Method of production of methanol

FIELD: chemistry.

SUBSTANCE: method includes contact of gas mixture containing carbon oxides and hydrogen ballasted down with nitrogen with copper-containing catalyst under heating, pressure and definite rate velocity of feeding into reactor. Reactor unit consists of two adiabatic-type reactors connected with a pipeline; the original gas mixture containing CO - 10-15 % v/v, CO2 - 0.3-5.0 % v/v, H2 - 15-40 % v/v, N2 -40.0-74.7 % v/v and volumetric ratio H2/(CO+CO2) equal to 1.00-2.91, at 200-260°C and pressure 3.5-5.0 MPa with rate velocity 2000-5000 h-1 is fed into the first reactor with larger main part of unconverted gas fed to circulation and produced at the outlet of the second reactor cooled to 15-20°C and further purified to remove methanol in tower washer and compressed; then the reaction mixture from the first reactor is fed into the second reactor along with the rest minor part of circulating gas indicated above as quench - cold circulation gas fed into the pipeline between the two rectors.

EFFECT: method allows increasing methanol yield, efficiency of the process and reducing energy consumption.

4 cl, 3 tbl, 1 dwg, 1 exsid1190496

 

The invention relates to the field of chemical technology, energy-saving processes for the production of methanol from gas mixtures containing carbon oxides and hydrogen and with a high content of nitrogen, i.e. gas mixtures of various chemical, petrochemical and metallurgical industries.

The synthesis of methanol from synthesis gas is a highly exothermic process. It is usually carried out in a fixed catalyst bed with the cold raw gas in the catalyst layers, with the removal of the heat of reaction between catalyst or in tubular reactors (AVI, V.ye.leonov and other Technology of synthetic methanol. M.: Chemistry, 1984, p.116-120). Closest to the isothermal mode of reaction reaches in a tubular reactor, but in this case, the wall temperature of the pipe along the length of the heated part, i.e. the temperature of the catalyst layer is changed almost 40-60°C.

A known method of producing methanol from synthesis gas containing hydrogen and oxides of carbon, in which fresh gas is fed into the reactor operated without circulation of the gas mixture and the unreacted gas after condensation of methanol in fridge-separator served in another reactor with circulating synthesis gas. Flow reactor work in isothermal mode (Application Germany 3518362, 27.11.86).

The disadvantage of this method is to use isawanya compressors high power for circulating the gas mixture in the second stage, consequently, significant energy consumption.

There is also known a method of producing methanol by contacting the gas mixture containing carbon monoxide, carbon dioxide and hydrogen, with a copper-containing catalyst at a temperature of 190-290°and the pressure of 5-10 MPa in two stages. In the first stage copper-containing catalyst is brought into contact with a gas mixture containing 5-30 vol.% of carbon monoxide and 0.3 to 20.0 vol.% carbon dioxide, when the volume ratio of carbon monoxide to carbon dioxide of 0.25-87 and the volume ratio of hydrogen to the sum of the oxides of carbon 2,0-3,65. This stage is carried out in a flow reactor or a cascade type flow rate of the source gas mixture 4500-100000 h-1thus the gas mixture containing carbon monoxide, carbon dioxide, hydrogen, methanol vapor and 0.02-1,38% vol. water vapors, these vapors of methanol and water are removed from the gas mixture. The remaining gas mixture containing carbon monoxide, carbon dioxide and hydrogen is fed to the second stage, which is carried into the reactor by circulation of the gas mixture with a bulk velocity 700-15000 h-1getting after the second stage of the gas mixture containing carbon monoxide, carbon dioxide and hydrogen, methanol vapor and water, which are removed from the gas mixture (WO 88/00580, 27.11.86).

The disadvantages of this method include low specific productivity of honey which contains the catalyst in the second stage, component depending on the synthesis conditions of 0.40-0.68 t/m3hour, a minor contribution of methanol obtained in the first stage, a total amount from 5.42 to 78,33%, high circulation rate of the gas mixture. This involves the use of a compressor of a large capacity and a significant expenditure of energy for circulating the gas mixture that significantly impairs the technical-economic indicators of the process.

