CN102021039A - Method and device for preparing methane-containing gas by multi-region coal gasification - Google Patents
Method and device for preparing methane-containing gas by multi-region coal gasification Download PDFInfo
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- 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
- C10J3/721—Multistage gasification, e.g. plural parallel or serial gasification stages
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- 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
- C10J3/48—Apparatus; Plants
- C10J3/482—Gasifiers with stationary fluidised bed
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- 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
- C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
- C10J3/60—Processes
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- 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
- C10L3/08—Production of synthetic natural gas
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- 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
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- 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
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- 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
- C10J2300/0973—Water
- C10J2300/0976—Water as steam
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- 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
- C10J2300/0983—Additives
- C10J2300/0986—Catalysts
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- 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)
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Abstract
The invention discloses a method for preparing methane-containing gas by multi-region coal gasification, comprising the following steps: a. putting the pulverized coal into the partial pyrolysis region of a gasification furnace that comprises a partial pyrolysis region, a catalytic gasification region and a residue gasification region and contacting with the gas flow from the catalytic gasification region to partially pyrolyze the pulverized coal and generate methane-containing gas flow and partially pyrolyzed pulverized coal; b. feeding the partially pyrolyzed pulverized coal into the catalytic gasification region and contacting with the gas flow from the residue gasification region in the presence of a catalyst; allowing the generated gas flow to enter the partial pyrolysis region and the coal residues that have not fully reacted to enter the residue gasification region; and c. contacting the coal residues with a gasifying agent in the residue gasification region and allowing the generated gas flow to enter the catalytic gasification region and the generated ash to be discharged from the gasification furnace. The invention also discloses a gasification furnace for preparing methane-containing gas by coal gasification.
Description
Technical field
The present invention relates to gasification and prepare the substitute natural gas field, specifically, relate to the method and apparatus that the preparation of multi-region gasification contains the gas of methane.
Background technology
China is the country of the oil-poor weak breath of rich coal, and along with society, rapid economy development, the China's natural gas demand is sharply soaring, and the ratio in energy structure increases sharply.And that domestic Sweet natural gas still is in exploratory development is early stage, and import also is in the starting stage, and deliverability seriously lags behind, and causes the Sweet natural gas imbalance between supply and demand to become increasingly conspicuous.Utilize the relatively large coal of china natural resources advantage, can not only promote efficient, the clean utilization of coal; And can utilize existing natural gas line, and with lower economic cost, effectively alleviate the imbalance between supply and demand of Sweet natural gas, this is the effective measure that the low-grade coal resource fully utilizes.
Common Coal Gasification Technology, promptly coal at high temperature carries out gasification reaction with the vaporized chemical that oxygen (or air) and/or steam (being also referred to as water vapour) are formed, and generates and contains a small amount of methane (CH
4) synthetic gas (mainly being hydrogen, carbon monoxide and carbonic acid gas), carry out hydrosphere transformation and methanation operation afterwards, adopt two-step approach to prepare methane.This Coal Gasification Technology have the required temperature height of gasification reaction, energy consumption big, to the equipment requirements height, and need three reaction units, technology than shortcomings such as complexity.
The catalytic coal gasifaction technology is the clean efficient a kind of important way utilized of coal, adopts the catalytic coal gasifaction technology, coal under relatively low temperature with steam (H
2O), hydrogen (H
2), the vaporized chemical formed of carbon monoxide (CO) carries out gasification reaction under the katalysis of catalyzer, generate the methane (CH of high density
4).The catalytic coal gasifaction technology is compared with other Coal Gasification Technology, has advantages such as the required temperature of methane content height, gasification reaction is low.
At present, the catalytic coal gasifaction technology of mentioning in the relevant patent, Optimal Temperature that gasification reaction is required and pressure range are 593～700 ℃ and 20～40atm, use alkaline carbonate as catalyzer.Adopt low temperature separation process that the methane in the aerogenesis is separated with carbon monoxide, hydrogen, hydrogen in the reactant gases and carbon monoxide are recycled in the vapourizing furnace, make it in vapourizing furnace, to carry out methanation reaction and be converted into methane, thus the output of raising system methane.This catalytic coal gasifaction technology has low, the long reaction time of gasification reaction speed, and efficiency of carbon conversion is lower, and gas separation system is invested high shortcoming; For satisfying the thermally equilibrated needs of reactor, need to advance the stove superheated vapour and be heated to comparatively high temps, steam superheating system and heat exchange system load are higher, less economical.
