CN106957694B - A kind of supercritical carbon dioxide soaks the preparation method of the double carbon source fuel of molten coal slurry - Google Patents
A kind of supercritical carbon dioxide soaks the preparation method of the double carbon source fuel of molten coal slurry Download PDFInfo
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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
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- C10J2300/00—Details of gasification processes
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- C10J2300/00—Details of gasification processes
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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
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- C10J2300/093—Coal
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- 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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- 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
- C10J2300/0969—Carbon dioxide
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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
- C10J2300/0953—Gasifying agents
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- 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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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
A kind of supercritical carbon dioxide soaks the preparation method of the double carbon source fuel of molten coal slurry, the following steps are included: (1) makes modified coal dust: composite modifier to be added in raw coal or be injected directly into coal mill in ratio of the raw coal quality than 0.5~8%, it is mixed together grinding, modified coal dust is made；(2) supercritical CO processed2It soaks the double carbon source fuel of molten coal slurry: modified coal dust is placed in pressure vessel, control temperature in container and be not less than 5 DEG C, be not higher than 50 DEG C, use supercritical CO2Molten modified coal dust is directly soaked, produces quality of pc than the supercritical CO for 68~88%2Soak the double carbon source fuel of molten coal slurry；(3) supercritical CO2Soak the gasification of the double carbon source fuel of molten coal slurry.The method of the present invention is simple, is transformed using existing dry or wet process system, using the gasification process of existing maturation, operating cost can be greatly reduced, and gas purification and the removing CO of existing gasification system is effectively reduced2Cost.
Description
Technical field
The present invention relates to clean energy technology fields, and in particular to a kind of supercritical CO2Soak the double carbon source fuel of molten coal slurry
Preparation method.
Background technique
Coal gasification refers to the organic matter and gasifying agent generation series of chemical made in coal under certain temperature and pressure,
Convert solid coal to the process of lime-ash and imflammable gas.According to used gasifying agent difference (air, pure oxygen, oxygen-enriched air,
Vapor, carbon dioxide etc.) and gasification process difference, the gas composition of output is different.Coal gasifying process is with as-fired coal in furnace
Interior process dynamics can be divided into moving bed (fixed bed) gasification, fluidized gasification, entrained flow gasification and molten bath gasifica tion technique etc..
The development trend of current Coal Gasification Technology is to replace beans with fine coal, replaces fixed bed with air flow bed and fluidized bed, especially by
The referred to as entrained flow gasification method of high effect cleaning coal gasification method, and to high-pressure trend (8.5MPa) and high temperature (1500~
1600 DEG C) gasification and gasifying agent diversified development, and deslagging mode to liquefied develop.
Entrained flow gasification method is using the fines of partial size < 0.1mm as raw material, including using superfine coal dust as the dry of raw material
Method technique and using water-coal-slurry as the wet processing two types of raw material.Dry and wet technique is both steamed with oxygen, overheat
Vapour is gasifying agent, and is gasified or suspended using parallel type and gasified, and is sprayed into oxygen, superheated steam (gasifying agent) and coal dust with nozzle
Gasification furnace reaction chamber.In-furnace temperature is up to 1400 DEG C ~ 2000 DEG C, and coal dust enters the i.e. moment kindling of furnace, rapid reaction, the intensity of gasification
Pyrolysis, burning almost occur simultaneously and is converted to CO, H with gasifying agent generation combustion reaction and gasification reaction, a step for height2 、
CO2Equal gases.Because of hot conditions, tar, phenol and hydro carbons (being practically free of liquid hydrocarbon and CH4) are free of in gasification gas, CO contains
Amount up to 58% ~ 62%, is secondly H2、CO2Deng major impurity H2S and a small amount of COS.
The main distinction of dry and wet entrained flow gasification method is on the feed-type of gasification furnace fuel, and dry method is first will
Coal dust is made in raw coal grinding, and then, coal dust is directly sprayed into furnace with pneumatic conveying to nozzle, representational as K-T gasifies
Furnace, shell furnace (shell, SCGP, pressurization K-T), GSP furnace etc.；Wet process is first to help raw coal and water and emulsifier, friction reducer etc.
Water-coal-slurry is made in agent combined grinding, or raw coal grinding is first made coal dust, then plus the auxiliary agents such as emulsifier, friction reducer, through high-speed stirring
Mix and be mixed and made into water-coal-slurry, then, be pumped to nozzle spray into furnace in, it is representative have Texaco's coal slurry gasifier (Texaco,
GE), using the water-coal-slurry of 60% ~ 65% concentration as feeding manner, make gasifying agent with pure oxygen, the oxygen consumption for gasifying required is 1kg
O2/ kg dry coal, water-coal slurry pump and nozzle are easy to wear, and the replacement frequency is high, influence the gasifier operation period.Two kinds of processes
Respectively there is feature, coal grain is all big to the abrasion of nozzle.Dry method is fed the coal and low-order coal for being well suited for high activity, but it is generallyd use
High pressure dense-phase air transportation system it is complicated and discharge pressure is subject to certain restrictions, be fed and lock device for coal in pressurized conditions failure
Also more, coal dust conveying technology has become the important restriction factor of dry gasification technology development.And water-coal-slurry form is easy pressurization
Pumping can solve the problems, such as dry method feed and lock device for coal under an increased pressure, but contained a large amount of moisture content (general moisture content 35
~42%) gasification absorbs a large amount of latent heats of vaporization, and the thermal efficiency is lower, and overall thermal efficiency and the gasification for seriously affecting gasification furnace are strong
Degree.