Known sorbent methanol vapors and method for producing methanol according to which methanol is produced from synthesis gas containing carbon monoxide and/or carbon dioxide and hydrogen at a pressure of 1-20 MPa, a temperature of 175-300°in the presence of the methanol synthesis catalyst in which to shift the reaction equilibrium towards the products of reaction formed methanol vapor is removed from the reaction mixture by adsorption of methanol vapor sorbent. As the sorbent (matrix)having the micro-, meso - and macropores in the form of spherical particles with a diameter of 0.5 to 6 mm, or cylindrical particles with a diameter of 0.5 to 5 mm, are inorganic oxides, porous carbons, natural sorbents, or a mixture thereof. The matrix additionally contains the active substance is placed in the pores and is capable of reversible processes of sorption/desorption of methanol vapor. As active substances used are halides and nitrates of alkali, alkaline earth IU allow and metals of the iron subgroup in the amount of not less than 5 wt.% (application No. 2005108449 28. 03. 2005).

A significant disadvantage of this method is that the process of sorption of methanol is periodic, which complicates instrumentation process and requires the creation of two intermittently operating adsorbers, as a necessary stage of regeneration of the sorbent.

A known method of producing methanol according to which methanol is produced by contacting a gas mixture containing carbon oxides and hydrogen, with a copper-containing catalyst at a temperature of 190-290°C, pressure of 5.0-10.0 MPa and flow rate 4500-100000 h-1. The source gas mixture containing 1.0 to 33,7% vol. oxide of carbon, 0.3 to 22,5% vol. carbon dioxide, when the volume ratio of hydrogen to the sum of the oxides of carbon, equal 1,91-the ceiling of 5.60 and 0.5-50,0% vol. nitrogen, sequentially passed through the cascade isothermal flow reactors in a single phase, while the methanol and water are condensation after each reactor (EN 2181117, 10.04.2002).

This known method the technical essence is the closest to the claimed invention, i.e. it is a prototype. The disadvantages of this method are:

- low specific productivity of a copper-containing catalyst, not exceeding for a cascade of three reactors of 0.58 kg/l hour at work on tabulations the synthesis gas with a sufficiently large value of N2/(CO+CO 2), equal 3,22.

- the use of expensive compressors more power to the gas mixture under a pressure of 50 ATM and above, and therefore, significant energy consumption.

Proposed in the prototype method uneconomical to recycle methanol gases with low (less than 2) by the relation H2/(CO+CO2), although on industrial sites such necessity exists.

When the ratio of reactants is substantially below the stoichiometric decreases the degree of conversion of carbon oxides to methanol due to the lack of hydrogen in the loop.

When using a gas with a high nitrogen content decreases sharply specific productivity of the catalyst in the low content of reactive components of carbon monoxide, carbon dioxide and hydrogen gas in direct contact with the catalyst. While it is impossible to achieve high economic performance of the process because of increased energy costs on the circulation of the gas, which consists mainly of nitrogen - inert component in the synthesis of methanol.

Existing methods methane conversion (for example, obtaining synthesis gas using methane conversion on the internal combustion engine of the compression type G(GCN/45) allow to obtain gases with a lower ratio of hydrogen to the sum of the oxides of carbon, stated in the prototype and equal 1,91, and with a higher concentration of nitrogen than the stated 50,0%vol.

In the present invention as a raw material gas is supposed to be used, and such synthesis gas obtained in the internal combustion engine of the compression type.

The technical objective of the claimed invention is a further improvement of the method of producing methanol from gas mixtures with a high content of dietary nitrogen and depleted in hydrogen, i.e. compounds with low adverse reaction ratio of N2/(CO+CO2) less than 2, as well as increasing the specific productivity of the catalyst, the degree of conversion of carbon oxides to methanol and quality of crude methanol.

The goal of the project is achieved by a method of producing methanol by contacting the gas mixture containing carbon oxides and hydrogen and tabulations nitrogen, with a copper-containing catalyst by heat, pressure and supplied to the reactor block with a certain bulk velocity, in which the reactor block consists of two adiabatic reactors type, connected by a pipeline, the source gas mixture of CO - 10-15 vol.%, CO2of 0.3 to 5.0 vol.%, H2- 15-40 vol.%, N2- 40,0-74,7% vol. and the volume ratio of N2/(CO+CO2), is equal to 1.00-2.91 in, when 200-260°and a pressure of 3.5 to 5.0 MPa with a bulk velocity 2000-5000 h-1 fed to the first reactor along with most (main) part of the unreacted gas generated at the output of the two reactors, cooled to 15-20°and further past the compression and purification from methanol scrubber water purification, and then the reaction mixture from the first reactor is served in the second reactor together with the remaining lower part of the above circulating gas in the quench - cold circulating gas fed into the pipeline between the two reactors.

