CN110408438B - Process and device for biomass gasification by enhancing molten salt decoking through nickel-based catalyst - Google Patents
Process and device for biomass gasification by enhancing molten salt decoking through nickel-based catalyst Download PDFInfo
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- CN110408438B CN110408438B CN201910805743.9A CN201910805743A CN110408438B CN 110408438 B CN110408438 B CN 110408438B CN 201910805743 A CN201910805743 A CN 201910805743A CN 110408438 B CN110408438 B CN 110408438B
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- gas
- decoking
- biomass
- molten salt
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- 238000002309 gasification Methods 0.000 title claims abstract description 223
- 238000005235 decoking Methods 0.000 title claims abstract description 128
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 239000002028 Biomass Substances 0.000 title claims abstract description 83
- 150000003839 salts Chemical class 0.000 title claims abstract description 82
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 19
- 230000002708 enhancing effect Effects 0.000 title claims abstract description 17
- 239000007789 gas Substances 0.000 claims abstract description 176
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 45
- 239000002245 particle Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000002407 reforming Methods 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 230000008016 vaporization Effects 0.000 claims description 30
- 239000000047 product Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000003860 storage Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 229910000831 Steel Inorganic materials 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 239000010959 steel Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 230000002572 peristaltic effect Effects 0.000 claims description 8
- 238000009834 vaporization Methods 0.000 claims description 8
- 239000012263 liquid product Substances 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000010902 straw Substances 0.000 claims description 6
- 239000002023 wood Substances 0.000 claims description 5
- -1 corncobs Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 230000005496 eutectics Effects 0.000 claims description 3
- 239000010903 husk Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 230000002093 peripheral effect Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000008878 coupling Effects 0.000 abstract description 3
- 238000010168 coupling process Methods 0.000 abstract description 3
- 238000005859 coupling reaction Methods 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000549548 Fraxinus uhdei Species 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a process and a device for biomass gasification by enhancing molten salt decoking through a nickel-based catalyst, wherein the process of biomass gasification comprises the following steps of: volatile matters generated by the reaction of biomass and gasifying agent are blown into molten salt through gas outlet holes on the upper side wall of the gasification cavity and gas channels between the outer side wall of the gasification cavity and the inner side wall of the bubble cap to carry out primary reforming decoking, the volatile matters escaping from the molten salt after primary reforming decoking flow into a nickel-based catalyst particle bed layer to carry out secondary reforming decoking, and after volatile matters subjected to secondary decoking enter a condenser to remove condensable gas (namely tar and redundant steam), hydrogen-rich synthetic gas is collected in a gas collecting bag. The device disclosed by the invention has good adaptability to biomass raw materials, and can effectively solve the problem of tar byproducts generated in the biomass gasification process and remarkably improve the energy utilization rate in a gasification system through biomass gasification and coupling of a nickel-based catalyst and molten salt multi-stage decoking.
Description
Technical Field
The invention relates to the field of energy conversion, in particular to a process and a device for biomass gasification by enhancing molten salt decoking through a nickel-based catalyst.
Background
Energy shortage and environmental pollution have become important issues facing human survival and development. The biomass pyrolysis gasification hydrocarbon gas fuel with the characteristics of low pollution, renewable, abundant resources, wide distribution and the like has become one of the hot spots for research in the energy field in recent years.
In the biomass pyrolysis gasification process, the design of the gasification furnace is important. The fixed bed gasifier is popularized and applied in the field of pyrolysis gasification, and the fixed bed gasifier (such as technologies disclosed in patents ZL96228197.2, ZL98243726.9, ZL201620710566.8, ZL201620638201.9 and the like) is characterized in that raw materials are not required to be pretreated, the equipment structure is simple and compact, the ash content in fuel gas is low, but the content of tar in produced fuel gas is higher, so that the gasification efficiency of biomass is lower, and meanwhile, equipment pipelines can be blocked. Tar removal has been one of the key and difficult problems in biomass gasification technology.
The yield of hydrogen-rich synthesis gas produced by conventional biomass steam gasification is still limited by thermodynamic equilibrium. In the experiment, the H/C in the product gas is lower and the tar content is higher. The production of tar reduces the yield of product gas and synthesis gas and increases the difficulty of cleaning the system pipeline. The patent ZL201610119442.7 and ZL201310077003.4 propose that molten salt is used for biomass pyrolysis, and the use of molten salt for biomass gasification is also a very novel process strengthening technology, which can effectively catalyze the reforming and conversion of tar in the gasification process and improve the gasification efficiency of biomass.
The nickel-based catalyst is gasified in biomass, cracked tar and CH 4 The catalyst has good catalytic promotion effect on the generation of hydrogen in various processes such as reforming.