It is adversely affected caused by large quantity of moisture to reduce, has developed polynary slurry gasification technology, i.e., be added in water-coal-slurry
A part of water in certain heavy oil or crude oil or pitch substitution water-coal-slurry, with the carbon containing effecting reaction object being added in furnace charge slurry
Concentration improves CO, H in generated coal gas2Content, reduce effective gas (CO+H2) specific yield oxygen and raw material consumption of coal.
But oil material need to be consumed and oil need to be expected pre-emulsification, will increase combined grinding energy consumption and generate secondary pollution.
For this purpose, domestic and international scientific worker has carried out a large amount of research with regard to gasification system and fuel mode of movement.Wherein have
Chinese patent CN103468320A discloses " a kind of carbon dioxide coal slurry preparation conveying and gasification system, which is characterized in that described
System by water-coal-slurry preparation unit, carbon dioxide coal slurry preparation unit, coal gasification unit, synthesis gas cooling and purifying unit and
Collecting carbonic anhydride separative unit composition;The water-coal-slurry preparation unit includes water-coal-slurry preparation vessel, and water-coal-slurry preparation vessel is set
There are coal powder entrance and water inlet, water-coal-slurry preparation vessel is connect by coal slurry pump one with coal slurry displacement slot;..., the dioxy
Change carbon coal slurry preparation conveying with gasification system mainly by water-coal-slurry preparation vessel, water-coal slurry pump, coal slurry displacement slot, coal slurry drain sump,
Coal slurry bubble trap ..., main process is as follows: coal dust is prepared as normal temperature and pressure water after mixing in coal slurry industry with water
Coal slurry (coal slurry mass concentration about 60%), reaches 6.0~8.0MPa, temperature remains room temperature after normal pressure water-coal-slurry is pressurized;
Pressure liquid carbon dioxide identical with water-coal-slurry is pumped into water-coal-slurry displacement slot by liquid carbon dioxide, carries out with water-coal-slurry
It is stirred, most of coal dust will be mixed to form carbon dioxide coal slurry with liquid carbon dioxide, and water, which is separated, is back to water-coal-slurry
Preparation unit, carbon dioxide coal slurry mass concentration about 30% at this time are right in order to further increase the concentration of carbon dioxide coal slurry
Carbon dioxide coal slurry is suitably heated, and reduces its pressure value 6.0MPa or so, temperature is reduced to about 25 DEG C, close to titanium dioxide
Carbon gas-liquid two-phase critical point is filtered out carbon dioxide coal slurry upper foam with filter, and the quality for improving carbon dioxide coal slurry is dense
Degree;Carbon dioxide coal slurry is delivered to gasifier nozzle from coal slurry slot using coal slurry pump ... ..., containing highly concentrated in the synthesis gas of purification
The carbon dioxide of degree carries out carbon dioxide by carbon dioxide capture system and separates with the effective gas of synthesis gas ...." this method
In terms of solving the problems, such as that gasification caused by a large amount of moisture content contained by water-coal-slurry absorbs a large amount of latent heats of vaporization, reduces the thermal efficiency
Advantage obviously is shown, but is primarily present following problem:
First, the coal dust sheet ground is the dry pulverized coal of dehydration, the water-coal-slurry of mass ratio about 60%, water-coal-slurry is made in dry pulverized coal
When being converted into the carbon dioxide coal slurry of mass ratio about 60% with carbon dioxide replacement, necessarily lead to a large amount of CO2Hydrate solids with
Ice state is present in carbon dioxide coal slurry, and the measures such as reflux can not isolate CO2Hydrate solids had both influenced carbon dioxide coal slurry
Mobility, may cause blocking again, and in vaporized furnace after CO2Hydrate solids need to absorb a large amount of latent heat of vaporization；
Second, sweeping along the ultrahigh concentration CO of coal dust particle2(CO2For the common extinguishing chemical of fire-fighting) to the coal dust sprayed into furnace
Fire behaviour can generate stop up the property put out influence, if without the moment a large amount of thermal energy of ignition ability sustainable supply of a large amount of coal dusts,
Then the temperature in gasification furnace can decline rapidly, and positive effect leaves a question open；
Third, being not directed to CO2As the effecting reaction condition of gasifying agent and carbon especially catalytic gasification condition, will lead to
Such as its " CO containing excessive concentrations described in the specification in coal gas2", it will increase dramatically the purification and decarburization cost of coal gas；
Fourth, the high CO in gasification gas as used in the description2Concentration, corresponding CO, H in coal gas2Ratio declines to a great extent,
That is gas quality and the decline of coal gas thermal energy, have objectively influenced the efficiency of gasification furnace；
Fifth, dry pulverized coal is prepared into common coal water slurry fuel first, the waste of the costs such as water and auxiliary agent is caused, is increased
A large amount of waste water for being dissolved with noxious pollutant, cause secondary pollution；
Sixth, water-coal-slurry is forced into 6.0~8.0MPa, liquid carbon dioxide is stirred with water-coal-slurry and is mixed,
Dehydration, separation reflux, obtain the carbon dioxide coal slurry of about 30% concentration, then suitably heated to carbon dioxide coal slurry, with filtering
Device filters out carbon dioxide coal slurry upper foam, improves the quality of carbon dioxide coal slurry, and more than complex procedures, equipment are more, throw
Money is big, is 31.06 DEG C, critical pressure 7.382MPa, critical density 468kg/m for critical-temperature3CO2For medium, equipment
Technical difficulty and energy consumption are significantly larger than the transportation problem of dry pulverized coal.
