CN111057585B - Method for fluidized coal gasification - Google Patents
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- CN111057585B CN111057585B CN201811207022.XA CN201811207022A CN111057585B CN 111057585 B CN111057585 B CN 111057585B CN 201811207022 A CN201811207022 A CN 201811207022A CN 111057585 B CN111057585 B CN 111057585B
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- 239000003245 coal Substances 0.000 title claims abstract description 102
- 238000002309 gasification Methods 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 111
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 68
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000005243 fluidization Methods 0.000 claims abstract description 55
- 238000000926 separation method Methods 0.000 claims abstract description 45
- 239000007787 solid Substances 0.000 claims abstract description 43
- 239000002893 slag Substances 0.000 claims description 96
- 239000002245 particle Substances 0.000 claims description 61
- 238000007599 discharging Methods 0.000 claims description 53
- 239000007789 gas Substances 0.000 claims description 48
- 239000003795 chemical substances by application Substances 0.000 claims description 40
- 239000003054 catalyst Substances 0.000 claims description 39
- 239000002994 raw material Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 18
- 238000000197 pyrolysis Methods 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000003570 air Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 238000007580 dry-mixing Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- -1 steam Substances 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 claims 2
- 238000009776 industrial production Methods 0.000 abstract 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 28
- 239000003077 lignite Substances 0.000 description 27
- 238000005516 engineering process Methods 0.000 description 18
- 229910000027 potassium carbonate Inorganic materials 0.000 description 14
- 238000002474 experimental method Methods 0.000 description 13
- 239000002956 ash Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000003034 coal gas Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000035425 carbon utilization Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000011335 coal coke Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/48—Apparatus; Plants
- C10J3/485—Entrained flow gasifiers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/82—Gas withdrawal means
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
The invention relates to a coal fluidization and gasification method, which mainly solves the problems of low carbon conversion rate, low gasification intensity and low methane yield in the prior art. According to the efficient coal fluidized gasification device and the reaction method, the fluidization index is controlled within an optimized range according to the reaction characteristics of each reaction zone through the height of the reasonably designed fluidized bed reactor, the fluidization quality and the carbon conversion rate in the reactor are improved, and meanwhile, the technical scheme of efficient separation through combined gas-solid separation equipment better solves the technical problems and can be applied to industrial production of coal gasification.
Description
Technical Field
The invention relates to a coal fluidization gasification device and a method.
Background
Coal gasification is a core technology for efficient and clean utilization of coal, and is the basis for developing the process industries such as coal-based chemical production, coal-based liquid fuel, Synthetic Natural Gas (SNG), IGCC power generation, hydrogen production, industrial gas and poly-generation systems. China is the largest coal gasification technology application market in the world. At present, various coal gasification technologies have been successfully applied to industrialization, and non-catalytic gasification technologies are adopted to increase the carbon conversion rate at the cost of high temperature and high pressure, which brings about the problems of large coal gas cooling strength, difficult gas purification, high energy consumption, strict requirements on equipment and the like. However, the catalytic gasification process of coal not only increases the gasification reaction rate, but also significantly reduces the gasification reaction temperature, enabling a mild gasification process of coal. Meanwhile, a plurality of synthesis processes can be carried out, and chemical raw materials such as methane, methanol, ammonia and the like can be synthesized while gasifying coal under the action of the catalyst, so that the process flow is shortened. Wherein, the method of coal catalytic gasification is used for directly preparing the synthesis gas rich in methane, which is an important research direction of coal catalytic gasification.
In the aspect of a reactor of a coal gasification technology, the method belongs to an entrained flow gasification technology. However, the technology needs to use high-quality coal with low ash melting point (< 1350 ℃) and low ash content (< 10-15%), and the method for solving the problem of high-ash melting point coal is usually to add 10-30% of fluxing agent, so that the ash content of the fed material is higher, and the operability and the economy of the high-ash melting point coal are influenced. At the same time, the excessive operating temperatures of entrained flow slag gasification technology increase the investment, maintenance and operating costs of the entrained flow. Research reports of the American Electric Power Research Institute (EPRI) indicate that the existing industrial entrained-flow gasifier is not suitable for the gasification of high-ash and high-ash fusion-point coal, and the world needs an industrialized fluidized bed gasification technology. The fluidized bed technology has the nature of adapting to high ash melting point and high ash coal types no matter combustion or gasification, and the evidence proves that the circulating fluidized bed boiler successfully combusts coal gangue.
