CN115772421A - System and method for preparing hydrogen-rich gas by biomass staged gasification - Google Patents
System and method for preparing hydrogen-rich gas by biomass staged gasification Download PDFInfo
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- 238000002309 gasification Methods 0.000 title claims abstract description 205
- 239000007789 gas Substances 0.000 title claims abstract description 172
- 239000001257 hydrogen Substances 0.000 title claims abstract description 64
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 64
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000002028 Biomass Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000002407 reforming Methods 0.000 claims abstract description 134
- 238000000197 pyrolysis Methods 0.000 claims abstract description 99
- 238000002485 combustion reaction Methods 0.000 claims abstract description 82
- 239000000571 coke Substances 0.000 claims abstract description 81
- 238000010438 heat treatment Methods 0.000 claims abstract description 50
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000003546 flue gas Substances 0.000 claims abstract description 47
- 238000000746 purification Methods 0.000 claims abstract description 38
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- 239000002918 waste heat Substances 0.000 claims description 44
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 43
- 239000001301 oxygen Substances 0.000 claims description 43
- 229910052760 oxygen Inorganic materials 0.000 claims description 43
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention provides a system and a method for preparing hydrogen-rich gas by biomass staged gasification, belonging to the field of biomass energy utilization, wherein the system comprises a pyrolysis reactor, a gasification reactor, a reforming reactor and a combustion reactor, wherein: the pyrolysis reactor is used for pyrolyzing biomass; the gasification reactor is divided into a purification area and a gasification area, and coke is gasified in the gasification area; the reforming reactor carries out catalytic reforming on the pyrolysis gas to obtain reformed gas, the reformed gas is sent into a gasification reactor purification area for purification, and the reformed gas is mixed with the purified gasified gas to obtain hydrogen-rich gas; the combustion reactor is used to combust the coke to heat the reforming reactor. The invention realizes the decoupling and grading optimization of the biomass pyrolysis, gasification and reforming processes, also decouples the reforming and combustion on the basis of self-heating, avoids the self-heating consumption of the reformed gas, separates the combustible gas and the flue gas, and further greatly improves the hydrogen concentration and the quality of the synthesis gas.
Description
Technical Field
The invention belongs to the field of biomass energy utilization, and particularly relates to a system and a method for preparing hydrogen-rich gas through biomass staged gasification.
Background
Exhaustion of fossil energy and aggravation of environmental pollution compel people to seek clean and high-quality renewable energy, and hydrogen is favored by various countries due to the characteristics of no toxicity, cleanness, high calorific value, good combustion performance and the like. However, at present, hydrogen is mainly obtained by gasification and reforming of fossil fuel, which accounts for about 92 percent and does not fundamentally get rid of the dependence on fossil energy. The biomass is a renewable clean energy source, and the biomass gasification hydrogen production has high energy efficiency,
Has remarkable advantages in the aspects of efficiency, economy and the like, and under the background of 'double carbon', the carbon neutrality of the biomass makes the biomass become a very ideal hydrogen production raw material which can be possibly reformed with the conventional natural gas to produce hydrogenCompetition
Currently, biomass gasification faces two major problems of lower carbon conversion and higher tar content. Tar is a viscous liquid, accounts for 5-15% of the total gas production energy, affects the gasification efficiency and the energy conversion efficiency, is easy to cause blockage of pipelines and valves, and brings great troubles to equipment operation and subsequent utilization of gas production. Thus, tar removal and char gasification are two key issues for biomass gasification. Higher temperatures favor tar removal and char gasification, but biomass is rich in alkali metals, and high temperatures can cause alkali metal transfer to the gas phase and corrosion of the reactor. The staged gasification is a novel biomass gasification technology, the gasification process is divided into a plurality of communicated systems, the biomass firstly undergoes slow pyrolysis reaction at a relatively low temperature to release volatile matters, the low pyrolysis temperature reduces the precipitation of alkali and alkaline earth metals, and simultaneously, the tar produced at a low temperature has low aromatizing degree and is easy to reform; then gasification reaction is carried out at higher temperature and different gasification media, and tar and coke are converted simultaneously. Under the condition, the yield of the tar is greatly reduced, the content of aromatic compounds in the tar is also greatly reduced, and in addition, the coke generated by biomass pyrolysis can be used as a heat carrier or a catalyst for further converting the tar. Therefore, the staged gasification can effectively improve the calorific value and the quality of the synthesis gas.