In the method, in particular, use the adiabatic reactors of the type with a single layer of a copper-containing catalyst; the multiplicity of circulation of the circulating gas is 5-6.

Complete cleaning of the circulating gas used in the claimed method and formed at the outlet of the reactor building, carried out in a scrubber by trapping traces of methanol-water backflow.

Thus, the technical problem is solved by the fact that in the inventive method, the methanol is produced by contacting strongly deballasting synthesis gas with a copper-containing catalyst fed to the first of two consecutive adiabatic reactors with a certain speed when heated and under pressure. Output 2 serial adiabatic reactor, the reaction gas is cooled in a refrigerator to a temperature of 15-20°enters the high pressure separator, where the separation of the liquid from the unreacted gas. Unreacted gas containing carry out the methanol enters the scrubber water washing gas from methanol. Completely cleared from the methanol gas is supplied to the compression unit, hereinafter referred to as the circulation of the gas, its main part is mixed with the fresh synthesis gas and then to the first of 2 adiabatic reactor, and a smaller part is used as the quench supplied to the pipeline between the two reactors.

As the source gas mixture using a gas mixture tabulation nitrogen composition WITH 10-15 vol.%, CO2of 0.3 to 5.0 vol.%, H2- 20-30 vol.%, N2- 50,0-69,7%, which is passed through two successive instantaneous adiabatic reactor with a bulk velocity 2000-5000 h-1(in calculating the total load of both reactors) at 200-260°C, a pressure of 3.5 to 5.0 MPa and the volume ratio of N2/(CO+CO2), is equal to 1.00-2.91 in.

The method according to the invention provides for the filing of the original gas mixture in the first adiabatic reactor with a bulk velocity 2000-5000 h-1the use of recycling unreacted synthesis gas after treatment in the scrubber of traces of methanol in the first of 2 consecutive reactors with multiplicity circulation 5-6, and the use of quench supplied to the pipeline between the two reactors.

Using the proposed method, the values of the ratio of circulation 5-6 suggests that at the exit of the reactor at steady state both reactors operate at a load corresponding to the volumetric throughput rate of the gas mixture, equal 10000-20000 h-1.

As copper-containing catalysts in the method according to the invention using various copper-containing catalysts, for example copper-zinc-aluminum catalyst C-79-7GL, production Zud Chemie, composition (wt.%): CuO - 62,0; ZnO - 28,0; Al2About3- 10,0 (in the form of cylindrical pellets with a diameter of 5.0 mm and a height of 4.0 mm); copper-zinc-aluminum - containing catalyst composition (wt.%): CuO - 53,2; ZnO - 27,0; Al2About3- 5,5; HgO - 2,0; copper-zinc-chromium catalyst containing (in wt.%): CuO - 56,0; ZnO - 24-28; Cr2O3- 15-19; copper-zinc catalyst type SNM-1 and others.

Thus, the essence of the claimed invention is as follows.

Methanol is produced by contacting a gas mixture containing carbon oxides and hydrogen, with a copper-containing catalyst at a temperature of 200-260°C, a pressure of 3.5 to 5.0 MPa and flow rate 2000-5000 h-1(in calculating the total load of both reactors), while according to the invention the source tabulation nitrogen (50-69,7 vol.%) a gas mixture containing 10-15% vol. carbon monoxide, 20 to 30% vol. hydrogen and 0.3-5% vol. carbon dioxide (when the lines the ratio of hydrogen to the sum of the oxides of carbon and 1.00-2.91 in), served in the first of two consecutive adiabatic reactors. The reaction gas at the outlet of the second reactor is cooled to a temperature of 15-20°after purification of traces of methanol in the scrubber is fed to the compression, and then in the form of a circulating gas main part after mixing with the fresh synthesis gas is fed into the first of 2 adiabatic reactors, while the smaller part is used as the quench supplied to the pipeline between the two reactors.

