A method of producing methanol

 

(57) Abstract:

The invention relates to a process for the catalytic conversion of hydrocarbons and the production of methanol from synthesis gas. The essence of the method is that the process of natural gas with a hydrogen content of 5 to 20% fuel in remote firing heater, cleaned of sulfur compounds, is mixed with steam pre-cooled natural gas by heat exchange with steam-gas mixture after carbonation, the temperature purified natural gas before saturation by 20 - 30oC higher than the temperature of the vapor-gas mixture after saturation, the gas-vapor mixture is heated to a temperature of 450 - 500oC by heat exchange with the converted gas after pit conversion, which is cooled to 580 - 620oWith, and sent for steam reforming and steam-oxygen and after preparation and compression of the synthesis gas fed to the methanol synthesis. Due to the efficient use of the heat budget process, the obtained converted gas does not require additional purification from carbon dioxide. 1 C.p. f-crystals.

The present invention relates to chemical technology and can be used at facilities that produce sinteticos conversion of hydrocarbons under pressure up to 30 ATM. In tube furnaces with fire heating, where the heat to cover the endothermic effect of the decomposition reaction of hydrocarbons with water vapor to hydrogen and oxides of carbon produced by burning fuel in the reaction tube furnace and passed to the reaction mixture. This convertible gas is factorial, characterizing the efficiency of hydrogen and oxides of carbon and defined as (H2- CO2)/(CO2+ CO) equal to 3, characterized by an excess of hydrogen in comparison with the required stoichiometry of the factorial value of 2.

Converted gas after the tube furnace and after mixing with the circulating gas is fed into the synthesis of methanol. After cooling the reacted mixture and condensation of methanol and water from the circulating mixture to maintain the circulating gas of the effective values of partial pressures of carbon oxides, part of the circulating gas in the form of blowdown containing excess hydrogen, derived from the synthesis loop, and is used in the furnace as fuel (ed. St. N 579220, class C 01 B 3/38, 1977).

Closest to the claimed invention is a method of producing methanol, comprising heating the technological nature of the military purified gas with getting gas mixture, which is sent on steam conversion in a tubular reactor, steam-oxygen conversion in the mine Converter-dvconverter, the cleaning gas from the carbon dioxide. Converted gas after preparation and compression are sent to the methanol synthesis (ed. St. N 1465410, class C 01 B 3/32, 1989).

The claimed invention is directed to providing a cost-effective process due to more efficient use of process heat: preheat the process of natural gas with a hydrogen content of 5-20% in remote firing heater, cooling the natural gas after desulfurization by heating of the gas mixture after saturation and heating the source gas mixture to a temperature of 450-500oC before catalytic steam conversion by using the heat of the reformed gas after mine steam-oxygen conversion cooled reformed gas to 580-620oC.

The essence of the method is that the process of natural gas with a hydrogen content of 5-20% is heated in the firing heater, cleaned of sulfur compounds, is fed to the saturation of the cooled natural gas from the receipt of gas-vapor mixture, served on steam catalytic conversion, after the ez methanol, and cooling the purified natural gas to provide steam and gas mixture after saturation, which is heated by heat exchange, the temperature of purified natural gas before saturation 20-30oC higher than the temperature of the vapor-gas mixture after saturation, and before steam catalytic conversion of initial gas-vapor mixture is heated to 450-500oC due to the heat of the reformed gas after the steam-oxygen catalytic conversion, which, after heat transfer in tubular Converter comes with a temperature of 580-620oC.

The methanol synthesis is carried out in shelving columns with stepped vipasyana at a temperature of 210-270oC, the pressure is 8.5-9.5 MPa for low-temperature copper-containing catalyst.

