CN110184094B - Method and device for removing tar in biomass pyrolysis gas by using molten salt - Google Patents
Method and device for removing tar in biomass pyrolysis gas by using molten salt Download PDFInfo
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- CN110184094B CN110184094B CN201910538502.2A CN201910538502A CN110184094B CN 110184094 B CN110184094 B CN 110184094B CN 201910538502 A CN201910538502 A CN 201910538502A CN 110184094 B CN110184094 B CN 110184094B
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- 150000003839 salts Chemical class 0.000 title claims abstract description 147
- 239000002028 Biomass Substances 0.000 title claims abstract description 54
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000002309 gasification Methods 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims description 163
- 238000005235 decoking Methods 0.000 claims description 28
- 239000010410 layer Substances 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 13
- 239000003546 flue gas Substances 0.000 claims description 13
- 239000011229 interlayer Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 238000005336 cracking Methods 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 238000005485 electric heating Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 239000010902 straw Substances 0.000 claims description 5
- 239000002154 agricultural waste Substances 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- -1 znCl 2 Chemical compound 0.000 claims description 2
- 238000004227 thermal cracking Methods 0.000 abstract 1
- 239000011269 tar Substances 0.000 description 67
- 239000003054 catalyst Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002641 tar oil Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 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
- 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
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
- C10K1/16—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids
-
- 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
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0916—Biomass
-
- 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
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0946—Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Industrial Gases (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method and a device for removing tar in biomass pyrolysis gas by using molten salt, wherein the device for removing tar in biomass pyrolysis gas by using the molten salt comprises a biomass gasification device, a molten salt bubble cap reactor containing the molten salt, an air outlet pipe and a heating and heat preserving device, wherein a bubble cap riser and a bubble cap are fixedly arranged on the bottom wall in the molten salt bubble cap reactor, the top end of the bubble cap riser is positioned above the molten salt liquid level, the bubble cap is arranged on the outer side of the bubble cap riser, a gap is arranged between the top end of the bubble cap riser and the inner wall of the top of the bubble cap, a plurality of exhaust tooth gaps with equal height are uniformly arranged at the lower part of the bubble cap along the circumference, the exhaust tooth gaps are positioned below the molten salt liquid level, and an air outlet of the biomass gasification device is communicated with the bubble cap riser. The invention replaces the conventional secondary thermal cracking by utilizing the advantages of high thermal conductivity, high specific heat capacity and high stability of the fused salt system, the bubble cap reactor greatly increases the reaction contact area, the fused salt layer can well catalyze and crack tar, the gas yield is increased, the heat value is improved, and the tar in the cracked gas is eliminated.
Description
Technical Field
The invention relates to the field of biomass gasification pyrolysis, and discloses a method and a device for removing tar in biomass pyrolysis gas by using molten salt.
Background
Energy and environmental problems have become a focus of attention today. The biomass gasification technology is widely utilized, the environmental pollution problem caused by straw burning and other phenomena can be greatly reduced, and simultaneously, gasification products can be used as high-quality fuel or chemical raw materials to realize resource utilization. However, a large amount of tar is inevitably produced in this process.
The tar contains hundreds of components, mainly benzene derivatives, has complex structure and toxicity, and has great harm to human health and environmental quality. Meanwhile, tar has larger viscosity and acidity, is easy to adhere to the pipeline and the hearth, causes pipeline blockage and can continuously corrode the pipeline and the furnace body, thereby shortening the service life.
Most of the existing tar treatment methods are secondary pyrolysis gasification methods, high-temperature atmosphere above 900 ℃ and different catalyst compositions are generally required, and the problems of poor service life of the catalyst and incomplete tar conversion limit the prospect of tar treatment technology. Thus, there is an urgent need for a tar processing apparatus with high conversion and lower cost.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method and a device for removing tar in biomass pyrolysis gas by using high-efficiency, flexible and low-cost molten salt.
