Method of producing methanol, dimethyl ether and low-carbon olefins from synthesis gas

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing methanol, dimethyl ether and low-carbon olefin from synthesis gas. The method includes a step of contacting synthesis gas with a catalyst under conditions for converting the synthesis gas into methanol, dimethyl ether, and low-carbon olefins, characterised, wherein the catalyst contains an amorphous alloy consisting of components M-P, M-B or M-B-P, wherein component M represents two or more elements selected from lanthanides and the third, fourth and fifth series of groups IIIA, IVA, VA, IB, IIB, IVB, VB, VIB, VIIB and VIII of the Periodic Table of Elements.

EFFECT: method increases selectivity of the target product by conducting the process in conditions which ensure high conversion of CO and availability of carbon.

16 cl, 3 dwg, 3 tbl, 11 ex

 

The technical field

The invention relates to a process for the production of methanol, dimethyl ether, and low carbon olefins from synthesis gas.

BACKGROUND of INVENTION

The methanol synthesis is an important process in chemical technology. Currently, the catalyst Cu-Zn-Al is the main component of the widely used industrial catalyst for methanol synthesis at low pressure. Basically, it is prepared by the coprecipitation method, and the catalyst is a mixture of copper, zinc, and oxides of aluminum. For example, U.S. patent 4436833 reveals the coprecipitation method comprising mixing a solution of copper, zinc and aluminum nitrate with sodium carbonate as agent deposition to form a precipitate carbon, then sodium ions are washed with distilled water, and the precipitate is dried and made red-hot residue, to obtain a mixture of copper, zinc, and oxides of aluminum for the catalytic synthesis of methanol. However, this catalyst has the disadvantage that it is difficult to wash off the sodium ions and to adjust the temperature in the recovery process, which significantly reduces the catalyst activity.

In U.S. patent 4366260 disclosed a method for the production of methanol or mixtures of methanol and dimethyl ether. The catalyst used in this method, copper is a catalyst of Raney to the th obtained from the alloy, containing from 35 to 60% by weight of aluminum, from 0.1 to 25% by weight of zinc and the remainder mainly in the form of copper. Specialists in this field it is known that the copper alloy catalyst of Raney - crystalline alloy. The yield of methanol under the action of the catalyst under the reaction conditions suitable for the production of methanol from synthesis gas is relatively low (only 10,9%).

Dimethyl ether (DME) is a widely used, environmentally friendly, ultra-pure product - substitute automobile and household fuel. There are basically two ways to produce dimethyl ether: single-stage and two-stage. A two-step method consists in the synthesis of methanol from synthesis gas, followed by dehydration to obtain dimethyl ether. Single-stage method involves synthesis of dimethyl ether from the original raw synthesis gas for one stage and contains three stages of reaction, which are interdependent, are as follows:

CO+2CH3OH(1)

2CH3OHCH 3OCH3+H2O(2)

CO+H2OCO2+H2(3)

Although all three reactions are reversible, the whole process of the reaction can continue in a state that deviates from thermodynamic equilibrium, because the products from each reaction stage is spent in the following reaction. Therefore, compared with only reaction of methanol synthesis conditions for the reaction of synthesis of dimethyl ether directly from synthesis gas are much more moderate, and single-stage conversion is much more efficient. Compared with two-way, single-stage method for the synthesis of dimethyl ether is performed without intermediate procedure for the synthesis of methanol, and it has the advantage of a simpler process, with the least amount of equipment and requires less production and operating costs. Thus, the single-stage method for the synthesis of dimethyl ether is very interesting for research and commercial developments in many of the x countries. System catalysts for one-step synthesis of dimethyl ether, in General, a physical mixture of catalyst for synthesis of methanol and catalyst for dehydration of methanol. Industrial catalyst for methanol synthesis, mainly contains one or more atoms of Cu, Zn, Al and Cr, and specialists in this field it is known that the catalyst is a crystalline alloy, while the catalyst for the dehydration of methanol, mostly selected from solid acidic materials.

U.S. patent 5389689 discloses the preparation method of catalyst for dimethyl ether in one stage, comprising spraying a mixture containing zinc oxide, copper oxide or chromium oxide and aluminum oxide with a particle size of from about 0.1 to 20 μm, the compression pressure of 100-500 kg/cm2to compress the oxides in a single mass, weighing in solvent with repeated spraying of liquid sludge, to obtain from him the catalyst. Reaction conditions include a molar ratio of H2/CO equal to one, the reaction temperature 280°C and pressure of the reaction of 3 MPa; the degree of conversion is WITH 60.1 percent, the yield of dimethyl ether is 42.8% and output CO2is 14.4%. The catalyst for dimethyl ether has a low activity, the desired temperature is relatively high, and the converting video WITH is relatively low. In addition, approximately one third WITH converted into useless CO2due to the low activity of the catalyst during dehydration. During the reaction there are other side reactions, leading to reduction of the carbon for the reaction, mainly to 60% and below. The reaction less efficient.

Light olefins, mainly related to ethylene and propylene are very important raw material for chemical production. Currently, more than 90% of light olefins produced by the cracking of light oil. However, the suggestion of light olefins does not meet the needs of the market. Due to the development of the economy and the increasing shortage of oil, it is absolutely necessary to find a replacement source of light olefins. The technique directly to the production of olefins from synthesis gas derived from traditional synthesis F-t As a carbon number of product obtained from the synthesis of F-T catalyst, followed by the distribution of S-T, selectivity lower carbon olefins is low. Preparation of catalysts having a high activity and selectivity is of great interest to modern scholars.

Patent CN 1065026 discloses A catalyst for producing ethylene from synthesis gas. The catalyst contains one oxide of element selected from Cu, Al, Ti, Nb and Hf, one or two oxides selected item is CSO of Nb, Y, Ga, Ge, In, and TL, one or more oxides of an element selected from Sn, Pb, Sc, La, Pr, CE and Nd, and is prepared by a process comprising impregnation, coprecipitation, mechanical mixing, the stirring of the suspension, the combination of impregnation and coprecipitation or mechanical mixing and impregnation. Although the selectivity of ethylene can be up to 94%when the catalyst is used for the production of ethylene from synthesis gas, the conversion is only 15%.

Patent CN 1390640A reveals nano-copper catalyst for synthesis of methanol or dimethyl ether and the method of its preparation. The catalyst consists of a metal of copper, ZnO, alumina, etc. and the molar ratio of these components: 30-60% copper, 60-30% zinc: 10-15% Al. Nano-copper has a particle size of from 2 to 10 nm and dispersed around the ZnO-oxide-aluminum. The catalyst is prepared by forming a liquid solution containing the components Cu, Zn and Al, a coprecipitation method; and then direct reaction liquid solution Coosada with a reducing agent to recover the copper; the reducing agent remains in solution as oxidized si2+and C2+composite component size in one millimicron restored, and the resulting crystalline elemental copper millimicron size is distributed on the carrier; then the precipitate is filtered by suction, washed and dried under WAC the mind; in conclusion, the product tabletroute or made red-hot in inert gas or under vacuum at 250-400°C. to obtain the catalyst. However, the yield of methanol or dimethyl ether synthesis using the catalyst, is relatively low. For example, the yield of methanol at 240°C is only 6.5%. In addition, the catalyst must be subjected to a complicated and time-consuming process of the provisional restoration before it can be used in the synthesis process.

DISCLOSURE of INVENTIONS

The present invention aims to overcome the shortcomings of low levels of conversion, selectivity of the target product and the availability of carbon from a previous preparation of methanol, dimethyl ether and/or lower carbon olefins from synthesis gas and to provide a process for the production of methanol, dimethyl ether and/or lower carbon olefins from synthesis gas with high conversion and good selectivity of the target product and the availability of carbon.

The present invention provides a process for the production of methanol, dimethyl ether, and low carbon olefins from synthesis gas, while the specified process includes a stage of contact of synthesis gas with a catalyst under conditions that promote conversion of synthesis gas to methanol, dimethyl ether and noscope odity olefin, characterized in that the catalyst contains an amorphous alloy consisting of components M and X, in which the component X is an element of B (boron) and/or the element P (phosphorus), and the component M contains two or more elements selected from groups IA, IIIA, IVA, VA, IB, IIB, IVB, VB, VIB, VIIB and VIII, and a number of lanthanides of the periodic table of elements.

In the inventive process for the production of methanol, dimethyl ether, and low carbon olefins from synthesis gas, is used a catalyst containing amorphous alloy consisting of component b and/or P, and two or more elements selected from groups IA, IIIA, IVA, VA, IB, IIB, IVB, VB, VIB, VIIB and VIII, and some of the lanthanides of the periodic table of the elements, resulting in a very high conversion, selectivity of the target product and the availability of carbon.

DESCRIPTION of FIGURES

Figures 1-3 are the XRD spectrum of the alloys prepared according to examples and comparative examples of the invention.

The term "synthesis gas" means a gaseous mixture of raw materials containing CO and H2as the main components. The synthesis gas is mainly extracted from the solid raw materials (coal, coke), liquid raw materials (light oil, crude oil) and gaseous raw materials (natural gas, associated gas). For example, synthesis gas may be one or more gases selected from the coke oven gases, liquefied gases, Wodan the x gases, poluvagonah gases, natural gas and associated gas from oil fields.

The present invention provides a process for the production of methanol, dimethyl ether and/or low carbon olefins from synthesis gas, which process includes the stage of contact of synthesis gas with a catalyst under conditions that promote conversion of synthesis gas to methanol, dimethyl ether and/or low carbon olefin, wherein the catalyst contains an amorphous alloy consisting of components b and X, with the specified component X is an element And/or P, and the component M represents two or more elements selected from groups IA, IIIA, IVA, VA, IB, IIB, IVB, VB, VIB, VIIB and VIII, and some of the lanthanides of the periodic table of elements.

According to the process of the present invention, preferably, the molar ratio between the component M and the component X in the amorphous alloy is equal to or more than 0.1, more preferably equal to or more than 0.05 and most preferably equal to or more than 0.2, but equal to or less than 15, more preferably equal to or less than 10 and most preferably M is equal to or less than 5.

According to the process of the present invention, it is preferable that the specified component M represents two or more elements selected from a number of lanthanides and tert what it the fourth and fifth rows of groups IIIA, IVA, VA, IB, IIB, IVB, VB, VIB, VIIB and VIII of the periodic table of elements, more preferably two or more elements selected from si, Zn, V, Cr, Mn, Fe, Co, Ni, Zr, Mo, Sn, S, Si, La, and R. In some preferred examples of embodiment, the specified component M contains si. In some preferred examples of embodiment of the specified component M contains si and Zn. In some example embodiments, the component M excludes Al.

