CN107445785A - The synthetic method and synthesis system of methane - Google Patents

The synthetic method and synthesis system of methane Download PDF

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Publication number
CN107445785A
CN107445785A CN201611074011.XA CN201611074011A CN107445785A CN 107445785 A CN107445785 A CN 107445785A CN 201611074011 A CN201611074011 A CN 201611074011A CN 107445785 A CN107445785 A CN 107445785A
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carbon monoxide
synthetic method
hydrogen
reaction
methane
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王明华
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China Shenhua Energy Co Ltd
Shenhua Science and Technology Research Institute Co Ltd
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China Shenhua Energy Co Ltd
Shenhua Science and Technology Research Institute Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0485—Set-up of reactors or accessories; Multi-step processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0405—Apparatus
    • C07C1/041—Reactors
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/11—Purification; Separation; Use of additives by absorption, i.e. purification or separation of gaseous hydrocarbons with the aid of liquids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/86—Other features combined with waste-heat boilers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • C10L3/103—Sulfur containing contaminants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • C10L3/104—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/093—Coal
    • C10J2300/0936—Coal fines for producing producer gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0959—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C10J2300/1662—Conversion of synthesis gas to chemicals to methane (SNG)

Abstract

This application provides the synthetic method of methane and synthesis system.The synthetic method includes：Step S1, the gaseous mixture containing hydrogen and carbon monoxide is prepared using coal gas technique；Step S2, the hydrogen in gaseous mixture and the mol ratio of carbon monoxide are adjusted to 0.9~1.1:1.1~0.9；Step S3, under conditions of molybdenum sulfide makees catalyst, hydrogen is set to obtain methane with reaction of carbon monoxide.The synthetic method is simple, less energy intensive.

Description

The synthetic method and synthesis system of methane
Technical field
The application is related to methane synthesis field, in particular to the synthetic method and synthesis system of a kind of methane.
Background technology
With society, economic fast development, China's natural gas demand drastically rises, and the ratio in energy resource structure is rapid Increase.And domestic natural gas and shale gas be still in exploration and development early stage, import is also at the starting stage, and deliverability is built tight Lag again, cause natural gas imbalance between supply and demand to become increasingly conspicuous.Expect the year two thousand twenty, demand is up to 260,000,000,000 Nm3, demand gap can at that time 80,000,000,000 Nm can be reached3, and natural gas supply safety problem also will gradually show.
According to the resource situation of the few gas of China richness coal, coal synthetic natural gas as a kind of Modern Coal-based Chemical technology, due to The huge breach of the market demand, while the advantage being also readily transported by its higher transformation efficiency and synthetic natural gas, and again The arena of history on new website.But in the new historical stage, how the technique improves system energy efficiency, reduces CO2Emission reduction energy consumption etc. Aspect, still there are very big potentiality can explore.
More CO is usually contained in coal gas caused by coal gasification, such a coal gas is because its calorific value is low and CO is toxic, no Suitable for the fuel use directly as gas and circulating power station；In the presence of a catalyst, CO can be completely converted into Methane, here it is synthetic natural gas (SNG).
At present, research and practice are mostly according to reaction equationCarry out, using containing cobalt or containing Raney nickel, CO catalytic hydrogenation reactions generate methane at 200~350 DEG C.But needed according to reaction equation (1) reaction by hydrogen carbon Than being adjusted to 3 so that the quantity of steam of conversion process consumption is larger, and is enriched with CO2Concentration it is relatively low, generally 30%~40%, In separate absorbent CO2Process energy consumption it is more.
The content of the invention
The main purpose of the application is the synthetic method and synthesis system for providing a kind of methane, to solve in the prior art Gas reforming for methane process be enriched with CO2Concentration it is relatively low, separate absorbent CO2Process energy consumption it is more the problem of.
To achieve these goals, according to the one side of the application, there is provided a kind of synthetic method of methane, the synthesis Method includes：Step S1, the gaseous mixture containing hydrogen and carbon monoxide is prepared using coal gas technique；Step S2, will be above-mentioned mixed The mol ratio for closing the hydrogen in gas and carbon monoxide is adjusted to 0.9~1.1:1.1~0.9；Step S3, make catalyst in molybdenum sulfide Under conditions of, above-mentioned hydrogen is obtained methane with above-mentioned reaction of carbon monoxide.