To solve superelevation solubility CO2To the effect of burying in oblivion for entering gasification furnace coal dust, ADL company (the Arthur D in the U.S.
Little lnc) using the CO of liquid2Water and coal slurry is replaced to be mixed and made into CO2When coal slurry, in the terminal of conveyance conduit, by setting
Setting fibrous filter makes CO2Volatilization and by coal dust and CO2Separate, the coal dust separated be it is dry, can carry out immediately
Burning, the CO separated2It recycles, but needs the fabric filter of flash chamber and setting valuableness.
In order to further play the advantage of entrained flow gasification method, the fuel transportation problem, abrasion for mitigating nozzle, big is resolved
The overall thermal efficiency and the intensity of gasification of width raising gasification furnace and the green clean energy technology for realizing emission reduction, there is an urgent need to open
Send out a kind of completely new technical method.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a kind of simple process, without secondary dirt
Dye, environmental protection, the supercritical carbon dioxide for being adapted to existing airflow bed gasification furnace soak the preparation method of the double carbon source fuel of molten coal slurry.
The technical solution used to solve the technical problems of the present invention is that a kind of supercritical carbon dioxide soaks the double carbon sources of molten coal slurry
The preparation method of fuel, uses CO2A part of oxygen and feed coal are substituted, using coal dust carbon and carbon dioxide simultaneously as the carbon of gasification furnace
Source, can improve the catalysis burning-rate accelerator of coal powder ignition performance and improve CO2Catalytic gasification agent with coal dust reactivity is as multiple
It closes modifying agent and produces modified coal dust, with supercritical CO2It soaks the modified coal dust of miscible conjunction, quality of pc is made than surpassing for 68~88%
Critical CO2The double carbon source fuel of molten coal slurry are soaked, are conveyed with high-pressure coal pulp pump, spray into air flow bed gas together with superheated steam, oxygen etc.
Change and carries out mixing gasifying reaction in furnace, specifically includes the following steps:
(1) modified coal dust is made:
Using existing/mature coal dust technique processed, during grinding coal dust, composite modifier is pressed into raw coal quality
Ratio than 0.5~8% is added in raw coal or is injected directly into coal mill, and grinding is mixed together, and it is composite modified for being made with coal grain
The mixed and modified coal dust of agent carrier；
(2) supercritical CO processed2Soak the double carbon source fuel of molten coal slurry:
Mixed and modified coal dust obtained by step (1) is placed in pressure vessel, control in container temperature not less than 5 DEG C, it is not high
In 50 DEG C, supercritical CO is used2The modified coal dust of miscible conjunction is directly soaked, produces quality of pc than the supercritical CO for 68~88%2It soaks molten
The double carbon source fuel of coal slurry；
(3) supercritical CO2Soak the gasification of the double carbon source fuel of molten coal slurry:
Referring to existing wet process fuel feedstock process, by supercritical CO obtained by step (2)2Soak the double carbon source combustions of molten coal slurry
Material is conveyed with coal slurry pump, is sprayed into airflow bed gasification furnace through gasification burner tip together with superheated steam, oxygen etc. and is carried out mixing gasifying
Reaction.
Further, the composite modifier selects commercially available catalysis burning-rate accelerator, catalytic gasification agent, helps in mass ratio for catalysis
Fire the compound rear use of ratio of agent 10~60%, catalytic gasification agent 40~90%；Or select catalysis burning-rate accelerator, catalytic gasification agent direct
Addition uses in proportion；Or selecting has catalytic combustion-supporting and the marketable material of catalytic gasification effect directly to use.