According to the process of the present invention, the amorphous alloy represented by M-X can be M-R, M-or an amorphous alloy M In p case M-b-R, the molar ratio between V and R preferably from 0.05 to 3. Components in the amorphous alloy may be present in pure amorphous state or in the form of a mixture of amorphous and microcrystalline alloys and/or crystalline alloys (i.e., the portion of the alloy is in an amorphous state), in which microcrystalline and crystalline alloys are present in a total amount of preferably less than 30% of the total weight of the alloy. For example, the amorphous alloy M-b-R may be present in polycrystalline form in which amorphous alloys M-b-R, or a mixture of M-P amorphous alloy M-coexist with them microcrystalline and/or crystalline alloys (i.e., the portion of the alloy is in an amorphous state), and microcrystalline and crystalline alloys are present in a total amount of preferably less than 30% by weight of the total weight of the alloy.

According to the process provided by the present invention, the method of preparation of the amorphous alloy contains, for example, the stage of contact and reaction of an aqueous solution containing the ion of M with a water solution containing the ion of H2RHO2and/or ion NR4in which M represents two or more elements selected from groups IIIA, IVA, VA, IB, IIB, IVB, VB, VIB, VIIB, VIII and the series of lanthanides of the periodic table of elements. An aqueous solution of P and/or as a reducing agent preferably is added to the reaction mixture dropwise slowly or

In the preparation method of the above-mentioned amorphous alloy, preferably, the ratio between the molar amount of the above ion M and complete molar amount of the ion H2RHO2and ion NR4from 0.05 to 5.

In the preparation method of the above-mentioned amorphous alloy, the molar concentration of ion M in the specified aqueous solution containing the ion of M, preferably, from 0.01 to 5.0 mol/l; molar concentration of the ion of H2RHO2in the specified aqueous solution containing the ion of H2RHO2, 0.01 to 5.0 mol/l; molar concentration of ion NR4in the specified aqueous solution containing ion NR4, 0.01 to 5.0 mol/L.

In the preparation method of the above-mentioned M-P or M-amorphous alloy with an aqueous solution containing the ion of H2RHO2or an aqueous solution containing ion BH4includes OpenID and reacts with the aqueous solution, containing ion M In the preparation method of the above-mentioned amorphous alloy M-b-R the total number (for example, a relatively low number) of an aqueous solution containing the ion of H2RHO2in a certain concentration (for example, a relatively low concentration), uniformly mixed composite solution containing the ion of M to obtain a clean solution, and then an aqueous solution containing ion BH4dropwise added to a clean reaction solution.

In the method of preparing the above-mentioned amorphous alloy contact and reaction are carried out mainly at room temperature and the precipitate formed rapidly. Then the precipitate is washed and dried (preferably in a natural way).

The presence of an amorphous alloy in the product obtained by the above method, can be identified by the method of x-ray diffraction analysis (XRD). A broad diffraction peak in the XRD spectrum indicates that the alloy is in the amorphous state.

In the process of the present invention, the specified catalyst preferably contains media in which or on which distributed amorphous alloy. Preferably the amount of the amorphous alloy is 3-90% of the total weight of the catalyst, more preferably 10-60% by weight, and the number of media - 10-897% by weight, more preferably 40-90% by weight.

For p is ocess of the present invention, the carrier may be selected from those materials which are often used as catalysts in this technology, for example, one or more non-oxidizing porous inorganic oxides, molecular sieves, active carbon, clay, phosphates (for example, aluminum orthophosphate), sulfates (e.g., magnesium sulfate) and metal halide compounds (e.g., FeCl, SnCl4, ZnCl2).

Non-oxidizing the porous inorganic oxide is known to specialists in this field and can be selected as one or more of alumina, silica, silica alumina, zirconium dioxide, titanium dioxide, zinc oxide, gallium oxide, boron oxide and the oxide of the alkali earth metal. Non-oxidizing the porous inorganic oxide available on the market or can be prepared by coprecipitation method, which is known to specialists in this field.

These molecular sieves are known in the art, such as silicon-aluminum molecular sieves, heteroatomic molecular sieve.

These clays are known to specialists in this field, such as kaolin, halloysite, montmorillonite, kieselguhr, saponite, hectorite, thick, attapulgite, hydrotalcite, bentonite; of these, the most preferred kaolin and montmorillonite.

As is well known to specialists in this field, for example, the carrier can the t to be loaded heteroalicyclic, phosphomevalonate acid and/or phosphomolybdenum acid.

In accordance with the process of the present invention, preferably, the specified media contains an additive, which is loaded on/in the carrier and selected from one or more elements or oxides of group IA, IIA, IIIA, IVA, VA, IB, IIB, IVB and VIII and some of the lanthanides of the periodic table of elements. More preferably, the specified additive is one or more elements or their oxides, selected from a number of lanthanides and third, fourth and fifth rows of groups IA, IIIA, IVA, VA, IB, IIB, IVB, VB, VIB, VIIB and VIII of the periodic table of elements, more preferably from one or more elements or oxides selected from K, CA, Mg, Ga, Sn, P, si, Zn, Zr, Fe, and La. Download the additives in the media can increase the activity and selectivity of the reaction.

In accordance with the process of the present invention, preferably, the amount of the additive is 0.5 to 40% by weight of the carrier. The specified additive can be loaded in/on the part of the media or all media ion exchange method, an impregnation method, a method of mixing or deposition method, which is known to specialists in this field.

In the method of ion exchange, for example, the media sticks to N+and/or Na+on the surface, and an aqueous solution containing ions of the additive element may be ravnomerno is mixed, heated to 80°C and stirred for 1 hour, then the mixture is filtered, and the product is filtered and repeatedly washed with distilled water and dried at 110°C.

For example, in the method of impregnating the carrier may be impregnated in an aqueous solution containing ions of the additive element at 60°C. for 8 hours, dried at 110°C. and then fired at 550°C for 2 hours.

In the deposition method, for example, a carrier and an aqueous solution containing ions of the additive element can be evenly mixed, then add the agent deposition, for example sodium carbonate, to create a precipitate, and the precipitate is repeatedly washed with distilled water and dried at a temperature of 110°C and then burned at 550°C for 2 hours.

A catalyst consisting of an amorphous alloy and the media, has a high catalyst activity, selectivity of the target product, resistance to poisoning and repeatability properties of the catalyst. However, the stability of the catalyst is high. The period of regeneration of the catalyst may be equal to 3 months or more. In addition, the catalyst is conveniently used in the reaction. Regeneration and activation of the catalyst, which otherwise must be performed prior to reaction in the prior art and are often complex compounds is observed difficult and time-consuming this process can be skipped. The inventive method for preparation of the catalyst is simple, easy to implement and is easily extended to an industrial scale.

In the preferred case, when the amorphous alloy is loaded in/on a medium, the catalyst may be a homogeneous mixture of media that you downloaded amorphous alloy, but not loaded with other carriers. These two pieces of media can be the same or different from each other. Thus, it is possible to improve the catalytic properties.

The catalyst may be prepared as follows:

1) mechanically mixing the amorphous alloy and the media, to obtain a catalyst in which the amorphous alloy is distributed in the media;

2) using impregnation method-recovery or restore method is the impregnation impregnation amorphous alloy on a carrier to obtain a catalyst in which the amorphous alloy is loaded on the carrier; or

3) using the coprecipitation method, to directly apply the amorphous alloy on a carrier and to obtain a catalyst in which the amorphous alloy is loaded on the carrier; or any combination of these methods(1)-(3).

The mechanical mixing of the amorphous alloy and media known to specialists in this field. Amorphous alloy and the media can be the ü mechanically mixed without any other component, or adding glue to mechanical mixing. Specified adhesive may be the salt of silica, a salt of aluminum oxide or mixtures thereof.

Also known experts in this field that the amorphous alloy may be deposited on the carrier by impregnation method restore. For example, the method may be carried out as follows.

The impregnation method-contains a stage of impregnation of the carrier with an aqueous solution containing the ion of M, followed by drying the impregnated carrier at a temperature of 100-130°C, annealing at 300-900°C for 1-10 hours, repeating the impregnation process one or more times if necessary; then calcined carrier comes in contact with a reducing agent containing ion H2PO2and/or ion NR4within 1-4 hours, then filtering and drying at a temperature below the crystallization temperature of the amorphous metal in the alloy.

The impregnation method is the recovery stage contains simultaneous or separate impregnation of the carrier in the solution of the reducing agent ion H2RHO2and/or ion NR4followed by filtering and drying, and repeating the impregnation process one or more times if necessary; adding an aqueous solution containing the ion of M, the resulting carrier with stirring in a bath of ice water to the reaction during the course the e 1-4 hours; additional stirring for 10-60 minutes after completion of the reaction, filtration and drying at a temperature below the crystallization temperature of the amorphous metal in the alloy.

The presence of an amorphous alloy in the catalyst obtained by the above method, may be identified by way XRD. A broad diffraction peak in the XRD spectrum indicates that the alloy M-R, M-or M-b-R loaded on the carrier in the catalyst is in the form of an amorphous alloy.

The coprecipitation method for the deposition of amorphous alloy on a carrier known to specialists in this field. For example, the method may be carried out as follows.

The carrier is dispersed in an aqueous or organic solution containing the ion of M to obtain a suspension, which must be selected ion concentration M (for example, the relatively low concentration)to achieve a balanced state in a mixture with the carrier, not by the state precipitate; NaOH solution is added as a reducing agent containing separately ion H2RHO2or ion NR4to adjust pH, in the range 7 to 11, preferably in an atmosphere of air or nitrogen, the above-mentioned reducing agent, pH adjustment of the solution containing the ion of H2RHO2and/or NR4added dropwise to the above suspension to Coosada components the options. During coprecipitation M metal is reduced and at the same time slowly out on the surface of the carrier, and finally deposited on the carrier surface in an amorphous state, M -, P-M or alloy M-b-R due to the slow recovery process and functions of the barrier reductant In or atom R. Then performs an additional step of washing and drying at a temperature below the crystallization temperature of the metal in the amorphous state, to obtain a catalyst.

The presence of an amorphous alloy in the catalyst obtained by the above method can also be identified by way XRD. A broad diffraction peak in the XRD spectrum indicates that M-R, M-or alloy-M-P loaded on the carrier in the catalyst is in the form of an amorphous alloy.

In the above-mentioned impregnation method-recovery and the coprecipitation method for the preparation of the inventive catalyst, as well as in the method for the preparation of amorphous alloy, an aqueous solution containing the ion of M can be obtained by dissolving in water one or more substances selected from water-soluble chloride, sulfate, nitrate or acetate salt ion M is the Molar concentration of ion M in the specified aqueous solution containing the ion of M can be about 0.01 to 5.0 mol/l; composition containing ion H2RHO2that can be used in the above with the persons, can be selected from KH2PO2or NaH2PO2that may or may not be crystalline water, and the molar concentration of ion H2RHO2in the solution containing the ion of H2RHO2may be from 0.01 to 5.0 mol/l; component containing ion NR4and which can be used in the aforementioned methods, may be selected from KBH4or NaBH4and the molar concentration of ion NR4in the solution containing the ion NR4may be in the range from 0.01 to 5.0 mol/L.