Further, above-mentioned steps S2 includes：Make vapor with the above-mentioned reaction of carbon monoxide in above-mentioned gaseous mixture to adjust The mol ratio of whole above-mentioned hydrogen and above-mentioned carbon monoxide.
Further, before above-mentioned vapor and above-mentioned reaction of carbon monoxide is made, above-mentioned synthetic method also includes will be upper State the process that gaseous mixture is cooled to 150~220 DEG C.
Further, the above-mentioned process that above-mentioned gaseous mixture is cooled to 150~220 DEG C includes：Using refrigerant to above-mentioned mixed Close gas to be cooled, obtain high steam of the pressure between 8~14MPa, the above-mentioned high steam of preferred pair is recycled.
Further, the temperature of the preparation process in above-mentioned steps S1 is between 1200 DEG C~1400 DEG C, pressure 4~ Between 6.5MPa.
Further, in above-mentioned steps S2, the reaction temperature of above-mentioned vapor and above-mentioned carbon monoxide is at 210~420 DEG C Between, reaction pressure is between 2~6MPa.
Further, middle pressure steam of the pressure in 2~6MPa is produced in above-mentioned steps S3, above-mentioned synthetic method also includes： The process recycled to above-mentioned middle pressure steam.
Further, above-mentioned steps S3 includes：Step S31, under the catalytic action of above-mentioned molybdenum sulfide, above-mentioned hydrogen with it is upper State the mixed gas that reaction of carbon monoxide generates above-mentioned methane and carbon dioxide；Step S32, remove upper in above-mentioned mixed gas State carbon dioxide.
Further, the temperature of the reaction in above-mentioned steps S31 is between 210~280 DEG C, the pressure of reaction 2.5~ Between 6MPa.
Further, above-mentioned steps S32 also includes：Remove the sulfide in above-mentioned mixed gas.
According to the another aspect of the application, there is provided a kind of synthesis system of methane, the synthesis system include：For providing The coal gasification apparatus of hydrogen and carbon monoxide needed for methane synthesis；The conversion of mol ratio for adjusting hydrogen and carbon monoxide is anti- Device is answered, is connected by first gas conveyance conduit with above-mentioned coal gasification apparatus；Methanator, pass through second gas delivery pipe Road is connected with above-mentioned shift-converter.
Further, above-mentioned synthesis system also includes：Heat recovering device, it is connected to absorb with above-mentioned coal gasification apparatus The sensible heat of above-mentioned carbon monoxide and above-mentioned hydrogen and/or it is connected to absorb above-mentioned methanation reaction with above-mentioned methanator Sensible heat caused by device.
Further, above-mentioned synthesis system also includes：Desulfurization and decarburization device, pass through the 3rd gas with above-mentioned methanator Body conveyance conduit is connected.
Using the technical scheme of the application, the mol ratio of hydrogen and carbon monoxide is adjusted to 0.9~1.1 in step S2: 1.1~0.9, it is not necessary to which the mol ratio of hydrogen and carbon monoxide is adjusted to 3:1, during adjustment hydrogen with carbon monoxide The more energy need not be consumed；Also, the mol ratio of hydrogen and carbon monoxide is adjusted to 0.9~1.1:1.1~0.9 so that The synthetic reaction of methane is according to reaction equationCarry out, because the reaction equation is relative to reaction equationFor, reaction product includes CO2, can so be enriched with more CO2, i.e. concentration is higher CO2, the CO in mixed gas2Concentration can reach 50~60%, and useObtained CO2 Concentration be only 30~40%, be enriched with to obtain CO2Concentration is higher, absorbs the CO of equivalent2The amount of the processing gas needed is just few, and then Separate absorbent CO can be reduced2Process energy consumption.
Brief description of the drawings
The Figure of description for forming the part of the application is used for providing further understanding of the present application, and the application's shows Meaning property embodiment and its illustrate be used for explain the application, do not form the improper restriction to the application.In the accompanying drawings：
Fig. 1 shows the schematic flow sheet of the synthetic method for the methane that a kind of exemplary embodiments of the application provide；
Fig. 2 shows a kind of structural representation of the synthesis system of exemplary embodiments methane of the application；And
Fig. 3 shows a kind of structural representation of the synthesis system of embodiment methane of the application.