Patent CN201010279560.7 discloses a multilayer fluidized bed catalytic gasification methane production process, which divides a gasification furnace into a synthesis gas generation section, a coal methanation section and a synthesis gas methanation section. The combustion, gasification, methanation and pyrolysis reactions are carried out in sections, and the reaction degree and temperature distribution of each section are controlled, so that the methane yield is improved. However, in the pyrolysis section above the gasification furnace, fine pulverized coal escapes from the gasification furnace without reaction, so that the carbon content of the fly ash is high, and the unreacted coal coke is back-mixed to the slag hole at the bottom of the gasification furnace and directly discharged from the gasification furnace, so that the carbon conversion rate in the reaction process is low. When the retention time of the coke particles in the gasification furnace is 2-3 h, the carbon conversion rate is basically maintained within the range of 60-90%.
Patent CN101942344A discloses a method and device for gasification of multi-stage staged conversion fluidized bed, which comprises coal preparation, gas supply, gasification, slag discharge, and fine powder transportation, wherein the multi-stage staged conversion fluidized bed gasification device comprises a melt aggregation ash separation unit, a multi-stage staged fluidized bed pyrolysis gasification reactor, and a semicoke fine powder circulating transportation unit, and has the characteristics of high gasification furnace volume utilization rate, large treatment capacity, and high total carbon utilization rate, and is suitable for a coal staged conversion integrated system, and can be used alone to produce coal gas suitable for large-scale coal-based methane synthesis and coal chemical industry. The pyrolysis-derived tar gas is not completely utilized in the staged gasification of the technology, and the tar gas with higher added value is not more efficiently utilized in the aspect of coal quality staged utilization; on the other hand, the technology adopts the slag-removing technology to selectively separate the fused ash and then dry-remove the slag, which has a qualitative breakthrough compared with the prior art and has higher stability, but because the position and the size of the slag can not be controlled in the process of slag formation in the reactor, and simultaneously, in the slag-removing process, because of the restriction of the structure, the semicoke and the slag can not be completely separated, the slag-removing efficiency is not high, the carbon content in the slag is not low, and the total carbon conversion rate is not high.
How to realize the localization of gasification raw materials and develop a gasification furnace suitable for different coal characteristics and downstream products is crucial to the development of coal chemical industry in China. The upgrading of the existing gasification technology realizes the graded conversion of coal, and the integration and optimization of different technologies is also an important trend in the development of the coal gasification technology. Meanwhile, it is also necessary to develop a gasification technology suitable for solid substances containing carbon other than coal, including biomass, liquefied residues, petroleum residues, solid wastes containing carbon, and the like.
In view of the above, in the coal catalytic gasification technology, because methanation reaction is considered, the reaction temperature is low, and the reaction rate and the carbon conversion rate are reduced, it is necessary to develop a coal conversion method capable of improving the carbon conversion rate and improving the gasification intensity, the methane yield and the pulverized coal utilization rate.
Disclosure of Invention
The invention mainly solves the technical problems of low carbon conversion rate, low gasification intensity and low methane yield in the prior art, and provides a high-efficiency coal fluidization gasification method. The fluidized bed reactor in the method has the characteristics of good fluidization quality, high transfer contact efficiency between particles and gas and between particles, high carbon conversion rate, high gasification strength, high methane yield, stability and high efficiency and stable operation of the gasification furnace, and ensures the high efficiency and stability of the reaction.
The second technical problem to be solved by the present invention is to provide a reaction apparatus corresponding to the first technical problem.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: the method comprises the following steps:
(a) the catalyst and the pulverized coal raw material (C) enter a fluidized bed reactor (2) to react with a gasifying agent (B), the reacted crude gas (E) and the incompletely reacted semicoke are separated in a gas-solid separation device (4), and the separated crude gas (E) enters a subsequent device to be purified and separated;
(b) the separated semicoke and the gasifying agent (B) enter the fluidized bed reactor (2) through a material returning device to be mixed and reacted, the reacted large granular slag and part of incompletely reacted carbon-containing particles enter the slag discharging device (1) through valve control, the large granular slag is discharged from the bottom of the slag discharging device (1) after particle classification, and other carbon-containing particles flow into the upper end of the fluidized bed reactor (2) through the upper part of the slag discharging device (1) to continuously participate in the reaction;
the height of the fluidized bed reactor (2) is greater than 5 times the relative fluidization height:
in the above technical solution, the gasifying agent is at least one selected from oxygen, air, liquid water, water vapor, carbon dioxide and hydrogen. The catalyst is selected from at least one of alkali metal, alkaline earth metal and transition metal; the catalyst is loaded on the carbon-containing raw material in an impregnation method, a dry mixing method or an ion exchange method; the loading capacity of the catalyst accounts for 0.1-20% of the mass of the raw coal. The fluidization index in the fluidized-bed reactor 2 is in the range of 0.01 to 5, preferably in the range of 0.02 to 0.1. The temperature of any point in the fluidized bed reactor 2 is not lower than 500 ℃, and the pressure of any point is not lower than 1 MPa. The fluidization index is as follows,
in order to solve the second problem, the invention adopts the following technical scheme: a coal high-efficiency fluidized gasification device mainly comprises the following equipment: fluidized bed reactor 2, subside section 3, gas-solid splitter 4 and sediment device 1 of arranging, wherein fluidized bed reactor 2 upper end expands to be linked together with subside section 3 bottom after the hole, and subside section 3 is linked together with gas-solid splitter 4, and the bottom of gas-solid splitter 4 is linked together with fluidized bed reactor 2, and the upper end of sediment device 1 is linked together with fluidized bed reactor 2's bottom, fluidized bed reactor (2) highly be greater than 5 times of relative fluidization height, and this relative fluidization height is:
in the above technical solution, the diameter of the settling section 3 is 1.5 times larger than that of the fluidized bed reactor 2. The fluidized bed reactor 2 comprises a pyrolysis zone, a synthesis gas generation zone and a methane generation zone inside, and the three zones are sequentially arranged. The height of the fluidized bed reactor 2 is 6-12 times greater than the relative fluidization height. The gas-solid separation equipment 4 is formed by combining at least 2 groups of cyclone separators connected in series or at least 2 groups of cyclone separators and filters connected in series, and the gas-solid separation equipment 4 can be arranged inside or outside the settling section 3.
