CN101880553B - Integrated medium-high temperature coal gas purification method and device suitable for coal-based gas - Google Patents
Integrated medium-high temperature coal gas purification method and device suitable for coal-based gas Download PDFInfo
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- CN101880553B CN101880553B CN 201010205327 CN201010205327A CN101880553B CN 101880553 B CN101880553 B CN 101880553B CN 201010205327 CN201010205327 CN 201010205327 CN 201010205327 A CN201010205327 A CN 201010205327A CN 101880553 B CN101880553 B CN 101880553B
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Abstract
The invention relates to an integrated medium-high temperature coal gas purification method suitable for coal-based gas. The method comprises the following steps of: allowing high-temperature coal gas from a gasification furnace to enter from the lower inlet of a counter flow moving bed device; after impurity-containing hot coal gas is contacted with a solid purifying agent, absorbing impurities with the solid purifying agent; filtering the coal gas by using an upper ceramic high-temperature filtering unit and exhausting the filtered coal gas from a top outlet; and removing gas impurities in the coal gas at one time and removing dust in the coal gas by using a medium-high temperature filtering unit, wherein purification temperature is between 300 and 600 DEG C; gas pressure is normal pressure; and gas air speed is 1,000 h<-1>. The method has high purification efficiency and the impurity-containing gas is contacted with an approximately failed purifying agent from the bottom of a moving bed, so that the transformation ratio of the purifying agent is increased. On the upper part of the moving bed, a fresh purifying agent is contacted with gas having low impurity content so as to ensure high gas purification efficiency. When the temperature is between 400 and 600 DEG C, the impurity removing efficiency of the coal gas reaches over 99.9 percent.
Description
Technical field: the present invention relates to a kind of method for gas purification and equipment, especially a kind of integrated middle high temperature coal gas purification method and apparatus that is applicable to coal-based gas.
Background technology: China is the country take coal as main primary energy source, and coal occupies more than 65% of primary energy source.Coal in China output and total quantity consumed all are listed as first place, the world at present, and coal production reached nearly 2,500,000,000 tons in 2009 still rising.The most of electric power of China relies on the coal-burning power plant to produce, and annual owing to the coal-fired discharging that produces a large amount of atmospheric polluting materials, the at present discharging of China's sulfurous gas and oxynitride is first place, the world.Therefore, China faces the dual-pressure of the energy safety of supply and environment protection, and the development of clean coal technology is very urgent.According to the practical situation of China, coal-based Poly-generation and IGCC and liquidation of coal technology will be the mainstream technologys of coal in China clean utilization, will play a great role aspect guarantee China the energy safety of supply.
The desulfurizing and purifying of process matching is one of major technique of Poly-generation technology research and development, key link wherein is that coal gas high-temperature that the combustion gas that acts as a fuel is used for the coal gas steam combined cycle power generating purifies and purifies as the temperature of the alcohol-ether fuel synthetic gas of raw material, mainly comprises the presoma of sulphur, denitrifying oxide and removing of tar, particulate matter etc.In general, internal combustion turbine requires hydrogen sulfide content to be lower than 20-100ppmv with coal gas, and synthetic hydrogen sulfide content with unstripped gas requires to be lower than 0.5-10ppmv.The method of gas sweetening both at home and abroad is more a lot, but all have complicated operation, Selective adsorption is poor and desulfurization precision is relatively low or the high in cost of production shortcoming.The problems such as especially, poor, the regeneration difficulty of middle high temperature desulfuration agent ubiquity cyclical stability, atmosphere effect be serious.Developing low-cost and high efficiency middle desulfurizing agent for high-temp gas utilize the exploitation of technology to play a crucial role to coal clean conversion.
At present removing of gas with various impurity utilizes different clean units to carry out respectively, denitrogenation and remove tar and undertaken by catalytic unit, and particulate matter needs the high temperature filtration unit to carry out.The system that the accumulation of each unit forms bulky, operation is complicated, and maintenance cost is high, increases the complicacy of system operation, has improved the cost of system.
Summary of the invention: for above-mentioned the deficiencies in the prior art, the invention provides a kind of integrated middle high temperature coal gas purification method and apparatus that is applicable to coal-based gas.