After downloading amorphous alloy on/in the carrier by impregnation method-recovery or a coprecipitation method, preferably mechanically mixed media amorphous alloy and unloaded carrier. Mechanical method of mixing in this respect is the same as above described method of mechanical mixing.

The catalyst composition is determined by x-ray fluorescence spectrometer (XRFS). The experimental device used in x-ray fluorescence spectrometer of the type E, supplied by the Corporation Rigaku Industrial Corporation.

The excitation voltage rhodium goal of 50 kV, and used in the experiment, the excitation current is 50 mA; the intensity of the line spectrum of each element is detected with a scintillation counter, and using a proportional counter perform quantitative or semi-quantitative and the Alize.

In accordance with the process of the present invention, preferred conditions for the conversion of synthesis gas to methanol, dimethyl ether, and low carbon olefin include a reaction temperature of 200-400°C, pressure of the reaction of 0.5 to 6 MPa, the space velocity of the synthesis gas as a feedstock 1000-10000 ml/g h and the molar ratio between H2and CO in the synthesis gas from 1 to 3.

When this process is used for production of methanol and dimethyl ether as target products and low carbon olefins as by-products, the reaction temperature is preferably 200-270°C and pressure of the reaction preferably 1-6 MPa. When the result of this process, you need to get low carbon olefins as the target product and the methanol and dimethyl ether as by-products, the reaction temperature preferably 270-400°C and pressure of the reaction is preferably 0.5 to 2 MPa.

The reactor may be a reactor with a fluidized bed or reactor with a fixed layer, and the process can be performed in batch or continuous mode.

The process according to the present invention preferably contains a stage of recovery of the catalyst prior to contact of the catalyst with synthesis gas. The recovery phase includes loading into the reactor catalyst in an amount of from 1 to 5 grams and to the reaction cleanup reacto is a, containing the catalyst, reducing gas at a temperature of cleaning 130-600°C for 0.5-1 hour to the active catalyst. The reducing gas may be a mixture of hydrogen in the amount of 1-10% by weight with an inert gas, which may be selected from nitrogen, helium and argon.

After recovering the synthesis gas is fed into the reactor as a source of raw materials with a bulk velocity 1000-10000 ml/g hour at the reaction temperature of 200-400°C and an operating pressure of 0.5 to 6 MPa. Synthesis gas may be one or more gases, which contain H2and CO in a molar ratio of from 1 to 3, for example, one or more gases can be selected from coke oven gases, liquefied gas, water gas, poluvagonah gases, natural gas and associated gas from oil fields.

The following describes exemplary embodiments of embodiment within the present invention. The examples are given solely for illustration and should not be construed as limitations of the present invention, because there may be numerous changes without leaving the spirit and scope of this invention. For specialists in this field, various modifications of the invention in addition to the shown and described herein are obvious and are included in the scope of the applied claims.

Example 1

1. Preparation of amorphous alloy

To a solution of 300 ml of CuSO40.5 mol/l (Chi the th analysis, Cangwu SaintGreen Chemical Co., Ltd, following the same), was added 5 g of citric acid (industrial purity) as complexing reagent and added to 30 ml Ga(NO3)30.05 mol/l (pure for analysis, Zibo Rongruida Micro Materiaks Plant). The mixture was well stirred and to it was added dropwise 30 ml of a solution KVN40.5 mol/l (pure for analysis, Shanghai Bangcheng Chemical Co., Ltd., below is the same). The reaction was quickly formed black precipitate, pop-up liquid was poured, the precipitate was rinsed with water up until the filtrate did not become neutral, then the precipitate was washed with acetone several times and subjected to natural drying to obtain the product. The molar ratio among the components in the product, as determined by XRF technique was Cu:Ga:B=1:0,01:0,1.

For x-ray diffraction analysis of the obtained powder was used x-ray diffractometer (D/MAX-2500 Cu Kα ray company Rigaku Cooperation) with a current of 100 mA (below the same)to analyze the product obtained XRD. The obtained XRD spectrum showed that there was only wide diffusion peak at 2θ=42° (figure 1(1)), which is a typical characteristic of the amorphous alloy. Therefore, the obtained alloy Cu:Ga:B was the alloy in the amorphous state.

2. The preparation of a carrier mixed oxides

60 g of ZnO (industrial purity, following the same), 20 g of SiO2(micropa the East silica gel, Qingdao Haiyang Chemical Plant, below the same) and 200 g of distilled water were mixed, and then 130 g of an aqueous solution of 20% by weight ZrOCl2·8H2O (pure for analysis, Xinghua Songhe Chemical Reagent Factory, following the same), 5 g MP2(industrial purity), 49 g of an aqueous solution of 20% by weight l (industrial purity) and 10 g of an aqueous solution of 1% by weight l (pure for analysis, Beijing Chemical Works) were simultaneously added dropwise with intensive stirring, and then dropwise added 50 g of an aqueous solution of 5% by weight sodium carbonate (pure for analysis, Beijing Chemical Works, below is the same). When you are finished adding ingredients, the precipitate was filtered, repeatedly washed with distilled water to remove CL, dried at 110°C and hot at 550°C for 2 hours to obtain 160 g of a carrier containing a total of 27.5% by weight ZrO2, 70% by weight of ZnO and 2.5% by weight of the additive Cao.

3. Preparation of catalyst

Amorphous alloy and the carrier obtained in the above stage, mechanically mixed in a weight ratio of 2:3, tabletirovanii, sprayed and sifted to a particle having a size of from 20 to 40 mesh. The composition of the obtained catalyst are shown in table 1.

Example 2

1. Preparation of amorphous alloy

Every 20 ml of a solution of CuSO40.86 mol/l and 0.45 ml MP(SO4)2mol/l (pure for an is Lisa, Hunan Coran Chemical Co., LTD) was mixed with 344 ml NaH2PO20.1 mol/l (pure for analysis, Lufang Chemical Co., LTD, following the same) and thoroughly mixed. The temperature of the mixture was maintained at 30°C in a water bath, and then to 13.6 ml of a solution of NaBH45.0 mol/l (pure for analysis, Shanghai Bangcheng Chemical Co., Ltd., below is the same), pH of which was adjusted to 12 with alkali NaOH, added it to the mixture dropwise and carefully stir. After that, the mixture was additionally stir and was rinsed with water up until the filtrate did not become neutral, then the precipitate was washed with acetone several times and subjected to natural drying to obtain the product. The molar ratio among the components in the product, as determined by XRF technique was Cu:Mn:P:B=1:0,52:2:4.

For x-ray diffraction analysis of the obtained powder was used x-ray diffractometer XRD. The obtained XRD spectrum showed that there was only wide diffusion peak at 2θ=42° (figure 1(1)), which is a typical characteristic of the amorphous alloy. Therefore, the obtained product alloy Cu-Mn-P-B alloy in the amorphous state

2. The preparation of a carrier containing active carbon and metal chlorides 5 g Fel3(pure for analysis, Jiangyin Hengye Chemical Engineering Co. Ltd., China, following the same), 5 g of SnCl4(pure for analysis, Liaoyang Dngxin Chemical Engineering Co. Ltd., China), 30 g ZnCl2(industrial purity) and 60 g of active carbon powder (Xinsen Tanye Co. Ltd., the city Shaowu, the field of Forzani, China) stir, to obtain 100 g of a carrier containing 5% by weight Fl3a 5% by weight SnCl4, 30% by weight ZnCl2and 60% by weight of active carbon.

3. Preparation of catalyst

33 g of the amorphous alloy, 100 g matrix, 12.5 g Sol of silicic acid (40% by weight, Sinopec Catalyst Company Qilu) and 25 g of a Sol of alumina (20% by weight, Sinopec Catalyst Company Qilu) were mixed until a homogeneous composition was extracted using an extruder, was sprayed and sifted to a particle having a size of from 20 to 40 mesh, dried under vacuum of the order of 10-1PA and at a temperature of 120°C for 4 hours to obtain the catalyst, which contained 23% by weight of an amorphous alloy and its composition is shown in table 1.

Example 3

1. Preparation of amorphous alloy

To 60 ml of a solution of CuSO42.5 mol/l was added 3 g of citric acid and then 60 ml VCl20.05 mol/l (pure for analysis, Beijing Hengyunzhongyuan Chemical Co., Ltd.). The mixture was well stirred, and then 6 ml KN2RHO25.0 mol/l (pure for analysis, Lufang Chemical Co., LTD, following the same) was slowly added to the mixture, and the pH of the mixed solution was adjusted to 7 ammonia water (pure for analysis, Beijing Chemical Works, below is the same), and 10 ml of aq is solution of 0.01 NaBH 4mol/l was added at 20°C. After completion of the reaction was added ammonia water, and the mixture stir for 5 minutes. Pop-up fluid was drained. The precipitate was rinsed with water up until the filtrate did not become neutral, then the precipitate was washed with acetone several times and subjected to natural drying to obtain the product. The molar ratio among the components in the product, as determined by XRF technique was Cu:V:P=1:0,02:0.2. The quantity of the item was less than the lower limit of sensitivity of the XRF method and, thus, was not found.

For x-ray diffraction analysis of the obtained powder was used x-ray diffractometer (D/MAX-2500 C α ray company Rigaku Cooperation) with a current of 100 mA (below the same)to analyze the product obtained XRD. The obtained XRD spectrum showed that there was only wide diffusion peak at 2θ=42° (figure 1(1)), which is a typical characteristic of the amorphous alloy. Therefore, the obtained alloy Cu-V-P was the alloy in the amorphous state.

2. Preparation of medium molecular sieve ZSM-5

150 g of molecular sieve ZSM-5 (experimental sample from Sinopec Catalyst Company Jianchang filiale, patterns MFI: Na2O<0.2% by weight, Si/Al ratio=40) and 80 g GA2O3(pure for analysis, Zibo Rongruida Micro Materiaks Plant) were thoroughly mixed, and 500 ml (NO3)2 0.07 mg mol/l (pure for analysis, Beijing Chemical Works) was added to the mixture. The mixture was heated to 80°C. and stir for 1 hour. The precipitate was filtered and then repeatedly washed with distilled water until the filtrate was not neutral. The precipitate was dried at 110°C and then was hot at 550°C for 2 hours to get the media loaded MgO. The specified media contained 1% by weight MgO, 64,57% by weight molecular sieve ZSM-5 and 34,43% by weight Ga2O3.

3. Preparation of catalyst

Amorphous alloy obtained in the above-mentioned stages, the carrier obtained in the above-mentioned stages, and other media ZnO were mixed mechanically in a weight ratio of 3:3:4, tabletirovanii, sprayed and sifted to a particle having a size of from 20 to 40 mesh. The composition of the obtained catalyst are shown in table 1.

