CN102010284A - Method for producing substitute natural gas by coal based syngas through methanation - Google Patents
Method for producing substitute natural gas by coal based syngas through methanation Download PDFInfo
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- CN102010284A CN102010284A CN2009100348184A CN200910034818A CN102010284A CN 102010284 A CN102010284 A CN 102010284A CN 2009100348184 A CN2009100348184 A CN 2009100348184A CN 200910034818 A CN200910034818 A CN 200910034818A CN 102010284 A CN102010284 A CN 102010284A
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Abstract
The invention belongs to the technical field of coal gasification comprehensive application, which relates to a method for preparing substitute natural gas by coal based syngas through methanation reaction. The invention mainly comprises an air-cooled methanation reactor, a water-cooled methanation reactor and a heat insulation methanation reactor, wherein the air-cooled methanation reactor is used for pre-heating reaction raw material gas and realizing fine methanation; the water-cooled methanation reactor is a main reactor for completing a majority of CO methanation, a majority of discharged reaction heat is taken away through vaporation of the water to generate saturated steam; and high-temperature reaction gas of an outlet of the heat insulation methanation reactor is used for realizing the over-heat of the saturated steam. The method reasonably utilizes the intense heat energy discharged by methanation reaction with the byproduct of high-potential energy overheat steam, and can reduce the energy consumption caused by using high recycle ratio in the process for producing substitute natural gas by coal based syngas through methanation at the same time. Multi-reactors are connected in series and can be operated at higher space velocity in the premise of intensity permission of a catalyst, therefore, the yield of the reactors is improved, the cost of the unit product is reduced and the maximization of the economic benefit is realized.
Description
Technical field: the invention belongs to gasification comprehensive application technology field, relate to coal based synthetic gas methanation production substitute natural gas processing method.
Background technology: the seventies in 20th century, the oil supply crisis first time since the industrialization revolution has appearred in the world, has caused national governments and the entrepreneur extensive concern to the substitute energy exploitation.West Germany LURGI and South Africa coal, oil, gas company at that time, at an other cover half industrialization coal system substitute natural gas (the Substitute Natural Gas that built of South Africa F-T coal-to-oil factory, be called for short SNG) testing apparatus, simultaneously, LURGI and Austrian Ai Erpasuo natural gas companies have been built another set of half industrialized SNG testing apparatus at the Austria Vienna petroleum chemical plant.Two cover testing apparatuss have all carried out the running of long term, have obtained gratifying test result.On this basis, big plain in u.s.a in 1984 has built up 3,890,000 m
3The coal system SNG factory of/d produces SNG 12.7 hundred million m per year
3, product gas contains methane 96%, and this factory builds up so far, normally moves more than 20 year.The Sweet natural gas factory that Denmark Tops φ e company built up 7.2 ten thousand m3/d in the U.S. in 1978 was forced to close down because oil price is reduced to and can't keeps production in 1981.
In recent years, along with oil price is constantly soaring, the energy security problem has caused showing great attention to of all circles once more, produces SNG by coal through the synthetic gas methanation and receives publicity once more.2007, Tops φ e company released coal system SNG Technology again, and this technology is adjusted to appropriate H with the synthetic gas that gasification obtains through sulfur-resisting transformation
2/ CO (being slightly larger than 3) purifies the H that removes in the synthetic gas then
2S, CO
2Deng sour gas, pass through high-temperature methanation technology (TREMP at last
TM) make SNG.At present, Power Holding is just building 4Mt/a coal tubulation road Sweet natural gas project in the Illinois of the U.S., plan to go into operation in 2010.The TREMP methanation technology that this project adopts Tops φ e company to provide.
Year surplus the research of domestic employing gas methanation technology production city gas has carried out 20, and built factory.Its main purpose is to reduce the CO content in the coal gas and improve calorific value, usually, and CH in the product gas
4Content lower (about 10%), CO content higher (10～20%), the limited (＜15MJ/Nm of the raising of calorific value
3), although reached the combustion gas standard of national regulation, can not effectively solve CO
2Emission problem, the fuel gas supply system of samll cities and towns in being mainly used in.