Further, the catalysis burning-rate accelerator, which refers to, is effective against pure CO2Bury in oblivion effect, in CO2High temperature can be borrowed in environment
Ignite the catalyst containing active oxygen and/or ionic catalysis oxidation effect or combustion adjuvant or catalysis oxidation combustion adjuvant of coal dust；Such as weight
Chromic acid ammonia, ammonium metavanadate, ZC-7 type catalytic combustion adjuvant for coal, ZC-9 type catalytic combustion adjuvant for coal, ZC-19 moulded coal catalytic combustion-supporting
At least one of agent, ZC-11 type catalytic combustion adjuvant for coal etc.；Catalysis burning-rate accelerator dosage is that 0.03~3%(of raw coal quality is excellent
Select 0.1~1.5%).
Further, the catalytic gasification agent, which refers to, can be improved coal dust carbon and CO in 800 DEG C or more2Reactivity, promote
Coal dust carbon and CO2Reaction generates the substance of CO；Compound preferably containing elements such as lithium, potassium, vanadium, nickel, chromium, manganese, strontium, cerium, lanthanums；
As carbonyl ferronickel, salicylic acid cerium, the agent of ZC-G3 type catalytic gasification, the agent of ZC-G5 type catalytic gasification, the agent of ZC-G13 type catalytic gasification,
At least one of ZC-G7 type catalytic gasification agent etc., catalytic gasification agent dosage are 0.47~5%(preferably 0.5 of raw coal quality ratio
~3%).
Technical principle of the invention:
1) by CO2As a kind of carbon source, a part of oxygen and feed coal are substituted, meanwhile, utilize supercritical CO2 Density is bordering on liquid
Body, viscosity are bordering on gas, and diffusion coefficient is 100 times of liquid, strong to the solvability of coal dust, can effectively soak molten and softening coal dust
Particle and the low feature of good fluidity, transporting resistance, by supercritical CO2The molten medium of leaching and pumped (conveying) medium as coal dust solve
The transportation problem of aerobic fluidized gas producer fuel and the easily wear problem of nozzle.
2) using maturation application or existing coal dust technological equipment system processed, functional composite modifier is directly added
Enter in raw coal/spray into coal mill in, be mixed together grinding be made directly with coal grain be composite modified agent carrier modified coal dried bean noodles powder.
3) it borrows the anti-of catalytic combustion adjuvant for coal to bury in oblivion effect, resolves ultrahigh concentration CO2Stopping up for coal dust firing is put out in environment
Problem, it is ensured that by pure CO2Soaking can moment ignition in hot environment in the molten coal dust penetrating gasification furnace wrapped.
4) supercritical CO is utilized2It is good " intermiscibility " with dry pulverized coal, with supercritical CO2Soak molten carry with functional catalysis
Combustion-supporting and catalytic gasification composite modifier pulverized coal particle, is made gasification furnace supercritical CO2Soak double carbon sources combustion of molten coal dust carbon
Material improves coal dust carbon and CO with functional catalytic gasification agent2Reactivity, promote coal dust carbon and CO2Fast reaction generates CO,
Reduce effective gas (CO+H2) specific yield oxygen and raw material consumption of coal.
5) referring to the wet process fuel feedstock process of mature application, by supercritical CO2The double carbon source fuel of molten coal slurry are soaked to use
High-pressure coal pulp pump conveying, sprays into airflow bed gasification furnace together through gasification burner tip with superheated steam, oxygen etc. and carries out mixing gasifying
Reaction.
The present invention has innovated entrained flow bed gasification technology, uses " supercritical CO2Soak molten modified dry pulverized coal, with carbon dioxide
With coal dust charcoal be crude fuel " reaction full technical strategies, reduce effective gas (CO+H2) specific yield oxygen and feed coal
Consumption.
The present invention significantly increases an oxygen using the carbon in the carbon and coal dust in supercritical carbon dioxide simultaneously as carbon source
Change the output capacity of carbon.Reaction activity is reduced with functional catalytic gasification technology, the generation of selective catalysis CO promotes to react
CO2Compared with quickly carrying out under low energy consumption, " pure carbon " contained by the 1 kg coal dust to match theoretically can produce+C=2CO
4.66kg CO, and theoretically the pure carbon of 1 kg is completely converted into CO theoretically and only can produce 2.33 kg CO traditional technology.Its is excellent
The three kinds of oxidation reaction performance of gesture carbon is as follows:
C+O2 =CO2+409(KJ/mo l)
C+0.5O2=0.5CO+246 (KJ/mol)
C+CO2=2CO-162 (KJ/mol)
The method of the present invention is simple, is applicable to all kinds of coals, is environmental type coal gas technology.And using existing
The transformation of dry or wet process system, and can be used the gasification process of existing maturation, operating cost can be greatly reduced, can be with
Gas purification and the removing CO of existing gasification system is effectively reduced2Cost.
Specific embodiment
Make further statement with reference to embodiments.