The method of implementation is that natural gas from the factory network under pressure of 27 atmospheres mixed with technical hydrogen to content in the initial mixture of 5-20%, the mixture is heated in a remote firing the heater up to 380-400oC, passes through a stage desulfurization with preliminary hydrogenation of organic sulfur to hydrogen sulfide on lookbetteronline.com catalyst with subsequent absorption of hydrogen sulfide-zinc oxide. The cleaned gas kabyemela ratio of steam:gas, equal to 0.4-0.7, reach due to irrigation in the saturator purified from sulfur compounds in natural gas heated to 150-170oC gas condensate. Thus the temperature of the purified natural gas before saturation 20-30oC higher than the temperature of the vapor-gas mixture at the outlet of the saturator. High temperature regenerative heat exchanger gas-vapor mixture after saturation is mixed to a ratio of 2.2 to 2.8 with superheated to 450oC technical vapor so that the temperature of the source gas mixture at the inlet to the Converter becomes equal to 350-370oC. With this temperature of the source gas-vapor mixture is superheated by the heat of the converted gas stream after mine steam-oxygen conversion to 450-500oC and this temperature is fed to stage steam reforming, where due to the heat of the reformed gas after mine steam-oxygen conversion is partial decomposition of hydrocarbons technological natural gas to hydrogen and oxides of carbon. Converted gas after the first stage of conversion is fed to the second stage - mine doconversion, here moves the mixture of oxygen with a protective vapor. The temperature of the reformed gas after the primary reforming 650-750ooC. the Content of residual methane after mine deconverter 0.5 to 1.5%, and the value of factorial, depending on the mode and manner of conducting the process steam-oxygen conversion varies from 2,05 to 2.14. Converted gas after cooling HRSG steam pressure of 30 ATM and a temperature of saturation 230oC, passing through the heat recovery system due to heating nutritional deaerated and necesariamente of water entering the scrubber-cooler, where due to the circulating gas condensate is cooled reformed gas with obtaining heated to 150-170oC gas condensate. Hot gas condensate is used for saturation of the original technology of natural gas for the heating of heating water.

Saturated steam is superheated in a remote firing heater 450oC, and then is used for mixing with the flow of the gas mixture after saturation before the Converter steam-oxygen conversion.

The reaction mixture after cooling and separation of the water goes through the stage of drying, and then is supplied to the inlet of the booster compressor where it is compressed to a pressure of 8.5 to 9.5 MPa. Compressed to 8.5 to 9.5 MPa reaction So at 210-270oC on the low-temperature copper-containing catalyst.

Example 1. Natural gas from pipeline under pressure of 2.7 MPa mixed with hydrogen-rich recycle gas at a ratio of 1:0,1 so that the hydrogen content in the mixture before desulfurization was 8%, and the mixture is served in the convective coil firing of the heater where it is heated to a temperature of 400oC. With this temperature, the gas mixture passes through a stage hydrogenation of sulfur compounds to hydrogen sulfide and after hydrogen absorption in the absorber of zinc oxide passes the heat exchanger, where, being cooled to 220oC, heats the gas-vapor mixture after the saturator to 290oC. the Cooled gas mixture is fed into the saturator, where due to the heat circulating gas condensate is the saturation water vapor. The temperature of the gas mixture at the outlet of the saturator - 165oC and volumetric steam:gas ratio is equal to 0.65.

The heated gas-vapor mixture is mixed to the ratio of steam:gas, equal to 2.8, with superheated to 450oC water vapor and at 370oC is fed to the heater on the converted gas stream after mine Converter. The heater is installed after the tubular Converter and going on the th Converter, reaction tubes loaded Nickel catalyst. Heating of the reaction mixture is converted by hot gas after mine Converter of the second stage in indirect heat exchange. The temperature of the reformed gas at the outlet of the reaction tubes 634oC, and the concentration of residual methane in dry converted gas 42,67%. Converted gas after the reaction tubes is served in the shaft of the Converter, here moves oxygen-containing gas so that the ratio of natural gas : oxygen is 1:0,495. Oxygen-containing gas is fed into the mixture with a protective water vapor. The ratio of steam : oxygen-containing gas is 0.1: 1. The temperature of the reformed gas after mine Converter 923oC, the concentration of residual methane in the converted gas is 0.6%, and the value of the factorial of F, which characterizes the degree of efficiency of use of the produced synthesis gas for methanol synthesis, F = (H2- CO2)/(CO2+ CO) = 2.06 to. The temperature of the reformed gas after mine Converter during indirect heat exchange 600oC. Cooled in a tubular furnace to 600oC converted gas after mine Converter is supplied to the heater technological steam and gas is seeking vapor pressure of 3 MPa and a temperature of 230oC.