China is the country of " rich coal, oil-poor, weak breath ", exploitation coal system SNG technology and then the coal system of construction SNG device have good economic benefit in the soaring oil prices epoch, to solving the problem of complex utilization of coal resources, alleviate the present situation of Chinese hydrocarbon resources shortage, safeguard the energy security of China, realize CO
2Reduce discharging, protect environment all significant.
Usually contain more CO in the coal gas that gasification produces, this kind coal gas is low toxic with CO because of its calorific value, is unsuitable for direct fuel as gas and circulating power station and uses; In the presence of catalyzer, CO all can be converted into methane, substitute natural gas that Here it is.With gas reforming is the process (namely for methane reaction process) of methane, and contingent reaction comprises in the methanation:
CO+3H
2→CH
4+H
2O+206.2KJ/mol (1)
CO
2+4H
2→CH
4+2H
2O+165KJ/mol (2)
2CO+2H
2→CH
4+CO
2+247.5KJ/mol (3)
CO+H
2O→H
2+CO
2+41KJ/mol (4)
Peggy Y.Hou thinks CO and H
2Carry out according to reaction (3) on molybdenum sulfide catalyst, speed of reaction is 1 grade to CO, to H
2It is 0.5 grade.CO as reaction product
2, suppress CH
4Generating rate.MoS
2The activation energy of catalyzed reaction is 31kJ/mol, is significantly less than transition metal-catalyzed methanation.And research is at present mostly carried out according to reaction (1) with practice, uses to contain cobalt or nickel-containing catalyst, generates methane at 200～350 ℃ of following CO shortenings, is a kind of Special Circumstances of F-T method synthetic hydrocarbon liquid fuel.Methanation reaction has following two classes to use as a kind of purification techniques usually: (A) be used for removing process gas (as refining H
2Or ammonia synthesis gas) a spot of CO and CO in
2(B) town gas is detoxified by the CO methanation and is improved calorific value.
Because CO content is higher in the coal based synthetic gas, and the thermal discharge of methanation reaction is very big, about 70 ℃ of the thermal insulation warming that the CO methanation of one percentage point is brought.When the reaction mixture gas body during by the adiabatic beds temperature sharply raise, too high temperature can cause catalyst deactivation on the one hand, and molecular balance is moved to the left, and is unfavorable for improving outlet CH
4Concentration.Can take following mode to reduce reaction temperature rising:
A) gas---exhaust gas separated into two parts after overcooling that will come out from reactor, wherein a part enters subsequent processing, another part as circulation gas with enter reactor after virgin gas is mixed, to reduce CO content in the inlet tower gas, the high-temperature methanation technology (TREMP of typical technology such as the exploitation of Denmark Tops φ e company
TM).The shortcoming of this technology is in order to reach rational thermal insulation warming, and internal circulating load is bigger usually, causes energy consumption bigger;
B) adopt the mode that adds a large amount of water vapors to make the thermal insulation warming that the reduction of CO content is reacted with control in the imported raw material gas, typical technology such as the exploitation of ICI company once pass through methanation process, the shortcoming of this technology is that a large amount of steam also makes the available gas amount of reaction less relatively in diluting reaction gas, and the integral energy utilization ratio is lower;
C) adopt a plurality of reactors in series, the exhaust gas of last reactor enters a back reactor after cooling, stepwise reaction moves heat step by step, the shortcoming of this technology is the synthetic gas for high concentration CO, the difficult control of first section thermal insulation warming, produce high-quality substitute natural gas, required placed in-line number of reactors is many;
D) use drum to move the shell and tube-type reactor of heat; Take away a large amount of reaction heat by the vaporization of boiled water, keep reaction bed temperature in narrower warm area.
Summary of the invention: the object of the invention is to provide a kind of coal system SNG methanation process method of reasonable energy utilization, is the processing method of producing substitute natural gas with coal based synthetic gas through methanation reaction.