However, in industrial applications, it is often necessary to feed a portion of the oxygen or air into the furnace to generate heat and raise the reaction temperature, and gasification and combustion cannot be decoupled, which results in a lower hydrogen concentration in the syngas. Meanwhile, in the conventional staged gasification process, the reforming of the volatile matter and the gasification of the char often occur in the same reactor or the same region, and the gasification reaction rate of the char is very slow compared with the reforming of the volatile matter, resulting in mismatching of reaction time, resulting in incomplete gasification of the char and reduction of gasification efficiency and carbon conversion rate. While with respect to heterogeneous combustion of coke, H 2 The homogeneous combustion of (2) is easier to occur, and H in the synthesis gas is further reduced 2 The concentration of (c). In addition, catalytic reforming of tar tends to produce carbon deposits, which can lead to catalyst deactivation. In thatIn some published patents, for example, CN108467750a discloses a combined type staged gasification reaction apparatus and method thereof, which divides a gasification furnace into an upper section and a lower section through an innovative fluidized bed structure to achieve staged gasification of large and small particles. But the processes of pyrolysis, gasification, reforming, combustion and the like are not fundamentally decoupled, and a great breakthrough cannot be realized in the aspect of improving the concentration of hydrogen. For another example, CN104830358a discloses a device and a method for preparing hydrogen-rich gas by biomass staged gasification, which separate the pyrolysis process of biomass, the combustion of pyrolysis gas/tar and the gasification process of coke. However, the process method uses the volatile components (pyrolysis gas and tar) which account for most of the biomass for combustion to supply heat for coke gasification, and although the hydrogen concentration can be improved, the process method is not friendly to the yield of gas and hydrogen and the gasification efficiency. In a word, the existing biomass gasification technology has a series of defects of incomplete coke gasification, low gasification efficiency, low hydrogen concentration and yield, easy carbon deposition and inactivation of a catalyst and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a system and a method for preparing hydrogen-rich gas by biomass staged gasification, and aims to solve the problems of low gasification efficiency, low hydrogen concentration and low yield of the conventional biomass gasification system.
To achieve the above objects, according to one aspect of the present invention, there is provided a system for producing hydrogen rich gas by staged gasification of biomass, the system comprising a pyrolysis reactor, a gasification reactor, a reforming reactor, and a combustion reactor, wherein:
the pyrolysis reactor is respectively connected with the gasification reactor and the reforming reactor and is used for pyrolyzing biomass and respectively sending coke and pyrolysis gas generated by pyrolysis into the gasification reactor and the reforming reactor;
the gasification reactor is characterized in that a funnel-shaped partition plate is arranged in the gasification reactor, the surface of the funnel-shaped partition plate is provided with a hole, an annular air chamber is arranged below the funnel-shaped partition plate, so that the gasification reactor is divided into a purification area and a gasification area, a conical opening of the funnel-shaped partition plate connects the purification area and the gasification area through a central channel so as to send coke from the purification area to the gasification area for gasification, and exhaust pipes are arranged around the annular air chamber so as to communicate gas spaces of the purification area and the gasification area; in addition, a first gas outlet is arranged at the top of the gasification reactor, an overflow port is arranged at the bottom of the gasification reactor, the first gas outlet is used for outputting the prepared hydrogen-rich gas, and the overflow port is used for conveying coke to the combustion reactor;
the first gas inlet of the reforming reactor is connected with the pyrolysis reactor, and the second gas outlet of the reforming reactor is connected with the annular air chamber so as to carry out catalytic reforming on the pyrolysis gas to obtain reformed gas, and the reformed gas is sent into the purification zone to be purified and is mixed with the purified gasified gas to obtain hydrogen-rich gas;
the combustion reactor is arranged at the lower part of the reforming reactor and is separated from the reforming reactor through an intermediate partition plate, and the bottom of the combustion reactor is connected with an overflow port so as to combust coke and heat the reforming reactor.
Preferably, a preset number of impellers which coaxially rotate are arranged in the reforming reactor, catalysts are placed in spaces of adjacent blades in the impellers, and porous baffles are arranged above and below the impellers to prevent the catalysts from falling; the reforming reactor is symmetrically divided into a reforming chamber and a heating chamber by a vertical partition plate between adjacent impellers, the top of the reforming chamber is provided with a first air inlet which is connected with the pyrolysis reactor to send pyrolysis gas into the reforming chamber for catalytic reforming, and the bottom of the reforming chamber is provided with a second air outlet which is connected with an annular air chamber to send the reforming gas into a purification area for purification; the bottom of the heating chamber is connected with the combustion reactor and used for introducing flue gas to heat, the impeller rotates in the reforming chamber and the heating chamber in a circulating mode during work, the temperature of the catalyst is increased on one side of the heating chamber, and heat is released on one side of the reforming chamber.