A kind of supercritical CO2The preparation method for soaking the double carbon source fuel of molten coal slurry, uses CO2A part is substituted as a kind of carbon source
Oxygen and feed coal, meanwhile, utilize supercritical CO2Density is bordering on liquid, and viscosity is bordering on gas, and diffusion coefficient is the 100 of liquid
Times, it is strong to the solvability of coal dust, the molten feature low with softening pulverized coal particle and good fluidity, transporting resistance can be effectively soaked, it will
Supercritical CO2The molten medium of leaching and pumped (conveying) medium as coal dust, resolve the transportation problem and nozzle of airflow bed gasification furnace fuel
Problem easy to wear；Anti- with catalysis burning-rate accelerator buries in oblivion effect, it is ensured that by pure CO2It soaks the molten coal dust wrapped and sprays into height in gasification furnace
It can moment ignition in warm environment；With the generation of functional catalytic gasification agent selective catalysis CO, promote to react CO2+C
=2CO under low energy consumption compared with quickly carrying out；Using mature coal dust technological equipment system processed, by functional catalysis burning-rate accelerator
It is directly added into raw coal/sprays into coal mill with catalytic gasification agent composite modifier, be mixed together grinding and be made and be directly with coal grain
The modified coal dried bean noodles powder of composite modified agent carrier；Utilize supercritical CO2It is good " intermiscibility " with dry pulverized coal, with supercritical CO2Leaching
It is miscible to close the pulverized coal particle carried with functional catalytic combustion-supporting and catalytic gasification composite modifier, it is made and is adapted to mesohigh air-flow
Bed gasification, quality of pc are than the supercritical CO for 68~88%2The double carbon source fuel of molten coal slurry are soaked, are conveyed with high-pressure coal pulp pump, with mistake
Hot steam, oxygen etc. spray into together carries out mixing gasifying reaction in airflow bed gasification furnace.
Embodiment 1, the present embodiment carry out the preparation and gasification that supercritical CO 2 soaks the double carbon source fuel of molten coal slurry.
Supercritical CO used2Raw material selects commercially available liquid carbon dioxide, purity 99.6%；Raw coal is selected commercially available smokeless
Coal, butt volatile matter 7.3%, fixed carbon 65.3%, ash content 27.4%, calorific value Q 5961x4.18KJ/Kg, composite modifier choosing
It is catalyzed with the ZC-G3 type catalytic gasification agent of Hunan Province little Yin Wuji environmental energy Science and Technology Development Co., Ltd. and ZC-7 moulded coal
Composite modifier of the combustion adjuvant as coal dust.It prepares according to the following procedure and the supercritical CO that gasifies2Soak the double carbon source fuel of molten coal slurry.
(1) modified coal dust is made:
ZC-7 type catalytic combustion adjuvant for coal according to smokeless coal quality 0.5%, ZC-G3 type catalytic gasification agent press smokeless coal quality
The 3% of amount and anthracite be mixed together grinding be made 90 μm tail over 18% coal dust, being able to coal grain is that composite modified agent carrier changing
Property coal dust；
(2) supercritical CO processed2Soak the double carbon source fuel of molten coal slurry:
Modified coal dust obtained by step (1) is placed in pressure vessel, controls in container 28 DEG C~32 DEG C of temperature, use is overcritical
CO2The modified coal dust of miscible conjunction is directly soaked, quality of pc is made than the supercritical CO for 82%2Soak the double carbon source fuel of molten coal slurry；
(3) supercritical CO2Soak the gasification of the double carbon source fuel of molten coal slurry:
Using triple-channel burner as adjustable experimental wind flow bed burner, by supercritical CO obtained by step (2)2Soak molten coal slurry
Double carbon source fuel are conveyed with high-pressure coal pulp pump, spray into the gasification of experimental wind flow bed through gasification burner tip together with superheated steam, oxygen etc.
In furnace, 1450 DEG C~1550 DEG C of temperature, the pressure 3.1MPa of mixing gasifying reaction are carried out in control gasification furnace.
Through detecting, under gasification furnace stable state, effective gas (CO+H2): 88.6%, than coal consumption: 0.532Kg coal/Nm3(CO+
H2), it is consumed than oxygen: 0.326Nm3O2/Nm3(CO+H2), coal dust efficiency of carbon con version: 99.6%, CO2 conversion ratio: 83.5%.
Embodiment 2, the present embodiment carry out supercritical CO2Soak the preparation and gasification of the double carbon source fuel of molten coal slurry.
Supercritical CO used2Raw material selects commercially available liquid carbon dioxide, purity 99.6%, and raw coal selects commercially available half cigarette
Coal, butt volatile matter 18.4%, fixed carbon 55.8%, ash content 25.8%, calorific value 6137x4.18KJ/Kg, composite modifier choosing
It is catalyzed with the ZC-G5 type catalytic gasification agent of Hunan Province little Yin Wuji environmental energy Science and Technology Development Co., Ltd. and ZC-9 moulded coal
Composite modifier of the combustion adjuvant as coal dust.It prepares according to the following procedure and the supercritical CO that gasifies2Soak the double carbon source fuel of molten coal slurry.