A device of fused salt desorption living beings pyrolysis gas in tar, its characterized in that include biomass gasification device, inside contain fused salt bubble cap reactor of fused salt, set up outlet duct on fused salt bubble cap reactor and be used for carrying out the heating heat preservation device of heating to fused salt bubble cap reactor, the inside diapire of fused salt bubble cap reactor is fixed to be provided with bubble cap riser and bubble cap, bubble cap riser top is located above the fused salt liquid level, the bubble cap sets up in bubble cap riser outside and bubble cap riser top and bubble cap top inner wall between be equipped with the space, the bubble cap lower part sets up a plurality of exhaust tooth gaps of equi-height along circumference even interval, just exhaust tooth gap is located below the fused salt liquid level, biomass gasification device's outlet duct communicates with each other with the bubble cap riser, the inside and exhaust tooth gap bubble escape through bubble cap lower part of reentrant fused salt after the gas of biomass gasification device exhaust flows into the space between fused salt liquid level and the bubble cap through the bubble cap riser.
A device of fused salt desorption living beings pyrolysis gas in tar, its characterized in that still including setting up in the gas buffer tank of fused salt bubble cap reactor below, heating heat preservation device can carry out simultaneous heating to gas buffer tank and fused salt bubble cap reactor, bubble cap riser bottom stretches out from fused salt bubble cap reactor bottom and communicates with gas buffer tank top, be provided with tar gas intake pipe and be used for letting in O 2 or N 2's auxiliary intake pipe on the gas buffer tank, the gas buffer tank passes through tar gas intake pipe is connected with biomass gasification device's outlet duct.
The device for removing tar in biomass pyrolysis gas by using molten salt is characterized in that the heating and heat-preserving device comprises a heating jacket, a heat-preserving layer and an air heat-insulating layer, wherein the heating jacket, the heat-preserving layer and the air heat-insulating layer are sequentially sleeved on the outer side of the side part of a molten salt bubble cap reactor and the outer side of the side part of a gas buffer tank, so that the molten salt bubble cap reactor and the gas buffer tank are heated and preserved at the same time; and heat preservation layers are arranged at the top of the fused salt bubble cap reactor and the bottom of the gas buffer tank.
The device for removing tar in biomass pyrolysis gas by using molten salt is characterized by further comprising a first thermocouple and a second thermocouple, wherein the temperature measuring end of the first thermocouple stretches into molten salt in the molten salt bubble cap reactor, and the temperature measuring end of the second thermocouple stretches into the gas buffer tank.
The device for removing tar in biomass pyrolysis gas by using molten salt is characterized in that the bubble cap is of an inverted horn mouth-shaped structure, and the exhaust tooth slits are of a strip-shaped structure; the air outlet pipe on the fused salt bubble cap reactor is externally connected with a condensing device and a gas collecting device through pipelines.
The device for removing tar in biomass pyrolysis gas by using molten salt is characterized in that the heating jacket is an electric heating jacket or an interlayer sleeve, and a flue gas inlet and a flue gas outlet are arranged on the interlayer sleeve; one end of the tar gas inlet pipe is arranged on the inner side of the heating jacket and connected with the upper part of the gas buffer tank, and one end of the auxiliary gas inlet pipe is arranged on the inner side of the heating jacket and connected with the upper part of the gas buffer tank.
The method for removing tar in biomass pyrolysis gas by using molten salt is characterized by comprising the following steps of:
1) Starting a heating and heat preserving device to heat the fused salt bubble cap reactor to the reaction temperature, opening an auxiliary air inlet pipe to blow nitrogen, and ensuring that the gas buffer tank and the fused salt bubble cap reactor are kept in an oxygen-free atmosphere;
2) Closing an auxiliary air inlet pipe to stop introducing nitrogen, simultaneously gasifying and cracking biomass by a biomass gasification device, enabling tar gas obtained by gasifying and cracking to enter a gas buffer tank through a tar gas inlet pipe, then blowing the tar gas into molten salt in a bubble form through a bubble cap riser and a bubble cap to perform decoking reaction, and discharging reacted gas through an air outlet pipe;
3) When decoking reaction efficiency is reduced due to carbon deposition of molten salt in the molten salt bubble cap reactor, closing an tar gas inlet pipe, simultaneously opening an auxiliary gas inlet pipe to blow nitrogen, and switching gas introduced by the auxiliary gas inlet pipe to air or oxygen after purging the tar gas in the gas buffer tank and the molten salt bubble cap reactor completely so as to burn and remove carbon deposition in the molten salt;
4) And (3) repeating the operation processes of the steps 1) to 2) after the carbon deposition of the molten salt in the molten salt bubble reactor is removed, so as to realize continuous and stable decoking reaction.