For achieving the above object, the technical solution used in the present invention is: the integrated middle high temperature coal gas purification method flow that is applicable to coal-based gas is: enter from the coal gas of high temperature of the vapourizing furnace bottom entrance by counter-flow moving bed device, the heating gas that contains impurity is with after solid purificant contacts, impurity is absorbed by solid purificant, discharges from top exit after the ceramic high temperature filtering unit filtration of coal gas through top.Disposable gaseous impurities in the coal gas is removed, the dust in the coal gas is removed by the ceramic high temperature filtering unit simultaneously.Purification temperature is 300-600 ℃, and air pressure is normal pressure, and gas space velocity is 1000h
-1
The core apparatus of this polynary high temperature gas cleaning unit is the counter-flow moving bed device with the ceramic high temperature filtering unit.Counter-flow moving bed device comprises heating gas entrance, gas purification outlet, scavenging agent entrance, scavenging agent relief outlet, funnel type housing and is in the interior solid purificant of funnel type housing.The ceramic high temperature filtering unit is fixed on the top of counter-flow moving bed device.The ceramic high temperature filtering unit is passed in the gas purification outlet.The middle and lower part of funnel type housing is provided with the heating gas entrance, and top is provided with the scavenging agent entrance, is provided with the scavenging agent relief outlet below the funnel type housing.Solid purificant injects by the scavenging agent entrance, be in the ceramic high temperature filtering unit below.This system is towards the coal-mining industry background, and technology and equipment has great application prospect and market potential.The characteristics of integrated purifying device are that purification efficiency is high, and impure gas contacts with approaching the scavenging agent that lost efficacy from the moving-bed bottom, increases the transformation efficiency of scavenging agent.On moving-bed top, fresh scavenging agent contacts with the gas of low impurity content, guarantees the high-level efficiency of gas sweetening.When temperature is 400 ℃-600 ℃, the removal efficiency of impurity in the coal gas is reached more than 99.9%.
Characteristics of the present invention are as follows:
(1) equipment Highgrade integration.Present technique has adopted unique scheme in the design of technology and equipment, utilizes the multi-element metal scavenging agent take semicoke as carrier, realizes removing of sulfide, NO_x precursors, tar and particulate matter at a unit, installs highly integrated.
(2) technology and technique are simple, and maintenance cost is low, simplify polygenerations systeme, improve the efficient of system.
(3) gas purifying agent after using can be used for the catalyzer of direct coal liquefaction or other commercial runs as the catalyzer byproduct, therefore, improve polygenerations systeme economic benefit.
(4) towards the Coal Energy Source industry, industry background is large, and technology and equipment has great application prospect and market potential.
(5) purification efficiency is high.Impure gas contacts with approaching the scavenging agent that lost efficacy from the moving-bed bottom, increases the transformation efficiency of scavenging agent.On counter-flow moving bed device top, fresh scavenging agent contacts with the gas of low impurity content, guarantees the high-level efficiency of gas sweetening.The porous high-temperature ceramic filter unit at top further purifies coal gas.In 400-600 ℃ of temperature range, the overall removal efficiency of impurity reaches 99.5% in the coal gas
Description of drawings:
Fig. 1 is process flow sheet of the present invention
Fig. 2 is the structural representation of counter-flow moving bed device.
Fig. 3 is the pattern of the solid purificant particle cross section observed under the scanning electronic microscope.
Fig. 4 is the analytical results figure of the SEM/EDS of the Fe-Mo scavenging agent of semicoke load after desulfurization is processed.
Embodiment:
As shown in Figure 1: the coal gas of high temperature from vapourizing furnace removes S through counter-flow moving bed device, N, Hg and C
nH
mAfter the purification, enter that next unit generates electricity or for the synthesis of liquid fuel.Solid purificant after the use is used for the catalyzer of coal direct liquefaction or other commercial runs directly as the thick product of commercial catalysts.This integrated purification system has highly integrated characteristic.In clean unit, use be the multi-element metal base solid purificant of lignite semi-coke load.
As shown in Figure 2: counter-flow moving bed device comprises heating gas entrance 6, gas purification outlet 2, scavenging agent entrance 4, scavenging agent relief outlet 7, funnel type housing 1 and is in solid purificant 5 in the funnel type housing 1.Ceramic high temperature filtering unit 3 is fixed on the top of counter-flow moving bed device.Ceramic high temperature filtering unit 3 is passed in gas purification outlet 2.Filtering material in the ceramic high temperature unit 3 is porous non-metallic oxide compound such as zirconium white, magnesium oxide etc.The middle and lower part of funnel type housing 1 is provided with heating gas entrance 6, and top is provided with scavenging agent entrance 4, is provided with scavenging agent relief outlet 7 below the funnel type housing 1.Solid purificant 5 injects by scavenging agent entrance 4, be in ceramic high temperature filtering unit 3 below.Heating gas enters moving bed purifying device by the heating gas entrance 6 of counter-flow moving bed device, the heating gas that contains impurity is with after solid solid purificant 5 contacts, impurity is absorbed by solid purificant 5, enters next unit from gas purification outlet 2 after ceramic high temperature filtering unit 3 filtrations of coal gas through top.Scavenging agent after the inefficacy is discharged from the scavenging agent relief outlet 7 of moving-bed device, for the preparation of the commercial catalysts product.The scavenging agent that this moving-bed uses is the multi-element metal base solid purificant of lignite semi-coke load, this solid purificant has high reactive behavior and high porosity, high specific surface area, can remove simultaneously the major impurities such as sulfocompound, NO_x precursors, mercury vapour, tar steam.The solid purificant that the present invention uses as iron-based scavenging agent, composition is: Fe
yMo
x(Ce, Ca, Ni, Cu)
(0.6x)/ C.Wherein x is 0.1-0.6, and the value of y is 0.6-0.9.