The inventive method is compared with existing processing method, have the following advantages and the high-lighting effect, the huge heat that combination by reactor can the reasonable use methanation reaction be emitted, the superheated vapour of by-product high potential can reduce conventional methanation reaction simultaneously and produce the energy consumption that the high recycle ratio of substitute natural gas process using is brought.The series connection of employing multiple reactor under the prerequisite that catalyst strength allows, can be operated under higher space velocity, improves the output of reactor, reduces the cost of unit product, realizes maximization of economic benefit.
The inventive method is achieved like this: it is mainly finished by following system, and system mainly comprises: (a) air cooled methanator that carries out preheating for reactor feed gas and realize smart methanation; (b) one as main reactor, and the CO transformation efficiency is 60～80% water-cooled methanator; (c) realize saturation steam superheated adiabatic methanation reactor for one.
Usually, the inventive method is carried out as follows: coal based synthetic gas obtains H by conversion, purification
2/ CO is than the synthetic gas that is 2.5～3.5; Synthetic gas is divided into two-way, and one the tunnel enters the 3rd reactor---and the tube side of gas cooled reactor and the reactant gases of shell side carry out heat exchange; Another road and second reactor---the gas of adiabatic reactor outlet after the waste heat boiler heat exchange carries out heat exchange; The gas that two-way is preheated also becomes to lead up to a process furnace heating of opening very much first reactor---the inlet temperature of water cooled reactor shell side reaches 280～320 ℃ to guarantee to enter, to prevent forming nickle carbonoxide under the low temperature, water cooled reactor shell side filling nickel-base catalyst, adopting boiled water to move the thermal control temperature of reactor in the pipe is 280～450 ℃, and the reactor outlet temperature is 350 ℃～450 ℃; The gaseous mixture of first reactor outlet enters second reactor after the waste heat boiler heat exchange is reduced to 280～320 ℃, temperature of reaction is 280～550 ℃; It is overheated that the saturation steam that second reactor outlet gas produces the boiled water of the first reactor tube side carries out, reduce to the shell side that enters the 3rd reactor after 280～320 ℃ through high-duty boiler and interchanger heat exchange then, CO residual in the gas is converted into methane, and reaction heat is used for the preheating of tube side unstripped gas; Reacted gas is through the waste heat boiler heat exchange, and water cooler cools off, and can directly obtain containing the substitute natural gas of methane 94～96% after pressure-swing absorption apparatus separates.
Softening water is preheated to 300～350 ℃ through interchanger by reacted gas, enter the tube side of the water cooled reactor that links to each other with drum, absorption reaction heat and vaporization in tube side, the steam of generation enters drum, enter the superheater that links to each other with adiabatic reactor then, form superheated vapour.
The used catalyzer of above-mentioned methanation reaction is preferably with SiO
2Or Al
2O
3Ni catalyst system for carrier.
The synthetic gas H that above-mentioned coal based synthetic gas obtains by conversion, purification
2/ CO is good than 2.9～3.1, and water cooled reactor shell side inlet temperature is preferably 290～310 ℃, and the water cooled reactor temperature is preferably 300～450 ℃, and the adiabatic reaction actuator temperature is preferably 300～550 ℃, and the gas cooled reactor temperature is preferably 300～450 ℃.
The pressure of above-mentioned methanation reaction is preferably 3.0～5.0MPa.
The pressure of gas mixture behind the above-mentioned methanation reaction when entering pressure-swing absorption apparatus is good with 1.0～3.0MPa.
Description of drawings: Fig. 1 is the process flow diagram of embodiment of the invention coal based synthetic gas methanation system substitute natural gas.
Embodiment: be elaborated to of the present invention below in conjunction with drawings and Examples.
Embodiment: as shown in Figure 1, the method for the embodiment of the invention is mainly finished by following system, and this system mainly comprises: (a) air cooled methanator 3, for reactor feed gas carries out preheating and realizes smart methanation; (b) a water-cooled methanator 6 is main reactor, CO transformation efficiency 60～80%; (c) adiabatic methanation reactor 8 is realized the overheated of saturation steam.
