CN1288226C - Low activity dust coal catalytic gasifying method - Google Patents
Low activity dust coal catalytic gasifying method Download PDFInfo
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- CN1288226C CN1288226C CN 200410012272 CN200410012272A CN1288226C CN 1288226 C CN1288226 C CN 1288226C CN 200410012272 CN200410012272 CN 200410012272 CN 200410012272 A CN200410012272 A CN 200410012272A CN 1288226 C CN1288226 C CN 1288226C
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- fine coal
- fluidized bed
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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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Abstract
The present invention relates to a method for catalytically gasifying dust coal with low activity, which is characterized in that industrial waste lye is sprayed into dust coal with low activity or dry distillation coal coke to be mixed and dried, and then, the mixture enters a gasification furnace of a fluidized bed to be catalytically gasified with air / steam or water vapor under the conditions of certain gasification temperature and gasification time; basic clinker can be automatically discharged from the bottom or the side surfaces of the gasification furnace; a solid dealkalization auxiliary agent and the basic clinker together enter the calcining furnace of the fluidized bed after being mixed to generate composite silicate under the conditions of certain calcining temperature and calcining time; meanwhile, calcining heat generates superheated steam through heat exchange, and then, the superheated steam can be supplied to the gasification furnace. The present invention has the advantages that compared with a method without catalysis, the conversion rate and the gas generating rate of the present invention are improved by more than 2 times; the two processes of 'catalytic gasification and clinker calcination' are combined, the clean production technology of high efficiency gasification and residue conversion is realized, and the dealkalization process of clinker is harmless.
Description
Technical field:
The invention belongs to and a kind ofly adopt the industrial alkali waste catalyzer to carry out the efficient catalytic gasification less than 7% anthracite fine coal to improve gas yield, to improve coal gas Hot value and basic clinker is calcined innoxious method to volatile matter.
Background technology:
The coal catalytic gasification is a kind of reduction temperature of reaction, improves speed of reaction, the advanced gasification process of control gas composition.Since proposing first from English Patent in 1869, domestic and international many scholars had once carried out extensive studies with regard to the optimization of the catalytic gasification mechanism of relevant coal, multiple screening of catalyst, catalysis gasification technique condition, catalysis gasification technique (ECCG) interim test etc. of production substitute natural gas, but low activity coal inferior is converted into aspects such as town gas, synthetic gas, industrial combustion gas, metallurgical reduction gas through catalytic gasification, but is not reported; The cheapness of catalyzer and recovery, efficient conversion are the bottlenecks of catalysis gasification technique with cleaner production.China's 3/4 energy is from coal, coal reserves is abundant, occupy the third place in the world, because factors such as colliery skewness, regional price differences are very big, ature of coal does not good and badly wait, the lump coal exploitation is limited, seriously restricting with the coal Sustainable development of the multiple industry such as iron and steel, chemical fertilizer, cement, pottery, glass, building materials that are the source; With Fujian Province's coal reserves is example, more than 98% is to belong to the low (V of fugitive constituent
Ad＜5%), ash fusion point is low, point of ignition is high (＞950 ℃), poor, the comminuted strong low activity hard coal of incendivity, adopts conventional high temperature (＞1000 ℃) fluid bed powder coal gasification technology, the low (＜1Nm of gas yield
3/ kg coal), gas cost height, the not industrialized using value of tool.
Summary of the invention:
The object of the invention provides and a kind ofly adopts the industrial alkali waste catalyzer to carry out the efficient catalytic gasification to improve gas yield, improve coal gas Hot value, reduce gas cost, to realize that simultaneously basic clinker calcines innoxious method to fugitive constituent less than 7% anthracite fine coal.
The object of the present invention is achieved like this:
The fs-the catalytic gasification stage: the dipping combination drying (be called for short prefabricated stage of coal sample) that comprises anthracite fine coal one industrial alkali waste catalyzer with mix the catalytic gasification (abbreviation gasification reaction stage) of coal sample in fluidized-bed gasification furnace.
(1) the prefabricated stage of coal sample: the industrial alkali waste liquid under arbitrary normal temperature is sprayed in the agitated bed or revolving drier of a filling low activity fine coal, coal dust in agitated bed, stir or revolving drier in drench and dipping for waste lye in the lift-over process, and mix simultaneously with dry, both can prevent to soak reunion and knot cake between coal charge, and can realize that again salkali waste mixed the preparation and the supply of coal sample.
