CN105441135A - Coal gasification method - Google Patents
Coal gasification method Download PDFInfo
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- CN105441135A CN105441135A CN201410291399.3A CN201410291399A CN105441135A CN 105441135 A CN105441135 A CN 105441135A CN 201410291399 A CN201410291399 A CN 201410291399A CN 105441135 A CN105441135 A CN 105441135A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/16—Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
- Y02E20/18—Integrated gasification combined cycle [IGCC], e.g. combined with carbon capture and storage [CCS]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention discloses a coal gasification method which is as follows: a coal ram material, an additive and a gasification agent are introduced into a gasifier for reaction at a temperature of 1100-1600 DEG C to obtain gasification products, wherein the additive comprises a catalyst, the catalyst is one or more transition metals selected from the group comprising copper, manganese, cadmium, chromium, cobalt, molybdenum, nickel, vanadium and zinc. According to the coal gasification method, by addition of the additive, the carbon conversion rate during the coal gasification process is improved.
Description
Technical field
The present invention relates to gasification field, specifically, the present invention relates to a kind of method improving efficiency of carbon conversion in air-flow bed coal-gasification process.
Background technology
Coal is the abundantest getable fossil oil up to now on the earth.Coal is elementary composition primarily of carbon, hydrogen, oxygen, nitrogen, sulphur and phosphorus etc.Carbon is most important component in coal, and its content increases with the intensification of degree of coalification.According to the classification of coal carbonizing degree difference, can be divided into peat, brown coal, bituminous coal, semibituminous coal and hard coal etc. successively, wherein hard coal carbonizing degree is the highest, and peat carbonizing degree is minimum.
Coal Gasification Technology is Coal Clean, the basic technology of efficient and comprehensive utilization and gordian technique, and its research and development history of existing more than 200 year, remains core technology and the study hotspot of the energy and chemical field at present.Coal gasification course is a thermochemical process, it is for raw material with coal or coal tar, vaporized chemical (or claiming gasifying medium) is made with air, oxygen, water vapour or hydrogen etc., by chemical reaction, the combustible portion in coal or coal tar is converted into gas under the high temperature conditions, be called gasification gas, its main component comprises hydrogen, carbon monoxide, carbonic acid gas and methane, and wherein hydrogen and carbon monoxide are called as effective gas in material gas.Gasification gas can be used as town gas, industrial combustion gas or the material gas for the synthesis of ammonia, methyl alcohol etc., also can be used for combined cycle generation (IGCC) or generating, heat, chemical Poly-generation (multiple-supplying).
The sorting technique of Coal Gasification Technology has multiple, wherein can be divided into according to solid-fuelled kinestate that fixed bed (or moving-bed) gasifies, fluidized-bed gasification and entrained flow gasification, and reaction conditions is different, also corresponding different vapourizing furnace on device.Fixed bed gasification method gasifies also referred to as lump coal, belong to first-generation Coal Gasification Technology, represent the type of furnace and have strange (Lurgi) stove in Shandong, be that bed is substantially motionless or slowly move down, adopt lump coal, gasification temperature is lower, general below 900 DEG C, production load is little, and gas composition complexity (containing tar-acids etc.), wastewater treatment is more difficult.The relative fixed bed gasification of fluidized-bed gasification, vaporized chemical flow velocity is faster, bed is blown afloat, constantly fluctuate, the motion of solid particulate, as the liquid of boiling, is gasified also referred to as ebullated bed, belong to s-generation Coal Gasification Technology, temperature general control, below 1000 DEG C, does not need special refractory, and Typical Representative is Winkler (Winkle) vapourizing furnace of Germany.Air flow bed pressurized gasification technology then generally adopts pure oxygen to cook vaporized chemical, gas velocity is faster, with coal water slurry or dry pulverized coal for raw material, raw material is atomized by shower nozzle, spontaneous experience destructive distillation, burning, reduce several stage, coal raw material flows with gas in vaporized process, therefore air flow bed is called, throughput is larger, gasification efficiency is higher, it is main flow Coal Gasification Technology in the market, feature is that temperature of reaction is higher, be generally 1100 DEG C ~ 1600 DEG C, more specifically, it is 1200 DEG C ~ 1500 DEG C, reaction times is very short, be generally 1 ~ 10 second, as-fired coal granularity is very little, the industrialized air flow bed type of furnace has GE coal water slurry pressurization Texaco (Texaco) vapourizing furnace, shell (Shell) powdered coal pressuring gasified stove, multi-products production pressurized-gasification furnace, space flight stove etc.