How to realize the coupling of biomass gasification and decoking, designing a novel gasification furnace to solve the problem of tar in the biomass gasification process is one of the problems to be solved in the research of biomass gasification.
Disclosure of Invention
Aiming at the problems existing in the prior gasification technology, the invention aims to provide a process and a device for gasifying biomass by enhancing molten salt decoking by a nickel-based catalyst.
The biomass gasification device for enhancing molten salt decoking by using the nickel-based catalyst is characterized in that: the gasification decoking device comprises a gasification agent generating device, a biomass feeding device, a product collecting device, a gasification decoking reactor and a heating furnace sleeved on the outer side of the gasification decoking reactor for heating, wherein the gasification decoking reactor is connected with the product collecting device through a gas product outlet at the top through a pipeline, a gasification cavity with an upper opening is fixedly arranged on the bottom wall inside the gasification decoking reactor, molten salt is contained in an annular space between the gasification cavity and the gasification decoking reactor, a bubble cap is arranged on the outer side of the gasification cavity, and the upper opening of the gasification cavity is fixedly connected with the inner wall at the top of the bubble cap; the outer side of the upper part of the bubble cap is fixedly provided with a concave tray component for placing a nickel-based catalyst, and a nickel-based catalyst particle bed layer is placed on the concave tray component; the upper side wall of the gasification cavity is provided with a plurality of air outlet holes with equal height, the air outlet holes are uniformly distributed on the upper side wall of the gasification cavity in a circumferential direction, the air outlet holes and the concave tray component are positioned above the liquid level of the molten salt, and the lower end of the bubble cap is immersed in the molten salt; the gas outlet of the gasifying agent generating device and the discharge port of the biomass feeding device are both communicated with the inner space of the gasification cavity, volatile matters generated by gasifying reaction of gasifying agent and biomass in the gasification cavity flow out from the gas outlet, are blown into molten salt through a gas channel between the outer wall of the gasification cavity and the inner wall of the bubble cap, then flow through the nickel-based catalyst particle bed layer on the concave tray component, and finally flow out from a gas product outlet at the top of the gasification decoking reactor.
The biomass gasification device for enhancing molten salt decoking by using the nickel-based catalyst is characterized in that: the concave tray component comprises a tray plate fixedly arranged on the outer side of the upper part of the bubble cover and an annular cavity wall fixedly arranged at the peripheral edge of the upper surface of the tray plate, the outer side wall of the annular cavity wall is closely contacted with the inner wall of the gasification decoking reactor in a matched manner, a plurality of sieve holes for gas circulation are formed in the tray plate, a nickel-based catalyst particle bed layer is filled in a space between the concave tray component and the side surface of the upper part of the bubble cover, and the particle size of nickel-based catalyst particles is larger than the aperture of the sieve holes; the gas escaping from the molten salt flows into the nickel-based catalyst particle bed layer through the sieve pores and finally flows out of a gas product outlet at the top of the gasification decoking reactor.
The biomass gasification device for enhancing molten salt decoking by using the nickel-based catalyst is characterized in that: at least 3 gas baffles are arranged at intervals from bottom to top on the outer side of the bubble cap, the gas baffles are immersed in molten salt, the outer periphery of each gas baffle is tightly contacted with the inner wall of the gasification decoking reactor in a matched mode, gas passage ports for gas to flow are formed in each gas baffle, and the gas passage ports on two adjacent gas baffles are staggered in the vertical direction.
The biomass gasification device for enhancing molten salt decoking by using the nickel-based catalyst is characterized in that: the product collecting device comprises a condenser, a liquid product storage tank, a wet gas flowmeter and a gas collecting bag, wherein the inlet of the condenser is connected with a gas product outlet at the top of the gasification decoking reactor through a pipeline, the liquid outlet of the condenser is connected with the liquid product storage tank through a pipeline, and the gas outlet of the condenser is connected with the gas collecting bag through the wet gas flowmeter through a pipeline.
The biomass gasification device for enhancing molten salt decoking by using the nickel-based catalyst is characterized in that: the gasifying agent generating device comprises a gas steel bottle, a water storage tank, a peristaltic pump and a vaporizing chamber, wherein the water storage tank is connected with a liquid inlet of the vaporizing chamber through a pipeline, an air outlet of the gas steel bottle is connected with a gas inlet of the vaporizing chamber through a pipeline, a gas outlet of the vaporizing chamber is communicated with the inner space of the vaporizing chamber, and water vapor obtained in the vaporizing chamber is carried by gas exhausted from the gas steel bottle into the inner space of the vaporizing chamber.
