CN103373887B - 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 PDFInfo
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- CN103373887B CN103373887B CN201210121649.XA CN201210121649A CN103373887B CN 103373887 B CN103373887 B CN 103373887B CN 201210121649 A CN201210121649 A CN 201210121649A CN 103373887 B CN103373887 B CN 103373887B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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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
Technical field
The synthetic gas that the present invention relates to form with carbon monoxide, carbonic acid gas and hydrogen is the method for raw material production methane and the equipment that the method is used, i.e. isotherm formula methanator.
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, also had directly as fuel, to use.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, after adopting methanation technology that carbon monoxide, carbonic acid gas and hydrogen is wherein reacted, generate methane, isolate again methane, compressed natural gas CNG or the natural gas liquids LNG that just can obtain synthetic, improve the added value of coke-oven gas or water-gas effectively 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, conventionally 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 secondary methanator and carry out the reaction of secondary adiabatic methanation, through the adiabatic methanation reaction of secondary to three grade, the carbon monoxide in unstripped gas, the content of carbonic acid gas are reduced to a certain degree successively.The shortcoming of this technology is long flow path, it is high to invest, energy consumption is high.
Summary of the invention
Defect 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 hotbed methane reactor, can realize the object 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), or carbon dioxide content is greater than 0.5%(V), or carbon monoxide and carbon dioxide content summation are greater than 0.5%(V); Described synthetic gas first passes through detoxification as unstripped gas, and total sulfur content is less than 0.2ppm, pressure is 0.5-6.0MPa, through interchanger and well heater, is heated to 150-350 ℃; Unstripped gas enters in the tube side sleeve pipe of isothermal methanation reactor, this tube side sleeve pipe is nested and is formed by inner and outer tubes, in tube side sleeve pipe, methanation catalyst is housed, unstripped gas folds into the annular space between inner and outer tubes after arriving tube side bottom by inner tube, under methanation catalyst effect, realize described isothermal methanation reaction process, the methane gas effusion tube side sleeve pipe of generation; In the shell side of described isothermal methanation reactor, there is coolant circulating to absorb the heat that in tube side, methanation reaction produces, control the temperature of methanation reaction process in tube side; The described methane gas temperature of effusion tube side sleeve pipe reaches 250-500 ℃, enters successively described interchanger and described unstripped gas carry 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 finished product methane gas from isothermal methanation reactor outlet.
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 in cylindrical shell, are disposed radially are divided into unstripped gas storehouse, finished product gas storehouse and heat-eliminating medium region, on the cylindrical shell in unstripped gas storehouse, there is opening for feed, on the cylindrical shell in finished product gas storehouse, there is discharge port, on the cylindrical shell in heat-eliminating medium region, have coolant inlet and outlet; The tube side sleeve pipe that is nested and forms by inner and outer tubes in cylindrical shell, its middle external tube is suspended on lower tubesheet, and upper end open is communicated with finished product gas storehouse, and lower end cecum stretches in heat-eliminating medium region; Inner tube is suspended on upper tubesheet, and upper end open is communicated with unstripped gas storehouse, and lower ending opening stretches in outer tube bottom; In inner tube or in the annular space of inner tube and outer tube, be filled with methanation catalyst.
For increasing the degree of depth of reaction, the adiabatic methanation reactor of can connecting between described isothermal methanation reactor and described interchanger, described methane gas is first passed through this adiabatic methanation reactor from the outlet of isothermal methanation reactor, then enters described interchanger and described unstripped gas carries out heat exchange and realizes described heat recovering process.
The present invention waits hotbed methane reactor with one, or increase an adiabatic methanation reactor and can obtain and surpass the effect that multistage adiabatic methanation reaction can reach for increasing the degree of depth of reaction, compare with other technology of same domain, carbon monoxide transformation efficiency can reach 99.99%, and carbon dioxide conversion reaches 99.9%.After methanation, carbonic acid gas can drop to extremely lowly, needn't as traditional technology, by chemical process, slough carbonic acid gas, has reduced investment and working cost, and investment can reduce 20-30%.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the embodiment of the present invention.
Fig. 2 is the isotherm formula methanator structural representation in Fig. 1.
Embodiment
Below in conjunction with embodiments of the invention and accompanying drawing thereof, be described in further detail.
An embodiment as shown in Figure 1, synthetic gas is comprised of carbon monoxide, carbonic acid gas and hydrogen, as gas of coke-oven gas, water-gas, gasification etc., as long as wherein carbon monoxide content is greater than 0.5%(V), or carbon dioxide content is greater than 0.5%(V), or carbon monoxide and carbon dioxide content summation are greater than 0.5%(V), all can be as the raw material of the present embodiment.Synthetic gas first passes through detoxification (guide's operation of the present invention, not shown in the figures), reaches that total sulfur content is less than 0.2ppm, pressure is 0.5-6.0MPa, as unstripped gas, through interchanger 1 and well heater 2, is heated to 150-350 ℃, enters isothermal methanation reactor 3.
Isothermal methanation reactor 3 structures are shown in Figure 2, and the interior upper tubesheet being disposed radially 302 of cylindrical shell 301 and lower tubesheet 303 are divided into unstripped gas storehouse 304, finished product gas storehouse 305 and heat-eliminating medium region 306.On the cylindrical shell in unstripped gas storehouse 304, there is opening for feed 307, on the cylindrical shell in finished product gas storehouse 305, have discharge port 308, on the cylindrical shell in heat-eliminating medium region 306, have coolant inlet 309 and outlet 310.The tube side sleeve pipe 311 that is nested and forms by inner tube 313 and outer tube 312 in cylindrical shell 301, multi units tube journey sleeve pipe 311 is suspended on upper tubesheet 302 and lower tubesheet 303 with axially parallel 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 lower end cecum stretches in heat-eliminating medium region 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 stretches 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.In tube side sleeve pipe 311, be filled with methanation catalyst (not shown), the particular location of filling can be in inner tube 313, can be also in the annular space between inner tube 313 and outer tube 312.
