CN103373887A - Method and isothermal methanator for preparing methane by using synthesis gas - Google Patents

Method and isothermal methanator for preparing methane by using synthesis gas Download PDF

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CN103373887A
CN103373887A CN201210121649XA CN201210121649A CN103373887A CN 103373887 A CN103373887 A CN 103373887A CN 201210121649X A CN201210121649X A CN 201210121649XA CN 201210121649 A CN201210121649 A CN 201210121649A CN 103373887 A CN103373887 A CN 103373887A
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gas
methane
heat
isothermal
tube
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CN103373887B (en
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吴芳
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Anhui East China Chemical and Medical Engineering Co., Ltd.
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SHANGHAI HANXING ENERGY TECHNOLOGY Co Ltd
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Abstract

The invention provides a method and equipment for preparing methane by using a synthesis gas. The synthesis gas comprises carbon monoxide, carbon dioxide and hydrogen, is detoxicated and then heated to 150-350 DEG C through a heat exchanger and a heater and enters a tube pass sleeve of an isothermal methanator, and a methane gas generated under the action of a catalyst is escaped from the tube pass sleeve; a cooling agent inside the shell pass of the isothermal methanator circularly absorbs the heat generated through a methanation reaction in the tube pass to control the temperature of the reaction process inside the tube pass; the methane gas sequentially enters the heat exchanger to carry out heat exchange with a feed gas, enters a cooler to realize cooling and enters a liquor separator to be separated from water to obtain a finished product methane gas from the outlet of the isothermal methanator. According to the method and device provided by the invention, the effect which exceeds the effect achieved by a multilevel heat-insulating methanation reaction can be obtained by using an isothermal bed methane reactor or increasing a heat-insulating methanator for increasing reaction depth, and the carbon dioxide is unnecessary to remove by using a chemical method, so that the investment and operation cost is reduced.