The biomass gasification device for enhancing molten salt decoking by using the nickel-based catalyst is characterized in that: the biomass feeding device comprises a feeding pipe with openings at the top end and the bottom end, the feeding pipe is fixedly arranged on the gasification decoking reactor, a first ball valve and a second ball valve are arranged on the feeding pipe from top to bottom at intervals, the second ball valve is arranged above the gasification decoking reactor, and the lower end of the feeding pipe stretches into the inner space of the gasification cavity.
The biomass gasification device for enhancing molten salt decoking by using the nickel-based catalyst is characterized in that: the gasification decoking reactor is also fixedly provided with a gasification agent air inlet pipe, the top of the gasification decoking reactor and the top of the bubble cap are provided with a pipeline jack for inserting the gasification agent air inlet pipe, a thermocouple jack for inserting a thermocouple and a feeding pipe jack for inserting a feeding pipe, the lower ends of the gasification agent air inlet pipe, the thermocouple and the feeding pipe are inserted into the inner space of the gasification cavity, the upper wiring end of the thermocouple is connected with a temperature display instrument, and the upper end of the gasification agent air inlet pipe is connected with an air outlet of the gasification agent generating device.
The biomass gasification device for enhancing molten salt decoking by using the nickel-based catalyst is characterized in that: the bottom of the gasification cavity is of a conical bottom structure, and the bottommost part of the gasification cavity is communicated with a spiral ash discharging pipe, so that ash solids generated by the reaction of biomass and gasifying agent easily slide into the spiral ash discharging pipe along the inclined plane of the bottom wall inside the gasification cavity and are discharged through the spiral ash discharging pipe.
The biomass gasification process for enhancing molten salt decoking by using the nickel-based catalyst is characterized by comprising the following steps of:
1) Heating the gasification decoking reactor and the vaporization chamber respectively;
2) The deionized water is conveyed into a vaporization chamber through a peristaltic pump to be vaporized to generate vapor, air discharged from a gas steel cylinder is conveyed into the vaporization chamber to be mixed with the vapor to form a gasifying agent, the gasifying agent enters a gasification cavity of the gasification decoking reactor, meanwhile, granular biomass is conveyed into the gasification cavity of the gasification decoking reactor through a feeding pipe, and the gasifying agent and the biomass are subjected to gasification reaction in the gasification cavity of the gasification decoking reactor to generate volatile gas containing condensable tar and ash solids;
3) Volatile gas containing condensable tar flowing out of a gasification cavity of the gasification decoking reactor is blown into molten salt through a gas outlet hole on the upper side wall of the gasification cavity and a gas channel between the outer wall of the gasification cavity and the inner wall of a bubble cap to carry out primary reforming decoking, and escapes from the molten salt through a gas channel hole on a gas baffle plate on the outer side of the side part of the bubble cap, and the gas escaping from the molten salt flows into a nickel-based catalyst particle bed layer through a sieve mesh on a tray plate of a concave tray member to carry out secondary reforming decoking, and after the gas subjected to secondary decoking enters a condenser to remove the condensable gas, hydrogen-rich synthetic gas is collected in a gas collecting bag.
The biomass gasification process for enhancing molten salt decoking by using the nickel-based catalyst is characterized by comprising the following steps of: the biomass is at least one of wood chips, straws, corncobs, husks and straws, and the shape of biomass particles is sheet, spherical or columnar; the gasification reaction temperature in the gasification cavity of the gasification decoking reactor is 720-780 ℃, and the nickel-based catalyst consists of an alumina carrier and Ni metal loaded on the alumina carrier. The molten salt is a eutectic of lithium carbonate, sodium carbonate and potassium carbonate, and the mass ratio of the lithium carbonate to the sodium carbonate to the potassium carbonate is 30-35:30-35:32-38.
The beneficial effects of the invention are as follows: firstly, the biomass raw material is subjected to pressing shaping treatment before gasification, so that the unit treatment capacity of equipment is effectively improved, and the biomass after pressing shaping can be effectively prevented from being brought into a molten salt layer by carrier gas, so that the long-term recycling of molten salt is facilitated; secondly, nickel-based catalyst and molten salt are used as decoking catalyst, so that reforming conversion of tar can be effectively promoted, and yield of hydrogen-rich synthetic gas is improved; thirdly, a plurality of layers of gas baffles are arranged in the fused salt catalytic decoking link, so that the residence time of volatile gas in a fused salt layer is effectively prolonged, and the reforming and conversion of the volatile gas are facilitated; fourth, the device provided by the invention has good adaptability to biomass raw materials, effectively couples biomass gasification and nickel-based catalyst with molten salt multi-stage decoking, simplifies experimental devices, can effectively solve the problem of tar byproducts generated in the biomass gasification process, can store energy in a molten salt layer in a gasification decoking reactor, and also remarkably improves the energy utilization rate in a gasification system.