(1) modified coal dust is made:
ZC-9 type catalytic combustion adjuvant for coal according to semibituminous coal quality 1.0%, ZC-G5 type catalytic gasification agent press semibituminous coal matter
Amount 4.5% with semibituminous coal be mixed together grinding be made 90 μm tail over 21.4% coal dust, be able to coal grain be composite modified agent carrier
Modification coal dust；
(2) supercritical CO processed2Soak the double carbon source fuel of molten coal slurry:
Modified coal dust is placed in pressure vessel, 28 DEG C~32 DEG C of temperature is controlled in container, uses supercritical CO2It directly soaks molten
Quality of pc is made than the supercritical CO for 78% in mixed and modified coal dust2Soak the double carbon source fuel of molten coal slurry；
(3) supercritical CO2Soak the gasification of the double carbon source fuel of molten coal slurry:
Using triple-channel burner as adjustable experimental wind flow bed burner, by supercritical CO2Soak the double carbon source fuel of molten coal slurry
It is conveyed with high-pressure coal pulp pump, is sprayed into experimental wind flow bed gasification furnace through gasification burner tip together with superheated steam, oxygen etc., control gas
Change 1600 DEG C~1700 DEG C of temperature, the pressure 6.5MPa that mixing gasifying reaction is carried out in furnace.
Through detecting, under gasification furnace stable state, effective gas (CO+H2): 89.7%, than coal consumption: 0.506Kg coal/Nm3(CO+
H2), it is consumed than oxygen: 0.317Nm3O2/Nm3(CO+H2), coal dust efficiency of carbon con version: 99.7%, CO2Conversion ratio: 89.1%.
Embodiment 3, the present embodiment carry out supercritical CO2Soak the preparation and gasification of the double carbon source fuel of molten coal slurry.
Supercritical CO used2Raw material selects commercially available liquid carbon dioxide, purity 99.6%, and raw coal selects commercially available half cigarette
Coal, butt volatile matter 18.4%, fixed carbon 55.8%, ash content 25.8%, calorific value 6137x4.18KJ/Kg, composite modifier choosing
With the ZC-G13 type catalytic gasification agent of Hunan Province little Yin Wuji environmental energy Science and Technology Development Co., Ltd. and ZC-19 moulded coal with urging
Change composite modifier of the combustion adjuvant as coal dust.It prepares according to the following procedure and the supercritical CO that gasifies2Soak the double carbon source fuel of molten coal slurry.
(1) modified coal dust is made:
ZC-19 type catalytic combustion adjuvant for coal according to semibituminous coal quality 1.5%, ZC-G13 type catalytic gasification agent press semibituminous coal
Quality 1.8% with semibituminous coal be mixed together grinding be made 90 μm tail over 22.3% coal dust, be able to coal grain be composite modifier carry
The modification coal dust of body；
(2) supercritical CO processed2Soak the double carbon source fuel of molten coal slurry:
Modified coal dust is placed in pressure vessel, 30 DEG C~33 DEG C of temperature is controlled in container, uses supercritical CO2It directly soaks molten
Quality of pc is made than the supercritical CO for 79% in mixed and modified coal dust2Soak the double carbon source fuel of molten coal slurry；
(3) supercritical CO2Soak the gasification of the double carbon source fuel of molten coal slurry:
Using triple-channel burner as adjustable experimental wind flow bed burner, by supercritical CO2Soak the double carbon source fuel of molten coal slurry
It is conveyed with high-pressure coal pulp pump, is sprayed into experimental wind flow bed gasification furnace through gasification burner tip together with superheated steam, oxygen etc., control gas
Change 1800 DEG C~1900 DEG C of temperature, the pressure 8.5MPa that mixing gasifying reaction is carried out in furnace.
Through detecting, under gasification furnace stable state, effective gas (CO+H2): 90.1%, than coal consumption: 0.494Kg coal/Nm3(CO+
H2), it is consumed than oxygen: 0.299Nm3O2/Nm3(CO+H2), coal dust efficiency of carbon con version: 99.8%, CO2Conversion ratio: 90.7%.
Embodiment 4, the present embodiment carry out supercritical CO2Soak the preparation and gasification of the double carbon source fuel of molten coal slurry.
Supercritical CO used2Raw material selects commercially available liquid carbon dioxide, purity 99.6%, and raw coal selects commercially available bituminous coal,
Butt volatile matter 31.6%, fixed carbon 45.3%, ash content 23.1%, calorific value 6417x4.18KJ/Kg, composite modifier select lake
The ZC-G7 type catalytic gasification agent of Nan Sheng little Yin's Wuji environmental energy Science and Technology Development Co., Ltd. and ZC-11 moulded coal catalytic combustion-supporting
Composite modifier of the agent as coal dust.It prepares according to the following procedure and the supercritical CO that gasifies2Soak the double carbon source fuel of molten coal slurry.