United States Patent (USP) 4,077,778 propose to adopt the catalytic coal gasifaction technology of multistage fluidized bed reactor, eliminate the deficiency of former catalysis gasification technique, and gasification is carried out more efficiently, make full use of the feed carbon resource, improve efficiency of carbon conversion.Main fluidized-bed reactor operating gas velocity is higher, and the part carbon granule is carried secretly to the secondary streams fluidized bed reactor, than carrying out gasification reaction under the low gas velocity, increases the solid phase residence time, improves efficiency of carbon conversion to greatest extent.Adopt multistage gasification carbon utilisation rate can be increased to more than 95% by 70-85% than the single-stage gasification.But a plurality of fluidized-bed reactors of this catalytic coal gasifaction process using, the facility investment height, operation is complicated.
In addition, United States Patent (USP) 4,094,650 mention under catalytic alkali metal, carbonaceous solids can be gasified, preparation methane, catalyzer need reclaim again and use.Reclaim water-soluble catalyst by multistage washing, lime slaking reclaims non-dissolubility catalyzer.United States Patent (USP) 0277437 is at United States Patent (USP) 4,094, on 650 bases, adopting one-level to handle separates the basic metal material from the reactor solids residue, simplified the base metal catalysts removal process, improved the economy and the total efficiency of catalysis gasification technique, but this recovery system is still complicated, recovery method is expensive.
In addition,, produce coal gas in order to make full use of heat, United States Patent (USP) 5,064,444 propose the method for pressurization steam gasification, and fluidized-bed gasification furnace is divided into pyrolysis section, gasification section, cooling section, and each section separates with dividing plate.Pyrolysis section, gasification section are placed snake shape coil pipe (coil heat exchanger) in the vapourizing furnace, feed 900 ℃-950 ℃ high-temperature gas such as the gas heating coal dust after the fuel combustion in the pipe, and gasification, pyrolysis institute heat requirement are provided, and produce coal gas.This fluidized-bed gasification furnace can be for vertical, also can be horizontally, is vaporized chemical with 700 ℃-800 ℃ superheated vapours, and cooling section feeds saturation steam, and coal dust is entrained in superheated vapour and enters vapourizing furnace together.But the reaction volume utilization ratio in the vapourizing furnace is low, influences solid phase processing; Only be that vaporized chemical causes efficiency of carbon conversion not high with the superheated vapour, so carbon content is higher in the residue, coal is difficult to be utilized effectively; Caloric requirement in this method in the high-temperature gas passes to coal dust and steam by the tube wall of snake shape coil pipe, compares with the gas-solid transmission of heat by contact, and this indirect heating mode heat transfer rate is slow and thermo-efficiency is low, the solid phase inequality of being heated in the bed; Equipment is numerous and diverse simultaneously, particularly horizontal chamber oven.
Summary of the invention
The application provides a kind of multi-region gasification preparation to contain the method for the gas of methane, comprises the following steps:
A. coal dust is joined the partial thermal decomposition district that contains partial thermal decomposition district, catalytic gasification district and the vapourizing furnace of residue gasification zone and contacts with gas stream to generate and contain the gas stream of methane and the coal dust of partial thermal decomposition with the described coal dust of partial thermal decomposition from the catalytic gasification district,
B. the coal dust of described partial thermal decomposition is sent into the catalytic gasification district and in the presence of catalyzer, is contacted with gas stream from the residue gasification zone, the gas stream entering part pyrolysis zone of generation, fully the coal residue of reaction enter the residue gasification zone and
C. the coal residue is contacted with vaporized chemical in the residue gasification zone, the gas stream of generation enters the lime-ash of catalytic gasification district and generation and discharges vapourizing furnace.
The application also provides a kind of multi-region gasification preparation to contain the method for the gas of methane, comprises the following steps
1). coal dust joined the catalytic gasification district that contains the catalytic gasification district and the vapourizing furnace of residue gasification zone and gas stream from the residue gasification zone in the presence of catalyzer, contact with generation contain the gas stream of methane and fully the coal residue of reaction and
2). the coal residue of step 1) is sent into the residue gasification zone contact with vaporized chemical, the gas stream of generation enters the lime-ash of catalytic gasification district and generation and discharges vapourizing furnace.
