A method of producing methanol

 

(57) Abstract:

The invention relates to a method of producing methanol from natural gas. The method includes a preliminary satriawan feedstock and heat using gas condensate, mixing the mixture with oxygen in the mixer at a ratio of steam : gas 2,3-2,54, steam-oxygen conversion of natural gas using Nickel-containing catalyst, the carbon dioxide removal by single-stage leaching with an aqueous solution of monoethanolamine, drying the reaction mixture, compression and supply shelf in the synthesis column with stepped vipasyana using a copper-containing catalyst. Usually preliminary satriawan spend up to volume relationships steam : gas 0,58-0,62, as a rule, the temperature of the gas condensate used satriawan and heating gas mixture, support in the range 160-176oC, the temperature of the gas mixture supplied to the mixer is in the range 260-354oC and the pressure is in the range of 1.5-to 1.83 MPa, washing is carried out until obtaining functional f=2,01-2,34, compression is carried out to maintain the pressure at the inlet of the synthesis column in the range of 7.35-8,57 MPa, and the temperature in the column Sint the technological and energy costs with high conversion rate and quality of the produced methanol.

The invention relates to the chemical industry, namely the method of producing methanol from natural gas.

A known method of producing methanol from natural gas, including a preliminary satriawan feedstock to volume relationships steam : gas 0.4 to 0.7, a mixture of oxygen, steam-oxygen conversion of natural gas when the temperature of the gas mixture at the inlet to the Converter 260-300oWith, the volume ratio of steam : gas 2,2-2,8 and pressure of 2.0 MPa, the carbon dioxide removal by single-stage leaching solution of monoethanolamine to obtain functional f=2,05-2,2, drying the reaction mixture, composed of a mixture of carbon oxides and hydrogen, the compression ratio of the reaction mixture to a pressure of 8.5 to 9.5 MPa and its supply to the stage of synthesis in shelving columns with stepped vipasyana at 220-270oWith using a copper-containing catalyst (patent RF 2099320, class C 07 C 29/15, 31/04, 1997).

Preliminary satriawan carry the hot gas condensate, circulating in the system. Steam-oxygen conversion of natural gas is carried out in a shaft furnace at low volume ratio of steam : gas and the temperature of the gas mixture at the inlet to the Converter. Removing carbon dioxide plega subsequent regeneration. Dehydration of the gas mixture is carried out by freezing, moisture, or gas and the interaction with Almagell. The synthesis of methanol are at the specified temperature due to the step of bypassing gas.

The disadvantages of this method are that conversion catalysts and synthesis have insufficient service life. Due to the rapid at the initial stage of operation due to aging of the catalyst synthesis is reduced the volume of output of methanol, you cannot change the synthesis temperature in the range, ensure effective operation of the catalyst at all stages of the reduction of its efficiency. High pressure synthesis is not possible to implement a method for reconstruction of outdated equipment, and use of plants located remotely from each other.

The objective of the invention is to increase the service life of the catalysts, the reduction of technological and energy costs with a high conversion rate and quality of methanol, and process parameters that provide the possibility of its realization on the reconstructed production.

The problem is solved in that osushestvlenie, used satriawan and heating gas mixture, support in the range 160-176oC. After studioware spend a mixture of vapor-gas mixture with oxygen in the mixer, and the ratio of steam : gas is 2.3-2,54. The temperature of the gas mixture supplied to the mixer support in the range 260-354oC, and the pressure in the mixer is in the range of 1.5-to 1.83 MPa. From the mixer components are fed to a Converter with a Nickel-containing catalyst. After conversion to remove carbon dioxide, the reaction mixture is subjected to single-stage leaching with an aqueous solution of monoethanolamine. Washing is carried out until obtaining functional f=2,01-2,34. The purified reaction mixture is dried, and then compremised for submission to the shelf synthesis with step vipasyana using a copper-containing catalyst. The compression ratio is to maintain the pressure at the inlet of the synthesis column in the range of 7.35-8,57 MPa. The temperature in the synthesis column is maintained in the range 215-280oC.

Reducing the range of changing attitudes steam : gas phase saturation and the use of a condensate with a temperature lying in the range 160-176oTo provide effective naryshenie before mixing with oxygen and to reduce consumption of demineralized (river) and demineralized water. The increase compared with the known solution temperature of the reaction mixture fed to the Converter allows you to reduce the consumption of oxygen and the reduction of pressure conversion leads to an increase in the partial pressure of hydrogen and oxides of carbon which helps to increase the equilibrium yield of methanol synthesis step. An extension of the functionality of converted gas allows at the beginning of the run the catalyst conversion to maintain a minimum temperature in the catalyst bed, and at the end of the run. This results in higher term mileage catalyst conversion. An extension of the temperature during the synthesis also allows you to optimize the synthesis catalyst, i.e. at the beginning of the run synthesis catalyst to maintain a minimum temperature, and at the end of the run. As in the case of catalyst conversion, optimization of temperature modes of the synthesis catalyst can increase its service life. In General, reducing the pressure of the synthesis leads to a significant reduction in the content of impurities in methanol raw, which leads to improving the quality of the methanol produced before rectification. The service life of catalysts for conversion of synthesis of p which allows more time to use the equipment, moreover, the pressure drop of the reaction mixture can be achieved by passing through a long highways that allows you to use the reconstructed equipment scattered over a vast territory.