Example 4

1. Preparation of amorphous alloy

11 ml of a solution of CuSO44.5 mol/l, 200 ml of a solution of CE(NO3)30.05 mol/l (pure for analysis, Xiaxian Yunii Chemical Co. Ltd., Shangxi, China) and 2 g of citric acid (industrial purity) were mixed, thoroughly stirred, and then 10 ml KVN4, 5.0 mol/l was added dropwise. The reaction quickly formed black precipitate. Pop-up fluid was drained. The precipitate was rinsed with water up until the filtrate did not become neutral, then the wasp is OK was washed with acetone several times and subjected to natural drying, in order to obtain the product. The molar ratio among the components in the product, as determined by XRF technique was si:CE:In=1:0,2:1.

For x-ray diffraction analysis of the obtained product was used x-ray diffractometer XRD. The obtained XRD spectrum showed that there was only wide diffusion peak at 2θ=42° (figure 1(1)), which is a typical characteristic of the amorphous alloy. Therefore, the obtained product si-Se-In was the alloy in the amorphous state.

2. The preparation of a carrier gamma-Al2O3with additive

48.6 g of gamma-Al2O3(sample from the company Sinopec Catalyst Company Jianchang, the same below) was soaked in 40 g of an aqueous solution of 52.5% by weight of Zn(NO3)2(pure for analysis, Beijing Chemical Works, below is the same). The mixture was heated to 60°C for 8 hours for aging, dried at 110°C and then was hot at 550°C for 2 hours to obtain the carrier of gamma-Al2O3downloaded oxide ZnO. 10 grams Ag2O (pure for analysis, Shanghai Reagent Co., Ltd.) and the media gamma-Al2O3loaded ZnO were mixed mechanically to obtain a solid mixture.

5 g of La(NO3)3were loaded in 28 g of solution with a concentration of 22% by weight. A solution of La(NO3)3soaked the above obtained solid mixture isovolumetric by impregnation method. Prop is made of solid mixture was heated to 60°C for 8 hours for aging, dried at 110°C and then was hot at 550°C for 2 hours to obtain the carrier of gamma-AL2O3with an additive.

The media contained 70.7 percent by weight gamma-Al2O3, 13.1 percent by weight ZnO additives and 1.6% by weight of additives La2About3.

3. Preparation of catalyst

The above-mentioned amorphous alloy and the media are mechanically mixed in a weight ratio of 1:1, tabletirovanii, sprayed and sifted to a particle having a size of from 20 to 40 mesh. The composition of the obtained catalyst are shown in table 1.

Example 5

1. The preparation of a carrier from a mixture of oxides, loaded By the2About

130 g Mno2(industrial purity) and 22 g of SnO2(industrial purity, following the same) were placed in 333 ml solution KVN4, 0.03 mol/l (pure for analysis, Beijing Chemical Works), using isovolumetric the impregnation method, and then heated up to 60°C for 8 hours for aging, dried at 110°C, was hot at 850°C for 2 hours to obtain a carrier mixture of oxides, loaded By the2Oh, in which the number of IGOs2was 84,97% by weight, the amount of SnO2was 14,38% by weight, and the amount of additives2O amounted to 0.65% by weight.

2. Preparation of catalyst

146,24 g of the carrier obtained as described above was added to 100 ml of demineralized water. mesh in the reaction was continuously stir, to obtain a suspension in 20 ml of a solution of Fe(NO3)3, 2 mol/l and 100 ml of SnCl24 mol/l (pure for analysis, Liaoyang Dingxin Chemical Engineering Co. Ltd., China) was added to the mixture and thoroughly stirred, and then 10 ml of KVN40.5 mol/l was added dropwise to receive the sludge mixture. 30 ml of NaOH was added to the solution KN2RHO230 mol/l to adjust the pH to 11, and then the solution was added to the above-mentioned sludge mixture. Ions of Fe and Sn have been restored and at the same time slowly stood out on the surface of the carrier, then moved with reductants In atoms and R on the surface of the carrier, to get a black precipitate. After completion of the reaction, the pop-up liquid was drained, and the precipitate was rinsed with water up until the filtrate did not become neutral, then the precipitate was washed with acetone several times and subjected to natural drying to obtain the product on the media. The molar ratio among the components in the product alloy, determined by XRF technique was Fe:Sn:P:B=1:10:2,25:0,125, and the weight ratio between the alloy product and the carrier was 3:7.

For x-ray diffraction analysis of the obtained powder was used x-ray diffractometer to analyze the product on the media. The obtained XRD spectrum showed that there was only a wide diffusion the first peak (figure 2(1)), which is a typical characteristic of the amorphous alloy. Therefore, the obtained product of Fe-Sn-P-B alloy in the amorphous state.

The medium on which was deferred amorphous alloy, tabletirovanija, sprayed and sifted to a particle having a size of from 20 to 40 mesh. The composition of the obtained catalyst are shown in table 1.

Example 6

1. The preparation of a carrier mixture of oxides loaded ZrO2

60 g of Mno2(industrial purity), 60 g of active carbon and 20 g of SnO were mixed into a homogeneous mixture, which is then soaked up in 300 ml of 0.2 mol/l ZrOCl2isovolumetric by impregnation method. The mixture was heated to 60°C for 8 hours for aging, dried at 130°C, hot at 350°C for 7 hours to obtain a carrier mixture of oxides loaded ZrO2.

2. Preparation of catalyst

of 1.97 g of the above media was added to 100 ml of demineralized water. The reaction mixture was continuously mixed to form a slurry. 200 ml solution of 0.4 mol/l Fe(NO3)3and 20 ml of ZrOCl20.2 mol/l was added to the slurry and thoroughly stir, and then 20 ml KVN40.5 mol/l was added dropwise to receive the sludge mixture. 30 ml of NaOH 3.0 mol/l NaH2PO2was added to the solution to adjust vodorodny the second indicator to 9, and then the solution was added to the sludge mixture. Ions of Fe and Zr have been restored and at the same time slowly stood out on the surface of the carrier and at the final stage were deposited with reductants In atoms and R on the surface of the carrier to form a black precipitate. After completion of the reaction, the pop-up liquid was drained, and the precipitate was rinsed with water up until the filtrate did not become neutral, then the precipitate was washed with acetone several times and subjected to natural drying, in order to Deposit the alloy product to the media. The molar ratio among the components in the product alloy, determined by XRF technique was Fe:Zr:P:B=1:0.05 to:1,125:0,125, and the weight ratio between the alloy product and the carrier was 9:1.

For x-ray diffraction analysis of the obtained powder was used x-ray diffractometer to analyze the product on the media. The obtained XRD spectrum showed that there was only wide diffusion peak (figure 2(2), which is a typical characteristic of the amorphous alloy. Therefore, the obtained product of Fe-Zr-P-B alloy in the amorphous state.

The medium on which was deferred amorphous alloy, tabletirovanija, sprayed and sifted to a particle having a size of from 20 to 40 mesh. The composition of the obtained catalyst are shown in table 1.

Example 7

When is otoplenie catalyst

Using isovolumetric the impregnation method, 60 g of SiO2(macroporous silica gel was soaked in 60 ml KVN4, 2.5 mol/l filtered, dried under vacuum at 50°C for 8 hours, and then a mixed solution consisting of 50 ml of a solution of Fe(NO3)30.5 mol/l and 20 ml of Ni (NO3)20.5 mol/l (pure for analysis, Xiaxian Yunii Chemical Co. Ltd., Shangxi, China), was added dropwise to the mixture, stirred in the ice bath and reacted for 1 hour. After completion of the reaction, the mixture was additionally stir for 15 minutes, filtered and then dried under vacuum at 120°C for 2 hours. Then the product of the alloy was deposited on the media. The molar ratio among the components in the product alloy, determined by XRF technique was Fe:Ni:B=1:0,4:6, and the weight ratio between the alloy product and the carrier was 1:17,24.

For x-ray diffraction analysis of the obtained product alloy used x-ray diffractometer to analyze the product on the media. The obtained XRD spectrum showed that there was only wide diffusion peak (figure 3(1)), which is a typical characteristic of the amorphous alloy. Therefore, the obtained product of Fe-Ni-B alloy in the amorphous state.

The medium on which was deferred amorphous alloy, tabletirovanija, raspily the Xia and sifted particles, have a size of from 20 to 40 mesh. The composition of the obtained catalyst are shown in table 1.

Example 8

Preparation of catalyst

17 ml KN2RHO23.0 mol/l and 17 ml KVN43.0 mol/l were mixed, and then was added NaOH to adjust pH to 11 and get the solution of the mixture of reducing agents. Using isovolumetric the impregnation method, 60 g of carbon powder were soaked in a solution of the mixture of reducing agents, filtered and dried under vacuum at 110°C for 3 hours. Processed coal powder was soaked in 30 ml of a solution of NaBH40.01 mol/l isovolumetric by impregnation method, after impregnation was filtered, dried under vacuum at 70°C for 4 hours to get soaked and dried coal powder. A mixed solution consisting of 5 ml of molybdate ammonium solution 0,5 mol/l (pure for analysis, Xingbang W&M Technology Co., Ltd.), 2 ml of a solution of CO(NO3)20.5 mol/l (pure for analysis, Xiaxian Yunii Chemical Co. Ltd., Shangxi, China) and 40 ml of solution C(NO3)20.5 mol/l (pure for analysis, Zibo Rongruida Micro Materiaks Plant), was added dropwise in the impregnated and dried coal powder, placed in a bath of ice water, and reacted for 1 hour. After completion of the reaction, the mixture was additionally stir for 15 minutes, filter the eh and then dried under vacuum at 120°C for 2 hours. Then the product of the alloy was deposited on the media. The molar ratio among the components in the product alloy, determined by XRF technique was si:Mo:Co:R:=1:0,125:0,05:2,55:2,565, and the weight ratio between the alloy product and the carrier was 1:6,39.

For x-ray diffraction analysis of the obtained product alloy used x-ray diffractometer to analyze the product on the media. The obtained XRD spectrum showed that when 20=42° was present only broad diffusion peak (figure 1(1)), which is a typical characteristic of the amorphous alloy. Therefore, the obtained product alloy Cu-Mo-Co-P-B alloy in the amorphous state.

The medium on which was deferred amorphous alloy, tabletirovanija, sprayed and sifted to a particle having a size of from 20 to 40 mesh. The composition of the obtained catalyst are shown in table 1.