The application also provides a kind of gasification preparation to contain the vapourizing furnace of the gas of methane, comprises
A. partial thermal decomposition district is used for coal dust is contacted with gas stream from the catalytic gasification district, and the gas stream that contains methane of generation leaves the coal dust of the partial thermal decomposition of vapourizing furnace and generation and sends into the catalytic gasification district;
B. catalytic gasification district is used for and will contacts with gas stream from the residue gasification zone from the coal dust of the partial thermal decomposition in partial thermal decomposition district, the gas stream of generation enter described pyrolysis zone and fully the coal residue of reaction send into the residue gasification zone; With
C. the residue gasification zone is used for the coal residue from described catalytic gasification district is contacted with vaporized chemical, and the gas stream of generation enters the lime-ash of catalytic gasification district and generation and discharges vapourizing furnace.
The application also provides a kind of gasification preparation to contain the vapourizing furnace of the gas of methane, comprises
1). the catalytic gasification district, be used for coal dust is contacted in the presence of catalyzer with gas stream from the residue gasification zone, generate the coal residue that contains the gas stream of methane and fully react; With
2). the residue gasification zone, be used for the coal residue from described catalytic gasification district is contacted with vaporized chemical, the gas stream of generation enters the catalytic gasification district, and the lime-ash of generation is discharged vapourizing furnace.
Description of drawings
The structural representation of the vapourizing furnace that Fig. 1 provides for the embodiment of the invention;
Be understandable that accompanying drawing only is illustrative, do not plan to limit the scope of the invention by any way.Scope of the present invention should be determined by the content of claim.
Detailed Description Of The Invention
In first kind of embodiment, the application provides a kind of multi-region coal gasification preparation to contain the method for the gas of methane, comprises the following steps:
A. coal dust is joined the partial thermal decomposition district of the gasification furnace that contains partial thermal decomposition district, catalytic gasification district and residue gasification district and contacts with the described coal dust generation of partial thermal decomposition with gas stream from the catalytic gasification district and contain the gas stream of methane and the coal dust of partial thermal decomposition,
B. the coal dust of described partial thermal decomposition is sent into the catalytic gasification district and in the presence of catalyst, contact with gas stream from residue gasification district, the gas stream entering part pyrolysis zone of generation and fully the coal residue of reaction enter residue gasify distinguish and
C. described coal residue is contacted with gasifying agent in residue gasification district, the gas stream of generation enters the lime-ash of catalytic gasification district and generation and discharges gasification furnace.
The nucleus equipment that method of the present invention adopts is multi-zone gasification furnace. The general vertical placement of this gasification furnace or slant setting can use distribution grid that gasification furnace is divided into three districts from bottom to up, according to the function in each district, are followed successively by residue gasification district, catalytic gasification district and partial thermal decomposition district, as shown in Figure 1. Solid material wherein, coal for example, from the top down motion, finally the slag-drip opening from the gasification furnace bottom leaves gasification furnace, and gas material, then from bottom to top motion, finally the exhaust outlet from top of gasification furnace leaves gasification furnace. Solid material and gas material are the form of counter current contacting basically in gasification furnace. Gasification furnace of the present invention, basically more high the closer to bottom temp, more low the closer to head temperature.
In the method for the present invention, the feed entrance point of coal, gasifying agent and catalyst can be selected or be adjusted as required. For example, at least a portion coal can enter gasification furnace from the partial thermal decomposition district of gasification furnace of the present invention and/or any one or a few place in catalytic gasification district; Even catalytic gasification is temperature required when requiring when the heat that only depends on residue gasification to produce is not enough to keep, and also part of coal can be entered gasification furnace from residue gasification district. And the feeding manner of catalyst can be divided into two kinds, for can be under the high temperature in residue of the present invention gasification district the catalyst of generating gasification, alkali carbonate for example, can be from the partial thermal decomposition district of gasification furnace and/or catalytic gasification district and/or residue gasification district lead to into gasification furnace; And for catalyst that can not generating gasification under the high temperature in residue of the present invention gasification district, alkaline earth metal carbonate for example, then from the partial thermal decomposition district and/or the catalytic gasification district lead to into gasification furnace; Gasifying agent then leads to the gasification furnace from bottom and/or the side in residue gasification district. No matter which coal and catalyst distinguish charging from, their finally can be in contact with one another in the catalytic gasification district of gasification furnace, and simultaneously with comprise synthesis gas and contact at interior gas stream. Obviously, coal and catalyst also can mixed feedings, and for example coal dust directly mixes rear feeding with catalyst itself, or coal dust and aqueous catalyst solution mixing rear feeding, etc. When mixed feeding, one or the charging of several places that the mixture of the two can be from catalytic gasification district or coal pyrolysis zone. To the coal that uses among the present invention without limits, it can be selected from bituminous coal, anthracite, brown coal etc., and preferably is ground into coal dust before entering gasification furnace of the present invention, and the granularity of coal dust generally can be 0.1～1mm.