As a further preferred, a first cyclone separator is arranged above the pyrolysis reactor, the pyrolysis reactor adopts a fluidized bed working mode and is used for pyrolyzing biomass raw materials, and an air outlet of the pyrolysis reactor is connected with the first cyclone separator so as to separate pyrolysis gas and coke generated by pyrolysis; the first cyclone is connected to the gasification reactor and the reforming reactor, respectively, to feed the char and the pyrolysis gas into the gasification reactor and the reforming reactor, respectively.
Preferably, the combustion reactor is provided with a built-in second cyclone separator at the upper part, the gas outlet of the second cyclone separator is connected with the second gas inlet of the reforming reactor so as to introduce the flue gas generated by combustion in the combustion reactor into the heating chamber, and the ash outlet of the second cyclone separator is positioned outside the combustion reactor.
Preferably, the system for preparing hydrogen-rich gas by biomass staged gasification further comprises a flue gas waste heat boiler and a gas waste heat boiler, wherein an air inlet of the flue gas waste heat boiler is connected with a third air outlet of the heating chamber, and a first steam preheater and a first oxygen preheater are arranged inside the flue gas waste heat boiler so as to preheat steam, oxygen or air by using the flue gas waste heat of the heating chamber; the gas inlet of the gas waste heat boiler is connected with the third gas outlet of the gasification reactor, and meanwhile, a second steam preheater and a second oxygen preheater are arranged inside the gas waste heat boiler so as to preheat steam and oxygen or air by using the hydrogen-rich gas waste heat of the gasification reactor.
As a further preferred, the system for preparing hydrogen-rich gas by staged gasification of biomass further comprises a feeding unit, the feeding unit comprises a screw feeder and a silo, one end of the screw feeder is connected with the silo, and the other end of the screw feeder is connected with the pyrolysis reactor, so as to provide biomass raw material to the pyrolysis reactor.
Preferably, the number of the exhaust pipes in the gasification reactor is 6-12, the upper end of each exhaust pipe is higher than the lower end of the ash falling pipe of the first cyclone separator, 3-5 layers of rotating impellers are arranged in the reforming reactor, each layer of rotating impellers comprises 20-30 blades, and the vertical partition plate is in an I shape.
According to another aspect of the present invention, there is provided a method for producing hydrogen-rich gas by staged gasification of biomass, the method comprising the steps of:
(1) Biomass is pyrolyzed in a pyrolysis reactor, and generated coke and pyrolysis gas are respectively sent into a gasification reactor and a reforming reactor;
(2) The coke firstly falls into a purification area of a gasification reactor and falls into a gasification area through a central channel, the coke is gasified in the gasification area, the generated gasification gas is discharged to the upper part of the purification area through an exhaust pipe, and the coke at the bottom layer of the gasification area is sent into a combustion reactor through an overflow port;
(3) Burning coke in a combustion reactor, and introducing the generated flue gas into a reforming reactor to heat the reforming reactor;
(4) The pyrolysis gas is catalytically reformed in the reforming reactor to generate reformed gas, and the reformed gas is sent into a purification zone through an annular air chamber for purification and mixed with gasified gas to obtain hydrogen-rich gas, so that the preparation of the hydrogen-rich gas by biomass graded gasification is completed.
More preferably, the temperature of the pyrolysis reactor is 700 to 850 ℃, the temperature of the gasification reactor is 800 to 900 ℃, and the temperature of the reforming reactor is 900 to 1000 ℃.
As a further preference, in the pyrolysis reactor, the molar ratio of steam to oxygen is 1.1; in the gasification reactor, the molar ratio of steam to oxygen is 0.5 to 0.8.