Example 9

1. Preparation of the media loaded amorphous alloy

10 g of active carbon, 10 g Soo (industrial purity) and 5 g of SiO2uniformly mixed and were put in 200 ml of demineralized water under continuous stirring, and then 100 ml of a solution of Fe(NO3)3 0.4 mol/l, 30 ml of a solution of La(NO3)30.05 mol/l (pure for analysis, Zibo Rongruida Micro Materiaks Plant) and 2 g of citric acid (industrial purity) was added to the mixture and thoroughly stirred to : open the SQL suspension. To 50 ml KVN41.1 mol/l was added alkali NaOH to adjust pH to 7, and then the solution was added dropwise to the suspension. Ions of Fe and La have been restored and at the same time slowly stood out on the surface of the carrier and then were deposited In a atom of the reducing agent on the surface of the carrier, forming a black precipitate. Pop-up liquid was poured, the precipitate was rinsed with water up until the filtrate did not become neutral, then the precipitate was washed with acetone several times and subjected to natural drying, to highlight the product alloy on the media. The molar ratio among the components in the product alloy, determined by XRF technique was Fe:La:B=1:0,04:1.37, and the amount of the amorphous alloy in the product amounted to 10.1 per cent by weight.

For x-ray diffraction analysis of the obtained product was used x-ray diffractometer to analyze the product on the media. The obtained XRD spectrum showed that there was only wide diffusion peak (obtained XRD spectrum was similar to the spectrum in figure 2(2)), which is a typical characteristic of the amorphous alloy. Therefore, the obtained product of Fe-La-B was the alloy in the amorphous state.

2. Preparation of catalyst

The media, which was loaded amorphous alloy was mechanically mixed with molecular the m sieve SAPO-34 (experimental sample from Sinopec Catalyst Company Jianchang filiale, structures of SLEEP: Na2O<0.2% by weight, the ratio Si/Al=13), the media were mechanically mixed in a weight ratio of 7:3, tabletirovanija, sprayed and sifted to a particle having a size of from 20 to 40 mesh. The composition of the obtained catalyst are shown in table 1.

Example 10

Preparation of catalyst

3.75 g of ZnO and 0.9 g V2O5(pure for analysis, Wuhu Renben Alloy Co., Ltd) was added to 100 ml of demineralized water and continuously stir, then 100 solution of CuSO4, 0.5 mol/l 200 ml of a solution of Zn(NO3)40,025 mol/l (pure for analysis, Xiaxian Yunli Chemical Co. Ltd., Shangxi, China), 400 ml of 0.025 mol/l Cr(No3)3(pure for analysis, Xiaxian Yunii Chemical Co. Ltd., Shangxi, China) and 2 g of citric acid (industrial purity) was added to the mixture and thoroughly stirred to form a suspension. To 50 ml of 1.0 mol/l KVN4was added NaOH to adjust pH to 7, and then the solution was added dropwise to the suspension. Ions of Cu, Zn and CR were restored and at the same time slowly stood out on the surface of the carrier, and then evolved the restorer of the atom on the surface of the carrier to form a black precipitate. Pop-up liquid was poured, the precipitate was rinsed with water up until the filtrate did not become neutral, then the precipitate was washed with acetone several times and subjected to natural sushi is e, to highlight the product alloy on the media. The molar ratio among the components in the product alloy, determined by XRF technique was Cu:Zn:Cr:B=1:0,1:2:1, and the weight ratio between the alloy product and the carrier was 7:3.

For x-ray diffraction analysis of the obtained powder was used x-ray diffractometer to analyze the product of the alloy on the substrate. The obtained XRD spectrum showed that there was only wide diffusion peak 20=42 (figure 2(2)), (obtained XRD spectrum was similar to the spectrum in figures 1(1)), which is a typical characteristic of the amorphous alloy. Therefore, the obtained product alloy Cu-Zn-Cr-B alloy in the amorphous state.

The medium on which was deferred amorphous alloy, tabletirovanija, sprayed and sifted to a particle having a size of from 20 to 40 mesh. The composition of the obtained catalyst are shown in table 1.

Table 1
Number exampleThe composition of the amorphous alloy (molar ratio)The composition of the media (% by weight)The method of the additive% by weight of amorphous alloy catalyst
1Cu:a:B=1:0,01:0,1 ZrO2(10%), ZnO(60%), Cao(5%) SiO2(20%), MnO2(5%)Precipitation40
2Cu:Mn:P:B=1:0,52:2:4Fl3(5%), SnCl4(5%), ZnO(30%), active carbon(60%)Mixing23
3Cu:V:P=1:0,02:0,2molecular sieve ZSM-5 (64,57%), MgO (1%), GA2O3(34,43%)Ion exchange30
4Cu:Ce:B=1:0,2:1γ-Al2O3(70.7%), ZnO (13,1%) Ag2O(14,5%), La2O3(1,6%)Impregnation50
5Fe:Sn:P:B=1:10:2,25:0,125To2O(0,65%), Mno2(84,97%), SnO2(14.38%)Impregnation30
6Fe:Zr:P:B=1:0,05:1,125:0,125ZrO2(5,01%), MnO2(40.71%), SnO2(13,57%), active carbon(40.71%)Impregnation90
7Fe:N:B=1:0,4:6 SiO2Impregnation5,5
8Cu:Mo:Co:P:B=1:0,125:0,05:2,55:2,565Coal powderImpregnation13,52
9Fe:La:B=1:0,04:1.37Active carbon(27,09%), SiO2(13,55%), SAPO-34 molecular sieve(32,27%), COO(27,09%)Not modified7,07
10Cu:Zn:Cr:B=1:0,1:2:1ZnO(80,65%), V2O5(19.35%)Not modifilan70

Comparative examples

Comparative example 1

1. Preparation of amorphous alloy

To 300 ml of a solution of CuSO40.5 mol/l was added 5 g of citric acid as complexing reagent and added to 30 ml of a solution of La(NO3)3, 0.05 mol/l, the mixture was well stirred and to it was added 30 ml KVN4, 0.5 mol/l, and stirring was quick response. Quickly formed black precipitate, pop-up liquid was poured, the precipitate was rinsed with water up until the filtrate did not become neutral, then the precipitate was washed with acetone several the times and subjected to natural drying, in order to obtain the product. The molar ratio among the components in the product, as determined by XRF technique was Cu:La:B=1:0,01:0,1.

The resulting product of the alloy Cu-La-B was hot in nitrogen atmosphere at 600°C for 4 hours to obtain a crystalline powder of the alloy.

For x-ray diffraction analysis of the obtained powder was used x-ray diffractometer (D/MAX-2500 Cu Kα ray company Rigaku Cooperation) with a current of 100 mA (below the same)to analyze the product obtained XRD. The obtained XRD spectrum showed that there was only wide diffusion peak at 2θ=42° (figure 1(2)). Therefore, the obtained alloy Cu-La-B alloy was in the crystalline state.

2. The preparation of a carrier mixture of oxides

60 g of ZnO, 20 g of SiO2and 200 g of distilled water was mixed with 130 g of an aqueous solution of 20% by weight ZrOCl2·8H2O, 5 g of MnO2(industrial purity), 49 g of an aqueous solution of 20% by weight CaCl2(industrial purity) and 10 g of an aqueous solution of 1% by weight of HCl was added dropwise with vigorous stirring, and then 50 g of an aqueous solution of 5% by weight sodium carbonate was added dropwise. After that, the mixture was additionally stir for 1 hour, the precipitate was filtered and repeatedly washed with distilled water until complete washoutCmsubsup> l2', the precipitate was dried at 110°C and then was hot at 550°C for 2 hours to obtain 100 g of a carrier containing ZnO 60% by weight, SiO220% by weight ZrO210% by weight, additives MnO25% by weight and the additive CaO 5% by weight.

3. Preparation of catalyst

Crystalline alloy and the media were mechanically mixed in a weight ratio of 2:3, tabletirovanii, sprayed and sifted to a particle having a size of from 20 to 40 mesh, to obtain a catalyst.

Comparative example 2

The catalyst containing crystalline si and Ga, was prepared in the following way

70 g of SiO2were soaked in 40 g of an aqueous solution of 62.5% by weight of si(NO3)2(pure for analysis, Zibo Rongruida Micro Materiaks Plant), were dried at 80°C for 6 hours, at 120°C for 4 hours and then was hot at 550°C for 2 hours to obtain compound CuO-SiO2.

The obtained compound CuO-SiO2was impregnated with 40 g of an aqueous solution of 0.85% by weight Ga(NO3)3were dried at 80°C for 6 hours, at 120°C for 4 hours and then was hot at 550°C for 2 hours to obtain compound Ga2About3-CuO-SiO2. The molar ratio among the components in the product alloy, determined by XRF technique was Cu:Ga=1:0,01. Range of XRD of the product alloy is shown in figure 1(3), which proves that there is a sharp peak. Therefore, the product obtained alloy was an alloy in a crystalline state.

60 g of ZnO, 20 g of SiO2and 200 g of distilled water was mixed with 130 g of an aqueous solution of 20% by weight ZrOCl2·8H2O, 5 g of MnO2(industrial purity), 49 1 g of an aqueous solution of 20% by weight CaCl2(industrial purity) and 10 g of an aqueous solution of 1% by weight of Hcl was added dropwise with vigorous stirring, and then 50 g of an aqueous solution of 5% by weight sodium carbonate was added dropwise. After that, the mixture was additionally stir for 1 hour, the precipitate was filtered and repeatedly washed with distilled water until complete washout Cl2', the precipitate was dried at 110°C and then was hot at 550°C for 2 hours to obtain 100 g of a carrier containing ZnO 60% by weight, SiO220% by weight ZrO210% by weight, additives MnO25% by weight and the additive Cao 5% by weight.

Crystalline alloy and the media were mechanically mixed in a weight ratio of 2:3, tabletirovanii, sprayed and sifted to a particle having a size of from 20 to 40 mesh, to obtain a catalyst.

Comparative example 3

Preparation of catalyst

Using isovolumetric the impregnation method, 60 g of SiO2(agroforesty silica gel) were soaked in a solution of 60 ml of 2.5 mol/l KVN 4filtered, dried under vacuum at 50°C for 8 hours, and then a mixed solution consisting of 50 ml of 0.5 mol/l Fe(NO3)3and 20 ml of 0.5 mol/l of Ni(NO3)2was added dropwise, the mixture stirred in the ice bath and reacted for 1 hour. After completion of the reaction, the mixture was additionally stir for 15 minutes, filtered and then dried under vacuum at 120°C for 2 hours. Then the product of the alloy was deposited on the media. The molar ratio among the components in the product alloy, determined by XRF technique was Fe:Ni:B=1:0,4:6, and the weight ratio between the alloy product and the carrier was 1:17,24. The medium on which was deferred amorphous alloy, tabletirovanija, sprayed and sifted to a particle having a size of from 20 to 40 mesh, to obtain the catalyst. The catalyst was hot in nitrogen atmosphere at 600°C for 4 hours to obtain crystalline powder.

For x-ray diffraction analysis of the obtained powder was used x-ray diffractometer (D/MAX-2500 C α ray company Rigaku Cooperation) with a current of 100 mA (below the same)to analyze the product obtained XRD. The obtained XRD spectrum showed that there was only a sharp peak at 2θ=42° (figure 3(3)). Therefore, the obtained alloy Fe-Ni-B alloy was in the crystalline state.