The step a of first embodiment of the present invention occurs in the partial thermal decomposition district of gasification furnace, and the coal that joins in this district contacts with gas stream from the catalytic gasification district, and the described coal dust of partial thermal decomposition, generates to contain the gas stream of methane and the coal dust of partial thermal decomposition. All gas in this district leaves gasification furnace, and the coal behind the partial thermal decomposition moves downward along gasification furnace. In this step, at least a portion coal leads to into gasification furnace from described partial thermal decomposition district, preferred most coals in addition more preferably whole coal lead to into gasification furnace from described partial thermal decomposition district. The benefit of doing like this is to take full advantage of synthesis gas generation methanation reaction institute liberated heat in the catalytic gasification district, this heat along with catalytic gasification district reacted gas entering part pyrolysis zone after, contact with the coal that enters gasification furnace from the partial thermal decomposition district, make this coal preheating and fast pyrogenation, fugitive constituent pyrolysis in the coal is come out, owing to contain methane in the fugitive constituent of coal, therefore the effect of coal being carried out preheating is not only played in this district, but also has further increased methane content in the gas product by partial thermal decomposition. Pyrolysis has also produced tar, and tar leaves gasification furnace with the gas product under the condition in this district, and the coal dust behind the partial thermal decomposition enters into downwards then that each district continues reaction below the gasification furnace. Temperature in this partial thermal decomposition district is mainly regulated by the gas flow in following each district and the inlet amount that joins the coal dust in this district, generally is 450-650 ℃.
The step b of first embodiment of the present invention occurs in the catalytic gasification district of gasification furnace. In this step, the coal dust of partial thermal decomposition is admitted to behind the catalytic gasification district under the effect of catalyst and contacts with gas stream from residue gasification district and react, the coal residue that generates gas stream and fully do not react wherein mainly contains CH in the gas stream of this generation4、CO、H
2And CO2, and a small amount of H2S and NH3Deng. The main reaction that takes place in this catalytic gasification district is as follows:
2C+2H
2O→2H
2+2CO (1)
CO+H
2O→CO
2+H
2 (2)
3H
2+CO→CH
4+H
2O (3)
C+2H
2→CH
4 (4)
The reaction temperature in described catalytic gasification district is 650～750 ℃, and pressure is 0.1～4MPa (absolute pressure, lower same). In the catalytic gasification district, from CO and the H in gasification furnace residue gasification district2Methanation reaction takes place under the effect of catalyst, shown in reaction equation (3), increased methane production, the gas that the reaction heat of emitting is simultaneously reacted generation upwards motion is carried in the described partial thermal decomposition district to carry out step a, and fully the coal residue of reaction does not then enter residue gasification district. In addition, the reactions such as Carbon gasification reaction (1) and (4), carbon monoxide transformationreation (2) also take place. Wherein said catalyst is selected from alkali metal or alkaline earth oxide, alkali metal or alkaline earth metal carbonate or alkali metal or alkaline earth metal hydroxide or their mixture, such as oxidation sodium, calcium oxide, sodium carbonate, potash, carbonic acid lithium, calcium carbonate, potassium hydroxide, NaOH, calcium hydroxide etc., the catalyst in this district and coal dust weight ratio are 0.05～0.2.