(2) the gasification reaction stage: dried salkali waste catalyst mix coal sample enters in the fluidized-bed gasification furnace, can adopt gas mixture (air/water steam) or water vapor to gasify, and the caloric power of gas that is produced when gas mixture (air/water steam) catalytic gasification is Q
LHV＞6MJ/m
3, and the caloric power of gas that the water vapor catalytic gasification is produced is Q
LHV＞9MJ/m
3, both can reach V by the coal factor of created gase
g＞3m
3/ kg coal.
Subordinate phase-lime-ash calcination stage: at the lime-ash calcination stage; solid dealkalize auxiliary agent basic clinker behind catalytic gasification is entered in the fluidized bed calcination stove after mixing; be used for carrying out fluidisation to the preheated air of fluid-bed heat exchanger; alkaline matter will be stable to generate with multiple oxide compound generation vitreous reaction in the lime-ash, the composition silicate of indissoluble and corrosion resistant; make lime-ash dealkalize rate up to more than 95%, and have lower alkali-free result than the no catalytic gasification gained lime-ash of industrial high temperature (＞1000 ℃).
The phase III-integrated operate continuously: salkali waste catalyst mix coal sample is reacted under the lesser temps of 850 ℃～870 ℃ of fluidized-bed gasification furnaces Yu from calcining furnace superheated vapour generation catalytic gasification, the basic clinker of discharging produces superheated vapour with the air combustion heat exchange under 870 ℃～900 ℃ comparatively high tempss of fluidized bed calcination stove, be used to supply with vapourizing furnace, finished gasification and the balance between supply and demand of incendiary self-heating; The consistence that low activity fine coal catalytic gasification and discharge contain sode ash slag calcining process system has constituted " catalytic gasification-lime-ash calcining " the integrated combination of two processes and the pattern of operate continuously.
Method of the present invention comprises the steps:
(1) the industrial alkali waste liquid under the normal temperature to be sprayed into a filling particle diameter be 0.8～6mm and fugitive constituent less than the agitated bed or the revolving drier of 7% anthracite fine coal, waste lye cumulative volume amount is as the criterion with the loadings of flooding fine coal, wherein Na content is that the NaOH amount accounts for 2%～5% of fine coal weight with the conversion, under 110 ℃ of-130 ℃ of conditions, mix and dry 4～8 hours, make the mixing coal sample;
(2) mix coal sample and enter in the fluidized-bed gasification furnace, under 850 ℃～900 ℃ of gasification temperatures, gasification time 30～60min condition, mixes afterwards with water vapor/air=1～1.6kg/m with water vapor and preheated air from the fluidized bed calcination stove
3And water/coal=1.4～2.3kg/kg carries out catalytic gasification, perhaps carries out catalytic gasification with water vapor from the fluidized bed calcination stove with water/coal=3～5kg/kg, and vapourizing furnace bottom or side are discharged basic clinker automatically;
(3) accounting for basic clinker weighs 1%～3% solid dealkalize auxiliary agent enter the fluidized bed calcination stove after basic clinker mixes, carried out fluidisation from the fluid-bed heat exchanger preheated air, under 870 ℃～900 ℃ of calcining temperatures, calcination time 30～60min condition, generate the composition silicate of stable, indissoluble and corrosion resistant, calcine heat simultaneously and produce superheated vapour, be used to supply with vapourizing furnace through heat exchange;
(4) the automatic alkali-free residue of discharging of calcining furnace enters in the shallow-layer rectangular fluidized bed interchanger that is embedded with the air heat transfer tube with the solid pneumavalve, and its heat is used for preheated air, and the alkali-free residue after the heat exchange cooling is as material of construction.
Aforesaid industrial alkali waste is meant factory's by-product salkali waste, viscose fiber salkali waste, paper oar black liquor waste soda lye etc., even industrial solid caustic soda or liquid caustic soda also can.
Spraying into of waste lye will guarantee fully drenching or flooding of coal sample as mentioned above.
Aforesaid dealkalize auxiliary agent is meant the multiple cheap inorganic mineral of elements such as containing Si, Al, Ca, Fe, K, as: bauxitic clay, diatomite, kaolin, rhombspar, clay etc.
The present invention has following advantage:
(1) utilize multiple industrial alkali waste liquid (factory's by-product salkali waste, viscose fiber salkali waste, paper oar black liquor waste soda lye etc.) to carry out the catalytic gasification of low activity coal, Cheap highly effective, reduce and pollute, combine with multiple conventional industries (fiber factory, fibre-board plant, paper mill etc.), change traditional heat supply mode of coal firing boiler, reduce cost cleaner production, the new technology route of formation low activity coal catalytic gasification coproduction combustion gas and steam.