A high-efficiency coal fluidized gasification method comprises the following steps:
a. the catalyst and the pulverized coal raw material C enter a fluidized bed reactor 2 to react with a gasifying agent B, the reacted crude coal gas E and the incompletely reacted semicoke are separated in a gas-solid separation device 4, and the separated crude coal gas E enters subsequent equipment to be purified and separated;
b. the separated semicoke and the gasifying agent B enter the fluidized bed reactor 2 through the material returning device to be mixed and reacted, the reacted large granular slag and partial incompletely reacted carbon-containing particles enter the slag discharging device 1 through the valve control, the large granular slag is discharged from the bottom of the slag discharging device 1 after the particle classification, and other carbon-containing particles flow into the upper end of the fluidized bed reactor 2 through the upper part of the slag discharging device 1 to continuously participate in the reaction.
In the invention, the pulverized coal particles in the fluidized bed reactor 2 are violently circulated up and down and radially and do back mixing motion under the action of the gasifying agent and the gas generated by the reaction. The bed expansion of the fluidized bed is therefore easy to occur and it is desirable to meet the requirement of sufficient path and time for the circulation of the pulverized coal particles up and down in the bed as much as possible to avoid most of the particles flowing into the settling section, so the height of the fluidized bed reactor 2 is required to be greater than 5 times the relative fluidization height. The relative fluidization height was determined as follows:
in the present invention, the particles are easily blown off the fluidized bed reactor 2 after continuously reacting and thinning in the bed layer. And after the diameter of the settling section 3 is 1.5 times larger than that of the fluidized bed reactor 2, the larger part of particles can be effectively prevented from being entrained and separated.
In the invention, because the particles of the pulverized coal are thinned after gradual reaction, the carbocoal containing carbon fine powder is more, and the requirement on the separation equipment is high. The invention adopts a combined separation method, adds a plurality of cyclone separator groups in series, for example, within the allowable range of pressure drop, and adds a filter behind the cyclone separator group to meet the separation requirement and improve the carbon conversion rate. The filter can be a metal sintered filter or a ceramic filter. The filter can be a candle filter, or a plurality of filter elements can be selected to be connected in parallel to form a filter group to meet the separation requirement.
In the present invention, the fluidization index in the fluidized-bed reactor 2 is in the range of 0.01 to 5, preferably in the range of 0.02 to 0.1. The fluidization index is determined by the following equation:
the fluidization index is controlled within the optimal range (0.02-0.1) by adjusting the feeding mode of the coal as fired, the distributor of the gasifying agent, the temperature in the fluidized bed reactor and the components (such as proper flow guide baffles) in the fluidized bed reactor, so that the mass and heat transfer efficiency in the fluidized bed reactor is very high, and the high-efficiency conversion of the pulverized coal is facilitated. Because the fluidized bed reactor 2 is internally provided with a plurality of reactions such as pyrolysis, gasification, methanation and the like. The conditions for optimization of these three main reactions are also different, and a finer preferred fluidization index is proposed according to their respective reaction characteristics. Preferably, the fluidization index of the gasification zone is less than or equal to the fluidization index of the methanation zone.
In the invention, the fluidization form in the fluidized bed reactor 2 is a bubbling fluidized bed or a turbulent fluidized bed, and the gas phase velocity in the bed is controlled to be 0.1-2 m/s. The temperature of any point in the fluidized bed reactor 2 is not lower than 500 ℃, and the pressure of any point is not lower than 1 MPa.