In general, the above technical solution conceived by the present invention has the following advantages compared to the prior art
Has the advantages that:
1. the invention realizes the grading optimization of the gasification process by arranging the pyrolysis reactor, the gasification reactor, the reforming reactor and the combustion reactor, wherein biomass is pyrolyzed and gasified at a lower temperature in the pyrolysis reactor, the aromatizing degree of tar and coke generated by pyrolysis can be effectively reduced, and the rapid gasification of coke and the efficient removal of tar can be realized by matching with the subsequent higher-temperature gasification and reformingSet up the combustion reactor below the reforming reactor, the decoupling zero of reforming with the combustion process has been realized, gasification reactor sends the coke that reactivity is poor to the combustion reactor in burning through the overflow mouth, shorten coke reaction time, the high temperature flue gas that produces supplies heat for pyrolysis gas reforming, decoupling zero gasification reforming and burning on the basis of self-heating, the self-heating consumption of pyrolysis gas has been avoided, combustible gas and flue gas have been separated, hydrogen concentration and synthetic gas quality are greatly improved, also effectively avoid pyrolysis gas and oxygen to mix and take place the deflagration when self-heating, the security has effectively been improved, finally make the gasification efficiency of this system can reach 91.1% to the utmost, H, the most, the high pressure heater can not only be used for heating, the gasification efficiency of the system is improved to the greatest extent, the safety is improved 2 The concentration is as high as 43.4%;
2. particularly, the invention divides the reforming reaction chamber into the reforming chamber and the heating chamber, and introduces flue gas with the direction opposite to the gas flow direction of the reforming chamber into the heating chamber, adopts the principle of a rotary regenerative heat exchanger, the catalyst is simultaneously used as a regenerative medium to circulate between the reforming chamber and the heating chamber, the temperature is raised at one side of the heating chamber, the tar is catalyzed and reformed at one side of the reforming chamber, and heat is provided for the reforming reaction, thereby effectively isolating the reforming gas and the high-temperature flue gas, and the carbon deposit on the surface of the catalyst is burnt and removed in the heating chamber by supplying partial oxygen into the high-temperature flue gas, thereby improving the service life and the circulation stability of the catalyst;
3. meanwhile, the flue gas waste heat boiler and the gas waste heat boiler are arranged, and the flue gas and the hydrogen-rich gas are respectively utilized for heat exchange to generate steam and preheat oxygen or air, so that the waste heat is recycled deeply, and the energy utilization efficiency of the system is greatly improved;
4. in addition, the invention also carries out integrated optimization on system arrangement, the reforming reactor and the combustion reactor are designed integrally, high-temperature flue gas can be directly sent into the reforming reactor, the gasification reactor is connected with the combustion reactor through an overflow port, coke at the bottom of the gasification reactor is directly sent into the combustion reactor, heat loss is reduced, the structure is compact, the temperature distribution of the whole system is more reasonable, and low-temperature pyrolysis, medium-temperature gasification, high-temperature reforming and combustion are carried out in sequence.
Drawings
FIG. 1 is an overall schematic diagram of a system for producing hydrogen-rich gas by staged gasification of biomass according to an embodiment of the invention;
FIG. 2 isbase:Sub>A sectional view taken along line A-A of FIG. 1;
FIG. 3 is a three-dimensional view of a funnel-shaped baffle plate;
fig. 4 is a partial sectional view of a reforming reactor.
The same reference numbers will be used throughout the drawings to refer to the same or like elements or structures, wherein:
100-feeding unit, 110-storage bin, 120-spiral feeder, 200-pyrolysis reactor, 201-first air distribution plate, 202-first air chamber, 203-first slag cooling chamber, 210-first cyclone separator, 300-gasification reactor, 301-first air outlet, 302-second air distribution plate, 303-second air chamber, 304-funnel baffle plate, 305-annular air chamber, 306-exhaust pipe, 307-overflow port, 308-third air distribution plate, 309-third air chamber, 400-combustion reactor, 401-fourth air distribution plate, 402-fourth air chamber, 403-second slag cooling chamber, 410-second cyclone separator, 411-ash outlet, 500-reforming reactor, 510-reforming chamber, 511-first air inlet, 512-third air inlet, 513-fifth air distribution plate, 514-second air outlet, 520-second air inlet, 521-second air inlet, 522-sixth air distribution plate, 523-third air outlet 530-rotation chamber, impeller air outlet, 610-second air inlet, 611-waste heat water tank, 700-first steam preheater, 700-waste heat water tank, 600-waste heat boiler, 600-waste heat water tank, 700-waste heat preheater, and 700-waste heat water tank.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
As shown in fig. 1, the present invention provides a system for producing hydrogen rich gas by staged gasification of biomass, the system comprising a feed unit 100, a pyrolysis reactor 200, a gasification reactor 300, a reforming reactor 500, and a combustion reactor 400, wherein:
the feeding unit 100 includes a screw feeder 120 and a bin 110, and one end of the screw feeder 120 is connected to the bin 110 and the other end thereof is connected to a feeding port of the pyrolysis reactor 200 to supply the biomass raw material to the pyrolysis reactor;
the pyrolysis reactor 200 adopts a fluidized bed working mode for pyrolyzing biomass raw materials, a first cyclone separator 210 is arranged above the pyrolysis reactor 200 for separating pyrolysis gas and coke generated by pyrolysis, meanwhile, the first cyclone separator 210 is respectively connected with the gasification reactor and the reforming reactor, and an ash falling pipe of the first cyclone separator 210 extends into the gasification reactor 300 so as to respectively send the coke and the pyrolysis gas into the gasification reactor 300 and the reforming reactor 500;