The method for removing tar in biomass pyrolysis gas by using molten salt is characterized in that in the step 2), the biomass is agricultural waste or household garbage, and the agricultural waste is at least one of wood dust and straw.
The method for removing tar in biomass pyrolysis gas by using molten salt is characterized in that the molten salt is one or a mixture of a plurality of LiCl, naCl, KCl, znCl 2、Li2CO3、Na2CO3、K2CO3, preferably a mixture of Li 2CO3、Na2CO3 and K 2CO3.
The method for removing tar in biomass pyrolysis gas by using molten salt is characterized in that the decoking reaction temperature is 300-1050 ℃, preferably 750-800 ℃.
The beneficial effects of the invention are as follows:
1) The invention replaces the conventional secondary pyrolysis by utilizing the advantages of high heat conductivity, high specific heat capacity and high stability of the molten salt system, the bubble cap type reactor greatly increases the reaction contact area, the high-temperature molten salt layer can well catalyze and crack tar, the gas yield is increased, the heat value is improved, and the tar yield is reduced. Meanwhile, the high-temperature molten salt layer has the characteristic of long-acting recycling, so that the problem of poor service life of the catalyst in the conventional secondary cracking reaction is avoided. The device has the advantages of lower cost, convenient and accurate temperature control, high tar removal rate, energy conservation, environmental protection, no secondary pollution problem, simplicity and convenience in cleaning and maintenance, and the like, and is applicable to biomass gasification devices and can be directly added to follow-up working sections of most of existing devices. The bubble cap in the fused salt bubble cap reactor is of an inverted horn mouth shape, so that the inverted suction can be effectively prevented, the exhaust tooth gap is of a strip shape, and the range of the allowable gas flow rate is wide.
2) In the method for removing tar in biomass pyrolysis gas by using molten salt, tar gas with high temperature generated by biomass gasification is directly connected into a molten salt bubble cap decoking device without cooling, the tar gas with high temperature is heated and preserved by a heating jacket (tar condensation is prevented and a pipeline is blocked), then is connected into a molten salt bubble cap reactor by a gas buffer tank, and in the molten salt bubble cap reactor, gas is in contact reaction with a high-temperature molten salt layer in a bubbling mode, wherein tar in the tar gas is fully cracked into micromolecular gas and carbon, and gas generated by decoking reaction is discharged to a subsequent working section; after long-term use, carbon deposition in the molten salt layer is aggravated, the decoking efficiency is affected, and air or oxygen can be introduced at high temperature for combustion and carbon removal. By the method, tar oil gas with high temperature generated by biomass gasification is subjected to decoking reaction, and the tar removal rate can reach more than 95%.