Description

A kind of method of preparing methane by synthetic gas and isotherm formula methanator thereof
Technical field
The synthetic gas that the present invention relates to consist of with carbon monoxide, carbonic acid gas and hydrogen is method and the employed equipment of the method, i.e. the isotherm formula methanator of raw material production methane.
Background technology
The synthetic gas that contains carbon monoxide, carbonic acid gas and hydrogen, such as coke-oven gas, water-gas etc. was taken as raw material for the manufacture of methyl alcohol, synthetic ammonia in the past mostly, and also to have directly act as a fuel uses.Along with the rise of methyl alcohol, synthetic ammonia industry production capacity surplus and Gas Prices, the technology of synthetic Sweet natural gas obtains fast-developing.Coke-oven gas or water-gas contain the compositions such as carbon monoxide, carbonic acid gas, hydrogen and methane, adopt methanation technology to make wherein carbon monoxide, carbonic acid gas and the hydrogen rear generation methane that reacts, isolate again methane, just can obtain compressed natural gas CNG or the natural gas liquids LNG of synthetic, effectively improve the added value of coke-oven gas or water-gas with this.
The principle of methanation technology is as follows:
CO+3H 2==CH 4+H 2O △H = -206 kJ/mol
CO 2+4H 2==CH 4+2H 2O △H = -178.44 kJ/mol
It is a strong exothermal reaction process that carbon monoxide, carbonic acid gas and hydrogen building-up reactions generate methane, how can accomplish that a reaction heat effectively takes out and fully utilizes, and synthetic gas can be converted into methane efficiently again, is the difficult point place of this technology.
From disclosed patent and developing or industrialized methanation technology, usually adopt multistage adiabatic methanation technology, be to emit heat after the reaction of one-level adiabatic methanation, by waste heat boiler generation water vapour heat-obtaining, and reactant gases is lowered the temperature, then enter the secondary methanator and carry out secondary adiabatic methanation reaction, successively through the adiabatic methanation reaction of secondary to three grade, the content that makes carbon monoxide in the unstripped gas, carbonic acid gas is to a certain degree.The shortcoming of this technology is that long flow path, investment are high, energy consumption is high.
Summary of the invention
Defective for above-mentioned multistage adiabatic methanation technology, the invention provides a kind of method and apparatus of efficient, easy and economic preparing methane by synthetic gas, adopt one to wait the hotbed methane reactor, can realize the purpose that multistage adiabatic methanation reaction can reach, thereby reduce investment and energy consumption.
Technical scheme of the present invention is: a kind of preparing methane by synthetic gas method, comprise isothermal methanation reaction process, heat recovering process and process of cooling, it is characterized in that: described synthetic gas is comprised of carbon monoxide, carbonic acid gas and hydrogen, wherein carbon monoxide content is greater than 0.5%(V), perhaps carbon dioxide content is greater than 0.5%(V), perhaps carbon monoxide and carbon dioxide content summation are greater than 0.5%(V); Described synthetic gas passes through first detoxification as unstripped gas, and total sulfur content is 0.5-6.0MPa less than 0.2ppm, pressure, is heated to 150-350 ℃ through interchanger and well heater; Unstripped gas enters in the tube side sleeve pipe of isothermal methanation reactor, this tube side sleeve pipe is nested by inner and outer tubes and forms, in the tube side sleeve pipe methanation catalyst is housed, unstripped gas arrives the rear annular space that folds between the inner and outer tubes in tube side bottom by inner tube, under the methanation catalyst effect, realize described isothermal methanation reaction process, the methane gas effusion tube side sleeve pipe of generation; There is coolant circulating to absorb the heat that methanation reaction produces in the tube side in the shell side of described isothermal methanation reactor, the temperature of methanation reaction process in the control tube side; The described methane gas temperature of effusion tube side sleeve pipe reaches 250-500 ℃, enters successively described interchanger and described unstripped gas from the isothermal methanation reactor outlet and carries out heat exchange and realize described heat recovering process, enter water cooler and realize described process of cooling, enter skimmer and divide water to obtain the finished product methane gas.
For carrying out aforesaid method, the present invention also proposes a kind of isothermal methanation reactor, it is characterized in that the upper tubesheet and the lower tubesheet that are disposed radially in the cylindrical shell are divided into unstripped gas storehouse, finished product gas storehouse and heat-eliminating medium zone, on the cylindrical shell in unstripped gas storehouse opening for feed is arranged, on the cylindrical shell in finished product gas storehouse discharge port is arranged, coolant inlet and outlet are arranged on the cylindrical shell in heat-eliminating medium zone; The tube side sleeve pipe that is nested and forms by inner and outer tubes in the cylindrical shell, its middle external tube is suspended on lower tubesheet, and upper end open is communicated with finished product gas storehouse, and the lower end cecum is stretched in the heat-eliminating medium zone; Inner tube is suspended on upper tubesheet, and upper end open is communicated with the unstripped gas storehouse, and lower ending opening is stretched in the outer tube bottom; Be filled with methanation catalyst in the inner tube or in the annular space of inner tube and outer tube.
For increasing the degree of depth of reaction, the adiabatic methanation reactor of can connecting between described isothermal methanation reactor and the described interchanger, described methane gas is passed through first this adiabatic methanation reactor from the outlet of isothermal methanation reactor, enters described interchanger and described unstripped gas again and carries out heat exchange and realize described heat recovering process.