Efficiency of carbon conversion is one of important indicator weighing coal gasification course.Efficiency of carbon conversion has two kinds of method of calculation, and a kind of is calculate with the ratio of the carbon content in the carbon content in coal gas and coal raw material, and another kind asks calculation by the carbon content measured in residue after gasifying.Efficiency of carbon conversion, by the impact of gasifying process, such as, is compared with fluidized bed gasifying process with fixed bed, and the efficiency of carbon conversion of entrained flow gasification is general higher, and in addition, efficiency of carbon conversion is also subject to the impact of coal raw material reaction activity.The reactive behavior of coal refers under certain condition, and coal response capacity interactional from different vaporized chemicals, usually at a certain temperature, passes into carbonic acid gas with certain flow rate, represent the reactive behavior of coal with the reduction ratio of carbonic acid gas.In addition, the volatile content of coal also roughly can reflect the height of the reactive behavior of coal.Experiment shows, along with the increase of coal carbonization degree, its volatile content reduces, and is generally less than 15%, and its reactive behavior declines.Low carbon content coal (as brown coal, bituminous coal) is because its moisture, volatile content are high, in addition short texture, the coal tar reaction specific area that it generates is large, there is again abundant transitional pore and macropore, reagent is made easily to be diffused into these reaction surfaces, thus the reactive behavior of brown coal, bituminous coal is high, and the reactive behavior of hard coal, refinery coke is lower.In air-flow bed coal-gasification process, coal speed of response in gasification of high reaction activity is fast, and efficiency is high, and the coal of low reaction activity, as hard coal, refinery coke, efficiency of carbon conversion is lower, generally can be less than 90%, gasification gas ultimate production reduces simultaneously, thus effectively gas output also corresponding reduction.In a word, the height of coal raw material reaction activity is to gasification efficiency of carbon conversion and factor of created gase important.How ensureing low reaction activity coal, as hard coal, refinery coke, in air-flow bed coal-gasification process, keep high efficiency of carbon conversion, is the problem of nowadays gasification field face.
For the problems referred to above, the present invention proposes the method adding additive in coal gasifying process charging, described additive contains catalyzer, in coal gasification course, play katalysis, improves the efficiency of carbon conversion of low reaction activity coal.Although the history of the existing last 100 years of catalytic gasification research of coal, but research concentrates on by the low-temperature catalysis gasification reduced for the purpose of temperature of reaction, General reactions temperature is within the scope of 500 ~ 900 DEG C, using water vapour or carbonic acid gas as vaporized chemical, gasifying process generally adopts fluidized-bed, and in gasification product, methane content is higher.So far, the research for high temperature catalytic gasifications such as air flow bed have not been reported, and the problem reduced due to efficiency of carbon conversion in the active low entrained flow gasification technique caused of coal raw material reaction is also resolved not yet.
Summary of the invention
The present invention proposes a kind of coal gasification method, comprise and coal raw material, additive and vaporized chemical are passed in vapourizing furnace, react at the temperature of 1100 ~ 1600 DEG C, obtain gasification product, wherein said additive contains catalyzer, and this catalyzer contains one or more transition metal be selected from copper, manganese, cadmium, chromium, cobalt, molybdenum, nickel, vanadium, zinc.
Present invention further teaches a kind of gasification additive, containing catalyzer in described additive, this catalyzer contains one or more transition metal be selected from copper, manganese, cadmium, chromium, cobalt, molybdenum, nickel, vanadium, zinc, this additive and coal raw material, vaporized chemical are passed in vapourizing furnace, react at the temperature of 1100 ~ 1600 DEG C, obtain gasification product.
In addition, present invention further teaches a kind of charging for gasification, described charging contains coal raw material and additive, described additive contains catalyzer, this catalyzer contains one or more transition metal be selected from copper, manganese, cadmium, chromium, cobalt, molybdenum, nickel, vanadium, zinc, this charging and vaporized chemical are passed in vapourizing furnace, reacts at the temperature of 1100 ~ 1600 DEG C, obtain gasification product.
In order to ensure that low reaction activity coal has higher efficiency of carbon conversion in air-current bed gasification process, the present invention proposes the technical scheme adding additive in coal raw material, containing catalyzer in described additive, this catalyzer contains transition metal or transistion metal compound, according to electron transfer theory, the unoccupied orbital of transition metal can accept electronics, transfer transport in accelerating oxidation reduction reaction, in the active reaction sites that carbon crystal surface exists, help the formation of carbon-oxygen bond, make the combination of carbon-carbon bond weaken simultaneously, improve the reactive behavior of coal raw material, thus improve the efficiency of carbon conversion of low reaction activity coal in coal gasification course.
The invention has the advantages that the air-flow bed coal-gasification technique based on existing market main flow, by adding the additive containing transition metal or transistion metal compound, reduce the different impact for gasification efficiency of coal, ensure the efficiency of carbon conversion that air-flow bed coal-gasification technique is high, ensure effective gas ultimate production, thus the carbon content in corresponding reduction residue, reduce power loss, and be conducive to reducing environmental pollution.