The reaction device and the method of the invention are not only used in the rich methane production process, but also can be used in processes of preparing fuel gas by using pulverized coal, preparing hydrogen by using pulverized coal and the like.
Compared with the prior art, the technical scheme of the invention has the characteristics of good fluidization quality, high particle-to-gas and particle transfer contact efficiency, high carbon conversion rate, high gasification strength, high methane yield, stability, high efficiency and stable operation of the gasification furnace, ensures the high efficiency and stability of the reaction, improves the carbon conversion rate of the reactor outlet by 3 percent and the methane concentration by 6 percent, and obtains better technical effects.
Drawings
FIG. 1 is a schematic flow diagram of the process of the present invention;
in FIG. 1, 1 is a slag discharge device; 2 is a fluidized bed reactor; 3 is a settling section; 4 is a gas-solid separation device. A is ash residue; b is gasifying agent, selected from at least one in oxygen, air, liquid water, water vapor, carbon dioxide or hydrogen; c is catalyst and powdered coal raw material; d is circulating synthesis gas; e is crude gas.
The catalyst and the pulverized coal raw material C enter a fluidized bed reactor 2 to react with a gasifying agent B, the reacted crude coal gas E and the incompletely reacted semicoke are separated in a gas-solid separation device 4, and the separated crude coal gas E enters subsequent equipment to be purified and separated; the separated semicoke and the gasifying agent B enter the fluidized bed reactor 2 through the material returning device to be mixed and reacted, the reacted large granular slag and partial incompletely reacted carbon-containing particles enter the slag discharging device 1 through the valve control, the large granular slag is discharged from the bottom of the slag discharging device 1 after the particle classification, and other carbon-containing particles flow into the upper end of the fluidized bed reactor 2 through the upper part of the slag discharging device 1 to continuously participate in the reaction.
Detailed Description
The present invention will be further illustrated by the following examples, but is not limited to these examples.
[ example 1 ]
The reaction process is as follows: the catalyst and the pulverized coal raw material enter a fluidized bed reactor to react with a gasifying agent, the reacted crude gas and the incompletely reacted semicoke are separated in a gas-solid separation device, and the separated crude gas enters a subsequent device to be purified and separated; the separated semicoke and the gasifying agent enter the fluidized bed reactor through the material returning device to be mixed and reacted, the reacted large granular slag and partial incompletely reacted carbon-containing particles enter the slag discharging device through the valve control, the large granular slag is discharged from the bottom of the slag discharging device after the particle classification, and other carbon-containing particles flow into the upper end of the fluidized bed reactor through the upper part of the slag discharging device to continuously participate in the reaction.
The experiment selects inner Mongolia lignite, the inner Mongolia lignite is crushed to be less than 3mm to obtain pulverized coal, and the pulverized coal is mixed with 5% of potassium carbonate catalyst. The diameter ratio of the settling section to the fluidized bed reactor is 1.5, the height ratio of the fluidized bed reactor to the relative fluidization height is 5, the combination type of the gas-solid separation equipment is 2 groups of cyclone separators, the reaction temperature is 800 ℃, the reaction pressure is 2MPa, and the fluidization index is 0.01. The content of methane in the syngas at the gasifier outlet reached 20.3%, and the carbon conversion in the whole system was 91.5%, with the results detailed in table 1.
[ example 2 ]
The reaction process is as follows: the catalyst and the pulverized coal raw material enter a fluidized bed reactor to react with a gasifying agent, the reacted crude gas and the incompletely reacted semicoke are separated in a gas-solid separation device, and the separated crude gas enters a subsequent device to be purified and separated; the separated semicoke and the gasifying agent enter the fluidized bed reactor through the material returning device to be mixed and reacted, the reacted large granular slag and partial incompletely reacted carbon-containing particles enter the slag discharging device through the valve control, the large granular slag is discharged from the bottom of the slag discharging device after the particle classification, and other carbon-containing particles flow into the upper end of the fluidized bed reactor through the upper part of the slag discharging device to continuously participate in the reaction.
The experiment selects inner Mongolia lignite, the inner Mongolia lignite is crushed to be less than 3mm to obtain pulverized coal, and the pulverized coal is mixed with 5% of potassium carbonate catalyst. The diameter ratio of the settling section to the fluidized bed reactor is 3, the height ratio of the fluidized bed reactor to the relative fluidization height is 5, the combination type of the gas-solid separation equipment is 2 groups of cyclone separators, the reaction temperature is 800 ℃, the reaction pressure is 2MPa, and the fluidization index is 0.01. The content of methane in the syngas at the gasifier outlet reached 20.5%, and the carbon conversion in the whole system was 91.7%, with the results detailed in table 1.