(1) modified coal dust is made:
ZC-11 type catalytic combustion adjuvant for coal according to bituminous coal quality 0.9%, ZC-G7 type catalytic gasification agent is by bituminous coal quality
2.2% with bituminous coal be mixed together grinding be made 90 μm tail over 26.4% coal dust, be able to coal grain be composite modified agent carrier modification
Coal dust；
(2) supercritical CO processed2Soak the double carbon source fuel of molten coal slurry:
Modified coal dust is placed in pressure vessel, 30 DEG C~35 DEG C of temperature is controlled in container, uses supercritical CO2It directly soaks molten
Quality of pc is made than the supercritical CO for 73% in mixed and modified coal dust2Soak the double carbon source fuel of molten coal slurry；
(3) supercritical CO2Soak the gasification of the double carbon source fuel of molten coal slurry:
Using triple-channel burner as adjustable experimental wind flow bed burner, by supercritical CO2Soak the double carbon source fuel of molten coal slurry
It is conveyed with high-pressure coal pulp pump, is sprayed into experimental wind flow bed gasification furnace through gasification burner tip together with superheated steam, oxygen etc., control gas
Change 1800 DEG C~1900 DEG C of temperature, the pressure 8.5MPa that mixing gasifying reaction is carried out in furnace.
Through detecting, under gasification furnace stable state, effective gas (CO+H2): 89.5%, than coal consumption: 0.495Kg coal/Nm3(CO+
H2), it is consumed than oxygen: 0.301 Nm3O2/Nm3(CO+H2), coal dust efficiency of carbon con version: 99.7%, CO2 conversion ratio: 92.6%.
Embodiment 5, the present embodiment carry out supercritical CO2Soak the preparation and gasification of the double carbon source fuel of molten coal slurry.
Supercritical CO used2Raw material selects commercially available liquid carbon dioxide, purity 99.6%, and raw coal selects commercially available bituminous coal,
Butt volatile matter 31.6%, fixed carbon 45.3%, ash content 23.1%, calorific value 6417x4.18KJ/Kg, composite modifier select water
Poplar acid cerium, composite modifier of the ammonium bichromate as coal dust.It prepares according to the following procedure and the supercritical CO that gasifies2Soak the double carbon of molten coal slurry
Source fuel.
(1) modified coal dust is made:
Composite modifier salicylic acid cerium, ammonium dichromate are respectively in the 0.9% of bituminous coal quality and 1.5% ratio and bituminous coal one
Rise combined grinding be made 90 μm tail over 20.4% coal dust, be able to coal grain be composite modified agent carrier modification coal dust；
(2) supercritical CO processed2Soak the double carbon source fuel of molten coal slurry:
Modified coal dust is placed in pressure vessel, 30 DEG C~35 DEG C of temperature is controlled in container, uses supercritical CO2It directly soaks molten
Quality of pc is made than the supercritical CO for 76% in mixed and modified coal dust2Soak the double carbon source fuel of molten coal slurry；
(3) supercritical CO2Soak the gasification of the double carbon source fuel of molten coal slurry:
Using triple-channel burner as adjustable experimental wind flow bed burner, by supercritical CO2Soak the double carbon source fuel of molten coal slurry
It is conveyed with high-pressure coal pulp pump, is sprayed into experimental wind flow bed gasification furnace through gasification burner tip together with superheated steam, oxygen etc., control gas
Change 1900 DEG C~2000 DEG C of temperature, the pressure 10MPa that mixing gasifying reaction is carried out in furnace.
Through detecting, under gasification furnace stable state, effective gas (CO+H2): 90.7%, than coal consumption: 0.445Kg coal/Nm3(CO+
H2), it is consumed than oxygen: 0.293 Nm3O2/Nm3(CO+H2), coal dust efficiency of carbon con version: 99.9%, CO2Conversion ratio: 92.8%.
Comparative example 1 does not use composite modifier, carries out supercritical CO2Soak the preparation and gasification of the double carbon source fuel of molten coal slurry.
Supercritical CO used2Raw material selects commercially available liquid carbon dioxide, purity 99.6%, and raw coal is selected commercially available smokeless
Coal, butt volatile matter 7.3%, fixed carbon 65.3%, ash content 27.4%, calorific value Q 5961x4.18KJ/Kg, without using catalysis gas
The composite modifier of agent and catalysis burning-rate accelerator as coal dust.It prepares according to the following procedure and the supercritical CO that gasifies2Soak molten coal slurry combustion
Material.
(1) coal dust processed: by anchracite duff be milled into 90 μm tail over 17% coal dust；
(2) supercritical CO processed2Soak the double carbon source fuel of molten coal slurry:
Coal dust is placed in pressure vessel, 28 DEG C~32 DEG C of temperature is controlled in container, uses supercritical CO2Directly soak miscible conjunction
Quality of pc is made than the supercritical CO for 82% in coal dust2Soak the double carbon source fuel of molten coal slurry；
(3) supercritical CO2Soak the gasification of molten coal slurry fuel:
Using triple-channel burner as adjustable experimental wind flow bed burner, first firewood oil stablizes the temperature in gasification furnace extremely
1500 DEG C~1550 DEG C, pressure 3.1MPa, then, by supercritical CO2It soaks molten coal slurry fuel to be conveyed with high-pressure coal pulp pump, with overheat
Steam, oxygen etc. spray into experimental wind flow bed gasification furnace through gasification burner tip together, and rapid drop in temperature in gasification furnace sprays into repeatedly
Diesel oil is combustion-supporting, still can not effectively control the temperature in gasification furnace and stablize at 1450 DEG C~1550 DEG C, only sprays diesel oil at the same time and sprays
Oxygen amount increases 175%(compared with embodiment 1) Shi Caineng equilibrium temperature.