the gasification reactor 300 is internally provided with a funnel-shaped baffle plate 304, the surface of the funnel-shaped baffle plate 304 is provided with an opening, and a closed annular air chamber 305 is arranged below the funnel-shaped baffle plate 304, so that the gasification reactor 300 is divided into a purification area and a gasification area, the coke on the upper part mainly acts for adsorbing and purifying reformed gas, impurities such as tar, steam, ash and the like in the reformed gas are further removed by utilizing the adsorbability of the coke, and meanwhile, the reformed gas and oxygen supplied at the bottom of the gasification reactor are isolated, and the hydrogen in the reformed gas is prevented from being oxidized and consumed; meanwhile, the conical mouth of the funnel-shaped baffle plate 304 is connected with the inner wall of the annular air chamber 205 to form a central channel, the central channel connects the purification area with the gasification area so as to send the coke from the purification area to the gasification area for gasification, as shown in fig. 3, a plurality of exhaust pipes 306 are arranged around the annular air chamber 305 for exhausting the gasification gas generated in the gasification area; the top of the gasification reactor 300 is provided with a first gas outlet 301, the bottom of the gasification reactor is provided with an overflow port 307, the first gas outlet 301 is used for outputting the prepared rich hydrogen, and the overflow port 307 is used for conveying coke to the combustion reactor 400; the working mode of the gasification reactor 300 is a moving bed, after the bottom coke is consumed, the upper coke falls and is supplemented under the action of gravity, and along with the gasification, the gasification reactivity of the coke is gradually reduced, so that the reactivity of the carbon layer in the gasification reactor 300 is continuously reduced from top to bottom, one part of the coke with the worst bottom reactivity is combusted by oxygen or air introduced from the bottom to supply heat for the gasification reaction, and the other part of the coke is conveyed into the combustion reactor 400 through the overflow port 307 to generate high-temperature flue gas to supply heat for the reforming reaction;
the first air inlet 511 of the reforming reactor 500 is connected with the pyrolysis reactor, and the second air outlet 514 thereof is connected with the annular air chamber 305, so as to perform catalytic reforming on the pyrolysis gas to obtain reformed gas, send the reformed gas into a purification zone for purification, and mix the reformed gas with gasified gas to obtain hydrogen-rich gas;
the combustion reactor 400 is disposed at the lower portion of the reforming reactor 500 and separated from the reforming reactor 500 by an intermediate partition, as shown in fig. 2, the bottom of the combustion reactor 400 is connected to the overflow port 307 by a square pipe so as to transfer the coke at the bottom of the gasification reactor 300 to the combustion reactor 400 for burning the coke to heat the reforming reactor 500, the combustion reactor 400 is in a fluidized bed operation mode, a built-in secondary cyclone 410 is disposed at the upper portion of the combustion reactor 400, the outlet of the secondary cyclone 410 is connected to the reforming reactor 500 so as to introduce the flue gas generated by the combustion of the combustion reactor 400 into the heating chamber 520, and the ash outlet 411 of the secondary cyclone 410 is located at the outside of the combustion reactor 400. Reforming is endothermic, and if autothermal reforming is used, which requires oxygen or air to be fed to the reforming reactor, large amounts of H are inevitably consumed 2 CO formed 2 Further reduction of H 2 Concentration, safety problems of deflagration, explosion and the like exist at the same time, the coke gasification reactivity is poor, the reaction time is long, the method is a speed-limiting step of gasification, and H can be avoided by adopting a coke combustion mode to supply heat for reforming 2 The consumption of the device and the effective separation of combustible gas and flue gas.
Further, the reforming reactor 500 is a cylindrical structure, 3-5 layers of coaxially rotating impellers 530 are installed in the reforming reactor, each layer of rotating impeller 530 comprises 20-30 blades, the impeller 530 is divided into 20-30 chambers with uniform size, the space of adjacent blades in the impeller 530, namely the chambers, is filled with a catalyst, and meanwhile, porous baffles are arranged above and below the impeller 530 to prevent the catalyst from falling; the reforming reactor 500 is symmetrically divided into a reforming chamber 510 and a heating chamber 520 by a vertical partition plate between adjacent impellers 530, the top of the reforming chamber 510 is provided with a first air inlet 511 which is used for being connected with the air outlet of the first cyclone separator 210 so as to send pyrolysis gas into the reforming chamber 510 for catalytic reforming, and the bottom of the reforming chamber 510 is provided with a second air outlet 514 which is used for being connected with the annular air chamber 305 so as to send the reforming gas into a purification area for purification; the bottom of the heating chamber 520 is provided with a second air inlet 521 for introducing flue gas.
All the impellers 530 share a rotating shaft, the rotating shaft is positioned at the center of the reforming reactor 500, the motor of the rotating shaft is arranged outside the reforming reactor 500, and the residence time of the catalyst in the reforming chamber 510 can be controlled by controlling the rotating speed of the motor. The vertical partition plates are detachably connected with the inner wall of the reforming reactor 500 and do not move along with the rotating shaft, so that the partition plates and the impellers 530 can be integrally taken out of the reforming reactor 500 during troubleshooting or catalyst replacement. The vertical partition is I-shaped, the width of the upper end and the lower end of the vertical partition is larger than the radian of the chambers, each chamber cannot be communicated with the reforming chamber 510 and the heating chamber 520 at the same time, and gas in the reforming chamber 510 and the heating chamber 520 is prevented from mixing in a mixed mode.