[ example 3 ]
The reaction process is as follows: the catalyst and the pulverized coal raw material enter a fluidized bed reactor to react with a gasifying agent, the reacted crude gas and the incompletely reacted semicoke are separated in a gas-solid separation device, and the separated crude gas enters a subsequent device to be purified and separated; the separated semicoke and the gasifying agent enter the fluidized bed reactor through the material returning device to be mixed and reacted, the reacted large granular slag and partial incompletely reacted carbon-containing particles enter the slag discharging device through the valve control, the large granular slag is discharged from the bottom of the slag discharging device after the particle classification, and other carbon-containing particles flow into the upper end of the fluidized bed reactor through the upper part of the slag discharging device to continuously participate in the reaction.
The experiment selects inner Mongolia lignite, the inner Mongolia lignite is crushed to be less than 3mm to obtain pulverized coal, and the pulverized coal is mixed with 5% of potassium carbonate catalyst. The diameter ratio of the settling section to the fluidized bed reactor is 1.5, the height ratio of the fluidized bed reactor to the relative fluidization height is 6, the combination type of the gas-solid separation equipment is 2 groups of cyclone separators, the reaction temperature is 800 ℃, the reaction pressure is 2MPa, and the fluidization index is 0.01. The content of methane in the syngas at the gasifier outlet reached 20.7%, and the carbon conversion in the whole system was 92%, with the results detailed in table 1.
[ example 4 ]
The reaction process is as follows: the catalyst and the pulverized coal raw material enter a fluidized bed reactor to react with a gasifying agent, the reacted crude gas and the incompletely reacted semicoke are separated in a gas-solid separation device, and the separated crude gas enters a subsequent device to be purified and separated; the separated semicoke and the gasifying agent enter the fluidized bed reactor through the material returning device to be mixed and reacted, the reacted large granular slag and partial incompletely reacted carbon-containing particles enter the slag discharging device through the valve control, the large granular slag is discharged from the bottom of the slag discharging device after the particle classification, and other carbon-containing particles flow into the upper end of the fluidized bed reactor through the upper part of the slag discharging device to continuously participate in the reaction.
The experiment selects inner Mongolia lignite, the inner Mongolia lignite is crushed to be less than 3mm to obtain pulverized coal, and the pulverized coal is mixed with 5% of potassium carbonate catalyst. The diameter ratio of the settling section to the fluidized bed reactor is 1.5, the height ratio of the fluidized bed reactor to the relative fluidization height is 8, the combination type of the gas-solid separation equipment is 2 groups of cyclone separators, the reaction temperature is 800 ℃, the reaction pressure is 2MPa, and the fluidization index is 0.01. The content of methane in the syngas at the gasifier outlet reached 20.7%, and the carbon conversion in the whole system was 92%, with the results detailed in table 1.
[ example 5 ]
The reaction process is as follows: the catalyst and the pulverized coal raw material enter a fluidized bed reactor to react with a gasifying agent, the reacted crude gas and the incompletely reacted semicoke are separated in a gas-solid separation device, and the separated crude gas enters a subsequent device to be purified and separated; the separated semicoke and the gasifying agent enter the fluidized bed reactor through the material returning device to be mixed and reacted, the reacted large granular slag and partial incompletely reacted carbon-containing particles enter the slag discharging device through the valve control, the large granular slag is discharged from the bottom of the slag discharging device after the particle classification, and other carbon-containing particles flow into the upper end of the fluidized bed reactor through the upper part of the slag discharging device to continuously participate in the reaction.
The experiment selects inner Mongolia lignite, the inner Mongolia lignite is crushed to be less than 3mm to obtain pulverized coal, and the pulverized coal is mixed with 5% of potassium carbonate catalyst. The diameter ratio of the settling section to the fluidized bed reactor is 1.5, the height ratio of the fluidized bed reactor to the relative fluidization height is 5, the combination type of the gas-solid separation equipment is 3 groups of cyclone separators, the reaction temperature is 800 ℃, the reaction pressure is 2MPa, and the fluidization index is 0.01. The content of methane in the syngas at the gasifier outlet reached 21.3%, and the carbon conversion in the whole system was 93.2%, with the results detailed in table 1.
[ example 6 ]
The reaction process is as follows: the catalyst and the pulverized coal raw material enter a fluidized bed reactor to react with a gasifying agent, the reacted crude gas and the incompletely reacted semicoke are separated in a gas-solid separation device, and the separated crude gas enters a subsequent device to be purified and separated; the separated semicoke and the gasifying agent enter the fluidized bed reactor through the material returning device to be mixed and reacted, the reacted large granular slag and partial incompletely reacted carbon-containing particles enter the slag discharging device through the valve control, the large granular slag is discharged from the bottom of the slag discharging device after the particle classification, and other carbon-containing particles flow into the upper end of the fluidized bed reactor through the upper part of the slag discharging device to continuously participate in the reaction.