Drawings
FIG. 1 is a schematic diagram of a biomass gasification device for nickel-based catalyst enhanced molten salt decoking of the present invention;
FIG. 2 is a schematic structural view of the gasification decoking reactor of the present invention;
FIG. 3 is a schematic cross-sectional view of the blister of FIG. 2;
FIG. 4 is a top view of a first gas baffle outside the blister of FIG. 3;
FIG. 5 is a top view of a second gas baffle outside the blister of FIG. 3;
FIG. 6 is a top view of the attachment structure of the blister to its outer concave tray member;
FIG. 7 is a schematic view of the flow path of volatile gases containing condensable tar in gasification decoking reactor 5 outside the gasification chamber;
in the figure: 1-gas cylinder, 2-water storage tank, 3-peristaltic pump, 4-vaporization chamber, 5-gasification decoking reactor, 6-heating furnace, 7-condenser, 8-liquid product storage tank, 9-wet gas flowmeter, 10-gas collecting bag, 501-feeding pipe, 502-gasifying agent inlet pipe, 503-thermocouple, 504-gas product outlet, 505-bubble cap, 506-nickel-based catalyst particle bed, 507-molten salt, 508-spiral ash outlet pipe, 505-1-first gas baffle, 505-2-second gas baffle, 505-3-third gas baffle, 505-4-concave tray member, 505-5-pipeline jack, 505-6-feeding pipe jack, 505-7-thermocouple jack, 505-12-gas passage port, 504-11-sieve mesh, 11-gas outlet.
Detailed Description
The invention will be further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
Examples: comparing FIGS. 1 to 7
The utility model provides a nickel-based catalyst reinforces living beings gasification device of fused salt decoking, includes gasification agent generating device, living beings feed arrangement, product collection device, gasifies decoking reactor 5 and the cover is located the heating furnace 6 that is used for heating in the outside of gasifing decoking reactor 5, gasifies decoking reactor 5 and is connected by the pipeline with product collection device through the gas product export 504 at top.
The gasification decoking reactor 5 is fixed to be provided with upper portion open-ended cylindrical gasification chamber in the inside diapire, the upper portion lateral wall of gasification chamber is equipped with a plurality of ventholes 11 of equi-height, and ventholes 11 are evenly distributed in the annular at the upper portion lateral wall of gasification chamber. Referring to fig. 2, the gas outlet holes 11 are located above the liquid surface of the molten salt 507. Molten salt 507 is contained in an annular space between the gasification cavity and the gasification decoking reactor 5, a bubble cap 505 is arranged on the outer side of the gasification cavity, and the upper opening of the gasification cavity is fixedly connected with the inner wall of the top of the bubble cap 505 (the upper opening of the gasification cavity is attached to the inner wall of the top of the bubble cap 505, and then the upper opening of the gasification cavity and the inner wall of the top of the bubble cap 505 are fixedly connected through a nailing screw). Referring to fig. 2, the lower end of the blister 505 is submerged inside the molten salt 507.
The product collecting device comprises a condenser 7, a liquid product storage tank 8, a wet gas flowmeter 9 and a gas collecting bag 10, wherein an air inlet of the condenser 7 is connected with a gas product outlet 504 at the top of the gasification decoking reactor 5 through a pipeline, a liquid outlet of the condenser 7 is connected with the liquid product storage tank 8 through a pipeline, and a gas outlet of the condenser 7 is connected with the gas collecting bag 10 through the wet gas flowmeter 9 through a pipeline.
The gasifying agent generating device comprises a gas steel bottle 1, a water storage tank 2, a peristaltic pump 3 and a vaporizing chamber 4, wherein the water storage tank 2 is connected with a liquid inlet of the vaporizing chamber 4 through the peristaltic pump 3 by a pipeline, an air outlet of the gas steel bottle 1 is connected with a gas inlet of the vaporizing chamber 4 by a pipeline, a gas outlet of the vaporizing chamber 4 is communicated with an inner space of a vaporizing cavity, and vapor obtained in the vaporizing chamber 4 is carried by a gas medium discharged by the gas steel bottle 1 into the inner space of the vaporizing cavity.
The biomass feeding device comprises a feeding pipe 501 with openings at the top end and the bottom end, the feeding pipe 501 is fixedly arranged on a gasification decoking reactor 5, a first ball valve and a second ball valve are arranged on the feeding pipe 501 from top to bottom at intervals, the second ball valve is arranged above the gasification decoking reactor 5, and the lower end of the feeding pipe 501 extends into the inner space of a gasification cavity. The first ball valve and the second ball valve are arranged on the feeding pipe 501 from top to bottom at intervals, and the aim of the first ball valve and the second ball valve is that: the top end opening of the feed pipe 501 is kept in a state of not communicating with the gas in the inner space of the gasification chamber.