(2) in the catalytic gasification process, the industrial alkali waste catalyzer can form active intermediate complex with the edge carbon atom on the how thick aromatic ring structure in the coal, changes reaction path, reduce reaction activity, thereby under appropriate lower temperature conditions, overcome the restriction of coal reactive behavior and ash fusion point, reached the purpose that increases gasification reaction speed and gas yield.
(3) (fugitive constituent hangs down V to the smokeless coal of low activity
Ad＜7%) through industrial alkali waste normal pressure gas mixture (air/water steam) or water vapour fluidized-bed catalytic gasification, can obtain caloric power of gas＞6MJ/m
3Or＞9MJ/m
3With gas yield all＞3Nm
3The result of/kg coal, when its transformation efficiency and factor of created gase all reach no catalysis more than 2 times.
(4) solid dealkalize auxiliary agent mixes with basic clinker after the atmospheric air fluidized bed calcination, under 870 ℃～900 ℃ conditions of calcining temperature, multiple oxide compound generation vitrifying reaction is converted into the composition silicate of stable, indissoluble and corrosion resistant in alkaline matter and the lime-ash, lime-ash dealkalize rate is more than 95%, reaches the innoxious purpose with as the high-quality material of construction of lime-ash dealkalize.
(5) consistence of catalytic gasification and lime-ash calcining process condition has guaranteed continuous circulation and the stable operation of solid materials between vapourizing furnace and calcining furnace; Optimum combination by fluidized-bed gasification furnace, fluidized bed calcination stove, fluid-bed heat exchanger etc., make coal and the reaction of hyperthermia and superheating steam (from calcining furnace) generation catalytic gasification in the vapourizing furnace, lime-ash and air combustion reaction produces superheated vapour (supply vapourizing furnace) through heat exchange in the calcining furnace, system's gasification and the balance between supply and demand of incendiary self-heating have been finished, carry out the integrated combination of " catalytic gasification-lime-ash calcining " two processes, realized the clean production technology that high-efficiency gasification and residue transform.
Embodiment
Fig. 1 is a technological process synoptic diagram of the present invention.
As shown in the figure, anthracite fine coal and salkali waste catalyzer are gone into fluidisation bed gasification furnace 2 carry out catalytic gasification under gas mixture (water vapor/air) or water vapour atmospheres through impregnation drying device 1 is laggard by hot-air dry, and gasification needs heat to be supplied with by high-temperature water vapor or gas mixture; Gasification is discharged the basic clinker continuous pneumatic and is delivered into fluidized bed calcination stove 4 and high-temperature calcinations and vitreous take place and generate indissoluble composition silicate alkali-free residue; Then to produce preheated air, then the alkali-free residue is discharged with lesser temps to fluid-bed heat exchanger 7 in pneumatic transport; The coal gas of high temperature that catalytic gasification produced can make the waste heat boiler 3 that places fluidized-bed gasification furnace 2 tops produce saturation steam, sends into gas holder again after relevant gas cleaning system further reduces temperature; Superheated vapour is produced by the vapor superheater 6 that places calcining furnace 4 bottoms, for the required heat of gasification reaction in the vapourizing furnace 2; The preheated air part is produced by fluid-bed heat exchanger 7, and part is produced by the air preheater 5 of inserting fluidized bed calcination stove 4 tops, and these preheated airs will supply with impregnation drying device 1 respectively and fluidized-bed gasification furnace 2 uses.
Embodiment 1:
(1) the industrial alkali waste liquid under the normal temperature is sprayed into anthracite fine coal (volatile matter V in capital on the Fujian that a filling particle diameter is 0.8～2.0mm
Ad%=2.69%, ash content A
Ad%=18.37%) agitated bed, wherein waste lye cumulative volume amount is as the criterion with the loadings of flooding fine coal, and Na content is that the NaOH amount accounts for 3.8% of fine coal weight with the conversion, mixes under 110 ℃ of conditions and dry 8 hours, makes the mixing coal sample;
(2) mix coal sample and enter in the fluidized-bed gasification furnace, under 850 ℃ of gasification temperatures, gasification time 50min condition, mixes afterwards with water vapor/air=1.4kg/m with water vapor and preheated air from the fluidized bed calcination stove
3Reach water/coal=2kg/kg and carry out catalytic gasification, can obtain gas yield 3.18Nm after tested
3/ kg coal and caloric power of gas 7.07MJ/m
3The result, vapourizing furnace bottom or side can be discharged basic clinker automatically;
(3) accounting for basic clinker weighs 3% diatomite enter the fluidized bed calcination stove after basic clinker mixes, come to carry out fluidisation to the fluid-bed heat exchanger preheated air, under 870 ℃ of calcining temperatures, calcination time 40min condition, generate the composition silicate of stable, indissoluble and corrosion resistant, this moment, the lime-ash alkalinity was by calcining preceding 9.4 * 10
-3Gram alkali/gram coal is kept to 0.38 * 10
-3Gram alkali/gram coal, lime-ash dealkalize rate 96%; Calcine heat simultaneously and produce superheated vapour, be used to supply with vapourizing furnace through heat exchange;
(4) the automatic alkali-free residue of discharging of calcining furnace enters in the shallow-layer rectangular fluidized bed interchanger that is embedded with the air heat transfer tube with the solid pneumavalve, and its heat is used for preheated air, and the alkali-free residue after the heat exchange cooling is as material of construction.