No traces of unreacted methanol in the gas fed to recycling, after processing in the scrubber allows for undesirable for efficient reaction low ratio of H2/CO to displace the equilibrium towards the production of methanol, thereby leading to an increase in the conversion of carbon oxides and, accordingly, the yield of methanol. This is achieved in the absence of the phenomenon of inhibition of the reaction products (in circulation gas in the proposed method there is no even traces of methanol, while using traditional circulation concentration of methanol in the circulating gas can reach values of 1-2 vol.%).

In addition, the increasing conversion of carbon oxides and, accordingly, the yield of methanol is achieved using multiple circulation unreacted synthesis gas.

Pre the proposed method uses, in particular, the synthesis gas is obtained by using a diesel generator with a ratio of N2:(Up to 1.5-1.7)and below that required for stoichiometric reaction ratio equal to 2, i.e. stoichiometric excess in the reaction gas of carbon monoxide with respect to hydrogen automatically leads to incomplete conversion of CO in the reaction of methanol synthesis and, consequently, the necessity of application circulation to enhance the yield of methanol. Therefore, the use of gas circulation in the proposed method is the main attribute.

In the proposed method, the process pressure does not exceed 5 MPa, which makes possible the use of cheaper compressors low pressure in comparison with described as analogs and prototypes ways, where is the working pressure of not lower than 5 MPa.

When choosing a technology featured in implementing the setup for methanol production capacity of 10 thousand tons/year, were considered well-known scheme for methanol in the cascade of three isothermal reactor, the methanol and water are condensation after each reactor, one isothermal reactor recycle, the cascade of three adiabatic reactors with recycle, one adiabatic reactor with three chambers. Calculations showed that during the process without circulation in three isothermal the reactors at a given flow rate of synthesis gas (17 million mC/year) can receive no more than 7.5 to 8 tonnes/year of methanol. When using gas circulation with multiplicity up to 6-7 yield of methanol is increased to 10-11 tonnes/year, and using the washing of the circulation gas with water to remove traces of methanol to 12 tonnes/year. At the same time when the value of the ratio of the gas circulation 5-7 loses its economic sense, the use of isothermal reactors, has a rather complicated structure.

In the present invention, using the pressure of the source gas 5 MPa, the reaction for methanol can be done in two series of adiabatic reactors, resorting to the circulation of the unreacted gas in the first reactor, to increase the conversion of carbon monoxide and the use of quench - cold circulating gas fed to the second reactor, contributes to the necessary temperature reduction process, which also has a positive effect on the conversion of carbon oxide in an exothermic reaction.

The drawing schematically depicts a schematic diagram of installation for producing methanol according to claims 1 to 4 claims.

Raw synthesis gas pressure of 5.0 MPa and a temperature of 15-40°comes With installation methanol synthesis, where it is mixed with recycle gas supplied by a compressor PC-101. Next, gas is the mixture is heated in the recuperator heat exchanger T-101 due to the heat flow after reactor R-101/2, degraves in the heating furnace P-101 and fed to the inlet of the reactor R-101/1. A small part of the flow of gas recirculation is used as the quench is applied to the input of the second reactor R-101/2. Provided by the mixture of the raw synthesis gas from the circulation gas to the heat exchanger T-101.

Heated in a furnace P-101 gas mixture supplied to the methanol synthesis reactor R-101/1, where low-temperature catalyst at pressures up to 5 MPa and temperatures up to 200-234°flows through the reaction of methanol synthesis. In the reactor the reaction mixture is heated at Δ 25-34°C. Leaving the reactor R-101/1, the reaction mixture is mixed with quench (cold circulating gas), resulting in the temperature of the gas mixture is brought to the desired (210-220° (C), and then it goes to the second methanol synthesis reactor R-101/2. Reactor R-101/1 and P-101/2 adiabatic with one layer of catalyst.

Coming out of the reactor R-101/2, the reaction mixture gives off its heat in the heat exchangers of the T-101 is cooled in air refrigerator XB-101, then in the refrigerator for X-104, fueling the gas flow And after-101, then in the refrigerator for X-105 is cooled to a temperature of 15°and enters the high pressure separator E-101, where the separation of liquid from gas.