The upper outer side of the bubble cap 505 is fixedly provided with a concave tray member 505-4 for placing a nickel-based catalyst, the concave tray member 505-4 comprises a tray plate fixedly arranged on the upper outer side of the bubble cap 505 and an annular cavity wall fixedly arranged at the peripheral edge of the upper surface of the tray plate, the outer side wall of the annular cavity wall is tightly contacted with the inner side wall of the gasification decoking reactor 5 in a matched mode, a plurality of sieve holes 504-11 for gas circulation are formed in the tray plate, a nickel-based catalyst particle bed 506 is placed on the concave tray member 505-4, and the particle size of nickel-based catalyst particles is larger than the aperture of the sieve holes 504-11. The concave tray member 505-4 is located above the level of the molten salt 507.
At least 3 gas baffles are arranged at intervals from bottom to top on the outer side of the side part of the bubble cap 505, the gas baffles are immersed in molten salt 507, the outer periphery of each gas baffle is tightly contacted with the inner side wall of the gasification decoking reactor 5 in a matched mode, gas passage ports 505-12 through which gas flows are formed in each gas baffle, and the gas passage ports 505-12 on two adjacent gas baffles are staggered in the vertical direction.
Referring to fig. 3 to 5, a first gas baffle 505-1, a second gas baffle 505-2 and a third gas baffle 505-3 are disposed at intervals from bottom to top on the outer side of the side portion of the blister 505, and the shapes and structures of the first gas baffle 505-1 and the third gas baffle 505-3 are the same. It can be seen that the first gas baffle 505-1, the second gas baffle 505-2, and the third gas baffle 505-3 are provided with 4 gas passage openings 505-12 arranged in a uniform circumferential distribution. Wherein the gas passage openings 505-12 on the first gas baffle 505-1 and the third gas baffle 505-3 are disposed close to the inner sidewall of the gasification decoking reactor 5, and the gas passage opening 505-12 on the second gas baffle 505-2 is disposed close to the outer sidewall of the bubble cap 505, so that the gas passage openings 505-12 on the first gas baffle 505-1, the second gas baffle 505-2 and the third gas baffle 505-3 are staggered in the vertical direction, which is beneficial for uniform dispersion of gas inside the molten salt. Referring to fig. 7, a schematic diagram of the flow path of volatile gas containing condensable tar generated in the gasification chamber of the gasification decoking reactor 5 in the gasification decoking reactor 5 outside the gasification chamber is shown in fig. 7, and it can be seen that the volatile gas is uniformly dispersed in the gasification decoking reactor 5 outside the gasification chamber.
Referring to fig. 1 and 6, a thermocouple 503 and a gasifying agent air inlet pipe 502 are also fixedly arranged on the gasifying and decoking reactor 5, a pipeline jack 505-5 for inserting the gasifying agent air inlet pipe 502, a thermocouple jack 505-7 for inserting the thermocouple 503 and a feeding pipe jack 505-6 for inserting the feeding pipe 501 are also arranged on the top of the gasifying and decoking reactor 5 and the top of the bubble cap 505, the lower ends of the gasifying agent air inlet pipe 502, the thermocouple 503 and the feeding pipe 501 are inserted into the inner space of the gasifying cavity, the upper wiring end of the thermocouple 503 is connected with a temperature display, and the upper end of the gasifying agent air inlet pipe 502 is connected with a gas outlet of the gasifying chamber 4.
In order to facilitate the discharge of ash solids generated by the reaction in the internal space of the gasification cavity (i.e. ash solids are not easy to deposit at the inner bottom of the gasification cavity), the bottom of the gasification cavity is a conical bottom, and the bottom of the gasification cavity is communicated with a spiral ash discharge pipe 508, so that ash solids generated by the reaction of biomass and gasifying agent easily slide into the spiral ash discharge pipe 508 along the inclined plane of the bottom wall of the gasification cavity and are discharged through the spiral ash discharge pipe 508. Referring to fig. 2, the inclined plane of the cross section of the bottom wall of the gasification chamber forms an angle of 30 ° with the horizontal plane.