Embodiment 2:
(1) be Yongding, Fujian anthracite fine coal (volatile matter V of 1.0～4.0mm with 2% black liquor under the normal temperature (conversion is heavy for the NaOH amount accounts for coal) with particle diameter
Ad%=3.56%, ash content A
Ad%=19.94%) flood, Zhong revolving drier under 120 ℃ of conditions of Yu dry 4 hours then, make the mixing coal sample;
(2) mix coal sample and enter in the fluidized-bed gasification furnace, under 880 ℃ of gasification temperatures, gasification time 40min condition, mixes afterwards with water vapor/air=1.1kg/m with water vapor and preheated air from the fluidized bed calcination stove
3Reach water/coal=1.6kg/kg and carry out catalytic gasification, can obtain gas yield 4.33Nm after tested
3/ kg coal and caloric power of gas 7.01MJ/m
3The result, vapourizing furnace bottom or side can be discharged basic clinker automatically;
(3) accounting for basic clinker weighs 2% bauxitic clay enter the fluidized bed calcination stove after basic clinker mixes, come to carry out fluidisation to the fluid-bed heat exchanger preheated air, under 890 ℃ of calcining temperatures, calcination time 30min condition, generate the composition silicate of stable, indissoluble and corrosion resistant, this moment, the lime-ash alkalinity was by calcining preceding 9.4 * 10
-3Gram alkali/gram coal is kept to 0.38 * 10
-3Gram alkali/gram coal, lime-ash dealkalize rate 96%;
(4) the automatic alkali-free residue of discharging of calcining furnace enters in the shallow-layer rectangular fluidized bed interchanger that is embedded with the air heat transfer tube with the solid pneumavalve, and its heat is used for preheated air, and the alkali-free residue after the heat exchange cooling is as material of construction.
Embodiment 3:
(1) the viscose glue waste lye under the normal temperature being sprayed into a filling particle diameter is anthracite fine coal (volatile matter V in capital on 3.0～5.0mm Fujian
Ad%=2.69%, ash content A
Ad%=18.37%) agitated bed, wherein waste lye cumulative volume amount is as the criterion to flood the fine coal loadings, and Na content is that the NaOH amount accounts for 5.0% of fine coal weight with the conversion, mixes under 120 ℃ of conditions and dry 6 hours, makes the mixing coal sample;
(2) mix coal sample and enter in the fluidized-bed gasification furnace, under 900 ℃ of gasification temperatures, gasification time 60min condition, (water/coal=4.5kg/kg) carry out catalytic gasification can obtain gas yield 3.4Nm after tested with water vapor from the fluidized bed calcination stove
3/ kg coal and caloric power of gas 9.3MJ/m
3The result, vapourizing furnace bottom or side can be discharged basic clinker automatically;
(3) accounting for basic clinker weighs 1% rhombspar enter the fluidized bed calcination stove after basic clinker mixes, come to carry out fluidisation to the fluid-bed heat exchanger preheated air, under 900 ℃ of calcining temperatures, calcination time 60min condition, generate the composition silicate of stable, indissoluble and corrosion resistant, this moment, the lime-ash alkalinity was by calcining preceding 9.4 * 10
-3Gram alkali/gram coal is kept to 0.38 * 10
-3Gram alkali/gram coal, lime-ash dealkalize rate 96%;
(4) the automatic alkali-free residue of discharging of calcining furnace enters in the shallow-layer rectangular fluidized bed interchanger that is embedded with the air heat transfer tube with the solid pneumavalve, and its heat is used for preheated air, and the alkali-free residue after the heat exchange cooling is as material of construction.