Gas from the F-101, contain carry out the methanol enters the scrubber water washing gas from methanol And-101. The eyes of the military from methanol gas recuperare its cold in the heat exchanger H-104 and partially blown off the fuel network, and most of that comes in the form of the circulating gas is supplied to the compression in the PC 101. Kompremirovannyj gas, its main part is 80-90%, is fed to mixing with fresh synthesis gas, and a smaller part is 10-20% is used as the quench front R-101/2.

The liquid product from the tank S-101 enters the low pressure separator (not shown), which is the separation of methanol from dissolved gas, which is blown off by a candle. The methanol is mixed with raw Smetanina water from a-101 and through the heat recovery heat exchanger (not shown) is sent to a rectification column methanol (diagram not shown), where the top of the column there is a selection of commodity methanol. The bottom product, water, is partially discharged into the waste water, and partially served for irrigation in a-101. The refrigerant in the refrigerator X-104 is 85% methanol.

Table 1 shows the parameters (temperature, pressure, mass flow rate, the composition of gas mixtures) for the main gas flow setup for methanol synthesis performance methanol to 11.7 tonnes/year.

The gas at the outlet of the P-101/2
Table 1
IndexEd. MEAs.Gas inlet R-101/1The gas at the outlet of the P-101/1Gas inlet R-101/2+quenchQuench
Temperature(°)200.0234.0210.840.26225.4
Pressure(MPa)4.94.94.95.04.8
Mass flow(kg/h)643606436073080871273090
Molecular weight24.5124.9724.9124.51At 25.21
H2Wt. share0.0127Samples of 0.01130.01140.01270.0105
N20.80750.80410.80450.80750.8053
CH40.00480.00480.00480.00480.0048
CO20.06890.06870.06880.06890.0690
CO0.10520.09490.09610.10520.0894
CH3HE0.00050.158 0.01400.00050.0205

Example 1: Methanol receive in the reactor unit, representing two consecutive adiabatic reactor with the same load in each of the reactors (5 m3). The process parameters and the composition of the gas reaction and the source gas obtained in diesel generator, gas, and are shown in table 2.

Table 2
IndicesExample 1
Temperature, °200-234
Pressure, MPa4,8-5,0
The composition of the gas mixture at the inlet of the reactor block, excluding recycling H2,.%
N254,97
CO23,09
H226,77
H2About0,1
CH40,57
CO14,52
H2/(CO+CO2)1,52
The quantity of fresh gas fed to the first of the 2 reactors, kg/h10350
The volumetric feed rate of fresh gas, h-15000
The amount of gas taking into account recycling, kg/h 64360
The amount of quench is added in the 2nd reactor, kg/h8712
The amount of gas fed to the second reactor taking into account quench, kg/h73080
The composition of the gas mixture at the outlet of the reactor block,% vol.
N273,66
CO23,99
H213,31
H2O0,07
CH40,76
CO8,17
CH3HE0,0421
H2/(CO+CO2)1,10
The conversion of CO+CO2in methanol, %52,1
The yield of methanol on missed synthesis gas, %14,87
The performance of methanol, kg CH3HE/hour1539,41
The specific productivity of methanol, kg CH3HE/l Kt h0,16

As the results of research by the claimed method at pressures up to 5.0 MPa in two consecutive adiabatic reactors with the use of distinctive features of the method (recirculation gas with a ratio of 5-6, the use of quench and purification of recirculated gas from the traces of meth is Nol) can be recycled and not cabalistically nitrogen synthesis gas with a ratio of N 2/(CO+CO2) less than 1.9, achieving high performance of the catalyst is 0.3 to 0.5 kg of CH3HE/l-Kt hour, which exceeds the same indicator of modern industrial plants for production of methanol (0.1 to 0.3 kg of CH3HE/l-Kt h). For deballasting nitrogen at 55-60% of the synthesis gas catalyst productivity can reach the 0.15-0.25 kg CH3HE/l Kt h at conversion of carbon oxides to 60%, and the yield of methanol is 15-25% missed on the gas.

To increase the yield of methanol from deballasting synthesis gas low value of the ratio H2:(CO+CO2) applied the scheme of synthesis in the adiabatic reactor with recirculation purified from traces of methanol gas. The installation provides firming distillation column with bringing the commodity concentration of methanol up to 98.5%. Decisions increased the yield of methanol up to 15% on the initial strongly cabalistically nitrogen synthesis gas. The material balance of the installation is given in table 3.