Vapor pressure of 3 MPa is fed fire in the heater, where the radiation part is overheated steam to 420oC. the Superheated steam is mixed with the vapor-gas mixture after the saturator to the ratio of steam : gas = 2,75.

Converted gas after cooling in the HRSG and the use of heat for heating the nutrient deaerated and necesariamente water is fed into the scrubber-cooler, where due to the circulating gas condensate is cooled to a temperature of 115oC. Hot gas condensate with a temperature of 180oC after the scrubber-cooler is fed to the saturator and other consumers of low-grade heat.

Before compressing the converted gas to a pressure of 8.5 to 9.5 MPa in booster compressor and feeding it to the synthesis of methanol converted gas is dehydrated.

The methanol synthesis is carried out in the columns shelf type with stepped vipasyana gas at 210-270oC with a pressure of 8.5 to 9.5 MPa for low-temperature copper-containing catalyst.

Example 2. Natural gas from the factory manifold pressure 4.0 MPa is mixed with a hydrogen-containing gas to the hydrogen concentration in the mixture before desulfurization 5%, hlidays in the heat exchanger 190oC heating return flow of vapor-gas mixture after the saturator from 175 to 290oC. the Cooled gas mixture is fed into the saturator, where due to the heat circulating gas condensate supplied at 183oC, is the saturation water vapor. The temperature of the gas mixture at the outlet of the saturator 175oC and volumetric steam:gas ratio equal to 0.45:1.

The heated gas-vapor mixture is mixed to the ratio of steam:gas, equal to 2.3:1, with superheated to 450oC water vapor and temperature 350oC is fed to the heater on the converted gas stream between the tubular Converter and recovery boiler after secondary deconverter, heating up to 500oC, and is supplied to the reaction tubes of the primary reformer, where by cooling in indirect heat exchange of the converted gas stream after secondary deconverter is cooled to 580 995oC. the temperature of the reformed gas at the outlet of the reaction tubes 711oC, and the concentration of residual methane in dry converted gas - 35,5%. Converted gas after the reaction tubes fed to the mixer shaft deconverter, which served a 95% technical oxygen. Heated as a result of interaction coloredpoint dikonversi residual methane.

The temperature of the reformed gas after mine deconverter 995oC, and the converted gas, calculated on a dry gas has the following composition: CO2- 10,75%; CO - 16,77%; H2- BR70.63%; N2- 0,66%; Ar-0,58%, CH4-0,61%. The obtained converted gas has a value of factorial 2.20 can be used for methanol synthesis without additional purification from carbon dioxide.

Converted gas after secondary deconverter, cooled, passes tubular Converter, superheater source gas mixture and the heat recovery boiler, which produces process steam pressure of 4.5 MPa, and a temperature of 270oC heaters nutrient deaerated and necesariamente water and fed into the scrubber - cooler, where due to the circulating gas condensate is cooled. At the same time gas condensate is heated to 185oC. the Hot gas condensate is used for carbonation process natural gas and other needs as the coolant.

Received process steam is superheated in a remote firing heater 450oC and is mixed with steam and gas mixture after saturation.

The proposed method of producing the Mann and oxygen gas in comparison with similar due to the increase of the heated process gas at the stage of conversion, use low-grade heat, exclusion stage of purification of gas from carbon dioxide.

1. A method of producing methanol, comprising heating process natural gas to 380 - 400oC fire in the heater, the removal of sulfur compounds, saturation chilled purified natural gas from getting gas mixture, catalytic steam reforming steam-oxygen catalytic conversion, cooling, compressing the received converted gas and feeding it to the methanol synthesis, characterized in that the firing heater heats the process gas with a hydrogen content of 5 to 20%, cooling the purified natural gas to provide steam and gas mixture after carbonation, the temperature purified natural gas before saturation by 20 - 30oC higher than the temperature of the vapor-gas mixture after saturation, before steam conversion of gas-vapor mixture is heated to a temperature of 450 - 500oC due to the heat converted gas obtained after steam-oxygen catalytic conversion, which, after heat transfer in a tubular reactor comes with a temperature of 580 - 620oC.

2. The method according to p. 1, wherein the methanol synthesis osushestvleniya copper-containing catalyst.

 

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