In examples 2 to 3 below, the following steps are specific when biomass gasification treatment is performed by using the biomass gasification apparatus for enhancing molten salt decoking with the nickel-based catalyst of the present invention:
1) Heating the gasification decoking reactor 5 and the vaporization chamber 4 respectively;
2) The deionized water is conveyed into the vaporizing chamber 4 through the peristaltic pump 3 to be vaporized to generate water vapor, air discharged from the gas steel cylinder 1 is conveyed into the vaporizing chamber 4 to be mixed with the water vapor to form a gasifying agent, the gasifying agent enters into a gasification cavity of the gasification decoking reactor 5, meanwhile, granular biomass is conveyed into the gasification cavity of the gasification decoking reactor 5 through the feeding pipe 501, the gasifying agent and the biomass are subjected to gasification reaction in the gasification of the gasification decoking reactor 5 to generate volatile gas and ash solids, and the volatile gas contains condensable tar;
3) Volatile gas escaping from the gasification cavity of the gasification decoking reactor 5 is blown into the molten salt 507 through the gas outlet hole 11 at the upper side of the gasification cavity and a gas channel between the outer wall of the gasification cavity and the inner wall of the bubble cap 505 to carry out primary reforming decoking, and escapes from the molten salt 507 through the gas channel port 505-12 on the gas baffle plate at the outer side of the bubble cap 505, the gas escaping from the molten salt 507 flows into the nickel-based catalyst particle bed layer through the sieve holes 504-11 on the tray plate of the concave tray member 505-4 to carry out secondary reforming decoking, and the volatile gas after secondary decoking enters the condenser 7 to remove condensable gas (namely tar and redundant steam) to be collected in the gas collecting bag 10 to obtain hydrogen-rich synthetic gas.
Wherein the biomass is at least one of wood chips, straws, corncobs, husks and straws, and the shape of biomass particles is sheet, spherical or columnar; the gasification reaction temperature in the gasification cavity of the gasification decoking reactor 5 is 720-780 ℃, and the nickel-based catalyst consists of an alumina carrier and Ni metal loaded on the alumina carrier. The molten salt is a eutectic of lithium carbonate, sodium carbonate and potassium carbonate, and the mass ratio of the lithium carbonate to the sodium carbonate to the potassium carbonate is 32:33:35.
Example 1: the method is characterized in that the method takes massive fir wood chips as raw materials, takes 0.25 g/piece of compressed and shaped massive particles, the feeding mass ratio of water vapor to biomass is 1, the flow rate of air is 0.5L/min, adopts the structure of fig. 1 to carry out gasification reaction of biomass, but replaces a gasification decoking reactor 5 in fig. 1 with a gasification reaction kettle, molten salt and catalyst are not contained in the gasification reaction kettle, the biomass and gasifying agent carry out gasification reaction in the gasification reaction kettle at 750 ℃, and the product is mainly ash solid and volatile gas. The results of the examples are as follows: the tar yield was 3.7wt.% in the volatiles from biomass gasification.
Example 2: the gasification reaction of biomass is carried out by taking the blocky fir chips as raw materials, compressing and shaping blocky particles with the mass ratio of 0.25 g/piece, the feeding mass ratio of water vapor to biomass is 1, the flow rate of air is 0.5L/min, and the structure shown in fig. 1 is adopted, but only fused salt decoking is adopted in the gasification decoking reactor 5 in fig. 1, and no nickel-based catalyst is arranged in the gasification decoking reactor 5. The biomass and the gasifying agent are subjected to gasification reaction in a gasification cavity of the gasification decoking reactor 5 at 750 ℃, the products are mainly ash solids and volatile gas, the ash solids are discharged from a spiral ash outlet pipe 508 at the bottom of the gasification decoking reactor 5, the volatile gas and the gasifying agent are blown into molten salt to carry out decoking reaction, and the volatile and gasifying agent enter a condenser to remove condensable gas after decoking through the molten salt, so that the hydrogen-rich synthetic gas is obtained. The results of the examples are as follows: the tar yield was 0.4wt.% in the volatiles obtained from biomass gasification.
Example 3: takes the blocky fir wood chips as raw materials, takes 0.25 g/tablet compression shaped blocky particles, the feeding mass ratio of water vapor to biomass is 1, the flow rate of air is 0.5L/min, adopts the structure of figure 1 to carry out gasification reaction of biomass, and uses Ni/Al as the nickel-based catalyst 2 O 3 Wherein the loading of Ni was 15 wt%, the average particle diameter of the nickel-based catalyst particles was 3 mm, and the pore diameter of the mesh holes 504-11 on the tray plates of the concave tray member 505-4 was 2.4 mm. The adopted gasification decoking reactor is shown in fig. 2, molten salt and nickel-based catalyst are adopted for coupling decoking, biomass and gasifying agent are subjected to gasification reaction in a gasification cavity of the gasification decoking reactor 5 at 750 ℃, the product is mainly ash solids and volatile gas, the ash solids are discharged from a spiral ash outlet pipe 508 at the bottom of the gasification decoking reactor 5, the volatile gas and the gasifying agent are blown into the molten salt for decoking reaction, the volatile and the gasifying agent enter a nickel-based catalyst particle bed layer for re-reforming decoking after the molten salt decoking, and the volatile gas after secondary decoking enters a condenser for removing condensable gas, so that hydrogen-rich synthetic gas is obtained. The results of the examples are as follows: the tar yield is 0 in the volatile matters obtained by biomass gasification, namely the tar removal rate reaches 100 percent, so that the device has good decoking effect.