The step c of first kind of embodiment of the present invention occurs in the residue gasification district of gasification furnace. After the coal residue of step b enters this district downwards, contact with the gasifying agent that leads to into this district, wherein said gasifying agent contains oxygen and saturated vapor or superheated steam, wherein the temperature of superheated steam can be 200-500 ℃, lead to into the superheated steam of gasification furnace and the weight ratio of leading to into the coal of gasification furnace and be generally 0.5～5, lead to into oxygen and the weight ratio 0.1～1.0 that enters the coal dust of gasification furnace. Superheated steam and oxygen can lead to into this district with form of mixtures, also can lead to respectively this district and mix in this district. As follows in the main reaction that this district takes place:
C+O
2→CO
2 (5)
C+CO
2→2CO (6)
C+H
2O→CO+H
2 (7)
CO+H
2O→CO
2+H
2 (8)
These reactions generate gas stream and the lime-ash that comprises synthetic gas, and the total conversion rate of carbon can reach more than 90% in this district.The wherein said gas stream of synthetic gas that comprises also comprises carbonic acid gas and unreacted water vapour and possible gases such as oxygen, and this gas stream upwards enters described catalytic gasification district to carry out step b, and described lime-ash is then discharged vapourizing furnace.Because the reaction in this district is strong oxidizing reaction, emits a large amount of heats, so the temperature in this district is the highest in the vapourizing furnace.Feeding rate that can be by regulating vaporized chemical and/or form the temperature that will distinguish and be controlled at and be suitable for generating under the temperature of synthetic gas is generally 800-1200 ℃, and the reaction heat of being emitted provides heat for top catalytic gasification district.In this district, the water vapour of feeding is generally 0.5～5 with the weight ratio that enters the coal of vapourizing furnace, and the oxygen of feeding is generally 0.1～1.0 with the weight ratio that enters the coal of vapourizing furnace.If the catalyzer that adopts in the method for the present invention can not gasify under the temperature in this district, then this catalyzer enters into the catalyst recovery unit and reclaims along with lime-ash is discharged vapourizing furnace; If the catalyzer that adopts in the method for the present invention can gasify under the temperature in this district, then this catalyzer is gasificated into steam and along with the described gas stream of synthetic gas that comprises upwards enters into described catalytic gasification district, and is condensate in along with the reduction of gas temperature and repeats to bring into play katalysis on the coal.
Perhaps, more broadly, multi-region gasification of the present invention preparation contains in the method for gas of methane, can the clipped pyrolysis zone, and therefore, method of the present invention can may further comprise the steps:
1). coal dust joined the catalytic gasification district that contains the catalytic gasification district and the vapourizing furnace of residue gasification zone and gas stream from the residue gasification zone in the presence of catalyzer, contact generate contain the gas stream of methane and the coal residue that fully reacts and
2). the coal residue of step 1) is sent into the residue gasification zone contact with vaporized chemical, the gas stream of generation enters the catalytic gasification district and lime-ash is discharged vapourizing furnace.
Wherein at least a portion coal enters vapourizing furnace from described catalytic gasification district.In step 1), coal contacts in the presence of catalyzer with gas stream from the residue gasification zone in this catalytic gasification district and generates the coal residue that contains the gas stream of methane and fully react, wherein catalyzer, temperature, pressure process condition etc. are with above basic identical to the described processing condition of the step b of first kind of embodiment, the gas stream that contains methane that generates upwards flows out vapourizing furnace, and the coal residue that does not fully react moves downward the residue gasification zone.
In step 2) in, contact with vaporized chemical after entering the residue gasification zone from the coal residue of step 1), wherein step 2) in the processing condition such as composition, temperature, pressure of reaction, vaporized chemical kind and the composition, the gas stream that generated that are taken place also basic identical with the step c of above first kind of embodiment.
The invention still further relates to gasification preparation and contain the vapourizing furnace of the gas of methane, comprise
A. partial thermal decomposition district is used for coal dust is contacted with gas stream from the catalytic gasification district, and the gas stream that contains methane of generation leaves the coal dust of the partial thermal decomposition of vapourizing furnace and generation and sends into the catalytic gasification district;
B. catalytic gasification district is used for and will contacts with gas stream from the residue gasification zone from the coal dust of the partial thermal decomposition in partial thermal decomposition district, the gas stream of generation enter described partial thermal decomposition district and fully the coal residue of reaction send into the residue gasification zone; With
C. the residue gasification zone is used for the coal residue from described catalytic gasification district is contacted with vaporized chemical, and the gas stream of generation enters the catalytic gasification district, and the lime-ash of generation is discharged vapourizing furnace.