Claims (5)
1. the catalysis gasification method of an anthracite fine coal is characterized in that comprising the steps:
(1) the industrial alkali waste liquid under the normal temperature to be sprayed into a filling particle diameter be 0.8～6mm and fugitive constituent less than the agitated bed or the revolving drier of 7% anthracite fine coal, waste lye cumulative volume amount is as the criterion with the loadings of flooding fine coal, wherein Na content is that the NaOH amount accounts for 2%～5% of fine coal weight with the conversion, under 110 ℃ of-130 ℃ of conditions, mix and dry 4～8 hours, make the mixing coal sample;
(2) mix coal sample and enter in the fluidized-bed gasification furnace, under 850 ℃～900 ℃ of gasification temperatures, gasification time 30～60min condition, mixes afterwards with water vapor/air=1～1.6kg/m with water vapor and preheated air from the fluidized bed calcination stove
3And water/coal=1.4～2.3kg/kg carries out catalytic gasification, perhaps carries out catalytic gasification with water vapor from the fluidized bed calcination stove with water/coal=3～5kg/kg, and vapourizing furnace bottom or side are discharged basic clinker automatically;
(3) accounting for basic clinker weighs 1%～3% solid dealkalize auxiliary agent enter the fluidized bed calcination stove after basic clinker mixes, carried out fluidisation from the fluid-bed heat exchanger preheated air, under 870 ℃～900 ℃ of calcining temperatures, calcination time 30～60min condition, generate the composition silicate of stable, indissoluble and corrosion resistant, calcine heat simultaneously and produce superheated vapour, be used to supply with vapourizing furnace through heat exchange;
(4) the automatic alkali-free residue of discharging of calcining furnace enters in the shallow-layer rectangular fluidized bed interchanger that is embedded with the air heat transfer tube with the solid pneumavalve, and its heat is used for preheated air, and the alkali-free residue after the heat exchange cooling is as material of construction.
2, the catalysis gasification method of a kind of anthracite fine coal as claimed in claim 1 is characterized in that described industrial alkali waste is meant factory's by-product salkali waste, viscose fiber salkali waste or paper oar black liquor waste soda lye.
3, the catalysis gasification method of a kind of anthracite fine coal as claimed in claim 1 is characterized in that described dealkalize auxiliary agent is meant the inorganic mineral that contains Si, Al, Ca, Fe or K element.
4, the catalysis gasification method of a kind of anthracite fine coal as claimed in claim 3 is characterized in that described inorganic mineral is bauxitic clay, rhombspar or clay.
5, the catalysis gasification method of a kind of anthracite fine coal as claimed in claim 4 is characterized in that described clay is diatomite or kaolin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410012272 CN1288226C (en) | 2004-04-29 | 2004-04-29 | Low activity dust coal catalytic gasifying method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410012272 CN1288226C (en) | 2004-04-29 | 2004-04-29 | Low activity dust coal catalytic gasifying method |
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|---|---|
| CN1570025A CN1570025A (en) | 2005-01-26 |
| CN1288226C true CN1288226C (en) | 2006-12-06 |
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ID=34477988
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|---|---|---|---|
| CN 200410012272 Expired - Fee Related CN1288226C (en) | 2004-04-29 | 2004-04-29 | Low activity dust coal catalytic gasifying method |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101639324B (en) * | 2009-09-07 | 2012-06-13 | 华西能源工业股份有限公司 | Fluidized-bed boiler and application thereof |
| CN102021036B (en) * | 2009-09-14 | 2013-08-21 | 新奥科技发展有限公司 | Method for circulating catalyst in gasification process of coal |
| CN104232237B (en) * | 2013-06-07 | 2016-09-07 | 中国海洋石油总公司 | Catalytic coal gasification material and its preparation method and application |
| CN103881755B (en) * | 2014-03-31 | 2017-01-11 | 新奥科技发展有限公司 | Device and method for preparing raw materials |
| CN103952184B (en) * | 2014-05-14 | 2016-08-24 | 北京神雾环境能源科技集团股份有限公司 | Catalytic coal gasifaction prepares the method and system of shaft furnace reducing gases |
| CN105176589B (en) * | 2015-10-12 | 2017-11-14 | 大连金重鼎鑫科技有限公司北京分公司 | Coke fixed bed pressurization gasification device and process |
| CN110938474B (en) * | 2019-12-17 | 2021-10-26 | 新奥科技发展有限公司 | Method for loading papermaking black liquor on coal sample, fluidized bed furnace and system |
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