The experiment selects inner Mongolia lignite, the inner Mongolia lignite is crushed to be less than 3mm to obtain pulverized coal, and the pulverized coal is mixed with 5% of potassium carbonate catalyst. The diameter ratio of the settling section to the fluidized bed reactor is 1.5, the height ratio of the fluidized bed reactor to the relative fluidization height is 5, the combination type of the gas-solid separation equipment is that 2 groups of cyclone separators and filters are combined, the reaction temperature is 800 ℃, the reaction pressure is 2MPa, and the fluidization index is 0.01. The content of methane in the syngas at the gasifier outlet reached 23.4%, and the carbon conversion in the whole system was 97.8%, with the results detailed in table 1.
[ example 7 ]
The reaction process is as follows: the catalyst and the pulverized coal raw material enter a fluidized bed reactor to react with a gasifying agent, the reacted crude gas and the incompletely reacted semicoke are separated in a gas-solid separation device, and the separated crude gas enters a subsequent device to be purified and separated; the separated semicoke and the gasifying agent enter the fluidized bed reactor through the material returning device to be mixed and reacted, the reacted large granular slag and partial incompletely reacted carbon-containing particles enter the slag discharging device through the valve control, the large granular slag is discharged from the bottom of the slag discharging device after the particle classification, and other carbon-containing particles flow into the upper end of the fluidized bed reactor through the upper part of the slag discharging device to continuously participate in the reaction.
The experiment selects inner Mongolia lignite, the inner Mongolia lignite is crushed to be less than 3mm to obtain pulverized coal, and the pulverized coal is mixed with 5% of potassium carbonate catalyst. The diameter ratio of the settling section to the fluidized bed reactor is 1.5, the height ratio of the fluidized bed reactor to the relative fluidization height is 5, the combination type of the gas-solid separation equipment is 2 groups of cyclone separators, the reaction temperature is 800 ℃, the reaction pressure is 2MPa, and the fluidization index is 0.02. The content of methane in the syngas at the gasifier outlet reached 25.6%, and the carbon conversion in the whole system was 91.8%, with the results detailed in table 1.
[ example 8 ]
The reaction process is as follows: the catalyst and the pulverized coal raw material enter a fluidized bed reactor to react with a gasifying agent, the reacted crude gas and the incompletely reacted semicoke are separated in a gas-solid separation device, and the separated crude gas enters a subsequent device to be purified and separated; the separated semicoke and the gasifying agent enter the fluidized bed reactor through the material returning device to be mixed and reacted, the reacted large granular slag and partial incompletely reacted carbon-containing particles enter the slag discharging device through the valve control, the large granular slag is discharged from the bottom of the slag discharging device after the particle classification, and other carbon-containing particles flow into the upper end of the fluidized bed reactor through the upper part of the slag discharging device to continuously participate in the reaction.
The experiment selects inner Mongolia lignite, the inner Mongolia lignite is crushed to be less than 3mm to obtain pulverized coal, and the pulverized coal is mixed with 5% of potassium carbonate catalyst. The diameter ratio of the settling section to the fluidized bed reactor is 1.5, the height ratio of the fluidized bed reactor to the relative fluidization height is 5, the combination type of the gas-solid separation equipment is 2 groups of cyclone separators, the reaction temperature is 800 ℃, the reaction pressure is 2MPa, and the fluidization index is 0.04. The content of methane in the syngas at the gasifier outlet reached 25.5%, and the carbon conversion in the whole system was 92.3%, with the results detailed in table 1.
[ example 9 ]
The reaction process is as follows: the catalyst and the pulverized coal raw material enter a fluidized bed reactor to react with a gasifying agent, the reacted crude gas and the incompletely reacted semicoke are separated in a gas-solid separation device, and the separated crude gas enters a subsequent device to be purified and separated; the separated semicoke and the gasifying agent enter the fluidized bed reactor through the material returning device to be mixed and reacted, the reacted large granular slag and partial incompletely reacted carbon-containing particles enter the slag discharging device through the valve control, the large granular slag is discharged from the bottom of the slag discharging device after the particle classification, and other carbon-containing particles flow into the upper end of the fluidized bed reactor through the upper part of the slag discharging device to continuously participate in the reaction.
The experiment selects inner Mongolia lignite, the inner Mongolia lignite is crushed to be less than 3mm to obtain pulverized coal, and the pulverized coal is mixed with 5% of potassium carbonate catalyst. The diameter ratio of the settling section to the fluidized bed reactor is 1.5, the height ratio of the fluidized bed reactor to the relative fluidization height is 5, the combination type of the gas-solid separation equipment is 2 groups of cyclone separators, the reaction temperature is 800 ℃, the reaction pressure is 2MPa, and the fluidization index is 0.1. The content of methane in the syngas at the gasifier outlet reached 25.1%, the carbon conversion in the whole system was 93.2%, and the results are detailed in table 2.