When the device works, half of the chambers are communicated with the heating chamber 520, and the catalyst stores heat in the heating chamber 520; as the impeller 530 rotates, the chambers are communicated with the reforming chamber 510 in sequence, and at the moment, the catalyst contacts with the volatile component to catalyze tar reforming and simultaneously supply heat and reduce temperature; when the temperature is reduced to be not enough for reforming reaction, the chamber is turned back to the heating chamber 520, and the catalyst and the hot flue gas exchange heat to be heated; meanwhile, in the catalytic reforming process, carbon deposition is inevitably generated on the surface of the catalyst, so that the catalyst is inactivated, and the temperature of the catalyst is further increased while coke is oxidized by supplying partial oxygen or air into the heating chamber, so that the self-purification of the catalyst is realized, and the service life of the catalyst is prolonged.
Further, the system for preparing the hydrogen-rich gas through the biomass staged gasification further comprises a flue gas waste heat boiler 620 and a gas waste heat boiler 610, wherein an air inlet of the flue gas waste heat boiler 620 is connected with a third air outlet 523 of the heating chamber, a first steam preheater 621 and a first oxygen preheater 622 are arranged inside the flue gas waste heat boiler 620, a first water tank 623 is connected with the first steam preheater 621 so as to preheat steam and oxygen by utilizing the flue gas waste heat of the heating chamber, an outlet of the first steam preheater 621 is connected with a third air inlet 512, and an outlet of the first oxygen preheater 622 is connected with a second air inlet 521; an air inlet of the gas waste heat boiler is connected with a third air outlet 301 of the gasification reactor 300, the purifier 700 is used for purifying the prepared hydrogen-rich gas, meanwhile, a second steam preheater 611 and a second oxygen preheater 612 are arranged inside the gas waste heat boiler, a second water tank 623 is connected with the second steam preheater 611 so as to preheat steam and oxygen (or air) by using the hydrogen-rich gas waste heat of the gasification reactor 300, an outlet of the second steam preheater 612 is connected with the first air chamber 202, and an outlet of the second oxygen preheater 612 is connected with the first air chamber 202, the second air chamber 303, the third air chamber 309 and the fourth air chamber 402 so as to respectively provide preheated oxygen or air required by combustion and preheated steam required by gasification for each reactor.
Further, the number of the exhaust pipes 306 in the gasification reactor 300 is 6-12, and the upper ends of the exhaust pipes 306 are higher than the lower ends of the ash falling pipes of the first cyclone 210, so that the exhaust pipes are prevented from being blocked by coke accumulation.
Further, a first air distribution plate 201, a first air chamber 202 and a first slag cooling chamber 203 are sequentially arranged at the bottom of the pyrolysis reactor 200 from top to bottom, and the first slag cooling chamber 203 is communicated with the bottom of the pyrolysis reactor 200 through a slag discharge pipe; the bottom of the gasification reactor 300 is provided with a second air distribution plate 302 and a second air chamber 303 from top to bottom, the second air distribution plate 302 is arranged in an inclined way towards one side of the combustion reactor 400, and the inclined angle is 30-45 degrees; the bottom wall surface of the gasification reactor 300 is provided with an overflow port 307 which is communicated with the combustion reactor 400, and the bottom of the overflow port 307 is provided with a third air plate 308 and a third air chamber 309 from top to bottom so as to ensure that coke at the bottom of the gasification reactor 300 enters the combustion reactor 400 under the action of gravity and fluidization conveying; the bottom of the combustion reactor 400 is sequentially provided with a fourth air distribution plate 401, a fourth air chamber 402 and a second slag cooling chamber 403 from top to bottom, the second slag cooling chamber 403 is communicated with the bottom of the combustion reactor 400 through a slag discharge pipe, and the combustion share and the combustion temperature of coke can be adjusted by adjusting the air intake of the third air chamber 309 and the fourth air chamber 402. Gasifying agents uniformly enter the corresponding reactors from the air chambers and the air distribution plates respectively, and ash residues are discharged from the slag cooling chambers; the reforming reactor 500 is provided with a fifth air distribution plate 513 at the lower part of the first air inlet 511, a sixth air distribution plate 522 at the upper part of the second air inlet 514, and a filter layer at the upper part of the second air outlet 514.