Por what measures 11

The process of production of methanol, dimethyl ether, and low carbon olefins from synthesis gas was carried out using each of the catalyst prepared according to examples 1-10 and comparative examples 1-3.

The reaction of the gas phase was carried out by reaction under pressure in a sealed experimental reactor continuous fixed bed.

The reactor was loaded with 1.5 g of catalyst. Before the reaction, the reactor containing the catalyst was flushed reducing gas for 0.5 hour.

Then the reaction temperature was adjusted, and the reactor was fed with synthesis gas with desired volumetric rate. The composition of the reducing gas, the temperature of the purge, the operating conditions and the composition of the feedstock, a synthesis gas is shown in table 2. The sample for analysis was taken after the reaction for 3 hours. Carbon monoxide was analyzed by a gas chromatograph HP 6890, and the products of methanol, dimethyl ether, and low carbon olefins were analyzed chromatographic column PORAPAK-n

To compare example 1 with comparative examples 1-2 and example 7 with comparative example 3, example 1 and comparative examples 1-2 were used basically the same operating conditions and the composition of the feedstock, the synthesis gas, and also was the case with example 7 and comparative example 3.

Table 2
The number of catalystThe composition will restore. gas (% by weight)Temperature purge °CThe volumetric feed rate of the raw material
ml/g h
Pressure reactions, MPaThe temperature of the reaction, °CThe composition of the raw gas, % by weight
Example 15% N2, 95% N21301000423031%, 6% CO263% of N2
Comparative example 15% N2, 95% N21301000423031%, 6% CO263% of N2
Comparative example 25% H2, 95% N21301000423031%, 6% CO263% of N2
Example 2 1% N2, 99% N26001500425031%, 6% CO263% of N2
Example 35% H2, 95% No3001500427031% CO, 6% CO263% of N2
Example 45% N2, 95% N22401000620031% CO, 6% CO2, 63%H2
Example 55% N2, 95% AG4005000427042% CO,8% CO2, 50% H2
Example 65% N280% of N2, 15% AG3001500129042% CO, 8% CO2, 50% H2
Example 710% N290% of N2 2802700227026% CO, 2% CO2, 72% H2
Comparative example 310% H290% of N22802700227026% CO, 2% CO2, 72% H2
Example 85% H2, 75% He, 20% N24009000140026% CO, 2% CO2, 72% H2
Example 95% H2, 95% N230015000,535026% CO,2% CO2, 72% H2
Example 105% H2, 95% N240015000,530042% CO, 8% CO2, 50% H2

The conversion, selectivity of each product type, methanol, dimethyl ether, and ethylene propyl is on, as well as the availability of carbon during the production of methanol, dimethyl ether, and low carbon olefins from synthesis gas, were calculated by the following equations, and the results are shown in table 3.

The conversion of CO(%) = moles of CO, consumed by the reaction/mole, filed in response.

The selectivity of dimethyl ether (%) = moles of dimethyl ether produced by the reaction/moth WITH consumed by the reaction.

The selectivity of methanol (%) = moles of methanol produced by the reaction/moth WITH consumed by the reaction.

The selectivity of ethylene (%) = (moles of ethylene produced by the reaction × 2)/moles of CO, consumed by the reaction.

The propylene selectivity (%) = (moles of propylene produced by the reaction × 3)/moles of CO, consumed by the reaction.

The availability of carbon (%) = (moles of CO, consumed by the reaction moles of CO, produced by the reaction)/moles of CO, filed in response.

Table 3
CatalystThe conversion of CO (%)The selectivity of dimethyl ether (%)The selectivity of methanol (%)The selectivity of ethylene (%)The propylene selectivity (%)Availability is gerada(%)
Example 1859231,51,563
Comparative example 17072231,4159
Comparative example 26573201.3150
Example 2909421,91,664
Example 3909522,11,764
Example 4959140,7169
Example 5939222,31,766
Example 69430,1172467
Example 79640,2213372
Comparative example 385107152060
Example 89220,5192867
Example 99330,4172668
Example 10 9120,4203065

As can be seen from table 3, in the production of methanol, dimethyl ether, and low carbon olefins from synthesis gas, the catalyst of the present invention can provide a high degree of conversion, a high selectivity of the target product and high availability of carbon.

1. Method for the production of methanol, dimethyl ether, and low carbon olefins from synthesis gas containing phase contact of synthesis gas with a catalyst under conditions that promote conversion of synthesis gas to methanol, dimethyl ether, and low carbon olefin, the catalyst contains an amorphous alloy represented by the components of M-R, M-or M-b-R, in which M represents two or more elements selected from the group of lanthanides and third, fourth and fifth rows of group IIIA, IV, VA, IB, IIB, IVB, VB, VIB, VIIB and VIII of the periodic table of elements.

2. The method according to claim 1, in which the molar ratio between the component and M component P and/or B in the alloy is from 0.01 to 15.

3. The method according to claim 1, in which the molar ratio between the component and M component P and/or B in the alloy from 0.2 to 10.

4. The method according to claim 1, wherein said component M is two or more electronegative the customers, selected from Cu, Zn, V, Cr, Mn, Fe, Co, Ni, Zr, Mo, Sn, La.

5. The method according to claim 1, wherein said component of M contains Cu.

6. The method according to claim 1, wherein said component of M contains Cu and Zn.

7. The method according to claim 1, wherein said catalyst further comprises a carrier, in which or on which is dispersed or downloaded amorphous alloy, and based on the total weight of the catalyst, the amount of the amorphous alloy is 3-90% by weight and the amount of media - 10-97% by weight.

8. The method according to claim 7, wherein said carrier is one or more substances selected from the non-oxidizing porous inorganic oxides, molecular sieves, activated carbon, clays, phosphates, sulfates and metal halide compounds.

9. The method according to claim 7, wherein said catalyst additionally contains an additive, which is loaded on or in the carrier and selected from one or more elements or oxides of group IA, IIA, IIIA, IVA, VA, IB, IIB, IVB, VIII, and some of the lanthanides of the periodic table of elements.

10. The method according to claim 9, in which the basis weight of the carrier, the amount of the additive is 0.5 to 40% by weight.

11. The method according to claim 9, in which the specified additive is one or more elements or their oxides, selected from a number of lanthanides and third, fourth and fifth rows of groups IA, IIA, IIIA, IVA, VA, IB, IIB, IVB and VIII of the periodic table of elements.

12. The method according to claim 9, in cotromoxazole additive - one or more elements or their oxides selected from the group of K, CA, Mg, Ga, Sn, P, Cu, Zn, Zr, Fe and La.

13. The method according to claim 1, in which the conditions of synthesis gas conversion to methanol, dimethyl ether, and low carbon olefin include a reaction temperature of 200-400°C, pressure of the reaction of 0.5 to 6 MPa, space velocity of the feed synthesis gas 1000-10000 ml/g·h and the molar ratio between the H2and CO in the synthesis gas from 1 to 3.

14. The method according to item 13, in which the temperature of the reaction 200-270°C and pressure of the reaction - 1-6 MPa, when the methanol and dimethyl ether is produced as target products and low carbon olefins are produced as by-products.

15. The method according to item 13, in which the temperature of the reaction - 270-400°C and pressure of the reaction of 0.5-2 MPa, when the low-carbon olefins are produced as target products and methanol and dimethyl ether are produced as by-products.

16. The method according to claim 7, in which the catalyst is prepared by mechanical mixing of the amorphous alloy and the media, using the impregnation method restore or recovery method-impregnation to directly impregnate amorphous alloy on the media, or using the coprecipitation method to directly impose amorphous alloy on a carrier, or any combination of the above methods.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to improved methods of obtaining dimethyl ether (DME) from methanol (MeOH) by conversion, preferably by condensation, under conditions of acid catalysis, of raw MeOH, obtained by MeOH-synthesis, with splitting water in reactor (12) with obtaining DME, in which initial mixture, consisting of raw MeOH, and at least one obtained within the process and formed from unreacted MeOH and water from reaction backflow are supplied into column for MeOH (7) and subjected to evaporation, with distillate, consisting mainly of gaseous MeOH, is supplied to reactor. Reaction mixture, removed in reactor (12), in column for mixture (15) is separated into bottoms product, consisting mainly of water, and distillate, formed mainly from DME and MeOH, and said distillate in column for DME (18) is either separated into distillate, which mainly contains DME and non-condensable gases, removed in head part of column, and bottoms product, formed from MeOH with small content of water, which is supplied to head part of column for MeOH (7), or said distillate is supplied into bottom part of column for DME product (30), bottoms product from column for DME product, containing liquid MeOH, is supplied into head part of column for backflow of MeOH (32), distillate from which is supplied into bottom part of column for DME product (30), and its bottoms product is supplied into head part of column for MeOH (7). Invention also relates to installations for performing claimed methods.

EFFECT: methods make it possible to reduce consumption of exploitation materials, improve efficiency of heat-exchange apparatuses and increase catalyst service life.

32 cl, 4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to two versions of the method of using dimethyl ether (DME) synthesis products to convert oxygenates to olefins. One of the versions comprises the following steps: extracting from a DME reactor a stream containing DME, water and methanol; separating, in a liquid-gas separator, carbon dioxide gas from the stream from the DME reactor to obtain a degassed output stream; feeding the degassed output stream into a DME column to obtain crude DME material and a solvent stream containing methanol and water; feeding the crude DME material into a reactor for converting oxygenates to olefins to obtain an olefin-containing output stream which also contains oxygenates; separating the olefin-containing output stream to obtain a fraction containing light olefins and a fraction containing heavy olefins, wherein the fraction containing light olefins contains ethylene and the fraction containing heavy olefins contains C4+; bringing the fraction containing light olefins into contact with a first portion of a solvent stream in a first zone of reacting with solvent to obtain a first olefin-containing purified stream and a first oxygenate-containing extract; bringing the fraction containing heavy olefins into contact with a second portion of the solvent stream in a second zone for reacting with solvent to obtain a second olefin-containing purified stream and a second oxygenate-containing extract.

EFFECT: disclosed method enables integration of dimethyl ether synthesis with conversion of oxygenates to olefins.

8 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing a dimethyl ether product by catalytic conversion of synthesis gas to dimethyl ether, involving contact of a stream of synthesis gas containing carbon dioxide, at a dimethyl ether synthesis step in one or more reactors, with one or more catalysts which are active in formation of methanol and dehydration of methanol to dimethyl ether to obtain a product mixture containing the components dimethyl ether, methanol, carbon dioxide and unreacted synthesis gas, washing the product mixture containing carbon dioxide and unreacted synthesis gas in a gas washing zone with a liquid solvent which is rich in potassium carbonate or amine, thereby selectively absorbing carbon dioxide from the liquid solvent. The obtained treated product mixture undergoes distillation to separate methanol and water from a stream of dimethyl ether and unreacted synthesis gas with low content of carbon dioxide and the unreacted synthesis gas is separated from the dimethyl ether product.