3) In the device structure, the heat insulation layer and the air heat insulation layer reduce heat loss of the device and improve safety of personnel in the use process. The device core molten salt bubble reactor adopts bubble cap form to treat tar gas, and replaces conventional liquid phase reaction with high temperature molten salt layer to treat tar gas passing through molten salt layer; the high-temperature molten salt system has the advantages of high heat conductivity, high specific heat capacity, high stability, high fluidity, excellent decarboxylation effect and the like, can be used as a high-efficiency heat transfer medium and a catalyst to fully contact and react with tar gas to promote tar decomposition, reduce the acidity of a product, increase the gas yield, improve the heat value and the like, and the inverted horn-structure bubble cap is favorable for better dispersing the tar gas in a molten salt layer, and has the advantages of wide range of variation of allowed gas flow, reduced reverse suction probability and the like while improving the reaction contact area. In the device, the molten salt raw material is mixed salt of Li 2CO3、Na2CO3 and K 2CO3, the mixed salt with different proportions has different melting points, decomposition temperatures and costs, and the proportion can be selected according to actual conditions. Meanwhile, related researches show that the alkali metal molten salt has extremely strong catalytic action and decarboxylation action on cracking of tar, and is beneficial to the problems of increasing gas yield, improving heat value, reducing tar accumulation, prolonging pipeline service life, reducing environmental pollution and the like.
Drawings
FIG. 1 is a schematic flow chart of a method for removing tar in biomass pyrolysis gas by using molten salt;
FIG. 2 is a schematic structural view of an electrically heated molten salt blister decoking device;
FIG. 3 is a schematic structural view of a flue gas heated molten salt blister decoking device;
FIG. 4 is a schematic diagram of the structure between a molten salt bubble reactor and a gas surge tank;
In the figure: 1-tar gas inlet pipe, 2-auxiliary gas inlet pipe, 3-gas outlet pipe, 4-heating jacket, 5-heat insulation layer, 6-air heat insulation layer, 7-first thermocouple, 8-second thermocouple, 9-gas buffer tank, 10-fused salt bubble reactor, 11-bubble riser and 12-bubble.
Detailed Description
The invention will be further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
Examples: reference is made to FIGS. 1 to 4
The utility model provides a device of tar in fused salt desorption living beings pyrolysis gas (also referred to as fused salt bubble cap decoking device), including biomass gasification device, inside contain fused salt bubble cap reactor 10 of fused salt, set up outlet duct 3 on fused salt bubble cap reactor 10, set up in the gas buffer tank 9 of fused salt bubble cap reactor 10 below and be used for carrying out the heating heat preservation device of simultaneous heating to fused salt bubble cap reactor 10 and gas buffer tank 9, outlet duct 3 on the fused salt bubble cap reactor 10 has condensing equipment and gas collecting device through the external connection of pipeline, so that the gas after the reaction of outlet duct 3 exhaust is condensed and collected. The inside diapire of fused salt bubble cap reactor 10 is fixed to be provided with bubble cap riser 11 and bubble cap 12, bubble cap riser 11 top is located above the fused salt liquid level, and bubble cap 12 sets up in bubble cap riser 11 outside and bubble cap riser 11 top and bubble cap 12 top inner wall between be equipped with the space, bubble cap 12 lower part sets up a plurality of exhaust slits of equiheight along circumference even interval, just exhaust slit is located below the fused salt liquid level (bubble cap 12 is the shape of falling horn mouth, exhaust slit is rectangular shape structure). The bottom end of the bubble cap riser 11 extends out of the bottom of the molten salt bubble reactor 10 and is communicated with the top of the gas buffer tank 9, the gas buffer tank 9 is provided with a tar gas inlet pipe 1 and an auxiliary gas inlet pipe 2 used for introducing O 2 or N 2, the gas buffer tank 9 is connected with a gas outlet pipe of the biomass gasification device through the tar gas inlet pipe 1, and therefore the gas outlet pipe of the biomass gasification device is communicated with the bubble cap riser 11 through the gas buffer tank 9.
Referring to fig. 2 and 3, the heating and heat-preserving device comprises a heating jacket 4, a heat-preserving layer 5 and an air heat-insulating layer 6, wherein the heating jacket 4, the heat-preserving layer 5 and the air heat-insulating layer 6 are sequentially sleeved on the outer side of the side part of the fused salt bubble cap reactor 10 and the outer side of the side part of the gas buffer tank 9, so that the fused salt bubble cap reactor 10 and the gas buffer tank 9 are heated and preserved at the same time; the top of the fused salt bubble reactor 10 and the bottom of the gas buffer tank 9 are both provided with heat insulation layers 5 (the upper part of the fused salt bubble reactor 10 and the lower part of the gas buffer tank 9 can be designed as flanges so as to be beneficial to periodic opening, cleaning and replacing of fused salt).