Perhaps, partial thermal decomposition district wherein also can omit, and in this case, the vapourizing furnace that gasification preparation of the present invention contains the gas of methane comprises:
1). the catalytic gasification district, be used for coal dust is contacted in the presence of catalyzer with gas stream from the residue gasification zone, generate the coal residue that contains the gas stream of methane and fully react; With
2). the residue gasification zone, be used for the coal residue from described catalytic gasification district is contacted with vaporized chemical, the gas stream of generation enters the catalytic gasification district, and the lime-ash of generation is discharged vapourizing furnace.
Each district at vapourizing furnace all can be provided with as required and is used for material, the apparatus for feeding of feeding vapourizing furnaces such as coal, catalyzer, coal and mixture of catalysts, vaporized chemical for example, and these apparatuss for feeding are well known to a person skilled in the art.In addition, also be provided with the discharging equipment that supplied gas and lime-ash leave vapourizing furnace on the bottom of vapourizing furnace and top, these discharging equipment also well known to a person skilled in the art.
In a preferred embodiment, vapourizing furnace of the present invention comprise be used for part of coal at least from the partial thermal decomposition district of vapourizing furnace and/or any one or a few place in catalytic gasification district add the equipment of vapourizing furnace.These apparatuss for feeding can comprise feed bin, rotation feeding device and necessary connecting tube.Depend on that it still is high-pressure gasified that vapourizing furnace adopts atmospheric gasification, apparatus for feeding can move under normal pressure or high pressure.
In a further preferred embodiment, vapourizing furnace of the present invention comprises the equipment and the equipment that is used for catalyzer is directly added vapourizing furnace that is used for catalyzer is sneaked into coal dust.
In a further preferred embodiment, vapourizing furnace of the present invention also comprises and is used near small part pyrolytic coal dust is transported to the catalytic gasification district from pyrolysis zone equipment, upflow tube etc. for example, with the equipment that is used for the coal residue is transported to from the catalytic gasification district residue gasification zone, such equipment can be residue extraction mechanism known in the art.In preferred embodiments, in vapourizing furnace low side exit two placed in-line residue extraction mechanisms are set, wherein be provided with between one-level residue extraction mechanism and the vapourizing furnace between valve, secondary residue extraction mechanism and the one-level residue extraction mechanism and also be provided with valve, also be provided with emptying valve and pressurising valve on two residue extraction mechanisms.During deslagging, at first with the valve closes between first residue extraction mechanism and second residue extraction mechanism, and with the valve open between first residue extraction mechanism and the vapourizing furnace, lime-ash enters in first residue extraction mechanism.After treating that cindery quality that first residue extraction mechanism receives reaches setting threshold, the pressurising valve of opening second residue extraction mechanism is the second residue extraction mechanism pressurising, when the pressure of second residue extraction mechanism is consistent with the pressure of first residue extraction mechanism, open the valve that is communicated with between first residue extraction mechanism and second residue extraction mechanism, after solid in first residue extraction mechanism is sent into second residue extraction mechanism, close the valve that is communicated with between first residue extraction mechanism and second residue extraction mechanism, the emptying valve of opening second residue extraction mechanism is the second residue extraction mechanism release, and the lime-ash in second residue extraction mechanism is discharged.
Use vapourizing furnace of the present invention implement method of the present invention also comprise pulverized coal preparation equipment, with catalyzer and coal dust blended mixing equipment, with the equipment and the coal dust apparatus for feeding of batch mixing drying and preoxidation, these equipment all are well known in the art.
Use vapourizing furnace of the present invention to implement method of the present invention and comprise that also the gas stream that contains methane that will leave vapourizing furnace separates and equipment of purifying and the residue extraction mechanism that the lime-ash of vapourizing furnace bottom is discharged, these equipment also are well known in the art.
Embodiment
Provide following examples to illustrate the present invention, these embodiment are also nonrestrictive.