The possibility of carrying out the invention can be confirmed by the following example.

Natural gas containing 99% methane, with a temperature of 20oC at a pressure of 1.7 MPa served in the saturator, where is saturated with water vapor by spraying gas condensate at the temperature of the outlet gas mixture from the saturator 170oWith relationship to steam : gas 0,61. Next, the gas-vapor mixture is heated in the gas heat exchanger by the heat converted gas to 320oWith, mixed with steam and fed into the mixer Converter. There serves a mixture of steam and oxygen. The General attitude steam : gas is 2,45, oxygen : methane 0,735. In mine Converter on Nickel-containing catalyst is steam-oxygen conversion at a pressure of 1.7 MPa and the temperature at the outlet of the Converter 890oC. Next hot Congaz served in the boiler, where it is cooled to 320oWith using the heat of Congaz to obtain the saturated vapor pressure of 25 MPa. After the recovery boiler the Congaz served in the gas is of iterator. From heat exchanger Congaz served in the scrubber-cooler, where it is cooled to 130oWith using the heat of Congaz for heating gas condensate, circulating on the circuit saturator - scrubber-cooler, scrubber-cooler from Congaz separated more moisture. Further Congaz cooled in the heat exchanger 40oWith and then separated from the condensed water in the separator. The resulting gas, calculated on a dry composition contains 17,2% vol. WITH, 15,4% vol. C02, 1,1 vol.% CH4, 1,2.% inert gases (mainly argon), a total of 65.1% vol. H2. After that, Congaz served in the absorber monoethanolamine treating, where due to the absorption of carbon dioxide functionality set equal to 2.2. The composition of dry gas: 18,5% vol. WITH, 9,1 about. % CO2, 1,2.% CH4and 1.3% vol. inert gases, 69,9% vol. H2. The gas is fed to the absorber drying filled with silica gel, where the absorption of water vapor. Next, the gas is compressed in a multistage compressor to a pressure of 8 MPa and served on melanoplinae filters, where the cleaning gas from oil and iron CARBONYLS, you get a so-called "fresh synthesis gas", which is the raw material for the synthesis of methanol. The synthesis gas is mixed with circulating the tion with the nozzle heat exchanger, where the outlet temperature from the top shelf 225oWith and with bottom shelf 268oWith the process of methanol synthesis. Emerging from the column, the reaction mixture passing through the combined heat exchanger and releases heat input to the column synthesis gas, then served in the refrigerator, where cooling the reaction mixture to 40oAnd condensation of liquid products containing 85 wt. % methanol, 14,95 wt.% water and 0.05 wt.% organic impurities. Then the mixture enters the separation system, where liquid products (methanol-raw) is separated from the gaseous (circulating gas). The resulting methanol-raw fed to the rectification. Circulating gas having the composition: 1,0 vol.% WITH, of 2.0 vol.% CO2, 13,1% vol. CH4, 14,3% vol. inert gases, 70,0 about. % H2served on the suction of the circulation gas compressor, after which the gas is removed for purging, and the other part serves for mixing with fresh synthesis gas. On distillation of the methanol-raw cleaned to a water content of 0.01 wt. %, alcohols 0.002 wt. per cent, of volatile organic impurities 0,0003 wt.%. The resulting product - methanol-rectified - is a commodity.

A method of producing methanol, comprising the preliminary satriawan feedstock and heating with is 2,3-2,54, steam-oxygen conversion of natural gas using Nickel-containing catalyst, the carbon dioxide removal by single-stage leaching with an aqueous solution of monoethanolamine, drying the reaction mixture, compression and supply shelf in the synthesis column with stepped vipasyana using a copper-containing catalyst, characterized in that the preliminary satriawan spend up to volume relationships steam : gas 0,58-of 0.62, while the temperature of the gas condensate used satriawan and heating gas mixture, support in the range 160-176oC, the temperature of the gas mixture fed to the mixer is in the range 260-354oC and the pressure is in the range of 1.5-to 1.83 MPa, washing is carried out until obtaining functional f= 2,01-2,34, compression is carried out to maintain the pressure at the inlet of the synthesis column in the range of 7.35-8,57 MPa, and the temperature in the synthesis support in the range 215-280oC.