Embodiment
Coal gasification method of the present invention, comprise and coal raw material, additive and vaporized chemical are passed in vapourizing furnace, react at the temperature of 1100 ~ 1600 DEG C, obtain gasification product, containing catalyzer in wherein said additive, this catalyzer contains one or more transition metal be selected from copper, manganese, cadmium, chromium, cobalt, molybdenum, nickel, vanadium, zinc.
In coal gasification method of the present invention, temperature of reaction is generally between 1100 ~ 1600 DEG C, and preferably, temperature of reaction is between 1200 ~ 1500 DEG C.
In coal gasification method of the present invention, described coal raw material can be coal water slurry or dry pulverized coal.Wherein, described coal water slurry be by coal, water and a kind of low stain becoming slurry auxiliary agent to be obtained by Physical Processing, high-level efficiency, can the coal based fluid fuel of Cemented filling.
In coal gasification method of the present invention, described additive contains catalyzer, as one embodiment of the present invention, described catalyzer contains transistion metal compound, particularly, transistion metal compound is the hydrate of the oxide compound of transition metal, salt, double salt or salt, and described salt is selected from one or more combination following: vitriol, carbonate, supercarbonate, nitrate, muriate, formate, acetate, oxalate, oxyhydroxide, ammonia salt.
In coal gasification method of the present invention, catalyzer in described additive, passes in vapourizing furnace in certain proportion with coal raw material.As one embodiment of the present invention, the weight percent that catalyzer accounts for coal raw material and additive is 1ppm ~ 10
5ppm, preferably, the weight percent that catalyzer accounts for coal raw material and additive is 10ppm ~ 500ppm.
In coal gasification method of the present invention, described additive, except containing except catalyzer, also contains other composition, as one or more in tensio-active agent, pH adjusting agent, dispersion agent or rheological property conditioning agent.As one embodiment of the present invention, tensio-active agent can be ionic or nonionic surface active agent, for the wettability of the solvability and coal that improve additive; PH adjusting agent is stablized for the pH value of coal water slurry after keeping adding additive; Dispersion agent contributes to the dispersion of additive in coal; The use of dispersion agent and rheological property conditioning agent also can make water coal slurry concentration remain in suitable scope.
In coal gasification method of the present invention, comprise and coal raw material, additive and vaporized chemical are passed in vapourizing furnace, as one embodiment of the present invention, described additive and coal raw material can be pre-mixed, then mixture is passed in vapourizing furnace together with vaporized chemical.The mixture that additive and coal raw material are formed, both exist with physical mixed form, or additive is connected with chemical bond with coal raw material by the functional group reactions in or coal hole surperficial with coal at least partially, such as, additive can by generating chemical bond with the functional group reactions such as carboxyl, phenolic hydroxyl group in coal surface or coal hole.
In coal gasification method of the present invention, comprise and pass in vapourizing furnace by coal raw material, additive and vaporized chemical, as one embodiment of the present invention, described coal raw material contains low reaction activity coal, generally its volatile content is generally below 15%, as hard coal, refinery coke etc.
In coal gasification method of the present invention, comprise coal raw material under the existence of additive and vaporized chemical, react at the temperature of 1100 ~ 1600 DEG C, as one embodiment of the present invention, described vaporized chemical comprise in oxygen, oxygen-rich air or water vapour one or more.
Present invention further teaches a kind of charging for gasification, described charging contains coal raw material and additive, this charging and vaporized chemical are passed in vapourizing furnace, react at the temperature of 1100 ~ 1600 DEG C, obtain gasification product, described additive contains catalyzer, and this catalyzer contains one or more transition metal be selected from copper, manganese, cadmium, chromium, cobalt, molybdenum, nickel, vanadium, zinc.
About described gasification charging, this charging contains coal raw material and additive, and as one embodiment of the present invention, described coal raw material is coal water slurry.During charging, coal water slurry is squeezed in vapourizing furnace by pump.The coal water slurry of preparation containing additive generally has two kinds of methods, a kind of is in the preparation process of coal water slurry, additive is added together with one-tenth slurry auxiliary agent, and mix, such as, in coal water slurry preparation process, addition of C EC3110 is added together with one-tenth slurry auxiliary agent, fully mix, obtain the coal water slurry containing additive.Sample containing additive and the nature parameters of blank sample not adding additive is listed in table 1.After 24 hours, by contrast containing the sample of additive and the nature parameters of blank sample, can find additive and coal water slurry consistency fine, compared with blank sample, character does not have considerable change, and therefore, the existence of additive can not produce obviously impact to water coal slurry property.Preparation, containing the coal water slurry of additive, also can obtain by adding additive and mix after making in coal water slurry.