The present invention waits the hotbed methane reactor with one, perhaps for increasing an adiabatic methanation reactor, the degree of depth that increases reaction can obtain to surpass the effect that multistage adiabatic methanation reaction can reach, compare with other technology of same domain, the carbon monoxide transformation efficiency can reach 99.99%, and carbon dioxide conversion reaches 99.9%.Can drop to extremely lowly through carbonic acid gas after the methanation, needn't slough carbonic acid gas with chemical process as traditional technology, reduce investment and working cost, investment can reduce 20-30%.
Description of drawings
Fig. 1 is the process flow diagram of the embodiment of the invention.
Fig. 2 is the isotherm formula methanator structural representation among Fig. 1.
Embodiment
Be described in further detail below in conjunction with embodiments of the invention and accompanying drawing thereof.
An embodiment as shown in Figure 1, synthetic gas is comprised of carbon monoxide, carbonic acid gas and hydrogen, such as gas of coke-oven gas, water-gas, gasification etc., as long as wherein carbon monoxide content is greater than 0.5%(V), perhaps carbon dioxide content is greater than 0.5%(V), perhaps carbon monoxide and carbon dioxide content summation are greater than 0.5%(V), all can be as the raw material of present embodiment.Synthetic gas passes through first detoxification (guide's operation of the present invention, not shown in the figures), and reaching total sulfur content is 0.5-6.0MPa less than 0.2ppm, pressure, is heated to 150-350 ℃ as unstripped gas through interchanger 1 and well heater 2, enters isothermal methanation reactor 3.
Isothermal methanation reactor 3 structures are referring to shown in Figure 2, and the cylindrical shell 301 interior upper tubesheets that are disposed radially 302 and lower tubesheet 303 are divided into unstripped gas storehouse 304, finished product gas storehouse 305 and heat-eliminating medium zone 306.Opening for feed 307 is arranged on the cylindrical shell in unstripped gas storehouse 304, on the cylindrical shell in finished product gas storehouse 305 discharge port 308 is arranged, coolant inlet 309 and outlet 310 are arranged on the cylindrical shell in heat-eliminating medium zone 306.The tube side sleeve pipe 311 that is nested and forms by inner tube 313 and outer tube 312 in the cylindrical shell 301, multi units tube journey sleeve pipe 311 is suspended on upper tubesheet 302 and the lower tubesheet 303 with axially parallel and the state of being evenly distributed of cylindrical shell 301, its middle external tube 312 is suspended on lower tubesheet 303, upper end open is communicated with finished product gas storehouse 305, and the lower end cecum is stretched in the heat-eliminating medium zone 306; Inner tube 313 is suspended on upper tubesheet 302, and upper end open is communicated with unstripped gas storehouse 304, and lower ending opening is stretched in outer tube 312 bottoms.The suspension mode of connection has here overcome the difficult problem that the thermal expansion of inner and outer tubes system causes.Be filled with the methanation catalyst (not shown) in the tube side sleeve pipe 311, the particular location of filling can be in the inner tube 313, also can be in the annular space between inner tube 313 and the outer tube 312.
Unstripped gas is by the opening for feed 307 incoming stock gas storehouses 304 of isothermal methanation reactor 3, through folding into the annular space between inner tube 313 and the outer tube 312 behind the inner tube 313 arrival tube side bottoms, realize described isothermal methanation reaction process under the methanation catalyst effect, the methane gas effusion tube side sleeve pipe 311 of generation enters finished product gas storehouse 305.
There are water, vapour to absorb the heat that methanation reaction produces in the tube side as coolant circulating in the shell side in heat-eliminating medium zone 306, water enters heat-eliminating medium zone 306 from coolant inlet 309, endothermic conversion becomes saturated steam and water mixture to leave heat-eliminating medium zone 306 from coolant outlet 310 to enter gas bag 7 and be cooled to the shell side that returns heat-eliminating medium zone 306 behind the water, pressure-controlling in the gas bag 7 is in the scope of 2.0-9.0MPa, control accordingly the temperature of methanation reaction process in the tube side, prevent the temperature superelevation.
The methane gas of effusion tube side sleeve pipe 311 enters finished product gas storehouse 305, temperature reaches 250-500 ℃, from discharge port 308 enter successively that interchanger 1 carries out heat exchange with unstripped gas and after realizing heat recovering process, entering water cooler 5 and realize process of cooling, enter skimmer and obtained the finished product methane gas behind the water in 6 minutes.
As strengthening the assist measure of unstripped gas to finished product gas shift, increase reaction depth, the adiabatic methanation reactor 4 of can connecting between isothermal methanation reactor 3 and the interchanger 1, methane gas is passed through first this adiabatic methanation reactor 4 from discharge port 308, enters interchanger 1 again and carries out heat exchange and realize heat recovering process with unstripped gas.
Replace the heat that water produces as methanation reaction in the refrigerant absorption tube side if use thermal oil, the thermal oil heat absorption heats up, then needing to order about thermal oil with oil pump flows through and returns shell side after the scatterer cooling, control thermal oil flow and temperature in can be controlled the temperature of methanation reaction process in the tube side equally, prevent the temperature superelevation.So, can consist of the present invention and not have illustrated another embodiment.