 

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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

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing Cu/Zn/Al catalysts, to a catalyst produced using this method, as well as to its use in methanol synthesis, methanol reforming and for low-temperature conversion of carbon monoxide. A method is described for preparing Cu/Zn/Al catalysts, involving preparation of a first aqueous solution which contains at least copper formate and zinc formate, preparation of a second solution which contains a precipitation agent, wherein the first and/or second solution contains an aluminium hydroxide sol/gel mixture, combining both solutions, separating the obtained precipitate from the aqueous phase which forms waste water, washing the precipitate until an alkali content, based on a catalyst which calcined at 600°C, of not less than 500 parts per million is attained, and drying. A catalyst prepared using this method is described, and its use in methanol synthesis, methanol reforming and conversion of carbon monoxide.

EFFECT: simpler technology of producing catalyst and increased activity of the catalyst.

32 cl, 5 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalyst, suitable to application in reactions of conversion of carbon oxides, in form of granules, formed by pressing reduced and passivated catalyst powder, and claimed powder contains copper in the interval 10-80 wt %, zinc oxide in the interval 20-90 wt %, aluminium oxide in the interval 5-60 wt % and, optionally, one or several oxide promoter compounds, selected from compounds of Mg, Cr, Mn, V, Ti, Zr, Ta, Mo, W, Si and rare-earth elements, in quantity in the interval 0.01-10 wt %. Said granules have average crush strength in horizontal direction after production ≥6.5 kg, ratio of values of average crush strength in horizontal direction after reduction and after production ≥0.5:1 and area of copper surface over 60 m2/g Cu. Invention also relates to method of claimed catalyst production and to method of conversion of carbon oxides in presence of claimed catalyst.

EFFECT: catalyst has high strength of granules and high activity as a result of increased area of copper surface, which makes it possible to apply reactors of smaller size and increase process productivity.

15 cl, 9 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a methanol synthesis method, which includes the following steps: (i) conducting a reaction, in a reaction loop, of a process gas containing hydrogen, carbon dioxide and carbon monoxide over a catalyst to obtain a product gas, (ii) condensing methanol, water and secondary oxygenates from the product gas, (iii) returning unreacted gases into the reaction loop, where the catalyst includes pellets obtained by pressing from a reclaimed and passivated powdered catalyst, where said powder contains copper in the range of 15-70 wt %, zinc oxide, wherein the weight ratio Cu:Zn with respect to the oxide is in the range of 2:1 to 3.5:1, aluminium oxide in the range of 5-60 wt %, and optionally one or more oxide promoting compounds selected from Mg, Cr, Mn, V, Ti, Zr, Ta, Mo, W, Si and rare-earth elements, in the range of 0.01-10 wt %, wherein the catalyst is obtained by carrying out steps which include: (i) preparing, in an aqueous medium, a composition containing a homogeneous mixture of separate particles of copper, zinc, aluminium and optionally one or more promoting compounds of metals selected from Mg, Cr, Mn, V, Ti, Zr, Ta, Mo, W, Si and rare-earth elements, (ii) separating and drying the composition to form a catalyst precursor, (iii) exposing the dried catalyst precursor composition to reducing conditions so that copper compounds contained therein are reduced to copper, (iv) passivating the surface of the reduced copper, and (v) forming a reduced and passivated composition, where, before reducing the copper compounds, the homogeneous mixture is treated at the drying step at temperature in the range of 180-240°C.

EFFECT: when carrying out the disclosed method, total content of secondary oxygenates in the condensate is not more than 500 ppm.

12 cl, 7 tbl, 5 ex

FIELD: technology for production of methanol from syngas.

SUBSTANCE: claimed method includes mixing of hydrocarbon raw material with water steam to provide syngas by steam conversion of hydrocarbon raw material and subsequent methanol synthesis therefrom. Conversion of hydrocarbon raw material and methanol synthesis are carried out under the same pressure from 4.0 to 12.0 MPa. In one embodiment hydrocarbon raw material is mixed with water steam and carbon dioxide to provide syngas by steam/carbonic acid conversion of hydrocarbon raw material in radial-helical reactor followed by methanol synthesis therefrom under the same pressure (from 4.0 to 12.0 MPa). In each embodiment methanol synthesis is carried out in isothermal catalytic radial-helical reactor using fine-grained catalyst with grain size of 1-5 mm. Methanol synthesis is preferably carried out in two steps with or without syngas circulation followed by feeding gas from the first or second step into gasmain or power plant.

EFFECT: simplified method due to process optimization.

12 cl, 3 tbl, 3 dwg

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