Wherein, above-mentioned accompanying drawing marks including the following drawings：
1st, coal gasification apparatus；2nd, shift-converter；3rd, methanator；4th, heat recovering device；5th, desulfurization and decarburization fills Put；01st, first gas conveyance conduit；02nd, second gas conveyance conduit；03rd, third gas conveyance conduit.
Embodiment
It is noted that described further below is all exemplary, it is intended to provides further instruction to the application.It is unless another Indicate, all technologies used herein and scientific terminology are with usual with the application person of an ordinary skill in the technical field The identical meanings of understanding.
It should be noted that term used herein above is merely to describe embodiment, and be not intended to restricted root According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative It is also intended to include plural form, additionally, it should be understood that, when in this manual using term "comprising" and/or " bag Include " when, it indicates existing characteristics, step, operation, device, component and/or combinations thereof.
As the CO that background technology is introduced, and gas reforming of the prior art is enriched with for the process of methane2Concentration It is relatively low, separate absorbent CO2Process energy consumption it is more the problem of, in order to solve the problems, such as that as above, present applicant proposes methane Synthetic method and synthesis system.
In a kind of typical embodiment of the application, it is proposed that a kind of synthetic method of methane, as shown in figure 1, the party Method includes：Step S1, the gaseous mixture containing hydrogen and carbon monoxide is prepared using coal gas technique；Step S2, by above-mentioned mixing The mol ratio of hydrogen and carbon monoxide in gas is adjusted to 0.9~1.1:1.1~0.9；And step S3, it is catalyzed in molybdenum sulfide Under conditions of agent, above-mentioned hydrogen is set to obtain methane with above-mentioned reaction of carbon monoxide.
Using above-mentioned synthetic method, the mol ratio of hydrogen and carbon monoxide is adjusted to 0.9~1.1 in step S2:1.1 ~0.9, it is not necessary to which the mol ratio of hydrogen and carbon monoxide is adjusted to 3:1, during adjustment hydrogen with carbon monoxide not Need to consume the more energy；Also, the mol ratio of hydrogen and carbon monoxide is adjusted to 0.9~1.1:1.1~0.9 so that first The synthetic reaction of alkane is according to reaction equationCarry out, because the reaction equation is relative to reaction equationFor, reaction product includes CO2, can so be enriched with more CO2Concentration it is higher, mix Close the CO in gas2Concentration can reach 50~60%, and useObtained CO2Concentration only For 30~40%, CO is enriched with to obtain2Concentration is higher, absorbs the CO of equivalent2The volume of the processing gas needed is just few, and then can drop Low separate absorbent CO2Process energy consumption.
In order to which the mol ratio of hydrogen and carbon monoxide more efficiently is adjusted into 0.9~1.1:1.1~0.9, the application It is preferred that above-mentioned steps S2 includes：Make the above-mentioned reaction of carbon monoxide in vapor and above-mentioned gaseous mixture with adjust above-mentioned hydrogen and The mol ratio of above-mentioned carbon monoxide.Specifically reaction equation is
In a kind of embodiment of the application, preferably before above-mentioned vapor and above-mentioned reaction of carbon monoxide is made, above-mentioned conjunction Also include above-mentioned gaseous mixture being cooled to 150~220 DEG C of process into method.The temperature-fall period can be further ensured that the temperature Meet the reaction temperature demand of catalyst, that is, ensure that catalyst has higher activity.
In order to more easily and efficiently cool to above-mentioned gaseous mixture, gaseous mixture is preferably cooled to 150~220 DEG C of process Including：Above-mentioned gaseous mixture is cooled using refrigerant, obtains high steam of the pressure between 8~14MPa.
In order to efficiently utilize the energy, the waste of the energy is avoided, the above-mentioned high steam of the application preferred pair is recycled.
In another embodiment of the application, gaseous mixture of the preparation containing hydrogen and carbon monoxide in above-mentioned steps S1 The temperature of process is between 1200 DEG C~1400 DEG C, and pressure is between 4~6.5MPa.By the way that temperature, pressure is controlled in this scope It is interior, it is possible to increase the yield of hydrogen and carbon monoxide.