[ COMPARATIVE EXAMPLE 1 ]
The reaction process is as follows: the catalyst and the pulverized coal raw material enter a fluidized bed reactor to react with a gasifying agent, the reacted crude gas and the incompletely reacted semicoke are separated in a gas-solid separation device, and the separated crude gas enters a subsequent device to be purified and separated; the separated semicoke and the gasifying agent enter the fluidized bed reactor through the material returning device to be mixed and reacted, the reacted large granular slag and partial incompletely reacted carbon-containing particles enter the slag discharging device through the valve control, the large granular slag is discharged from the bottom of the slag discharging device after the particle classification, and other carbon-containing particles flow into the upper end of the fluidized bed reactor through the upper part of the slag discharging device to continuously participate in the reaction.
The experiment selects inner Mongolia lignite, the inner Mongolia lignite is crushed to be less than 3mm to obtain pulverized coal, and the pulverized coal is mixed with 5% of potassium carbonate catalyst. The diameter ratio of the settling section to the fluidized bed reactor is 1.1, the height ratio of the fluidized bed reactor to the relative fluidization height is 5, the combination type of the gas-solid separation equipment is 2 groups of cyclone separators, the reaction temperature is 800 ℃, the reaction pressure is 2MPa, and the fluidization index is 0.01. The content of methane in the syngas at the gasifier outlet reached 20.1%, and the carbon conversion in the whole system was 90.8%, with the results detailed in table 2.
[ COMPARATIVE EXAMPLE 2 ]
The reaction process is as follows: the catalyst and the pulverized coal raw material enter a fluidized bed reactor to react with a gasifying agent, the reacted crude gas and the incompletely reacted semicoke are separated in a gas-solid separation device, and the separated crude gas enters a subsequent device to be purified and separated; the separated semicoke and the gasifying agent enter the fluidized bed reactor through the material returning device to be mixed and reacted, the reacted large granular slag and partial incompletely reacted carbon-containing particles enter the slag discharging device through the valve control, the large granular slag is discharged from the bottom of the slag discharging device after the particle classification, and other carbon-containing particles flow into the upper end of the fluidized bed reactor through the upper part of the slag discharging device to continuously participate in the reaction.
The experiment selects inner Mongolia lignite, the inner Mongolia lignite is crushed to be less than 3mm to obtain pulverized coal, and the pulverized coal is mixed with 5% of potassium carbonate catalyst. The diameter ratio of the settling section to the fluidized bed reactor is 1.5, the height ratio of the fluidized bed reactor to the relative fluidization height is 3, the combination type of the gas-solid separation equipment is 2 groups of cyclone separators, the reaction temperature is 800 ℃, the reaction pressure is 2MPa, and the fluidization index is 0.01. The content of methane in the syngas at the gasifier outlet reached 19.5%, and the carbon conversion in the whole system was 88.9%, with the results detailed in table 2.
[ COMPARATIVE EXAMPLE 3 ]
The reaction process is as follows: the catalyst and the pulverized coal raw material enter a fluidized bed reactor to react with a gasifying agent, the reacted crude gas and the incompletely reacted semicoke are separated in a gas-solid separation device, and the separated crude gas enters a subsequent device to be purified and separated; the separated semicoke and the gasifying agent enter the fluidized bed reactor through the material returning device to be mixed and reacted, the reacted large granular slag and partial incompletely reacted carbon-containing particles enter the slag discharging device through the valve control, the large granular slag is discharged from the bottom of the slag discharging device after the particle classification, and other carbon-containing particles flow into the upper end of the fluidized bed reactor through the upper part of the slag discharging device to continuously participate in the reaction.
The experiment selects inner Mongolia lignite, the inner Mongolia lignite is crushed to be less than 3mm to obtain pulverized coal, and the pulverized coal is mixed with 5% of potassium carbonate catalyst. The diameter ratio of the settling section to the fluidized bed reactor is 1.5, the height ratio of the fluidized bed reactor to the relative fluidization height is 5, the combination type of the gas-solid separation equipment is 1 group of cyclone separators, the reaction temperature is 800 ℃, the reaction pressure is 2MPa, and the fluidization index is 0.01. The content of methane in the syngas at the gasifier outlet reached 17.5%, and the carbon conversion in the whole system was 82.4%, with the results detailed in table 2.