Table 3

The material balance of plant for methanol
ExpenditureThe value of consumption
kg/htonnes/year% of raw materials
Taken:
the synthesis gas1035082,8100
Total1035082,8100
Received:
- methanol1471,41211,77414,22
- gas in the fuel network879270,333384,9434
loss86,5880,69270,8366
Total1035082,80,8366

It should be noted that when using gas circulation by the present method significantly from 2-3 to 4-5 years extended service life of the catalyst, especially when working on unfavorable for methanol synthesis gas mixtures with low (less than 20-25%vol.) hydrogen content.

It should also be noted that when using highly selective copper-zinc-aluminum catalyst C-79-7G new generation produced methanol raw contains less than 2% water and less than 0.3% of other impurities (higher alcohols), which also improves process performance.

Thus, the claimed method allows to obtain the methanol of high quality are quite economical (energy-saving) way of various mixtures containing large amounts of nitrogen and a small amount of hydrogen (i.e. depleted in hydrogen), which leads to expansion of raw materials gas mixtures for conversion to methanol.

1. A method of producing methanol by contacting the gas mixture containing carbon oxides and hydrogen and tabulations nitrogen, with a copper-containing catalyst by heat, pressure and supplied to the reactor block with a certain bulk velocity, characterized in that the reactor unit consists of two adiabatic reactors type, connected by a pipeline, the source gas mixture containing CO - 10-15 vol.%, CO2of 0.3 to 5.0 vol.%, H2- 15-40 vol.%, N2- 40,0-74,7% vol. and the volume ratio of N2/(CO+CO2), is equal to 1.00-2.91 in, when 200-260°and a pressure of 3.5 to 5.0 MPa with a bulk velocity 2000-5000 h-1fed to the first reactor along with most of the main part of the unreacted gas supplied to the circulation and produced at the outlet of the second reactor is cooled to 15-20°and then last clearing of methanol in the scrubber water purification and compression, and then the reaction mixture from the first reactor is served in the second reactor together with the remaining lower part of the above circulating gas in the quench - cold circulating gas fed into the pipeline between the two reactors.

2. The method according to claim 1, characterized in that the use of adiabatic reactors tee is but one layer of a copper-containing catalyst.

3. The method according to claim 1, characterized in that the multiplicity of circulation of the circulating gas is 5-6.

4. The method according to claims 1 to 3, characterized in that a complete cleaning of the circulating gas at the outlet of the reactor block is in the scrubber by trapping traces of methanol-water backflow.



 

Same patents:

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to a methanol production process accomplished by contacting gas mixture containing carbon oxides and hydrogen with copper-containing catalyst supplied to a series of at least three flow reactors at specified rate on heating and at pressure while isolating methanol and water from each reactor. Nitrogen-ballasted starting gas mixture is composed of, vol %: CO 10-15, CO2 0.3-5.0, H2 15-40, and N2 40.0-74.7. It is consecutively passed through reactors at volume flow rate 2000-22000 h-1, 200-260°C, pressure 3.5-5.0 MPa, and H2/(CO+CO2) volume ratio 0.75-3.88, while recycling hydrogen separated from tail gases of first and second reactors.

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2 cl, 1 dwg, 1 tbl, 5 ex

FIELD: industrial organic synthesis and chemical engineering .

SUBSTANCE: invention relates to a process of producing liquid oxygenates, including methanol, C2-C4-alcohols, formaldehyde, lower organic acids, or mixtures thereof, and to installation for implementation the process. Process comprises successively supplying natural gas from complex gas preparation plant to a series of "gas-gas" heat exchangers and into annular space of at least one tubular reaction zone of reactor, wherein natural gas is heated to temperature of the beginning of reaction, whereupon heated gas is passed to the entry of the tubular reaction zone mixer, into which compressed air or oxygen is also injected to provide gas-phase oxidation in reaction zone of reactor. Resulting reaction mixture is discharged from reactor into a series of "gas-liquid" and "gas-gas" heat exchangers, wherein reaction mixture is cooled to ambient temperature and sent to separator, wherefrom liquid phase is passed through lower carboxylic acid recovery vessel to the system of rectification columns to isolate the rest of mixture components, whereas leaving gas is recycled to complex gas preparation plant. More specifically, oxidation is carried out within temperature range 240 to 450°C and pressure from 2 to 10 MPa at residence time of reaction mixture in reactor 2-6 sec and oxidant concentration 2 to 15 wt %. In reactor having mixers hollow and at least one tubular reaction zones, required temperature is maintained constant throughout all length of tubular reaction zone and at entries for compressed air or oxygen in mixers of each of tubular reaction zones and hollow reaction zone. Liquid oxygenate production plant is composed of aforesaid complex gas preparation plant, a series of "gas-gas" heat exchanger to heat natural gas, reactor, a series of "gas-liquid" and "gas-gas" heat exchangers to cool reaction mixture obtained in reactor, gas-liquid separator, lower carboxylic acid recovery vessel, and system of rectification columns to isolate the rest of products.