The mol ratio of hydrogen and carbon monoxide is efficiently adjusted to 0.9~1.1 in order to be further ensured that:1.1~0.9, The reaction temperature of the preferably above-mentioned vapor of the application and above-mentioned carbon monoxide between 210~420 DEG C, reaction pressure 2.5~ Between 6MPa.
It is above-mentioned to produce middle pressure steam of the pressure in 2~6MPa in above-mentioned steps S3 in the another embodiment of the application, on Stating synthetic method also includes：The process recycled to above-mentioned middle pressure steam.
Similarly, in order to efficiently utilize the energy, the waste of the energy is avoided, the above-mentioned middle pressure steam of preferred pair carries out recovery profit With.
In another embodiment of the application, above-mentioned steps S3 includes：Step S31, in the catalytic action of above-mentioned molybdenum sulfide Under, above-mentioned hydrogen generates the mixed gas of above-mentioned methane and carbon dioxide with above-mentioned reaction of carbon monoxide；And step S32, take off Except the above-mentioned carbon dioxide in above-mentioned mixed gas.
In another embodiment of the application, the temperature of the reaction in above-mentioned steps S31 is between 210~280 DEG C, reaction Pressure between 2.5~6MPa.By temperature control of the pressure of reaction with reacting within this range, one can be further ensured that Carbonoxide is with hydrogen according to reaction equationCarry out.
In order to obtain the higher methane of purity, preferably above-mentioned steps S32 also includes：Remove the vulcanization in above-mentioned mixed gas Thing.Specifically, the organic sulfur and inorganic sulfur in above-mentioned mixed gas are typically removed.
In another exemplary embodiment of the application, as shown in Figure 2, there is provided a kind of synthesis system of methane, this is System includes coal gasification apparatus 1, shift-converter 2 and methanator 3.Wherein, coal gasification apparatus 1 is used to provide methane synthesis Required hydrogen and carbon monoxide；Shift-converter 2 is used for the mol ratio for adjusting hydrogen and carbon monoxide, is conveyed by first gas Pipeline 01 is connected with above-mentioned coal gasification apparatus 1；Methanator 3 passes through second gas conveyance conduit 02 and above-mentioned transformationreation Device 2 is connected.
The hydrogen in gaseous mixture caused by coal gasification apparatus and one are aoxidized by the shift-converter in the synthesis system The mol ratio of carbon is adjusted to 0.9~1.1:1.1~0.9, so cause hydrogen and carbon monoxide according toCarry out, and then more CO can be enriched with2So that the CO in mixed gas2Concentration can reach To 50~60%, separate absorbent CO can be reduced2Process energy consumption.
In order to will obviously be reclaimed caused by the course of reaction in synthesis system, the utilization rate of the energy is improved, avoids energy The waste in source, the preferably above-mentioned synthesis system of the application also include heat recovering device, the heat recovering device and above-mentioned coal gasification Device connects, for absorbing the sensible heat of above-mentioned carbon monoxide and above-mentioned hydrogen, or the heat recovering device and methanation reaction Device connects, for absorbing sensible heat caused by above-mentioned methanator；Or as shown in figure 3, the heat recovering device 4 with Coal gasification apparatus 1 and methanator 3 connect simultaneously, can absorb above-mentioned coal gasification apparatus 1 and methanation reaction simultaneously Sensible heat caused by device 3.
In another embodiment of the application, as shown in figure 3, above-mentioned synthesis system also includes desulfurization and decarburization device 5, this is de- Sulphur decarbonization device 5 is connected with above-mentioned methanator 3 by third gas conveyance conduit 03.The desulfurization and decarburization device 5 is de- Organic sulfur, inorganic sulfur and carbon dioxide in the mixed gas generated except methanator 3, obtain molar concentration for 86%~ The synthetic natural gas of 96% methane, natural-gas transfer pipeline is sent into as gas.The sulphur simple substance of removing is reclaimed simultaneously, and Separate CO2, realize emission reduction.
In order that the technical scheme of the application can clearly be understood by obtaining those skilled in the art, below with reference to tool The embodiment of body is described in detail with comparative example.
Embodiment 1
Kinds of coals for gasification used in the present embodiment 1 uses Shaanxi Bin County bituminous coal, and its composition and Lower heat value are shown in Table 1.And give Coal amount is 5000 ton days.The synthesis of methane is carried out using the methane synthesis device shown in Fig. 3.