What has been described in this specification is merely an enumeration of possible forms of implementation for the inventive concept and may not be considered limiting of the scope of the present invention to the specific forms set forth in the examples.
Claims (8)
1. A biomass gasification device for enhancing molten salt decoking by a nickel-based catalyst is characterized in that: the gasification decoking device comprises a gasification agent generating device, a biomass feeding device, a product collecting device, a gasification decoking reactor (5) and a heating furnace (6) sleeved on the outer side of the gasification decoking reactor (5) for heating, wherein the gasification decoking reactor (5) is connected with the product collecting device through a pipeline through a gas product outlet (504) at the top, a gasification cavity with an upper opening is fixedly arranged on the bottom wall inside the gasification decoking reactor (5), molten salt (507) is contained in an annular space between the gasification cavity and the gasification decoking reactor (5), a bubble cap (505) is arranged on the outer side of the gasification cavity, and the upper opening of the gasification cavity is fixedly connected with the inner wall at the top of the bubble cap (505); the outer side of the upper part of the bubble cap (505) is fixedly provided with a concave tray component (505-4) for placing a nickel-based catalyst, and a nickel-based catalyst particle bed layer (506) is placed on the concave tray component (505-4); the upper side wall of the gasification cavity is provided with a plurality of air outlet holes (11) with equal height, the air outlet holes (11) are uniformly distributed on the upper side wall of the gasification cavity in a circumferential direction, the air outlet holes (11) and the concave tray component (505-4) are positioned above the liquid level of the molten salt (507), and the lower end of the bubble cap (505) is immersed in the molten salt (507);
the gas outlet of the gasifying agent generating device and the discharge port of the biomass feeding device are both communicated with the inner space of the gasification cavity, volatile matters generated by gasifying agent and biomass in the gasification cavity are discharged from the gas outlet (11), are blown into molten salt (507) through a gas channel between the outer wall of the gasification cavity and the inner wall of the bubble cap, then flow through a nickel-based catalyst particle bed layer on the concave tray member (505-4), and finally flow out from a gas product outlet (504) at the top of the gasification decoking reactor (5);
the concave tray component (505-4) comprises a tray plate fixedly arranged on the outer side of the upper part of the bubble cap (505) and an annular cavity wall fixedly arranged at the peripheral edge of the upper surface of the tray plate, the outer side wall of the annular cavity wall is tightly contacted with the inner wall of the gasification decoking reactor (5) in a matched mode, a plurality of sieve holes (504-11) for gas circulation are formed in the tray plate, a nickel-based catalyst particle bed layer is filled in a space between the concave tray component (505-4) and the side face of the upper part of the bubble cap (505), and the particle size of nickel-based catalyst particles is larger than the aperture of the sieve holes (504-11); the gas escaping from the molten salt (507) flows into the nickel-based catalyst particle bed layer through the sieve holes (504-11) and finally flows out from a gas product outlet (504) at the top of the gasification decoking reactor (5);
at least 3 gas baffles are arranged at intervals from bottom to top on the outer side of the bubble cap (505), the gas baffles are immersed in molten salt (507), the outer periphery of each gas baffle is tightly contacted with the inner wall of the gasification decoking reactor (5) in a matched mode, gas passage ports (505-12) for gas to flow are formed in each gas baffle, and the gas passage ports (505-12) on two adjacent gas baffles are staggered in the vertical direction.
2. The nickel-based catalyst-enhanced molten salt decoking biomass gasification device as claimed in claim 1, wherein: the product collecting device comprises a condenser (7), a liquid product storage tank (8), a wet gas flowmeter (9) and a gas collecting bag (10), wherein an inlet of the condenser (7) is connected with a gas product outlet (504) at the top of the gasification decoking reactor (5) through a pipeline, a liquid outlet of the condenser (7) is connected with the liquid product storage tank (8) through a pipeline, and a gas outlet of the condenser (7) is connected with the gas collecting bag (10) through the wet gas flowmeter (9) through a pipeline.