EFFECT: method improves output of the process and final purification of the obtained dimethyl ether.

6 cl, 1 ex, 3 tbl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to method of producing dimethyl ether (DME) from methanol, consisting of the following stages: initial methanol raw material is supplied to reactor with fluidised bed, where it contacts with catalyst to carry out dehydration reaction in order to obtain dehydrated reaction flow; said dehydrated reaction flow is passed to separator to separate gas from solid particles to obtain catalyst with coal layer and dehydrated reaction product on the output, part of catalyst or entire said catalyst with coal layer is supplied to regenerator to burn coke for catalyst regeneration by continuous or step-by-step method; regenerated catalyst is passed back to reactor, where it contacts with initial methanol raw material to perform reaction, said dehydrated reaction product is supplied to separator, which includes absorption column and column for DME rectification, and, optionally, column of methanol regeneration; product flow, mainly consisting of DME, is accumulated in upper part of DME rectification column; non-condensable gas, caught with DME and/or methanol, is obtained in upper part of DME rectification column; said non-condensable gas is supplied into absorption column to absorb DME and/or methanol which was caught with absorbing liquid, liquid on the bottom of DME rectification column mainly consisting of unreacted methanol and water; liquid on DME rectification column is arbitrarily separated by column of methanol regeneration to obtain methanol in upper part of column of methanol regeneration and discharge water on the bottom of regeneration column, and absorbing liquid, used in absorption column, is liquid on the bottom of DME rectification column and/or discharge water on the bottom of regeneration column.

EFFECT: method makes it possible to make complete use of heat resulting from DME production, reduce content of methanol in non-condensable waste gas.

25 cl, 14 ex, 3 tbl, 4 dwg

FIELD: chemistry.

SUBSTANCE: present invention relates to a catalytic method of producing dimethyl ether from methanol, which is realised in a reactor, wherein the catalyst is in fluidised state, involving: (1) feeding starting methanol through two or more inlet holes which can be on the bottom, in the lower, middle or top parts of the reactor; reaction with a catalyst to obtain dimethyl ether via dehydration of methanol; carrying out a reaction to obtain dimethyl ether via dehydration of methanol to obtain a stream of reaction products; separation of the stream of reaction products to obtain a carbided catalyst and a crude output product mainly containing the end product, dimethyl ether; and (2) feeding a portion of the carbided catalyst obtained at step (1), in a continuous or cyclic mode, into a regenerator to regenerate the catalyst by carbon burning, and the remaining portion is cooled and fed from below into the reactor, after catalyst regeneration, divided into two parts, one of which, after heat exchange, is fed directly into an apparatus for mixing the catalyst lying in the bottom of the lift-reactor, and the second part is mixed with fresh catalyst and fed into the reactor, wherein the reactor used is a combination of a lift-reactor and a fluidised-bed reactor, and the fluidised-bed reactor lies on top of the lift-reactor.

EFFECT: method enables to obtain an end product with high selectivity and high conversion of methanol.

18 cl, 11 ex, 7 tbl, 2 dwg

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing alkyl-tert-alkyl ethers or mixtures thereof, which can be used as gasoline high-octane additives. The method involves bringing mixtures of C4 hydrocarbons, which contain isobutene and C4 alcohol(s), into contact with heterogeneous acid catalysts in successive direct-flow reaction zones at temperature 30-110°C, which is lower in reaction zones after the first, with subsequent separation of the reaction mixture in a fractionation system and obtaining a stream containing a spent fraction of C4 hydrocarbons as distillate and an end product in form of a bottom stream. The process is carried out at pressure 0.5-2.5 MPa, which ensures the components are in liquid phase, molar ratio of reactants at the input of the first reaction zone C4 alcohol: isobutylene equal to (0.9-1.05):1.0 and volume rate of feeding material less than 2.5 h-1 (2.5-10 h-1), the end product primarily contains alkyl-tert-alkyl ether(s), the distillate of the fractionation system does not contain C4 alcohol(s) and alkyl-tert-alkyl ether(s).

EFFECT: method increases rate of etherification reaction, enables to carry out the process selectively and increases output of alkyl-tert-butyl ethers and/or mixtures thereof, and also reduces power consumption when extracting the spent C4 fraction.

3 cl, 9 ex, 2 tbl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to an oil medium which is suitable for producing dimethyl ether and/or methanol which is used in a synthesis reaction with a suspended layer as a medium which contains a basic component in form of a branched saturated aliphatic hydrocarbon containing 16-50 carbon atoms, 1-7 tertiary carbon atoms, 0 quaternary carbon atoms and 1-16 carbon atoms in branched chains bonded with tertiary carbon atoms; wherein at least one tertiary carbon atom is bonded with hydrocarbon chains with length of 4 or more carbon atoms, lying in three directions. The invention also relates to a method of producing dimethyl ether and a mixture of dimethyl ether and methanol using said oil medium.

EFFECT: use of the present oil medium ensures high efficiency of synthesis.

9 cl, 4 ex, 1 tbl, 1 dwg

FIELD: gas and oil production.

SUBSTANCE: invention refers to procedure for production of high-octane mixtures containing alkyl-tert-alkyl ethers with implementation of at least interaction of tert-pentene in fraction containing mainly hydrocarbons C5 and, possibly, hydrocarbons C6 with alcohol(s) C1-C4 at presence of acidic solid catalyst(s) at 20-100°C rectification. The procedure consists of processing in two stages. At the first stage there is performed synthesis of mainly alkyl-tert-amyl ether with contacting fraction of hydrocarbons C5 and partially C6 with alcohol(s) C1-C4 distillation of distillate. At the second stage alcohol is recuperated from the said distillate, for which purpose distillate is subjected to additional contacting with at least the said catalyst(s) and also with hydrocarbon mixture including isobutene and/or tert-pentene at amount sufficient for transformation of major portion of alcohol into alkyl-tert-alkyl ether(s). In case of their utilisation C4-hydrocarbons are removed from reaction mixture together with admixture of alcohol when limit of its concentration, allowed for benzene ingredients, is exceeded.

EFFECT: reduced power inputs due to improved recuperation of alcohol.

8 cl, 9 ex, 2 tbl, 3 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing tert-pentene(s) and/or alkyl C1-C2-tert-pentyl ether from mixtures of mainly C5-hydrocarbons, containing at least tert-pentenes, isopentane and an admixture of pentadiene(s), and C1-C2 alcohol, involving reaction of tert-pentene(s) with C1-C2 alcohol on a solid acid catalyst and extraction of products via rectification, characterised by that at least catalysed isomerisation of 2-methyl-1-butene into 2-methyl-2-butene [possibly in the presence of hydrogen] is carried out in the initial mixture, the formed mixture undergoes rectification and distillate is output, said distillate mainly containing isopentane, and a stillage residue mainly containing 2-methyl-2-butene, a portion of which preferably undergoes catalysed reaction with C1-C2 alcohol in ether synthesis zone(s), distillate is distilled out of the formed mixture, said distillate containing a mixture of unreacted C5-hydrocarbons with alcohol, which is further used to obtain ether(s), preferably by returning to the ether synthesis zone, and the stillage residue is output, said stillage residue containing alkyl C1-C2-tert-pentyl ether, which is collected as the product and/or undergoes catalysed decomposition and a mixture of pure tert-pentenes is extracted via rectification and removal of alcohol.

EFFECT: disclosed method virtually avoids the need to extract alcohol from mixtures with hydrocarbons and extraction thereof from the extract, where the need for basic equipment is at least twice less compared to existing methods.

9 cl, 2 tbl, 6 ex, 3 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing dioctyl ether, known as emollient, having softening action and is used in cosmetic agents and pharmaceutical emulsions. The method involves catalytic dehydration of octanol-1 in the presence of a Cu(acac)2-CBr4 catalyst system at temperature 195-200°C for 8-12 hours in molar ratio [Cu(acac)2]:[CBr4]:[octanol-1]=1:5:100.

EFFECT: method enables to obtain the desired product with high output.

1 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: invention relates to improved methods of obtaining dimethyl ether (DME) from methanol (MeOH) by conversion, preferably by condensation, under conditions of acid catalysis, of raw MeOH, obtained by MeOH-synthesis, with splitting water in reactor (12) with obtaining DME, in which initial mixture, consisting of raw MeOH, and at least one obtained within the process and formed from unreacted MeOH and water from reaction backflow are supplied into column for MeOH (7) and subjected to evaporation, with distillate, consisting mainly of gaseous MeOH, is supplied to reactor. Reaction mixture, removed in reactor (12), in column for mixture (15) is separated into bottoms product, consisting mainly of water, and distillate, formed mainly from DME and MeOH, and said distillate in column for DME (18) is either separated into distillate, which mainly contains DME and non-condensable gases, removed in head part of column, and bottoms product, formed from MeOH with small content of water, which is supplied to head part of column for MeOH (7), or said distillate is supplied into bottom part of column for DME product (30), bottoms product from column for DME product, containing liquid MeOH, is supplied into head part of column for backflow of MeOH (32), distillate from which is supplied into bottom part of column for DME product (30), and its bottoms product is supplied into head part of column for MeOH (7). Invention also relates to installations for performing claimed methods.

EFFECT: methods make it possible to reduce consumption of exploitation materials, improve efficiency of heat-exchange apparatuses and increase catalyst service life.

32 cl, 4 dwg

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing primary alkyl ethers of glycerol, which can be used as biofuel or as biofuel additives. The method involves activating treatment of a catalyst, reaction of a primary alcohol with glycerol in molar ratio of primary alcohol to glycerol ranging from 3:1 to 9:1, in the presence of a solid acid catalyst, at temperature ranging from 60 to 300°C for 5-8 hours with average hourly rate of feeding material of about 0.2 h-1, in a fixed-bed reactor and separating the required glycerol ethers which are converted to said reaction mixture.

EFFECT: disclosed method enables to selectively obtain primary alkyl ethers of glycerol with high output in moderate conditions over a much shorter period of time.

8 cl, 9 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing a dimethyl ether product by catalytic conversion of synthesis gas to dimethyl ether, involving contact of a stream of synthesis gas containing carbon dioxide, at a dimethyl ether synthesis step in one or more reactors, with one or more catalysts which are active in formation of methanol and dehydration of methanol to dimethyl ether to obtain a product mixture containing the components dimethyl ether, methanol, carbon dioxide and unreacted synthesis gas, washing the product mixture containing carbon dioxide and unreacted synthesis gas in a gas washing zone with a liquid solvent which is rich in potassium carbonate or amine, thereby selectively absorbing carbon dioxide from the liquid solvent. The obtained treated product mixture undergoes distillation to separate methanol and water from a stream of dimethyl ether and unreacted synthesis gas with low content of carbon dioxide and the unreacted synthesis gas is separated from the dimethyl ether product.