Specifically the building-up process of methane is：
First, the gaseous mixture containing hydrogen and carbon monoxide is prepared using coal gasification apparatus.
Oxygen is made in air air inlet separator, and oxygen and dry pulverized coal or water-coal-slurry enter coal gasification apparatus together, Generate the gaseous mixture of hydrogen and carbon monoxide.The coal gasification apparatus is made up of gasification furnace main body and waste heat boiler, coal gasification course Pressure be 4MPa, temperature is 1200 DEG C.Caused gaseous mixture reclaims through waste heat boiler to sensible heat, produces 8MPa height Steam is pressed, and gaseous mixture is cooled to 150 DEG C.The technological parameter of the building-up process of specific methane is shown in Table 2.
Secondly, the hydrogen in above-mentioned gaseous mixture and the mol ratio of carbon monoxide are adjusted to 0.9 using shift-converter~ 1.1:1.1~0.9.
Gaseous mixture after cooling is delivered to shift-converter by first gas conveyance conduit, in order that obtaining follow-up methane Change reaction carry out it is more complete, it is necessary to adjust the volume ratio of hydrogen and carbon monoxide in coal gas (i.e. hydrogen-carbon ratio), react with Co-Mo is as catalyst, and it is 210 DEG C to react for adiabatic reaction, temperature control, pressure 6MPa, according to reaction equationCarry out, adjust the mol ratio of the hydrogen carbon in coal gas, adjusted 0.9~1.1:1.1~0.9 models In enclosing.
Finally, in methanator, catalyst is made using molybdenum sulfide, makes above-mentioned hydrogen and above-mentioned reaction of carbon monoxide Obtain methane.
Mixed gas after adjustment mol ratio is delivered in methanator by second gas conveyance conduit, with sulphur Change molybdenum as catalyst, reaction temperature is 210 DEG C, pressure 2.5MPa, according to reaction equationEnter OK, the mixed gas of methane and carbon dioxide is generated, the methanation carried out by this reaction equation, in obtained mixed gas CO2Concentration (50%~60%) ratio pass through transformationreationObtained CO2Concentration (30%~ 40%) it is high, so as to reduce CO2The energy consumption of separation process, methanation reaction process release substantial amounts of heat by high temperature water-supply band Walk so that reaction temperature maintains 210 DEG C or so, and the middle pressure steam for producing 2~6MPa is sent into heat recovering device and carried out Utilize.
The mixed gas of methane and carbon dioxide is entered into desulfurization and decarburization device, using MDEA, NHD or low-temp methanol as suction Agent is received, to remove wherein main organic sulfur (H2S) and inorganic sulfur (COS), pass through Claus or the recovery of Complexing Iron sulphur technique is single Matter sulphur (S), and carbon dioxide is separated to realize emission reduction；In obtained synthetic natural gas methane molar content can reach 86~ 96%, gas system is sent into by natural gas line and is used as city domestic gas.The work of the building-up process of specific methane Skill parameter is shown in Table 2.
Embodiment 2
Difference with embodiment 1 is that the temperature of coal gasification course is 1400 DEG C, pressure 6.5MPa, caused mixing Gas is reclaimed through waste heat boiler to sensible heat, produces 14MPa high steam, and gaseous mixture is cooled into 220 DEG C, is steamed using water The temperature of the process of the mol ratio of the whole hydrogen of controlled atmosphere and carbon monoxide is 420 DEG C, pressure 2MPa, hydrogen and above-mentioned carbon monoxide The reaction temperature that reaction obtains the process of methane is 280 DEG C, reaction pressure 6MPa.The technique of the building-up process of specific methane Parameter is shown in Table 2.
Embodiment 3
Difference with embodiment 2 is that the temperature of coal gasification course is 1300 DEG C, pressure 5MPa, caused gaseous mixture Sensible heat is reclaimed through waste heat boiler, produces 11MPa high steam, and gaseous mixture is cooled to 180 DEG C, using vapor The temperature for adjusting the process of the mol ratio of hydrogen and carbon monoxide is 310 DEG C, pressure 4MPa, and hydrogen and above-mentioned carbon monoxide are anti- The reaction temperature that the process of methane should be obtained is 240 DEG C, reaction pressure 4MPa.The technique ginseng of the building-up process of specific methane Number is shown in Table 2.