In order to accurately detect the temperature of molten salt and the temperature of gas in the gas buffer tank 9, the device further comprises a first thermocouple 7 and a second thermocouple 8, wherein the temperature measuring end of the first thermocouple 7 stretches into the molten salt in the molten salt bubble cap reactor 10, and the temperature measuring end of the second thermocouple 8 stretches into the gas buffer tank 9.
When the heating jacket 4 is an interlayer sleeve, the upper end of the interlayer sleeve is provided with a flue gas inlet, and the lower end of the interlayer sleeve is provided with a flue gas outlet; when the heating jacket 4 adopts an electric heating jacket to carry out electric heating type temperature rise, the structure of the device is shown in figure 2; when the heating jacket 4 adopts the interlayer sleeve to heat the flue gas, the structure of the device is as shown in figure 3, and the high-temperature flue gas is introduced into the interlayer sleeve to heat the flue gas (compared with figure 3, the temperature of the hot flue gas is higher when the hot flue gas is initially introduced into the interlayer sleeve because the hot flue gas is introduced into the upper end of the interlayer sleeve). One end of the tar gas inlet pipe 1 is arranged on the inner side of the heating jacket 4 and is connected with the upper portion of the gas buffer tank 9 (namely, one end of the tar gas inlet pipe 1 is attached between the heating jacket 4 and the gas buffer tank 9), one end of the auxiliary gas inlet pipe 2 is arranged on the inner side of the heating jacket 4 and is connected with the upper portion of the gas buffer tank 9 (namely, one end of the auxiliary gas inlet pipe 2 is attached between the heating jacket 4 and the gas buffer tank 9), so that the tar gas inlet pipe 1 and the auxiliary gas inlet pipe 2 are preheated to a certain extent.
A schematic flow chart of a method for removing tar in biomass pyrolysis gas by using molten salt is shown in figure 1.
The application discloses a tar treatment process based on the fused salt bubble cap decoking device, which comprises the following steps:
Step S1: adding mixed salt of Li 2CO3、Na2CO3 and K 2CO3 in a certain mass ratio into the fused salt bubble reactor 10, and sealing the device and connecting a gas pipeline; the electric heating type heating jacket 4 is controlled by adjusting an external controller, so that the fused salt bubble reactor 10 is heated to more than 750 ℃ at the heating rate of 15-20 ℃/min, and the gas buffer tank 9 reaches more than 500 ℃; opening an auxiliary air inlet pipe 2, and purging nitrogen for 15-20min at a ventilation rate of 1-2L/min to ensure the anaerobic atmosphere of the device; keeping the temperature constant for 25-35min;
step S2: opening a tar gas inlet pipe 1, and regulating gas to a proper flow;
Step S3: the tar gas with high temperature is preheated to reach a gas buffer tank 9, then enters a fused salt bubble reactor through a bubble cap riser, and after being decomposed by high temperature fused salt layer reaction, the gas enters a subsequent condensation gas collecting device through a gas outlet pipe 3.
Based on the tar tail gas decoking process, the application discloses the following embodiments:
example 1: is connected with the tail end of the medium biomass gasification device
The heating reaction can be performed by adopting the device with the structure shown in fig. 2, and the temperature of the molten salt detected by the first thermocouple 7 is higher than the temperature of the gas in the gas buffer tank 9 detected by the second thermocouple 8 because the heat conduction property of the molten salt is higher than that of the gas.