Compared with the prior art, the invention has the following advantages:
(1) Realizes the grading optimization of the gasification process. Through the cooperation of pyrolysis reactor 200, gasification reactor 300 and reforming reactor 500, can realize the pyrolysis of living beings, the decoupling of coke gasification and volatile matter reforming, thereby optimize alone this three step, the living beings carry out pyrolysis gasification under the lower temperature at first in pyrolysis reactor 200, carry out volatile matter reforming and coke gasification in later sending volatile matter and coke respectively to higher temperature's reforming reactor 500 and gasification reactor 300, the tar and the coke aromatizing degree that the low temperature pyrolysis produced are lower, cooperate follow-up higher temperature reforming and gasification, can realize the quick gasification of coke and the effective desorption of tar.
(2) Decoupling of reforming and combustion processes is achieved. The present invention also provides structural innovations to the gasification reactor 300 and reforming reactor 500 and the addition of a combustion reactor 400 to decouple the reforming and combustion processes by self-heating of the combustion of the low reactivity char, avoiding H 2 The self-heating consumption of the reactor improves the hydrogen concentration and the safety of the reactor. Wherein: the gasification reactor 300 sends the coke with poor reactivity to the combustion reactor 400 through the overflow port for combustion, on one hand, the coke reaction time is shortened, the generated high-temperature flue gas supplies heat for pyrolysis gas reforming, gasification reforming and combustion are decoupled on the basis of self-heating, the self-heating consumption of the pyrolysis gas is avoided, combustible gas and flue gas are separated, the hydrogen concentration and the quality of synthesis gas are greatly improved, deflagration caused by the self-heating of the mixture of the pyrolysis gas and oxygen is also effectively avoided, and the safety is higher.
(3) The system has compact structure and optimized layout. According to the invention, biomass pyrolysis gasification, volatile catalytic reforming and coke gasification are decoupled in the process, gasification and combustion are decoupled on the basis of self-heat supply, but integrated optimization is performed on system arrangement, the reforming reactor 500 and the combustion reactor 400 are integrally designed, high-temperature flue gas can be directly fed into the reforming reactor 500, the gasification reactor 300 and the combustion reactor 400 are connected through the overflow port 307, coke at the bottom of the gasification reactor 300 is directly fed into the combustion reactor, heat loss is reduced, and the structure is compact. Meanwhile, the temperature distribution of the whole system is more reasonable, and low-temperature pyrolysis, medium-temperature gasification, high-temperature reforming and combustion are performed in sequence.
(4) The gasification reactor has innovative structure. The gasification reactor 300 provided by the invention is divided into an upper layer and a lower layer, the upper coke is used for purifying gasification gas and reformed gas and can further adsorb and reduce tar content, incompletely reacted steam can continue to react with or be adsorbed by the coke in the area, meanwhile, the reformed gas with higher temperature preheats the upper coke, and the two-layer structure prevents the reformed gas from directly contacting with oxygen at the bottom of the gasification reactor to be consumed, so that the hydrogen concentration can be effectively improved. The reforming reactor 500 adopts the principle of a rotary heat accumulating type heat exchanger, the catalyst is simultaneously used as a heat accumulating medium to circulate between the reforming chamber 510 and the heating chamber 520, reforming gas and high-temperature flue gas are effectively isolated, partial oxygen is supplied into the high-temperature flue gas, carbon deposition on the surface of the catalyst is also burnt and removed in the heating chamber, and the service life of the catalyst and the circulation stability are improved.
(5) High gasifying efficiency, high hydrogen concentration and high cleanliness. Through the decoupling pyrolysis and gasification processes of the staged gasification, the carbon conversion efficiency and the gasification efficiency can be greatly improved, the combustion and the reforming are decoupled on the basis of self-heating, so that the volatile matter can be subjected to pure steam reforming, the hydrogen concentration is greatly improved, the pyrolysis gas is subjected to coke adsorption and filtration after catalytic reforming, the tar content is further reduced, no extra cost is introduced, and finally the gasification efficiency of the system can reach 91.1% to the maximum extent, and the H content is high 2 The concentration is as high as 43.4%.
(6) The energy utilization rate is high. The gas waste heat boiler 610 and the flue gas waste heat boiler 620 respectively utilize high-temperature hydrogen-rich gas and flue gas to exchange heat to generate steam and preheat oxygen or air, and waste heat is recycled deeply, so that the energy utilization efficiency of the system is greatly improved.