EFFECT: enabled implementation of the process directly near gas and gas condensate deposits, increased conversion of methane per one passage through reactor, and increased yield of oxygenates due to improved design of plant.

6 cl, 1 dwg, 1 tbl

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to copper-containing catalysts for low-temperature synthesis of methanol in fluidized bed at high pressure and provides catalyst, whose preparation involves impregnation and which contains oxides of copper, zinc, chromium, magnesium, aluminum, boron, and barium and has following molar ratio: CuO:ZnO:Cr2O3, MgO:Al2O3:B2O3:BaO = 1:(0.7-1.1):(0.086-0.157):(0.05-0.15):(0.125-0.2):(0.018-0.029):(0.04-0.075).

EFFECT: increased mechanical strength and wear resistance of catalyst.

1 tbl

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to copper-containing catalysts for low-temperature synthesis of methanol in fluidized bed at low pressure and provides a wear-resistant catalyst, whose preparation involves impregnation and which contains oxides of copper, zinc, chromium, magnesium, aluminum, and boron and has following molar ratio: CuO:ZnO:Cr2O3, MgO:Al2O3:B2O3 = 1:0.3:(0.15-0.2):(0.1-0.025):(0.25-0.3):(0.08-0.1).

EFFECT: increased mechanical strength and wear resistance of catalyst.

1 tbl

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to copper-containing catalysts for low-temperature synthesis of methanol in fluidized bed at median pressure and provides catalyst, whose preparation involves impregnation and which contains oxides of copper, zinc, chromium, magnesium, aluminum, boron, and barium and has following molar ratio: CuO:ZnO:Cr2O3, MgO:Al2O3:B2O3:BaO = 1:0.3:(0.014-0.038):(0.047-0.119):(0.05-0.1):(0.007-0.014):(0.0292-0.054).

EFFECT: increased mechanical strength and wear resistance of catalyst.

1 tbl

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to copper-containing catalysts for low-temperature synthesis of methanol in fluidized bed at high pressure and provides catalyst, whose preparation involves impregnation and which contains oxides of copper, zinc, chromium, magnesium, aluminum, boron, and barium and has following molar ratio: CuO:ZnO:Cr2O3, MgO:Al2O3:B2O3:BaO = 1:(0.7-1.1):(0.086-0.157):(0.05-0.15):(0.125-0.2):(0.018-0.029):(0.04-0.075).

EFFECT: increased mechanical strength and wear resistance of catalyst.

1 tbl

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to copper-containing catalysts for low-temperature synthesis of methanol in fluidized bed at low pressure and provides a wear-resistant catalyst, whose preparation involves impregnation and which contains oxides of copper, zinc, chromium, magnesium, aluminum, and boron and has following molar ratio: CuO:ZnO:Cr2O3, MgO:Al2O3:B2O3 = 1:0.3:(0.15-0.2):(0.1-0.025):(0.25-0.3):(0.08-0.1).

EFFECT: increased mechanical strength and wear resistance of catalyst.

1 tbl

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to copper-containing catalysts for low-temperature synthesis of methanol in fluidized bed at median pressure and provides catalyst, whose preparation involves impregnation and which contains oxides of copper, zinc, chromium, magnesium, aluminum, boron, and barium and has following molar ratio: CuO:ZnO:Cr2O3, MgO:Al2O3:B2O3:BaO = 1:0.3:(0.014-0.038):(0.047-0.119):(0.05-0.1):(0.007-0.014):(0.0292-0.054).