Referring to Fig. 1, the vapourizing furnace among Fig. 1 comprises three districts from top to bottom, is respectively partial thermal decomposition district 40, catalytic gasification district 41, residue gasification zone 42.Raw coal is by pipeline 43 entering part pyrolysis zone 40, partial thermal decomposition district 40 temperature are 450～650 ℃, in partial thermal decomposition district 40, add hot feed raw coal coal dust from the gas stream in the catalytic gasification district 41, make it to take place partial thermal decomposition and hydropyrolysis, obtain containing the coal dust after gaseous product, tar and the pyrolysis of methane.Gaseous product and tar leave vapourizing furnace from outlet line 48, enter later separation equipment.Coal dust after the pyrolysis moves downward and enters into catalytic gasification district 41.Some coal and catalyzer enter into the catalytic gasification district with the form of mixture from pipeline 44 in addition, these coals are with reacting in catalytic gasification district 41 with from the gas stream of residue gasification zone from the coal dust after the pyrolysis in partial thermal decomposition district, react as mentioned shown in reaction formula (1)-(4), generate gaseous product.Mainly contain CH
4, CO, H
2And CO
2, and a spot of H
2S and NH
2Deng.These gaseous products move upward to reduce phlegm and internal heat in the partial thermal decomposition district 40 separates coal.The temperature in catalytic gasification district 41 is 650-750 ℃.Fully the coal residue of reaction does not then enter into residue gasification zone 42 downwards, under the effect of superheated vapour 46 that feeds and oxygen 47, reaction shown in above-mentioned reaction formula (5)-(8) takes place, generation comprises synthetic gas at interior gaseous product and solid lime-ash, these gaseous products move upward in the catalytic gasification district 41 and react, and lime-ash is then discharged vapourizing furnace by one-level residue extraction mechanism 50 and secondary residue extraction mechanism 51.Vapourizing furnace among this embodiment operates under the 3.5MPa pressure.
Advantage of the present invention is as follows:
(1) keep catalytic gasification characteristic and advantage, obtained the methane of high level, overcome the difficult point of independent catalytic gasification, more high such as reaction time lime-ash carbon content long, that discharge;
(2) multi-region coupled gasification, the fine coal that the partial thermal decomposition district of gasification furnace of the present invention utilizes the surplus temperature heating of catalytic gasification aerogenesis just to enter carries out partial thermal decomposition, produces the products such as methane gas, has increased methane and tar under the condition that does not increase energy consumption; Catalytic gasification master reaction takes place in the catalytic gasification district; Residue gasification district is by leading to into the gasifying agent residual residue that gasifies, and the heat by burning, gasification to residue provide catalytic gasification to need provides hydrogen and CO simultaneously, is conducive to the catalytic gasification reaction;
(3) prepare methane with two-step method and compare, this device integrates a plurality of reactors, realizes logistics coupling, thermal coupling, and confession reaction heat reduces the energy consumption of superheated steam, has solved the problem of residue carbon containing; Prolong the average time of staying, increased the gas production capacity, improved carbon conversion rate.
(4) from whole process, utilize this multi-region gasification furnace vaporizing system for being rich in methane gas, the thermal efficiency is higher, and the solid phase working depth is higher, and methane content is higher in the gas product, and equipment is simplified, easily operation.
Claims (18)
1. the preparation of multi-region gasification contains the method for the gas of methane, comprises the following steps:
A. coal dust is joined the partial thermal decomposition district that contains partial thermal decomposition district, catalytic gasification district and the vapourizing furnace of residue gasification zone and contacts with gas stream to generate and contain the gas stream of methane and the coal dust of partial thermal decomposition with the described coal dust of partial thermal decomposition from the catalytic gasification district,
B. the coal dust of described partial thermal decomposition is sent into the catalytic gasification district and in the presence of catalyzer, is contacted with gas stream from the residue gasification zone, the gas stream entering part pyrolysis zone of generation and fully the coal residue of reaction enter the residue gasification zone and
C. described coal residue is contacted with vaporized chemical in the residue gasification zone, the gas stream of generation enters the lime-ash of catalytic gasification district and generation and discharges vapourizing furnace.
2. according to the process of claim 1 wherein that at least a portion coal enters vapourizing furnace from the partial thermal decomposition district of vapourizing furnace and/or any one or a few place in catalytic gasification district.
3. according to the process of claim 1 wherein that described catalyzer is selected from the oxide compound of basic metal or alkaline-earth metal, carbonate, oxyhydroxide or their mixture.
4. claim 1 or 2 method, wherein the temperature in partial thermal decomposition district is in 450-650 ℃ of scope, and catalytic gasification district temperature is in 650-750 ℃ of scope, and residue gasification zone temperature is in 800-1200 ℃ of scope, and the pressure in the vapourizing furnace is in the 0.1-4MPa scope.
5. according to the method for claim 1 or 2, described vaporized chemical feeds from the vapourizing furnace bottom, and it contains oxygen and saturation steam or superheated vapour.