The preparation of solid purificant is in two steps: the 1) implantation of active ingredient; 2) steam gasification.
1) implantation of active ingredient
The implantation of active ingredient refers to the method for active ingredient by ion-exchange and co-precipitation, with metal active constituents such as Fe, Mo, Ce, Ca, Ni, Cu according to certain ratio (Fe as previously described
yMo
x(Ce, Ca, Ni, Cu)
(0.6x)/ C, wherein x is 0.1-0.6, the value of y is 0.6-0.9.Utilize the aqueous solution of these metal-salts, by mechanical stirring, methods such as control temperature, time and pH value etc., make these active ingredients evenly enter the inside of brown coal, and be evenly distributed in the chemical structure of the micropore surface of brown coal and matrix.Requirement to brown coal is: ash content is less than 5% (wt) in the brown coal, and granular size is less than 1 millimeter.
2) steam gasification
The brown coal of implanting active ingredient are put into fluidized-bed reactor, pass into water vapour, (700-900 ℃) makes the brown coal of active ingredient produce pyrolysis, partial gasification by the process of steam gasification at a certain temperature, thereby reaches the effect of activating solid scavenging agent.The solid product of preparation is the solid purificant of lignite semi-coke load.
The active ingredient of utilizing said process preparation is evenly distributed on the micropore surface of lignite semi-coke with the form of nano-metal-oxide particle, as shown in Figure 3.These nano-metal-oxide particles namely are the active ingredients of scavenging agent, have high chemical reactivity and catalytic reaction activity, can high-level efficiency remove the impurity such as sulfide contained in the coal gas, NO_x precursors, tar steam, micropore surface can also adsorb a part of impurity simultaneously, obtains the decontamination effect improving of good coal gas of high temperature.
Ultimate principle:
In counter-flow moving bed device, metal solid scavenging agent through the lignite semi-coke load of special composition design is housed, the main ingredient of solid contains Fe, Mo, Ce, Cu, Ni, the metallic elements such as Ca, these metallic elements in the carbon base body of semicoke, have high activity with the form high dispersing of metal oxide nanoparticles.After the heating gas that contains impurity enters reactor from counter-flow moving bed device bottom, contact with metal oxide, namely produce the rapid chemical effect.Its medium sulphide content (hydrogen sulfide and carbonylsulfide) and metal oxide generation chemical reaction generate metallic sulfide.Reaction process is as follows:
M
yO
x+xH
2S→yMS
(x/y)+xH
2O
COS+H
2→H
2S+CO
M
yO
x+xCOS→yMS
(x/y)+xCO
2
NO_x precursors mainly is NH
3And HCN, the destruction effect by Cu and Ni is decomposed into N
2, transformation efficiency is reached more than 95%; Tar is decomposed into lighter-than-air gas under the katalysis of Ni, Cu, transformation efficiency is more than 98%; So just make these main gaseous impuritieies can in moving-bed, carry out disposable removing.Solid impurity mainly is the fine particle thing, and a part is adsorbed on the pore surface of semicoke, and a part is filtered by the ceramic high temperature filtering unit that is installed in counter-flow moving bed device top and carried out effective elimination in addition.Simultaneously, the ceramic high temperature filtering unit further removes remaining tar steam.In the heating gas through the integrated apparatus imurity-removal, the total content of various impurity can effectively be reduced to 10mg below every cubic metre, thereby makes the disposal of pollutants of polygenerations systeme be reduced to bottom line.
Embodiment:
The Fe-Mo high-temp solid scavenging agent that utilizes said process to prepare the lignite semi-coke load has carried out tentative experiment to desulfurization, adopts counter-flow moving bed device, and curing temperature is 400-600 ℃, and gas space velocity is 1000h
-1Test-results shows that this sample can remove sulfide contained in the coal gas (hydrogen sulfide and carbonylsulfide) very effectively.Be lower than 5ppmv (corresponding to 7.1mg/m through the coal gas medium sulphide content content after the scavenging agent purification at 400 ℃
3), be lower than 50ppmv (corresponding to 71.4mg/m at 500 ℃-600 ℃
3), this purification coal gas can be used as in fuel and carry out combustion power generation in internal combustion turbine.Shown in Figure 4, the physical structure of the scavenging agent after the desulfurization does not significantly change, and the as a result nano-metal-oxide of EDS face scanning all changes into nano metal sulphide, still is evenly distributed on the surface of the micropore of semicoke matrix, can be used as catalyzer and uses.Among Fig. 4, (a) SEM pattern photo; (b) face of the ferro element corresponding with a distributes; (c) face of the molybdenum element corresponding with a distributes; (d) face of the element sulphur corresponding with a distributes.