3. A nickel-based catalyst enhanced molten salt decoking biomass gasification device as defined in claim 2, wherein: the gasifying agent generating device comprises a gas steel bottle (1), a water storage tank (2), a peristaltic pump (3) and a vaporizing chamber (4), wherein the water storage tank (2) is connected with a liquid inlet of the vaporizing chamber (4) through the peristaltic pump (3) through a pipeline, an air outlet of the gas steel bottle (1) is connected with a gas inlet of the vaporizing chamber (4) through a pipeline, a gas outlet of the vaporizing chamber (4) is communicated with an inner space of a vaporizing cavity, and water vapor obtained in the vaporizing chamber (4) is carried into the inner space of the vaporizing cavity by gas discharged from the gas steel bottle (1).
4. A nickel-based catalyst enhanced molten salt decoking biomass gasification apparatus as defined in claim 3, wherein: the biomass feeding device comprises a feeding pipe (501) with openings at the top end and the bottom end, the feeding pipe (501) is fixedly arranged on a gasification decoking reactor (5), a first ball valve and a second ball valve are arranged on the feeding pipe (501) from top to bottom at intervals, the second ball valve is arranged above the gasification decoking reactor (5), and the lower end of the feeding pipe (501) extends into the inner space of the gasification cavity.
5. The nickel-based catalyst-enhanced molten salt decoking biomass gasification device as claimed in claim 4, wherein: the gasification decoking reactor (5) is further fixedly provided with a gasification agent air inlet pipe (502), pipeline jacks for inserting the gasification agent air inlet pipe (502), thermocouple jacks for inserting thermocouples (503) and feeding pipe jacks (505-6) for inserting the feeding pipes (501) are formed in the top of the gasification decoking reactor (5) and the top of the bubble cap (505), the lower ends of the gasification agent air inlet pipe (502), the thermocouples (503) and the feeding pipes (501) are inserted into the inner space of the gasification cavity, the upper connecting ends of the thermocouples (503) are connected with the temperature display, and the upper ends of the gasification agent air inlet pipes (502) are connected with the air outlets of the gasification agent generating device.
6. The nickel-based catalyst enhanced molten salt decoking biomass gasification device as claimed in claim 5, wherein: the bottom of the gasification cavity is of a conical bottom structure, and a spiral ash discharging pipe (508) is connected to the bottommost part of the gasification cavity, so that ash solids generated by the reaction of biomass and gasifying agent easily slide into the spiral ash discharging pipe (508) along the inclined plane of the bottom wall inside the gasification cavity and are discharged through the spiral ash discharging pipe (508).
7. A process for biomass gasification plant using a nickel-based catalyst enhanced molten salt decoking as defined in claim 6, characterized by comprising the following steps:
1) Heating the gasification decoking reactor (5) and the vaporization chamber (4) respectively;
2) The deionized water is conveyed into a vaporization chamber (4) through a peristaltic pump (3) to be vaporized to generate water vapor, air discharged from a gas steel cylinder (1) is conveyed into the vaporization chamber (4) to be mixed with the water vapor to form a gasifying agent, the gasifying agent enters a gasification cavity of a gasification decoking reactor (5), meanwhile, granular biomass is conveyed into the gasification cavity of the gasification decoking reactor (5) through a feeding pipe (501), and the gasifying agent and the biomass are subjected to gasification reaction in the gasification cavity of the gasification decoking reactor (5) to generate volatile gas and ash solids containing condensable tar;
3) Volatile gas containing condensable tar flowing out of a gasification cavity of the gasification decoking reactor (5) is blown into molten salt (507) through a gas outlet hole (11) on the upper side wall of the gasification cavity and a gas channel between the outer wall of the gasification cavity and the inner wall of a bubble cap (505), primary reforming decoking is carried out, the gas escapes from the molten salt (507) through a gas channel port (505-12) on a gas baffle plate on the outer side of the side part of the bubble cap (505), the gas escaping from the molten salt (507) flows into a nickel-based catalyst particle bed layer through a sieve mesh (504-11) on a tray plate of a concave tray member (505-4) to carry out secondary reforming decoking, and the gas after secondary decoking enters a condenser (7) to remove the condensable gas, and then the hydrogen-rich synthetic gas is collected in a gas collecting bag (10).
8. The process of claim 7, wherein: the biomass is at least one of wood chips, straws, corncobs, husks and straws, and the shape of biomass particles is sheet, spherical or columnar; the gasification reaction temperature in the gasification cavity of the gasification decoking reactor (5) is 720-780 ℃, and the nickel-based catalyst consists of an alumina carrier and Ni metal loaded on the alumina carrier; the molten salt is a eutectic of lithium carbonate, sodium carbonate and potassium carbonate, and the mass ratio of the lithium carbonate to the sodium carbonate to the potassium carbonate is 30-35:30-35:32-38.
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