6. according to the method for claim 5, wherein the superheated vapour of Tong Ruing is 0.5-5 with the weight ratio that enters the coal of vapourizing furnace, and the oxygen of feeding is 0.1-1.0 with the weight ratio that enters the coal of vapourizing furnace.
7. the preparation of multi-region gasification contains the method for the gas of methane, comprises the following steps
1). coal dust joined the catalytic gasification district that contains the catalytic gasification district and the vapourizing furnace of residue gasification zone and gas stream from the residue gasification zone in the presence of catalyzer, contact with generation contain the gas stream of methane and fully the coal residue of reaction and
2). the coal residue of step 1) is sent into the residue gasification zone contact with vaporized chemical, the gas stream of generation enters the lime-ash of catalytic gasification district and generation and discharges vapourizing furnace.
8. according to the method for claim 7, wherein said catalyzer is selected from basic metal or alkaline earth metal oxide, basic metal or alkaline earth metal carbonate or basic metal or alkaline earth metal hydroxides or their mixture.
9. the method for claim 7, wherein catalytic gasification district temperature is in 650-750 ℃ of scope, and residue gasification zone temperature is in 800-1200 ℃ of scope, and vapourizing furnace pressure is in the 0.1-4MPa scope.
10. the method for claim 7, described vaporized chemical feeds from the vapourizing furnace bottom, and it contains oxygen and saturation steam or superheated vapour.
11. the gasification preparation contains the vapourizing furnace of the gas of methane, comprises
A. partial thermal decomposition district is used for coal dust is contacted with gas stream from the catalytic gasification district, and the gas stream that contains methane of generation leaves the coal dust of the partial thermal decomposition of vapourizing furnace and generation and sends into the catalytic gasification district;
B. catalytic gasification district is used for and will contacts with gas stream from the residue gasification zone from the coal dust of the partial thermal decomposition in partial thermal decomposition district, the gas stream of generation enter described partial thermal decomposition district and fully the coal residue of reaction send into the residue gasification zone; With
C. the residue gasification zone is used for the coal residue from described catalytic gasification district is contacted with vaporized chemical, and the gas stream of generation enters the catalytic gasification district, and the lime-ash of generation is discharged vapourizing furnace.
12. the vapourizing furnace of claim 11, further comprise be used for part of coal at least from the partial thermal decomposition district of vapourizing furnace and/or any one or a few place in catalytic gasification district add the equipment of vapourizing furnace.
13. the vapourizing furnace of claim 11 or 12 also comprises the equipment and the equipment that is used for catalyzer is directly added vapourizing furnace that are used for catalyzer is sneaked into coal dust.
14. the vapourizing furnace of claim 11 or 12 also comprises the equipment and the equipment that is used for the coal residue is transported to from the catalytic gasification district residue gasification zone that are used for the coal dust of partial thermal decomposition is transported to from pyrolysis zone the catalytic gasification district.
15. the gasification preparation contains the vapourizing furnace of the gas of methane, comprises
1). the catalytic gasification district, be used for coal dust is contacted in the presence of catalyzer with gas stream from the residue gasification zone, generate the coal residue that contains the gas stream of methane and fully react; With
2). the residue gasification zone, be used for the coal residue from described catalytic gasification district is contacted with vaporized chemical, the gas stream of generation enters the catalytic gasification district, and the lime-ash of generation is discharged vapourizing furnace.
16. the vapourizing furnace of claim 15 also comprises the equipment and the equipment that is used for catalyzer is directly added vapourizing furnace that are used for catalyzer is sneaked into coal dust.
17. the vapourizing furnace of claim 15 also comprises the equipment that is used for the coal residue is transported to from the catalytic gasification district residue gasification zone.
18. the vapourizing furnace of claim 11 or 15 also comprises two placed in-line residue extraction mechanisms that are arranged on exit, vapourizing furnace bottom.
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| CN 200910170386 CN102021039A (en) | 2009-09-14 | 2009-09-14 | Method and device for preparing methane-containing gas by multi-region coal gasification |
| PCT/CN2010/001406 WO2011029282A1 (en) | 2009-09-14 | 2010-09-14 | Method for preparing methane-containing gas through multi-region coal gasification and gasification furnace thereof |
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| CN 200910170386 CN102021039A (en) | 2009-09-14 | 2009-09-14 | Method and device for preparing methane-containing gas by multi-region coal gasification |
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