acid salt or their combination, in concentration from 2.0% mass to 30.0% mass, and (b) putting a compound, chosen from a group, consisting of methylacetate, dimethyl simple ether, acetic anhydride and their mixture in the reaction zone.

EFFECT: perfection of the method of obtaining acetic acid.

26 cl, 1 dwg, 4 ex, 1 tbl

FIELD: chemical technology.

SUBSTANCE: invention relates to technology for synthesis of acetic acid by carbonylation of methanol. Method for synthesis of acetic acid is carried out by the carbonylation reaction of methanol and/or its reactive derivative in one or some reactors in the liquid reactive composition comprising iridium catalyst for the carbonylation reaction, ruthenium promoter, methyl iodide co-catalyst, methyl acetate, acetic acid and water. Liquid reactive composition from one or some reactors is fed for one or some separation steps by a single equilibrium evaporation to yield (I) vapor fraction containing component able to condensing and exhausting gas of low pressure containing carbon monoxide, and (II) liquid fraction containing iridium catalyst for the carbonylation reaction, ruthenium promoter and acetic acid as a solvent. Components able for condensing are isolated from exhausting gas of low pressure. The concentration of carbon monoxide in exhausting gas is maintained according to the formula: Y > mX + C wherein Y means the molar concentration of carbon monoxide in exhausting gas of low pressure; X means the concentration of ruthenium in the liquid reactive composition as ppm; m means about 0.012, and C means about -8.7. The concentration of carbon monoxide in exhausting gas of low pressure is in the range from 55 to 65 mole%, and the concentration of ruthenium in the liquid reactive composition is up to 5500 ppm. Method provides decreasing loss of the catalyst components at step for isolation of acetic acid based on enhancing stability of the catalytic system.

EFFECT: improved method of synthesis.

29 cl, 6 tbl, 2 dwg, 34 ex

FIELD: chemical industry; other industries; methods and devices for production of acetic acid.

SUBSTANCE: invention is pertaining to the production process of the acetic acid by carbonylation of methanol by carbon monoxide in the bubble reactor with fluidized heterogeneous catalyst. Carbonylation reaction is conducted at concentration of the solid catalyst of no less than 100 kg/m3 in terms of the volume of the reaction system. Catalyst is formed with the help vinylpyridine resin with the complex of rhodium deposited on it. Partial pressure of the carbon monoxide in the reactor is between 1.0 and 2.5 MPa, at that the degree of exhaustion of carbon monoxide is between 3 and 15 % of the theoretical reaction volume of carbon monoxide and reduced speed of the liquid is in the interval between 0.2 and 1.0 m/s. Promoter is methyl iodide, and acetic acid and methyl acetate are used in the capacity of the dissolvent. Concentration of water in the reactor makes from 2 up to 10 mass %. The bubble cylindrical reactor column used for realization of the method has the ratio its length L to the diameter D of no less than 8 and is equipped with the external line of circulation and the heat exchanger, which is built in the line of circulation. Besides, the bubble column has the holes used for injection of carbon monoxide, which are located at least on two levels, and also has the narrowed section in the lower part of the cylindrical reactor with the inner diameter from 30 up to 70 % from the rest part of the cylindrical reactor. The hole for injection of carbon monoxide is located in the upper part of the narrowed section for fluidization of the solid catalyst, while other hole for injection of carbon monoxide is located near to the coupling of the reactor and the outer line of circulation located on the bottom of the narrow section for separation and fluidization of the solid catalyst in the outer line of circulation. Technical result of the invention is improvement of the technological form of the production process with the increased yield of the end product.

EFFECT: invention ensures improvement of the technological form of the production process with the increased yield of the end product.

22 cl, 4 tbl, 4 dwg

FIELD: chemistry.

SUBSTANCE: present invention relates to an improved method of producing at least one product of partial oxidation and/or ammoxidation of a hydrocarbon, chosen from a group containing acrolein, acrylic acid, methacrolen, methacrylic acid, acrylonitrile and methacrylonitrile. At least one saturated hydrocarbon is subjected to heterogeneous catalysed dehydrogenation in a gas phase, obtaining a gas mixture, containing at least one partially dehydrogenated hydrocarbon. Components of the gas mixture except saturated hydrocarbon and partially dehydrogenated hydrocarbon are left in the mixture. Alternatively, the extra gas mixture obtained is partially or completely separated, and the gas mixture and/or extra gas mixture are used for obtaining another gas mixture, containing molecular oxygen and/or molecular oxygen and ammonia. This gas mixture is subjected to at least single heterogeneous catalysed partial oxidation and/or ammoxidation of at least one partially dehydrogenated hydrocarbon contained in the gas mixture and/or extra gas mixture. The gas mixture, extra gas mixture and/or the other gas mixture, before at least one partial heterogeneous catalysed oxidation and/or ammoxidation, are subjected to at least a single mechanical separation, aimed at separating particles of solid substance contained in the above mentioned gas mixtures.

EFFECT: reliable and continuous realisation of the process for relatively long periods of time.

6 cl, 1 ex

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