[ COMPARATIVE EXAMPLE 4 ]
The reaction process is as follows: the catalyst and the pulverized coal raw material enter a fluidized bed reactor to react with a gasifying agent, the reacted crude gas and the incompletely reacted semicoke are separated in a gas-solid separation device, and the separated crude gas enters a subsequent device to be purified and separated; the separated semicoke and the gasifying agent enter the fluidized bed reactor through the material returning device to be mixed and reacted, the reacted large granular slag and partial incompletely reacted carbon-containing particles enter the slag discharging device through the valve control, the large granular slag is discharged from the bottom of the slag discharging device after the particle classification, and other carbon-containing particles flow into the upper end of the fluidized bed reactor through the upper part of the slag discharging device to continuously participate in the reaction.
The experiment selects inner Mongolia lignite, the inner Mongolia lignite is crushed to be less than 3mm to obtain pulverized coal, and the pulverized coal is mixed with 5% of potassium carbonate catalyst. The diameter ratio of the settling section to the fluidized bed reactor is 1.5, the height ratio of the fluidized bed reactor to the relative fluidization height is 5, the combination type of the gas-solid separation equipment is 2 groups of cyclone separators, the reaction temperature is 800 ℃, the reaction pressure is 2MPa, and the fluidization index is 0.005. The content of methane in the syngas at the gasifier outlet reached 18.3%, and the carbon conversion in the whole system was 90.8%, with the results detailed in table 1.
[ COMPARATIVE EXAMPLE 4 ]
Adopting a new Olympic group PDU gasification reaction device, adopting lignite as a raw material, adding 10% potassium carbonate as a catalyst, wherein the linear speed is 1m/s, the operating temperature is 800 ℃, the methane content in an outlet gas component obtained by gasification is 14%, but the carbon conversion rate is 90%, and the result is detailed in Table 1.
TABLE 1
TABLE 2
Wherein,
Claims (6)
1. a method for fluidizing coal and gas includes the following steps:
(a) the catalyst and the pulverized coal raw material (C) enter a fluidized bed reactor (2) to react with a gasifying agent (B), the reacted crude gas (E) and the incompletely reacted semicoke are separated in a gas-solid separation device (4), and the separated crude gas (E) enters a subsequent device to be purified and separated;
(b) the separated semicoke and the gasifying agent (B) enter the fluidized bed reactor (2) through a material returning device to be mixed and reacted, the reacted large granular slag and part of incompletely reacted carbon-containing particles enter the slag discharging device (1) through valve control, the large granular slag is discharged from the bottom of the slag discharging device (1) after particle classification, and other carbon-containing particles flow into the upper end of the fluidized bed reactor (2) through the upper part of the slag discharging device (1) to continuously participate in the reaction;
the height of the fluidized bed reactor (2) is greater than 6 times the relative fluidization height:
the apparent linear velocity of the gas is 0.1-2 m/s;
the fluidization index in the fluidized bed reactor (2) is in the range of 0.02-0.1, the fluidization index is,
the main equipment of the coal fluidized gasification device adopted by the method comprises: the device comprises a fluidized bed reactor (2), a settling section (3), gas-solid separation equipment (4) and a slag discharging device (1), wherein the upper end of the fluidized bed reactor (2) is communicated with the bottom of the settling section (3) after being expanded in diameter, the settling section (3) is communicated with the gas-solid separation equipment (4), the bottom of the gas-solid separation equipment (4) is communicated with the fluidized bed reactor (2), and the upper end of the slag discharging device (1) is communicated with the bottom of the fluidized bed reactor (2);
the diameter of the settling section (3) is 1.5 times larger than that of the fluidized bed reactor (2).
2. The method of fluidizing coal according to claim 1, wherein said gasifying agent is selected from at least one of oxygen, air, liquid water, steam, carbon dioxide, or hydrogen.
3. The coal fluidization gasification process according to claim 1, characterized in that said catalyst is selected from at least one of the group consisting of alkali metals, alkaline earth metals, transition metals; the catalyst is loaded on the carbon-containing raw material in an impregnation method, a dry mixing method or an ion exchange method; the loading capacity of the catalyst accounts for 0.1-20% of the mass of the raw coal.
4. The coal fluidization gasification method according to claim 1, characterized in that the temperature at any point in the fluidized bed reactor (2) is not lower than 500 ℃ and the pressure at any point is not lower than 1 MPa.
5. The coal fluidization gasification process according to claim 1, characterized in that the gas-solid separation device (4) is composed of at least 2 sets of serial cyclones or at least 2 sets of serial cyclones and filters, and the gas-solid separation device (4) is arranged inside or outside the settling section (3).
6. The coal fluidization gasification method according to claim 1, characterized in that the fluidized-bed reactor (2) comprises a pyrolysis zone, a syngas generation zone and a methane generation zone inside, and the three zones are arranged in sequence.
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