EFFECT: method improves output of the process and final purification of the obtained dimethyl ether.

6 cl, 1 ex, 3 tbl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to method of producing dimethyl ether (DME) from methanol, consisting of the following stages: initial methanol raw material is supplied to reactor with fluidised bed, where it contacts with catalyst to carry out dehydration reaction in order to obtain dehydrated reaction flow; said dehydrated reaction flow is passed to separator to separate gas from solid particles to obtain catalyst with coal layer and dehydrated reaction product on the output, part of catalyst or entire said catalyst with coal layer is supplied to regenerator to burn coke for catalyst regeneration by continuous or step-by-step method; regenerated catalyst is passed back to reactor, where it contacts with initial methanol raw material to perform reaction, said dehydrated reaction product is supplied to separator, which includes absorption column and column for DME rectification, and, optionally, column of methanol regeneration; product flow, mainly consisting of DME, is accumulated in upper part of DME rectification column; non-condensable gas, caught with DME and/or methanol, is obtained in upper part of DME rectification column; said non-condensable gas is supplied into absorption column to absorb DME and/or methanol which was caught with absorbing liquid, liquid on the bottom of DME rectification column mainly consisting of unreacted methanol and water; liquid on DME rectification column is arbitrarily separated by column of methanol regeneration to obtain methanol in upper part of column of methanol regeneration and discharge water on the bottom of regeneration column, and absorbing liquid, used in absorption column, is liquid on the bottom of DME rectification column and/or discharge water on the bottom of regeneration column.

EFFECT: method makes it possible to make complete use of heat resulting from DME production, reduce content of methanol in non-condensable waste gas.

25 cl, 14 ex, 3 tbl, 4 dwg

FIELD: chemistry.

SUBSTANCE: present invention relates to a catalytic method of producing dimethyl ether from methanol, which is realised in a reactor, wherein the catalyst is in fluidised state, involving: (1) feeding starting methanol through two or more inlet holes which can be on the bottom, in the lower, middle or top parts of the reactor; reaction with a catalyst to obtain dimethyl ether via dehydration of methanol; carrying out a reaction to obtain dimethyl ether via dehydration of methanol to obtain a stream of reaction products; separation of the stream of reaction products to obtain a carbided catalyst and a crude output product mainly containing the end product, dimethyl ether; and (2) feeding a portion of the carbided catalyst obtained at step (1), in a continuous or cyclic mode, into a regenerator to regenerate the catalyst by carbon burning, and the remaining portion is cooled and fed from below into the reactor, after catalyst regeneration, divided into two parts, one of which, after heat exchange, is fed directly into an apparatus for mixing the catalyst lying in the bottom of the lift-reactor, and the second part is mixed with fresh catalyst and fed into the reactor, wherein the reactor used is a combination of a lift-reactor and a fluidised-bed reactor, and the fluidised-bed reactor lies on top of the lift-reactor.

EFFECT: method enables to obtain an end product with high selectivity and high conversion of methanol.

18 cl, 11 ex, 7 tbl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to use of heteropoly acid catalysts for converting oxygenates to alkenes. Described is a method of producing an alkene (alkenes) from an oxygenate starting material through dehydration in a reactor in the presence of a heteropoly acid catalyst deposited on a support, characterised by that the specific pore volume thereof satisfies the following relationship: OP>0.6-0.3 [amount of heteropoly acid catalyst/surface area of dried catalyst], where OP denotes the specific pore volume of the dried heteropoly acid catalyst deposited on the support (given in ml/g catalyst); the amount of the heteropoly acid catalyst is the amount of heteropoly acid contained in the dried heteropoly acid catalyst deposited on the support (given in micromole/g); the surface area of the dried catalyst is the specific surface area of the dried heteropoly acid catalyst deposited on the support (given in m2/g). Described is a method of converting a hydrocarbon to an alkene (alkenes), involving the following successive steps: a) converting hydrocarbon starting material in a synthetic gas reactor into a mixture of carbon oxide (oxides) and hydrogen, b) converting said mixture of carbon oxide (oxides) and hydrogen from step a) in the presence of a powdered catalyst in a reactor at temperature ranging from 200 to 400°C and at pressure ranging from 50 to 200 bars into starting material containing at least one monoatomic aliphatic paraffin alcohol and/or the corresponding ether containing 2-5 carbon atoms, and c) continuing to realise the method as described above to obtain alkenes, owing to which the oxygenate starting material contains at least a portion of alcohol (alcohols) and/or ethers obtained at step b). Described is use of the heteropoly acid catalyst deposited on a support in the method of producing alkene (alkenes) from oxygenate starting material for increasing alkene selectivity and output while simultaneously preventing formation of alkanes, in the presence of the catalyst described above.

EFFECT: high efficiency of producing alkenes and low amount of alkanes formed.

20 cl, 7 tbl, 1 dwg, 19 ex

FIELD: chemistry.

SUBSTANCE: invention relates to versions of a novel method of producing a (E)-stilbene derivative of formula

,

used to produce polyhydroxystilbenes, particularly resveratrol or piceatannol, which exhibit antioxidant effect, novel intermediate compounds of formula , , and

used in said methods, as well as use of the compound of formula

, ,

(III), (IV) or (VII) as an intermediate compound in the synthesis of the (E)-stilbene derivative of formula (VI) or polyhydroxystilbene. Values of substitutes R1, R1', R2', R, A, Ar, R' are given in the claim.

EFFECT: improved properties of the compound.

26 cl, 1 dwg, 32 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing dioctyl ether, known as emollient, having softening action and is used in cosmetic agents and pharmaceutical emulsions. The method involves catalytic dehydration of octanol-1 in the presence of a Cu(acac)2-CBr4 catalyst system at temperature 195-200°C for 8-12 hours in molar ratio [Cu(acac)2]:[CBr4]:[octanol-1]=1:5:100.

EFFECT: method enables to obtain the desired product with high output.

1 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: method is proposed for processing a mixture of hydrogen and carbon oxides at high temperature and excess pressure (three versions) by bringing the mixture into contact with a catalyst at the first stage, where the catalyst consists of a methanol synthesis catalyst and a solid acid catalyst, and bringing products of the first stage into contact with a zeolite-containing catalyst at the second stage. One of the versions of the method is characterised by that, the initial mixture has volume ratios (H2-CO2)/(CO+CO2)=1-3 and CO/CO2=0-100 and on both stages, the process is carried out with separate recirculation of gas streams. The first contacting stage is carried out at pressure from 20 to 80 atm, bulk speed of supplying the initial mixture of 500 to 10000 h-1, circulation ratio of 3 to 20. The methanol synthesis catalyst and the acid catalyst can be placed in form of a mixture in one reaction zone and the process is carried out at temperature from 200 to 320°C or these catalysts can be placed separately in different reaction zones and in the zone of the methanol synthesis catalyst, the process is carried out at temperature from 200 to 320°C, and in the zone with the acid catalyst the process is carried out at temperature from 200-400°C. Reaction products from the first stage are cooled and separated into a liquid fraction and a gas stream, which contains dimethyl ether and unconverted components of the initial mixture. The liquid fraction is separated by rectification with extraction of CO2-containing gas, dimethyl ether, water-methanol solution and water; the gas stream of the products of the first stage is fed into a washing column being washed with water-methanol solution, after which it is divided into two streams, one of which is directed in form of a recycle for mixing with the initial mixture, and the other is either bled-off or directed to the second stage of the process, and the enriched water-methanol solution coming from the washing column is taken for rectification together with liquid products from the first stage, after which the extracted water-methanol solution is partially directed into the washing column, and the other part is taken to the second stage of the process, where at pressure from 1 to 40 atm, temperature from 320 to 460 °C, mass flow rate from 0.5 to 10 h-1, it is brought into contact with a catalyst while recirculating gaseous products from the second stage with circulation ratio of 1 to 10. Products from the second stage are separated with extraction of a high-octane benzene fraction or aromatic hydrocarbons and a light benzene fraction, water and fraction(s) of hydrocarbon gases, including propane, butane fraction, part of which is used in form of a recycle for the second stage. Components of the solid acid catalyst at the first stage are aluminium oxide and/or crystalline silico aluminophosphate and/or zeolite with ZSM-5 or ZSM-11 structure, with molar ratio SiO2/Al2O3 not greater than 200, and/or zeolite of the type β (beta), L, erionite, mordenite, and the catalyst at the second stage contains zeolite with ZSM-5 or ZSM-11 structure, with molar ratio SiO2/Al2O3 not greater than 200.

EFFECT: wider assortment of desired products and increased versatility of the process, as well as increased output of C3+ hydrocarbons in terms of total amount of hydrocarbons.

3 cl, 8 ex, 7 dwg

FIELD: industrial organic synthesis and catalysts.

SUBSTANCE: invention provides a method for processing methanol into dimethyl ether and liquid hydrocarbons, the latter being used as high-octane components of gasolines Ai-92, 95. Processing comprises contacting of raw material, in at least one step, in at least one reactor containing catalyst: Pentasil-type zeolite and binder, followed by cooling resulting products, condensation and separation thereof to isolate methanol conversion hydrocarbon gases, water, and desired products, after which cooled hydrocarbon gases are recycled to methanol conversion stage in at least one reactor. Catalyst is characterized by SiO2/Al2O3 molar ratio 20-100, content of sodium oxide not higher than 0.2%, and additionally contained silicon dioxide and zirconium dioxide at following proportions of components: 1.0-15.0% silicon dioxide, 1.0-5.0% zirconium dioxide, 20-70% zeolite, and binder - the balance.

EFFECT: increased yield of desired products and improved performance characteristics of catalyst.

4 cl, 5 tbl, 18 ex

FIELD: chemistry.

SUBSTANCE: invention describes a methanol synthesis method which comprises conversion of hydrocarbon-containing material to obtain synthesis gas (1) containing carbon monoxide and hydrogen and a reaction between components of fresh synthesis gas in a synthesis loop (10) to obtain raw methanol and removing hydrogen-containing purge gas (20) from the synthesis loop. The purge gas is heated by heat recuperation via indirect heat exchange with at least one high-temperature heat source in said method, said heat source being adapted to heat purge gas to temperature not lower than 200°C to obtain a heated purge gas (33), and said heated purge gas, as such, is expanded in a corresponding expander (34), and energy is obtained due to expansion of the purge gas in the expander, wherein said high-temperature heat source used is hot waste gas from the conversion process, wherein the material is converted to fresh synthesis gas (1) or a stream of hot steam. The invention also relates to a methanol synthesis apparatus and a method of reconstructing a methanol synthesis apparatus.

EFFECT: disclosed objects improve overall energy balance of the process.

13 cl, 2 dwg, 2 ex

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