Connecting an air outlet pipe of a medium biomass gasification device taking straw as a raw material with an tar gas inlet pipe of a fused salt pyrolysis tail gas decoking device; adding Li 2CO3、Na2CO3 and K 2CO3 mixed molten salt with the mass ratio of 1:1:1.3 into the molten salt bubble reactor 10, and sealing the device; controlling a heating jacket 4 to heat the molten salt temperature in the molten salt bubble reactor 10 to 800 ℃ at a heating rate of 20 ℃/min, and enabling the gas temperature in the gas buffer tank 9 to reach 550 ℃; after the mixed molten salt is completely melted, an auxiliary air inlet pipe 2 is opened, nitrogen is purged for 20min at a ventilation rate of 1.5L/min, and the anaerobic atmosphere of the device is ensured; after keeping the constant temperature for 30min, stopping introducing nitrogen, starting a medium biomass gasification device and feeding and reacting, gasifying the straws into tar gas by the medium biomass gasification device, enabling gas generated by gasification and uncondensed tar to enter a fused salt bubble cap reactor 10 in sequence through a tar gas inlet pipe 1 and a gas buffer tank 9 for decoking reaction, and finally discharging the tar gas to a subsequent working section through an air outlet pipe 3. Compared with a medium-sized biomass gasification device, the method has the advantages that the medium-sized biomass gasification device is combined with the device for removing tar in biomass pyrolysis gas through molten salt, the decoking efficiency is kept stable within 20 hours after continuous decoking reaction, and the detection result shows that: the tar yield is reduced by more than 95%, and the gas yield is increased by more than 15%.
Example 2: cleaning and maintenance of fused salt pyrolysis tail gas decoking device
After 120 hours of continuous decoking reaction in example 1, the detection result shows that the decoking efficiency is reduced, the temperature of the fused salt bubble cap reactor 10 and the gas buffer tank 9 is kept unchanged, the tar gas inlet pipe 1 is closed, an auxiliary vent pipe 2 is opened, a proper amount of nitrogen is introduced for purging, air is introduced, the gas flow rate is adjusted to be proper, and carbon deposition in the reaction removing device is removed until the total concentration of CO and CO 2 in the tail gas is reduced to below 3%. Then repeating the decoking reaction, and the experimental result shows that the decoking efficiency is close to the reaction result of the embodiment 1, namely, the tar yield is reduced by more than 95%, the gas yield is increased by more than 15%, which shows that the regeneration of molten salt is realized by burning for decoking.
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 (10)
1. The device for removing tar in biomass pyrolysis gas by using molten salt is characterized by comprising a biomass gasification device, a molten salt bubble cap reactor (10) filled with molten salt in the interior, an air outlet pipe (3) arranged on the molten salt bubble cap reactor (10) and a heating and heat preservation device for heating the molten salt bubble cap reactor (10), wherein a bubble cap riser (11) and a bubble cap (12) are fixedly arranged on the bottom wall in the molten salt bubble cap reactor (10), the top end of the bubble cap riser (11) is positioned above the molten salt liquid level, the bubble cap (12) is arranged outside the bubble cap riser (11) and a gap is arranged between the top end of the bubble cap riser (11) and the inner wall at the top of the bubble cap (12), a plurality of equal-height exhaust tooth gaps are uniformly arranged at the lower part of the bubble cap (12) along the circumference and are positioned below the molten salt liquid level, the air outlet of the biomass gasification device is communicated with the bubble cap riser (11), and gas discharged by the biomass gasification device flows into a space between the molten salt liquid level and the bubble cap (12) through the bubble cap riser (11) and then enters the interior and escapes through the exhaust tooth gaps at the lower part of the bubble cap (12);
The biomass gasification device further comprises a gas buffer tank (9) arranged below the fused salt bubble reactor (10), the bottom end of the bubble cap riser (11) extends out of the bottom of the fused salt bubble reactor (10) and is communicated with the top of the gas buffer tank (9), a tar gas inlet pipe (1) and an auxiliary gas inlet pipe (2) for introducing O 2 or N 2 are arranged on the gas buffer tank (9), and the gas buffer tank (9) is connected with a gas outlet of the biomass gasification device through the tar gas inlet pipe (1);
The heating and heat-preserving device comprises a heating jacket (4), a heat-preserving layer (5) and an air heat-insulating layer (6), wherein the heating jacket (4), the heat-preserving layer (5) and the air heat-insulating layer (6) are sequentially sleeved on the outer side of the side part of the fused salt bubble cap reactor (10) and the outer side of the side part of the gas buffer tank (9) so as to heat and preserve heat of the fused salt bubble cap reactor (10) and the gas buffer tank (9) at the same time; the top of the fused salt bubble reactor (10) and the bottom of the gas buffer tank (9) are both provided with heat insulation layers (5);
the bubble cap (12) is of an inverted horn mouth-shaped structure, and the exhaust tooth slits are of a strip-shaped structure.