Claims (2)
1. integrated middle high temperature coal gas purification method that is applicable to coal-based gas, it is characterized in that, flow process is: enter from the coal gas of high temperature of the vapourizing furnace bottom entrance by counter-flow moving bed device, the heating gas that contains impurity is with after solid purificant contacts, impurity is absorbed by solid purificant, discharges from top exit after the ceramic high temperature filtering unit filtration of coal gas through top; Disposable gaseous impurities in the coal gas is removed, the dust in the coal gas is removed by middle ceramic high temperature filtering unit simultaneously; Purification temperature is 300-600 ℃, and air pressure is normal pressure, and gas space velocity is 1000h
-1Described counter-flow moving bed device comprises heating gas entrance, gas purification outlet, scavenging agent entrance, scavenging agent relief outlet, funnel type housing and is in the interior solid purificant of funnel type housing; The ceramic high temperature filtering unit is fixed on the top of counter-flow moving bed device; The ceramic high temperature filtering unit is passed in the gas purification outlet; The middle and lower part of funnel type housing is provided with the heating gas entrance, and top is provided with the scavenging agent entrance, is provided with the scavenging agent relief outlet below the funnel type housing; Solid purificant injects by the scavenging agent entrance, be in the ceramic high temperature filtering unit below; Described solid purificant is the multi-element metal base solid purificant of lignite semi-coke load, and composition is: Fe
yMo
x(Ce, Ca, Ni, Cu)
(0.6x)/ C, wherein x is 0.1-0.6, the value of y is 0.6-0.9; Ceramic high temperature filtering unit filtering material is the porous non-metallic oxide compound.
2. a kind of integrated middle high temperature coal gas purification method that is applicable to coal-based gas as claimed in claim 1, it is characterized in that: described porous non-metallic oxide compound is zirconium white or magnesium oxide.
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| CN102964124B (en) * | 2011-01-07 | 2015-02-11 | 宜兴市鑫帝豪高科陶瓷厂 | High-temperature gas-solid ceramic filter tube and preparation method |
| CN103706381B (en) * | 2012-09-29 | 2016-08-24 | 任相坤 | A kind of catalyst for coal liquefaction and use the coal liquefaction method of this catalyst |
| CN103706380B (en) * | 2012-09-29 | 2016-08-10 | 任相坤 | Catalyst for coal liquefaction and use the coal liquefaction method of this catalyst |
| CN103265978B (en) * | 2013-05-31 | 2014-07-30 | 陕西煤业化工技术研究院有限责任公司 | Integrated system and method for catalytic cracking and dust removal of medium-and-low temperature dry distillation coal gas |
| CN104774652B (en) * | 2015-03-31 | 2018-07-20 | 成都易态科技有限公司 | Coal reburner flue gas cleaning system |
| CN104774653B (en) * | 2015-03-31 | 2018-08-17 | 成都易态科技有限公司 | Coal reburner flue gas cleaning system |
| CN105694989A (en) * | 2016-02-03 | 2016-06-22 | 山东佳星环保科技有限公司 | High-temperature coal gas purification technique |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5154900A (en) * | 1988-02-10 | 1992-10-13 | Mitsubishi Jukogyo Kabushiki Kaisha | Method for purifying high-temperature reducing gas |
| CN1478872A (en) * | 2003-06-25 | 2004-03-03 | 中国科学院山西煤炭化学研究所 | Integrated method and device of high temperature coal gas desulfur and dust removing |
| CN101029256A (en) * | 2007-03-16 | 2007-09-05 | 沈阳航空工业学院 | High-temperature semi-tar gas desulfurizer and its use |
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| DE102007046260A1 (en) * | 2007-09-26 | 2009-04-09 | Uhde Gmbh | Process for purifying the raw gas from a solid gasification |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5154900A (en) * | 1988-02-10 | 1992-10-13 | Mitsubishi Jukogyo Kabushiki Kaisha | Method for purifying high-temperature reducing gas |
| CN1478872A (en) * | 2003-06-25 | 2004-03-03 | 中国科学院山西煤炭化学研究所 | Integrated method and device of high temperature coal gas desulfur and dust removing |
| CN101029256A (en) * | 2007-03-16 | 2007-09-05 | 沈阳航空工业学院 | High-temperature semi-tar gas desulfurizer and its use |
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