Claims (5)

1. preparing methane by synthetic gas method, comprise isothermal methanation reaction process, heat recovering process and process of cooling, it is characterized in that: described synthetic gas is comprised of carbon monoxide, carbonic acid gas and hydrogen, wherein carbon monoxide content is greater than 0.5%(V), perhaps carbon dioxide content is greater than 0.5%(V), perhaps carbon monoxide and carbon dioxide content summation are greater than 0.5%(V); Described synthetic gas passes through first detoxification as unstripped gas, and total sulfur content is 0.5-6.0MPa less than 0.2ppm, pressure, is heated to 150-350 ℃ through interchanger and well heater; Unstripped gas enters in the tube side sleeve pipe of isothermal methanation reactor, this tube side sleeve pipe is nested by inner and outer tubes and forms, be filled with methanation catalyst in the tube side sleeve pipe, unstripped gas arrives the rear annular space that folds between the inner and outer tubes in tube side bottom by inner tube, under the methanation catalyst effect, realize described isothermal methanation reaction process, the methane gas effusion tube side sleeve pipe of generation; There is coolant circulating to absorb the heat that methanation reaction produces in the tube side in the shell side of described isothermal methanation reactor, the temperature of methanation reaction process in the control tube side; The described methane gas temperature of effusion tube side sleeve pipe reaches 250-500 ℃, enters successively described interchanger and described unstripped gas from the isothermal methanation reactor outlet and carries out heat exchange and realize described heat recovering process, enter water cooler and realize described process of cooling, enter skimmer and divide water to obtain the finished product methane gas.
2. described preparing methane by synthetic gas method according to claim 1, it is characterized in that the adiabatic methanation reactor of connecting between described isothermal methanation reactor and the described interchanger, described methane gas is passed through first this adiabatic methanation reactor from the outlet of isothermal methanation reactor, enters described interchanger and described unstripped gas again and carries out heat exchange and realize described heat recovering process.
3. described preparing methane by synthetic gas method according to claim 1 is characterized in that the refrigerant in the described shell side is water, and the water endothermic conversion becomes saturated steam to enter to return shell side after gas bag is cooled to water, and the pressure control range in the gas bag is 2.0-9.0MPa.
4. described preparing methane by synthetic gas method according to claim 1 is characterized in that the refrigerant in the described shell side is thermal oil, and the thermal oil heat absorption heats up, and ordered about by oil pump, returns shell side after the scatterer of the flowing through cooling.
5. isothermal methanation reactor that is used for the described preparing methane by synthetic gas method of claim 1, has a cylindrical shell, it is characterized in that the upper tubesheet and the lower tubesheet that are disposed radially in the cylindrical shell are divided into unstripped gas storehouse, finished product gas storehouse and heat-eliminating medium zone, on the cylindrical shell in unstripped gas storehouse opening for feed is arranged, on the cylindrical shell in finished product gas storehouse discharge port is arranged, coolant inlet and outlet are arranged on the cylindrical shell in heat-eliminating medium zone; The tube side sleeve pipe that is nested and forms by inner and outer tubes in the cylindrical shell, its middle external tube is suspended on lower tubesheet, and upper end open is communicated with finished product gas storehouse, and the lower end cecum is stretched in the heat-eliminating medium zone; Inner tube is suspended on upper tubesheet, and upper end open is communicated with the unstripped gas storehouse, and lower ending opening is stretched in the outer tube bottom; Be filled with methanation catalyst in the inner tube or in the annular space of inner tube and outer tube.
CN201210121649.XA 2012-04-24 2012-04-24 Method and isothermal methanator for preparing methane by using synthesis gas Active CN103373887B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104862024A (en) * 2014-02-21 2015-08-26 托普索公司 Methanation Process With A Passive Heat Exchange Medium
CN105582855A (en) * 2014-10-23 2016-05-18 新煤化工设计院（上海）有限公司 Radial-flow uniform-temperature methanation furnace with byproduct steam

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4043945A (en) * 1974-11-11 1977-08-23 Hitachi, Ltd. Method of producing thin layer methanation reaction catalyst
CN102234213A (en) * 2010-04-20 2011-11-09 中国科学院过程工程研究所 Complete methanation reaction device for synthesis gas

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4043945A (en) * 1974-11-11 1977-08-23 Hitachi, Ltd. Method of producing thin layer methanation reaction catalyst
CN102234213A (en) * 2010-04-20 2011-11-09 中国科学院过程工程研究所 Complete methanation reaction device for synthesis gas

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104862024A (en) * 2014-02-21 2015-08-26 托普索公司 Methanation Process With A Passive Heat Exchange Medium
CN104862024B (en) * 2014-02-21 2017-08-18 托普索公司 Using the methanation process and system of passive heat exchange medium
CN105582855A (en) * 2014-10-23 2016-05-18 新煤化工设计院（上海）有限公司 Radial-flow uniform-temperature methanation furnace with byproduct steam

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Effective date of registration: 20160309

Address after: 201204, No. 555, Lane 46, Ring Bridge Road, Shanghai, Pudong New Area

Patentee after: Shanghai Huaxi Chemical Science & Technology Co., Ltd.

Address before: Pudong Peony Road 201204 Shanghai City Dongchen No. 60 building room 1406

Patentee before: Shanghai Hanxing Energy Technology Co., Ltd.

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Effective date of registration: 20180426

Address after: 230000 room 1601, block C, blue ocean International Building, Shushan District, Hefei, Anhui.

Patentee after: Anhui East China Chemical and Medical Engineering Co., Ltd.

Address before: No. 555, Ring Bridge Road, Pudong New Area, Shanghai, Shanghai

Patentee before: Shanghai Huaxi Chemical Science & Technology Co., Ltd.