This method is carried out as follows: coal based synthetic gas obtains H by conversion, purification
2/ CO is divided into two-way than the synthetic gas 1 that is 3.0, and wherein one road gas 101 enters the 3rd reactor---and the tube side of gas cooled reactor 3 and the reactant gases of shell side carry out heat exchange; Another road gas 102 enters interchanger 11, carries out heat exchange with the gas after vapor superheater 9 heat exchange that comes out from adiabatic reactor 8; The gas that two-way is preheated is merged into one the tunnel, open very much process furnace heating 4 by one and guarantee to enter first reactor---the synthetic gas temperature of water cooled reactor 6 shell sides reaches 300 ℃, water cooled reactor 6 shell sides filling self-control nickel-base catalyst, adopting boiled water to move the thermal control temperature of reactor in the pipe is 300～450 ℃, the reactor outlet temperature is 350 ℃, the gas of first reactor, 6 outlets is cooled to 300 ℃ through interchanger 7 and enters second reactor---adiabatic reactor 8, temperature of reaction is 300～550 ℃, the exit gas of reactor 8 enters vapor superheater 9, the saturation steam that produces with drum 5 carries out heat exchange, reducing to 300 ℃ of shell sides that enter the 3rd reactor 3 through boiler water preheater 10 and feed gas heater 11 heat exchange then is methane with residual gas reforming, reaction heat is used for the preheating of tube side unstripped gas, reacted gas is through waste heat boiler 12 heat exchange, water cooler 13 cools off, and can directly obtain containing the substitute natural gas 15 of methane 94～96% after pressure-swing absorption apparatus 14 separates.
Softening water elder generation is through the exit gas heat exchange of waste heat boiler 12 and the 3rd reactor, again through boiler water preheater 10 with the reactant gases heat exchange and be preheated to 340～350 ℃, enter the tube side of the water cooled reactor that links to each other with drum, absorption reaction heat and vaporization in tube side, the steam that produces enters drum, enter the superheater that links to each other with adiabatic reactor then, form superheated vapour.
Claims (6)
1. the method for a coal based synthetic gas methanation production substitute natural gas is characterized in that this method finishes by following system, and system mainly comprises: (a) air cooled methanator that carries out preheating for reactor feed gas and realize smart methanation; (b) one as main reactor, and the CO transformation efficiency is 60～80% water-cooled methanator; (c) realize saturation steam superheated adiabatic methanation reactor for one.
2. the method for claim 1 is characterized in that this method carries out as follows:
Coal based synthetic gas obtains H by conversion, purification
2/ CO is than the synthetic gas that is 2.5～3.5; Synthetic gas is divided into two-way, and one the tunnel enters the 3rd reactor---and the tube side of gas cooled reactor and the reactant gases of shell side carry out heat exchange; Another road and second reactor---the gas of adiabatic reactor outlet after the waste heat boiler heat exchange carries out heat exchange; The gas that two-way is preheated also becomes to lead up to a process furnace heating of opening very much first reactor---the inlet temperature of water cooled reactor shell side reaches 280～320 ℃ to guarantee to enter, to prevent forming nickle carbonoxide under the low temperature, water cooled reactor shell side filling nickel-base catalyst, adopting boiled water to move the thermal control temperature of reactor in the pipe is 280～450 ℃, and the reactor outlet temperature is 350 ℃～450 ℃; The gas of first reactor outlet enters second reactor after interchanger is cooled to 280～320 ℃, temperature of reaction is 280～550 ℃; It is overheated that the saturation steam that second reactor outlet gas produces the first reactor gas bag carries out, reduce to the shell side that enters the 3rd reactor after 280～320 ℃ through the interchanger heat exchange then, CO residual in the gas is converted into methane, and reaction heat is used for the preheating of tube side unstripped gas; Reacted gas is through the waste heat boiler heat exchange, and water cooler cools off, and can directly obtain containing the substitute natural gas of methane 94～96% after pressure-swing absorption apparatus separates.