Table 1 blank sample and the coal water slurry performance containing additive
Gasification charging of the present invention, as another kind of embodiment, the coal raw material in described charging is dry pulverized coal.For the dry pulverized coal granularity of entrained flow gasification generally below 0.1 millimeter, the dry pulverized coal of preparation containing additive generally has two kinds of methods, and one is directly mixed with dry pulverized coal by additive; Another kind is pickling process, joins in dry pulverized coal, the solution containing additive is filled in coal dust hole by the appropriate solution containing additive.
Although describe the present invention in conjunction with specific embodiment, those skilled in the art will appreciate that and can make many amendments and distortion to the present invention.Therefore, recognize, the intention of claims is to be encompassed in all such modifications in true spirit of the present invention and scope and modification.
Claims (18)
1. a coal gasification method, comprising:
Pass in vapourizing furnace by coal raw material, additive and vaporized chemical, wherein said additive contains catalyzer, and this catalyzer contains one or more transition metal be selected from copper, manganese, cadmium, chromium, cobalt, molybdenum, nickel, vanadium, zinc;
Coal raw material, under additive and vaporized chemical exist, reacts, obtains gasification product at the temperature of 1100 ~ 1600 DEG C.
2. coal gasification method according to claim 1, this temperature of reaction is 1200 ~ 1500 DEG C.
3. coal gasification method according to claim 1, this catalyzer contains the hydrate of the oxide compound of transition metal, salt, double salt or salt, and described salt is selected from one or more combination following: vitriol, carbonate, supercarbonate, nitrate, muriate, formate, acetate, oxalate, oxyhydroxide, ammonia salt.
4., according to the coal gasification method in claim 1-3 described in any one, the weight percent that this catalyzer accounts for coal raw material and additive is 1ppm ~ 10
5ppm.
5., according to the coal gasification method in claim 1-3 described in any one, the weight percent that this catalyzer accounts for coal raw material and additive is 10ppm ~ 500ppm.
6. coal gasification method according to claim 1, this additive is also containing one or more in tensio-active agent, pH adjusting agent, dispersion agent or rheological property conditioning agent.
7. coal gasification method according to claim 1, this additive and coal raw material are pre-mixed, then pass into together in vapourizing furnace.
8. coal gasification method according to claim 1, in this coal raw material containing volatile content lower than 15% coal.
9. coal gasification method according to claim 1, this vaporized chemical comprise in oxygen, oxygen-rich air or water vapour one or more.
10. a gasification additive, described additive contains catalyzer, this catalyzer contains one or more transition metal be selected from copper, manganese, cadmium, chromium, cobalt, molybdenum, nickel, vanadium, zinc, this additive and coal raw material, vaporized chemical are passed in vapourizing furnace, react at the temperature of 1100 ~ 1600 DEG C, obtain gasification product.
11. gasification additives according to claim 10, this temperature of reaction is 1200 ~ 1500 DEG C.
12. gasification additives according to claim 10, this catalyzer contains the hydrate of the oxide compound of transition metal, salt, double salt or salt, and described salt is selected from one or more combination following: vitriol, carbonate, supercarbonate, nitrate, muriate, formate, acetate, oxalate, oxyhydroxide, ammonia salt.
13. gasification additives according to claim 10, this additive is also containing one or more in tensio-active agent, pH adjusting agent, dispersion agent or rheological property conditioning agent.
14. 1 kinds of chargings for gasification, described charging contains coal raw material and additive, described additive contains catalyzer, this catalyzer contains one or more transition metal be selected from copper, manganese, cadmium, chromium, cobalt, molybdenum, nickel, vanadium, zinc, this charging and vaporized chemical are passed in vapourizing furnace, react at the temperature of 1100 ~ 1600 DEG C, obtain gasification product.
15. chargings according to claim 14, this temperature of reaction is 1200 ~ 1500 DEG C.
16. chargings according to claim 14, this catalyzer is the hydrate of the oxide compound of transition metal, salt, double salt or salt, and described salt is selected from one or more combination following: vitriol, carbonate, supercarbonate, nitrate, muriate, formate, acetate, oxalate, oxyhydroxide, ammonia salt.
17. according to charging described in any one in claim 14-16, and the weight percent that this catalyzer accounts for coal raw material and additive is 1ppm ~ 10
5ppm.
18. according to charging described in any one in claim 14-16, and the weight percent that this catalyzer accounts for coal raw material and additive is 10ppm ~ 500ppm.
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| CN201410291399.3A CN105441135A (en) | 2014-06-25 | 2014-06-25 | Coal gasification method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020133552A1 (en) * | 2018-12-24 | 2020-07-02 | 茏源（北京）环保科技有限公司 | Self-cleaning type coal-to-gas boiler |
| CN114797904A (en) * | 2022-04-15 | 2022-07-29 | 新奥科技发展有限公司 | Application of supported sodium catalyst in catalytic coal gasification reaction |
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