2. The device for removing tar in biomass pyrolysis gas by using molten salt according to claim 1, further comprising a first thermocouple (7) and a second thermocouple (8), wherein the temperature measuring end of the first thermocouple (7) stretches into molten salt in the molten salt bubble reactor (10), and the temperature measuring end of the second thermocouple (8) stretches into the gas buffer tank (9).
3. The device for removing tar in biomass pyrolysis gas by using molten salt according to claim 1, wherein an air outlet pipe (3) on the molten salt bubble cap reactor (10) is externally connected with a condensing device and a gas collecting device through pipelines.
4. The device for removing tar in biomass pyrolysis gas by using molten salt according to claim 1, characterized in that the heating jacket (4) is an electric heating jacket or an interlayer sleeve, and a flue gas inlet and a flue gas outlet are arranged on the interlayer sleeve; one end of the tar gas inlet pipe (1) is arranged on the inner side of the heating jacket (4) and is connected with the upper part of the gas buffer tank (9), and one end of the auxiliary gas inlet pipe (2) is arranged on the inner side of the heating jacket (4) and is connected with the upper part of the gas buffer tank (9).
5. A method for removing tar from biomass pyrolysis gas based on the molten salt of the apparatus according to any one of claims 1 to 4, characterized by comprising the steps of:
1) Starting a heating and heat preserving device to heat the fused salt bubble cap reactor (10) to a reaction temperature, opening an auxiliary air inlet pipe (2) to blow nitrogen, and ensuring that the gas buffer tank (9) and the fused salt bubble cap reactor (10) are kept in an oxygen-free atmosphere;
2) Closing an auxiliary air inlet pipe (2) to stop introducing nitrogen, gasifying and cracking biomass by a biomass gasification device, enabling tar gas obtained by gasifying and cracking to enter a gas buffer tank (9) through a tar gas inlet pipe (1), and then blowing the tar gas into molten salt in a bubble form through a bubble cap riser (11) and a bubble cap (12) to perform decoking reaction, and discharging reacted gas through an air outlet pipe (3);
3) When decoking reaction efficiency is reduced due to carbon deposition of molten salt in the molten salt bubble cap reactor (10), an tar gas inlet pipe (1) is closed, an auxiliary gas inlet pipe (2) is opened to blow in nitrogen, after the tar gas in the gas buffer tank (9) and the molten salt bubble cap reactor (10) is purged completely, the gas introduced by the auxiliary gas inlet pipe (2) is switched to air or oxygen, so that carbon deposition in the molten salt is removed by burning;
4) And (3) repeating the operation processes of the steps 1) to 2) after the carbon deposition of the molten salt in the molten salt bubble reactor (10) is removed, so as to realize continuous and stable decoking reaction.
6. The method according to claim 5, wherein in the step 2), the biomass is agricultural waste or household garbage, and the agricultural waste is at least one of wood chips and straws.
7. The method according to claim 5, characterized in that the molten salt is one or a mixture of several of LiCl, naCl, KCl, znCl 2、Li2CO3、Na2CO3、K2CO3.