Unstripped gas is by the incoming stock gas of opening for feed 307 storehouse 304 of isothermal methanation reactor 3, after arriving tube side bottom, inner tube 313 folds into the annular space between inner tube 313 and outer tube 312, under methanation catalyst effect, realize described isothermal methanation reaction process, the methane gas effusion tube side sleeve pipe 311 of generation enters finished product gas storehouse 305.
In the shell side in heat-eliminating medium region 306, there are water, vapour to absorb as coolant circulating the heat that in tube side, methanation reaction produces, water enters heat-eliminating medium region 306 from coolant inlet 309, endothermic conversion becomes saturated steam and water mixture to leave heat-eliminating medium region 306 from coolant outlet 310 to enter gas bag 7 and be cooled to the shell side that returns to heat-eliminating medium region 306 water, pressure-controlling in gas bag 7 is in the scope of 2.0-9.0MPa, the temperature of controlling accordingly methanation reaction process in tube side, prevents temperature superelevation.
The methane gas of effusion tube side sleeve pipe 311 enters finished product gas storehouse 305, temperature reaches 250-500 ℃, enters successively interchanger 1 carry out heat exchange with unstripped gas and realize heat recovering process, enter water cooler 5 and realize process of cooling, enter skimmer and after water, obtain finished product methane gas in 6 minutes from discharge port 308.
Assist measure as strengthening unstripped gas to finished product gas shift, increase reaction depth, the adiabatic methanation reactor 4 of can connecting between isothermal methanation reactor 3 and interchanger 1, methane gas is first passed through this adiabatic methanation reactor 4 from discharge port 308, then enters interchanger 1 and carry out heat exchange and realize heat recovering process with unstripped gas.
If replacing water, application thermal oil absorbs as refrigerant the heat that in tube side, methanation reaction produces, thermal oil heat absorption heats up, needing to order about thermal oil with oil pump flows through after scatterer cooling and returns to shell side, control thermal oil flow and temperature in and can control equally the temperature of methanation reaction process in tube side, prevent temperature superelevation.So, can form the present invention and there is no illustrated another embodiment.
Claims (4)
1. a 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), or carbon dioxide content is greater than 0.5%(V), or carbon monoxide and carbon dioxide content summation are greater than 0.5%(V); Described synthetic gas first passes through detoxification as unstripped gas, and total sulfur content is less than 0.2ppm, pressure is 0.5-6.0MPa, through interchanger and well heater, is heated to 150-350 ℃; Unstripped gas enters in the tube side sleeve pipe of isothermal methanation reactor, this tube side sleeve pipe is nested and is formed by inner and outer tubes, in tube side sleeve pipe, be filled with methanation catalyst, unstripped gas folds into the annular space between inner and outer tubes after arriving tube side bottom by inner tube, under methanation catalyst effect, realize described isothermal methanation reaction process, the methane gas effusion tube side sleeve pipe of generation; In the shell side of described isothermal methanation reactor, there is coolant circulating to absorb the heat that in tube side, methanation reaction produces, control the temperature of methanation reaction process in tube side; The described methane gas temperature of effusion tube side sleeve pipe reaches 250-500 ℃, enters successively described interchanger and described unstripped gas carry 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 finished product methane gas from isothermal methanation reactor outlet;
The adiabatic methanation reactor of connecting between described isothermal methanation reactor and described interchanger, described methane gas is first passed through this adiabatic methanation reactor from the outlet of isothermal methanation reactor, then enters described interchanger and described unstripped gas carries out heat exchange and realizes described heat recovering process.
2. preparing methane by synthetic gas method according to claim 1, is characterized in that the refrigerant in described shell side is water, and water endothermic conversion becomes saturated steam to enter after gas bag is cooled to water to return to shell side, and the pressure control range in gas bag is 2.0-9.0MPa.
3. preparing methane by synthetic gas method according to claim 1, is characterized in that the refrigerant in described shell side is thermal oil, and thermal oil heat absorption heats up, and ordered about by oil pump, after the scatterer of flowing through cooling, returns to shell side.
4. the isothermal methanation reactor for preparing methane by synthetic gas method described in claim 1, there is a cylindrical shell, it is characterized in that the upper tubesheet and the lower tubesheet that in cylindrical shell, are disposed radially are divided into unstripped gas storehouse, finished product gas storehouse and heat-eliminating medium region, on the cylindrical shell in unstripped gas storehouse, there is opening for feed, on the cylindrical shell in finished product gas storehouse, there is discharge port, on the cylindrical shell in heat-eliminating medium region, have coolant inlet and outlet; The tube side sleeve pipe that is nested and forms by inner and outer tubes in cylindrical shell, its middle external tube is suspended on lower tubesheet, and upper end open is communicated with finished product gas storehouse, and lower end cecum stretches in heat-eliminating medium region; Inner tube is suspended on upper tubesheet, and upper end open is communicated with unstripped gas storehouse, and lower ending opening stretches in outer tube bottom; In inner tube or in the annular space of inner tube and outer tube, be filled with methanation catalyst.
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| EP2910523A1 (en) * | 2014-02-21 | 2015-08-26 | Haldor Topsoe A/S | 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)
| 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 |
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Patent Citations (2)
| 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 |
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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. |