Comparative example
Kinds of coals for gasification used is identical with embodiment 1, and coal-supplying amount is 5000 ton days.Traditional preparing methane from coal process It is coal through gasifying after (4MPa, 1300 DEG C), obtains mainly containing CO and H2Synthesis gas, it is transformed and purification after, carry out methane Separated again after changing reaction to obtain methane.The methanation reaction process, which uses, contains cobalt or nickel-containing catalyst, at 200~350 DEG C CO catalytic hydrogenations are methane, and the mol ratio for generally closing the hydrogen in gas and carbon monoxide is 3:1.
Using ASPEN analogy methods, the gas finally given of the various embodiments described above and comparative example is tested, methane Yield and isolated CO2Amount be shown in Table 3.
Table 1
Table 2
Table 3
From the content of table 3, compared with comparative example, methane in the product that embodiment 1 obtains to embodiment 3 compared with It is more, and CO2More, i.e. the concentration of carbon dioxide is higher, and synthesizing methane Lower heat value efficiency is higher.
As can be seen from the above description, the application the above embodiments realize following technique effect：
1), using the synthetic method of the application, the mol ratio of hydrogen and carbon monoxide is adjusted to 0.9 in step s 2 ~1.1:1.1~0.9, it is not necessary to which the mol ratio of hydrogen and carbon monoxide is adjusted to 3:1, in adjustment hydrogen and carbon monoxide During need not consume the more energy；Also, the mol ratio of hydrogen and carbon monoxide is adjusted to 0.9~1.1:1.1~ 0.9 so that the synthetic reaction of methane is according to reaction equationCarry out, because the reaction equation is relative to anti- Answer formulaFor, reaction product includes CO2, can so be enriched with the CO of high concentration2, gaseous mixture CO in body2Concentration can reach 50~60%, and useObtained CO2Concentration be only 30~40%, it is enriched with to obtain CO2Concentration is higher, can reduce separate absorbent CO2Process energy consumption, realize CO2Emission reduction.
2), by the shift-converter in the synthesis system by the hydrogen in gaseous mixture caused by coal gasification apparatus and an oxygen The mol ratio for changing carbon is adjusted to 0.9~1.1:1.1~0.9, so cause hydrogen and carbon monoxide according toCarry out, and then more CO can be enriched with2So that the CO in mixed gas2Concentration can reach To 50~60%, separate absorbent CO can be reduced2Process energy consumption, realize CO2Emission reduction.
The preferred embodiment of the application is the foregoing is only, is not limited to the application, for the skill of this area For art personnel, the application can have various modifications and variations.It is all within spirit herein and principle, made any repair Change, equivalent substitution, improvement etc., should be included within the protection domain of the application.

Claims (13)

1. a kind of synthetic method of methane, it is characterised in that the synthetic method includes：
Step S1, the gaseous mixture containing hydrogen and carbon monoxide is prepared using coal gas technique；
Step S2, the hydrogen in the gaseous mixture and the mol ratio of carbon monoxide are adjusted to 0.9~1.1:1.1~0.9；And
Step S3, under conditions of molybdenum sulfide makees catalyst, the hydrogen is set to obtain methane with the reaction of carbon monoxide.
2. synthetic method according to claim 1, it is characterised in that the step S2 includes：
Make vapor and the reaction of carbon monoxide in the gaseous mixture to adjust rubbing for the hydrogen and the carbon monoxide That ratio.
3. synthetic method according to claim 2, it is characterised in that make the vapor and the reaction of carbon monoxide Before, the synthetic method also includes the gaseous mixture being cooled to 150~220 DEG C of process.
4. synthetic method according to claim 3, it is characterised in that described that the gaseous mixture is cooled to 150~220 DEG C Process include：The gaseous mixture is cooled using refrigerant, obtains high steam of the pressure between 8~14MPa, preferably The high steam is recycled.
5. synthetic method according to claim 1, it is characterised in that the temperature of the preparation process in the step S1 exists Between 1200 DEG C~1400 DEG C, pressure is between 4~6.5MPa.
6. synthetic method according to claim 2, it is characterised in that in the step S2, the vapor and described one The reaction temperature of carbonoxide is between 210~420 DEG C, and reaction pressure is between 2~6MPa.