EFFECT: increased mechanical strength and wear resistance of catalyst.

1 tbl

The invention relates to a method of producing methanol from natural gas

The invention relates to a method for producing methanol, which finds application in the field of organic synthesis

The invention relates to methods for nizkoatomnye linear alcohols from synthesis gas at pressures not exceeding 100 atmospheres in the presence of a catalyst

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to copper-containing catalysts for low-temperature synthesis of methanol in fluidized bed at median pressure and provides catalyst, whose preparation involves impregnation and which contains oxides of copper, zinc, chromium, magnesium, aluminum, boron, and barium and has following molar ratio: CuO:ZnO:Cr2O3, MgO:Al2O3:B2O3:BaO = 1:0.3:(0.014-0.038):(0.047-0.119):(0.05-0.1):(0.007-0.014):(0.0292-0.054).

EFFECT: increased mechanical strength and wear resistance of catalyst.

1 tbl

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to copper-containing catalysts for low-temperature synthesis of methanol in fluidized bed at low pressure and provides a wear-resistant catalyst, whose preparation involves impregnation and which contains oxides of copper, zinc, chromium, magnesium, aluminum, and boron and has following molar ratio: CuO:ZnO:Cr2O3, MgO:Al2O3:B2O3 = 1:0.3:(0.15-0.2):(0.1-0.025):(0.25-0.3):(0.08-0.1).

EFFECT: increased mechanical strength and wear resistance of catalyst.

1 tbl

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to copper-containing catalysts for low-temperature synthesis of methanol in fluidized bed at high pressure and provides catalyst, whose preparation involves impregnation and which contains oxides of copper, zinc, chromium, magnesium, aluminum, boron, and barium and has following molar ratio: CuO:ZnO:Cr2O3, MgO:Al2O3:B2O3:BaO = 1:(0.7-1.1):(0.086-0.157):(0.05-0.15):(0.125-0.2):(0.018-0.029):(0.04-0.075).

EFFECT: increased mechanical strength and wear resistance of catalyst.

1 tbl

FIELD: chemistry.

SUBSTANCE: method includes contact of gas mixture containing carbon oxides and hydrogen ballasted down with nitrogen with copper-containing catalyst under heating, pressure and definite rate velocity of feeding into reactor. Reactor unit consists of two adiabatic-type reactors connected with a pipeline; the original gas mixture containing CO - 10-15 % v/v, CO2 - 0.3-5.0 % v/v, H2 - 15-40 % v/v, N2 -40.0-74.7 % v/v and volumetric ratio H2/(CO+CO2) equal to 1.00-2.91, at 200-260°C and pressure 3.5-5.0 MPa with rate velocity 2000-5000 h-1 is fed into the first reactor with larger main part of unconverted gas fed to circulation and produced at the outlet of the second reactor cooled to 15-20°C and further purified to remove methanol in tower washer and compressed; then the reaction mixture from the first reactor is fed into the second reactor along with the rest minor part of circulating gas indicated above as quench - cold circulation gas fed into the pipeline between the two rectors.

EFFECT: method allows increasing methanol yield, efficiency of the process and reducing energy consumption.

4 cl, 3 tbl, 1 dwg, 1 exsid1190496

FIELD: chemistry.

SUBSTANCE: invention pertains to the method of methanol obtaining from a concentrated mixture of hydrogen and carbon oxides with the following components in vol %: H2 - 62.0-78.5; Ar - 0.02-0.07; N2 - 0.05-2.2; CH4 - 1.0-3.5; CO - 10.4-29.5; CO2 - 3.2-10.7. The methanol is obtained by concentrating it in a copper containing catalyst at high temperature and pressure in two stages. The gas mixture from the reformer is divided into two streams in volume ratios of 100 : (1-50), one of which is in direct contact with the catalyst in the flow reactor at the first stage, at temperature of 200-285°C, pressure of 5-15 MPa and volume rate of 800-2000 h-1. The other stream is mixed with a cycled gas in volume ratio of 10 : (10-100) and with volume rate of 2500-10000 h-1. This stream is then channelled to the second stage, with separation of methanol and water on each stage in corresponding devices.

EFFECT: increased production of methanol and increased efficiency of the process.

1 tbl, 1 dwg

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