This test display: the CO of ultrahigh concentration2Have significantly to stop up and put out effect, seriously hinders the moment ignition of coal dust
Ability.The anti-of catalytic combustion adjuvant for coal need to be borrowed to bury in oblivion effect, resolve ultrahigh concentration CO2Coal dust firing stops up to put out and asks in environment
Topic, just can ensure that by pure CO2Soaking can moment ignition in hot environment in the molten coal dust penetrating gasification furnace wrapped.
Claims (7)
1. the preparation method that a kind of supercritical carbon dioxide soaks the double carbon source fuel of molten coal slurry, which comprises the following steps:
(1) modified coal dust is made:
During grinding coal dust, by composite modifier in ratio addition raw coal of the raw coal quality than 0.5~8% or straight
It connects and sprays into coal mill, be mixed together grinding, the mixed and modified coal dust with coal grain for composite modified agent carrier is made；
(2) supercritical CO processed2Soak the double carbon source fuel of molten coal slurry:
Mixed and modified coal dust obtained by step (1) is placed in pressure vessel, temperature in container is controlled and is not less than 5 DEG C, is not higher than 50
DEG C, use supercritical CO2The modified coal dust of miscible conjunction is directly soaked, produces quality of pc than the supercritical CO for 68~88%2Soak molten coal slurry
Double carbon source fuel；
(3) supercritical CO2Soak the gasification of the double carbon source fuel of molten coal slurry:
Referring to wet process fuel feedstock process, by supercritical CO obtained by step (2)2Soak the double carbon source fuel coal stock pumps of molten coal slurry
Conveying sprays into through gasification burner tip together with superheated steam, oxygen and carries out mixing gasifying reaction in airflow bed gasification furnace；
The composite modifier selects catalysis burning-rate accelerator, catalytic gasification agent, is in mass ratio catalysis burning-rate accelerator 10~60%, catalysis
It is used after the ratio of gasifying agent 40~90% is compound；Or select catalysis burning-rate accelerator, catalytic gasification agent directly addition use in proportion；
Or selecting has catalytic combustion-supporting and the raw material of catalytic gasification effect directly to use；
The catalysis burning-rate accelerator, which refers to, is effective against pure CO2Bury in oblivion effect, in CO2Can ignite coal dust in environment by means of high temperature
Catalyst, combustion adjuvant or catalysis oxidation combustion adjuvant containing active oxygen and/or ionic catalysis oxidation effect；
The catalytic gasification agent, which refers to, can be improved coal dust carbon and CO in 800 DEG C or more2Reactivity, promote coal dust carbon and CO2Instead
The substance of CO should be generated.
2. supercritical carbon dioxide according to claim 1 soaks the preparation method of the double carbon source fuel of molten coal slurry, feature exists
In the catalysis burning-rate accelerator is ammonium bichromate, ammonium metavanadate, ZC-7 type catalytic combustion adjuvant for coal, ZC-9 moulded coal are helped with catalysis
Fire at least one of agent, ZC-19 type catalytic combustion adjuvant for coal, ZC-11 type catalytic combustion adjuvant for coal.
3. supercritical carbon dioxide according to claim 1 or 2 soaks the preparation method of the double carbon source fuel of molten coal slurry, feature
It is, the catalysis burning-rate accelerator dosage is the 0.03~3% of raw coal quality ratio.
4. supercritical carbon dioxide according to claim 3 soaks the preparation method of the double carbon source fuel of molten coal slurry, feature exists
In the catalysis burning-rate accelerator dosage is the 0.1~1.5% of raw coal quality ratio.
5. supercritical carbon dioxide as claimed in claim 1 or 2 soaks the preparation method of the double carbon source fuel of molten coal slurry, feature exists
In, the catalytic gasification agent be containing lithium, potassium, vanadium, nickel, chromium, manganese, strontium, cerium, lanthanum element compound.
6. the preparation method that supercritical carbon dioxide as claimed in claim 5 soaks the double carbon source fuel of molten coal slurry, which is characterized in that
The catalytic gasification agent is carbonyl ferronickel, salicylic acid cerium, the agent of ZC-G3 type catalytic gasification, the agent of ZC-G5 type catalytic gasification, ZC-
At least one of the agent of G13 type catalytic gasification, ZC-G7 type catalytic gasification agent.
7. supercritical carbon dioxide as claimed in claim 1 or 2 soaks the preparation method of the double carbon source fuel of molten coal slurry, feature exists
In the catalytic gasification agent dosage is the 0.47~5% of raw coal quality ratio.
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