7. synthetic method according to claim 1, it is characterised in that pressure is produced in the step S3 2~6MPa's Middle pressure steam, the synthetic method also include：
The process recycled to medium pressure steam.
8. synthetic method according to claim 1, it is characterised in that the step S3 includes：
Step S31, under the catalytic action of the molybdenum sulfide, the hydrogen and the reaction of carbon monoxide generate the methane with The mixed gas of carbon dioxide；And
Step S32, remove the carbon dioxide in the mixed gas.
9. synthetic method according to claim 8, it is characterised in that the temperature of the reaction in the step S31 210~ Between 280 DEG C, the pressure of reaction is between 2.5~6MPa.
10. synthetic method according to claim 8, it is characterised in that the step S32 also includes：
Remove the sulfide in the mixed gas.
11. a kind of synthesis system of methane, it is characterised in that the synthesis system includes：
For providing the coal gasification apparatus of hydrogen and carbon monoxide needed for methane synthesis；
For the shift-converter for the mol ratio for adjusting hydrogen and carbon monoxide, pass through first gas conveyance conduit and the coal gas Makeup is put connected；And
Methanator, it is connected by second gas conveyance conduit with the shift-converter.
12. synthesis system according to claim 11, it is characterised in that the synthesis system also includes：
Heat recovering device, with the coal gasification apparatus be connected to absorb the carbon monoxide and the hydrogen sensible heat and/ Or it is connected to absorb sensible heat caused by the methanator with the methanator.
13. synthesis system according to claim 11, it is characterised in that the synthesis system also includes：
Desulfurization and decarburization device, it is connected with the methanator by third gas conveyance conduit.
CN201611074011.XA 2016-11-29 2016-11-29 The synthetic method and synthesis system of methane Pending CN107445785A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101074397A (en) * 2007-06-22 2007-11-21 清华大学 Combined system and process for producing electric-substituted natural gas based on coal gasification and methanation
CN101245262A (en) * 2008-01-23 2008-08-20 清华大学 Gas-steam combined cycle system and technique based on coal gasification and methanation
CN102079685A (en) * 2009-11-26 2011-06-01 新奥科技发展有限公司 Coal gasification process for methane preparation by two stage gasification stove
CN102660339A (en) * 2012-04-27 2012-09-12 阳光凯迪新能源集团有限公司 Gas-steam efficient cogeneration process and system based on biomass gasification and methanation
CN103897758A (en) * 2012-12-26 2014-07-02 浦项产业科学研究院 Equipment and method for producing synthesized gas with low H2/CO ratio
CN104628508A (en) * 2015-01-30 2015-05-20 华南理工大学 System and process for preparing alkene from raw materials of coal and natural gas by virtue of synthesis
CN106220461A (en) * 2016-07-19 2016-12-14 青岛科技大学 A kind of device and method directly preparing methane based on coal chemistry chain gasification

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101074397A (en) * 2007-06-22 2007-11-21 清华大学 Combined system and process for producing electric-substituted natural gas based on coal gasification and methanation
CN101245262A (en) * 2008-01-23 2008-08-20 清华大学 Gas-steam combined cycle system and technique based on coal gasification and methanation
CN102079685A (en) * 2009-11-26 2011-06-01 新奥科技发展有限公司 Coal gasification process for methane preparation by two stage gasification stove
CN102660339A (en) * 2012-04-27 2012-09-12 阳光凯迪新能源集团有限公司 Gas-steam efficient cogeneration process and system based on biomass gasification and methanation
CN103897758A (en) * 2012-12-26 2014-07-02 浦项产业科学研究院 Equipment and method for producing synthesized gas with low H2/CO ratio
CN104628508A (en) * 2015-01-30 2015-05-20 华南理工大学 System and process for preparing alkene from raw materials of coal and natural gas by virtue of synthesis
CN106220461A (en) * 2016-07-19 2016-12-14 青岛科技大学 A kind of device and method directly preparing methane based on coal chemistry chain gasification

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
梁仁杰等编著: "《化学工艺学》", 31 March 1998, 重庆大学出版社 *
邵景景主编: "《煤炭深加工与利用》", 31 January 2014, 中国矿业大学出版社 *

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Application publication date: 20171208