3. method as claimed in claim 2 is characterized in that the synthetic gas H that described coal based synthetic gas obtains by conversion, purification
2/ CO ratio is 2.9～3.1, and water cooled reactor shell side inlet temperature is 290～310 ℃, and the water cooled reactor temperature is 300～450 ℃, and the adiabatic reaction actuator temperature is 300～550 ℃, and the gas cooled reactor temperature is 300～450 ℃.
4. method as claimed in claim 2 is characterized in that described catalyzer is with SiO
2Or Al
2O
3Ni catalyst system for carrier.
5. method as claimed in claim 2, the pressure that it is characterized in that described methanation reaction is 3.0～5.0MPa.
6. method as claimed in claim 2 is characterized in that the pressure when described gas enters pressure-swing absorption apparatus is 1.0～3.0MPa.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102247850A (en) * | 2011-05-26 | 2011-11-23 | 肖天存 | Methanation catalyst, preparation process thereof and methanation reaction device |
| CN102344841A (en) * | 2011-09-20 | 2012-02-08 | 中国石油化工集团公司 | Method for preparing substitute natural gas by coal-based syngas |
| CN103865600A (en) * | 2012-12-12 | 2014-06-18 | 中国石油化工股份有限公司 | Methanation technology |
| CN104445064A (en) * | 2013-09-13 | 2015-03-25 | 杭州林达化工技术工程有限公司 | Syngas CO combined conversion method and apparatus |
| CN104845689A (en) * | 2014-02-18 | 2015-08-19 | 中国石油化工股份有限公司 | Technology for preparing synthetic natural gas through methanation of coal-based synthetic gas |
| CN106111022A (en) * | 2016-08-10 | 2016-11-16 | 湖南安淳高新技术有限公司 | Reactor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4964606A (en) * | 1972-09-08 | 1974-06-22 | ||
| US4028067A (en) * | 1974-06-10 | 1977-06-07 | Imperial Chemical Industries Limited | Process for producing combustible gases |
| CN101508922A (en) * | 2009-03-16 | 2009-08-19 | 西南化工研究设计院 | Methanation reaction process using oven gas to prepare substitute natural gas |
-
2009
- 2009-09-09 CN CN 200910034818 patent/CN102010284B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4964606A (en) * | 1972-09-08 | 1974-06-22 | ||
| US4028067A (en) * | 1974-06-10 | 1977-06-07 | Imperial Chemical Industries Limited | Process for producing combustible gases |
| CN101508922A (en) * | 2009-03-16 | 2009-08-19 | 西南化工研究设计院 | Methanation reaction process using oven gas to prepare substitute natural gas |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102247850A (en) * | 2011-05-26 | 2011-11-23 | 肖天存 | Methanation catalyst, preparation process thereof and methanation reaction device |
| CN102247850B (en) * | 2011-05-26 | 2013-06-26 | 肖天存 | Methanation catalyst, preparation process thereof and methanation reaction device |
| CN102344841A (en) * | 2011-09-20 | 2012-02-08 | 中国石油化工集团公司 | Method for preparing substitute natural gas by coal-based syngas |
| CN103865600A (en) * | 2012-12-12 | 2014-06-18 | 中国石油化工股份有限公司 | Methanation technology |
| CN103865600B (en) * | 2012-12-12 | 2016-06-08 | 中国石油化工股份有限公司 | A kind of methanation process |
| CN104445064A (en) * | 2013-09-13 | 2015-03-25 | 杭州林达化工技术工程有限公司 | Syngas CO combined conversion method and apparatus |
| CN104445064B (en) * | 2013-09-13 | 2018-11-02 | 杭州林达化工技术工程有限公司 | A kind of synthesis gas CO combined transformation method and apparatus |
| CN104845689A (en) * | 2014-02-18 | 2015-08-19 | 中国石油化工股份有限公司 | Technology for preparing synthetic natural gas through methanation of coal-based synthetic gas |
| CN106111022A (en) * | 2016-08-10 | 2016-11-16 | 湖南安淳高新技术有限公司 | Reactor |
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