8. The method according to claim 7, characterized in that the molten salt is a mixture of Li 2CO3、Na2CO3 and K 2CO3.
9. The process according to claim 5, wherein the decoking reaction is carried out at a temperature of 300-1050 ℃.
10. The process according to claim 9, characterized in that the temperature of the decoking reaction is 750-800 ℃.
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| CN114939332A (en) * | 2022-06-15 | 2022-08-26 | 浙江工业大学 | Method and device for removing coke by bubbling and spraying molten salt |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1962012A (en) * | 2006-11-01 | 2007-05-16 | 褚雅志 | Bubble cap integrated stereo sieve plate |
| CN200970489Y (en) * | 2006-11-28 | 2007-11-07 | 褚雅志 | Bubble-cap sieve plate |
| CN202052340U (en) * | 2011-04-27 | 2011-11-30 | 临安惠通玻璃钢有限公司 | Stripped bubble cap |
| CN202754969U (en) * | 2012-08-03 | 2013-02-27 | 襄阳品冠恒大环境工程有限公司 | Garbage pyrolysis coal gas desulfuration dedusting tar-removing dioxin-removing deodorization tower |
| CN202962482U (en) * | 2012-11-09 | 2013-06-05 | 洪湖市祥龙石化塔内件有限公司 | Round bubble-cap tower plate |
| CN103977590A (en) * | 2014-05-26 | 2014-08-13 | 万华化学集团股份有限公司 | Gas-liquid mass transfer element |
| CN104399732A (en) * | 2014-04-17 | 2015-03-11 | 大连理工大学 | Apparatus for pyrolyzing solid wastes through molten salt, and method thereof |
| CN105623687A (en) * | 2016-03-02 | 2016-06-01 | 大连理工大学 | Device and method for jointly preparing bio-oil and multihole biochar through fuse salt by spraying biomass for pyrolysis |
| CN109562301A (en) * | 2016-06-23 | 2019-04-02 | 苏伊士集团 | Method for by converting-plastics being fuel |
| CN210103861U (en) * | 2019-06-20 | 2020-02-21 | 浙江工业大学 | Device of tar in fused salt desorption living beings pyrolysis gas |
-
2019
- 2019-06-20 CN CN201910538502.2A patent/CN110184094B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1962012A (en) * | 2006-11-01 | 2007-05-16 | 褚雅志 | Bubble cap integrated stereo sieve plate |
| CN200970489Y (en) * | 2006-11-28 | 2007-11-07 | 褚雅志 | Bubble-cap sieve plate |
| CN202052340U (en) * | 2011-04-27 | 2011-11-30 | 临安惠通玻璃钢有限公司 | Stripped bubble cap |
| CN202754969U (en) * | 2012-08-03 | 2013-02-27 | 襄阳品冠恒大环境工程有限公司 | Garbage pyrolysis coal gas desulfuration dedusting tar-removing dioxin-removing deodorization tower |
| CN202962482U (en) * | 2012-11-09 | 2013-06-05 | 洪湖市祥龙石化塔内件有限公司 | Round bubble-cap tower plate |
| CN104399732A (en) * | 2014-04-17 | 2015-03-11 | 大连理工大学 | Apparatus for pyrolyzing solid wastes through molten salt, and method thereof |
| CN103977590A (en) * | 2014-05-26 | 2014-08-13 | 万华化学集团股份有限公司 | Gas-liquid mass transfer element |
| CN105623687A (en) * | 2016-03-02 | 2016-06-01 | 大连理工大学 | Device and method for jointly preparing bio-oil and multihole biochar through fuse salt by spraying biomass for pyrolysis |
| CN109562301A (en) * | 2016-06-23 | 2019-04-02 | 苏伊士集团 | Method for by converting-plastics being fuel |
| CN210103861U (en) * | 2019-06-20 | 2020-02-21 | 浙江工业大学 | Device of tar in fused salt desorption living beings pyrolysis gas |
Non-Patent Citations (1)
| Title |
|---|
| Mian Xu等.Novel findings in conversion mechanism of toluene as model compound of biomass waste tar in molten salt.《Journal of Analytical and Applie Pyrolysis》.2018,第134卷第275页左栏第3-5段，右栏第1段，图1. * |
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