The working process of the system for preparing the hydrogen-rich gas by biomass staged gasification provided by the invention comprises the following steps:
s1, biomass pyrolysis: preheated oxygen or air and steam from the gas waste heat boiler 610 are uniformly supplied into the pyrolysis reactor 200 from the first air chamber 202 and the first air distribution plate 201, biomass is fed into the pyrolysis reactor 200 from the feeding unit 100, low-temperature auto-thermal pyrolysis and partial gasification are firstly carried out, generated pyrolysis gas and coke are separated by the first cyclone separator 210, the pyrolysis gas is fed into the reforming reactor 500 through the first air inlet 511 for high-temperature catalytic reforming, and the coke falls into the gasification reactor 300 through an ash falling pipe;
s2, coke gasification: the coke firstly falls into the upper part of the gasification reactor 300 and slides into the lower part through the central channel, the upper coke is a purification area, and the lower coke is a gasification area; preheated oxygen or air and steam from the gas waste heat boiler 610 are sent to the bottom of the gasification reactor 300 through the second air chamber 303 and the second air distribution plate B302, the coke is gasified and consumed and falls down under the action of gravity, and the gasification reactivity of the coke is gradually deteriorated along with the gasification, so that the gasification reactivity of the carbon layer is continuously reduced from top to bottom, the coke at the bottom layer preferentially reacts with the supplied oxygen to supply heat for gasification, the coke at the upper layer reacts with the steam and carbon dioxide for gasification, and the generated gasification gas is transferred to the upper part of the gasification reactor 300 through the exhaust pipe 306 for purification;
s3, coke burning: part of coke at the bottom of the gasification reactor 300 is sent into the combustion reactor 400 through an overflow port 307, preheated oxygen or air from a gas waste heat boiler 610 also enters the combustion reactor 400 through a fourth air chamber 402 and a fourth air distribution plate 401, and high-temperature flue gas generated by coke combustion is sent to the bottom of the heating chamber 520 after being dedusted by a second cyclone separator 410, so that heat is provided for the catalytic reforming of the pyrolysis gas; the inlet and outlet of the reforming chamber 510 are provided with temperature sensors, and the amount of coke conveyed to the combustion reactor 400 and the oxygen inlet amount of the combustion reactor 400 are controlled by controlling the air inlet amount of the overflow port 307 and the air chamber at the bottom of the combustion reactor 400, so that the temperature of flue gas is controlled;
s4, catalytic reforming and adsorption purification of pyrolysis gas: the gas flow direction of the reforming chamber 510 is from top to bottom, the pyrolysis gas from the first cyclone separator 210 and the preheated steam from the flue gas waste heat boiler 620 are sent to the top of the reforming chamber 510 through the first gas inlet 511, and the tar is cracked or reformed into small molecule gas through high-temperature catalytic reforming to generate reformed gas; the impeller 530 continuously rotates in the heating chamber 520 and the reforming chamber 510, the catalyst simultaneously serves as a heat storage medium, tar is catalytically reformed in the reforming chamber 510 and provides heat, the tar is cooled and then rotates into the heating chamber 520 to be heated by high-temperature flue gas, in order to ensure that the axial temperature distribution of the reforming chamber 510 is uniform, the airflow direction of the heating chamber 520 is from bottom to top, and simultaneously, preheated oxygen or air of the flue gas waste heat boiler 620 is sent to the bottom of the heating chamber 520 through the second air inlet 521 to oxidize and eliminate carbon deposit on the catalyst;
the reformed gas is then sent into the annular air chamber 305 in the middle of the gasification reactor 300 through a second air outlet 514 at the bottom of the reforming chamber 510, and uniformly passes through a coke bed layer on the upper part of the gasification reactor 300, so that the reformed gas is further filtered and tar is adsorbed, and meanwhile, the high-temperature reformed gas is also used for preheating coke; the reformed gas after filtration and purification is mixed with gasified gas at the lower part of the gasification reactor 300 to form hydrogen-rich gas;
s5, waste heat utilization: the high-temperature hydrogen-rich gas and the flue gas are respectively sent into a gas waste heat boiler 610 and a flue gas waste heat boiler 620 for cooling, preheated steam and oxygen or air are produced through a steam heat exchanger and an oxygen heat exchanger in sequence and are supplied to each reactor, and finally the cooled low-temperature hydrogen-rich gas is subjected to processes of dust removal, desulfurization, drying and the like to produce clean hydrogen-rich gas.
Further, the temperature of the pyrolysis reactor 200 is 700-850 ℃, the temperature of the gasification reactor 300 is 800-900 ℃, and the temperature of the reforming reactor 500 is 900-1000 ℃. The temperature distribution is matched with the system structure and sequentially comprises low-temperature pyrolysis, medium-temperature gasification and high-temperature combustion reforming. In the pyrolysis reactor 200, the molar ratio of steam to oxygen is 1.1 to 1.3; in the gasification reactor 300, the molar ratio of steam to oxygen is 0.5. The temperature in the pyrolysis reactor and the gasification reactor can be controlled separately by adjusting the steam to oxygen molar ratio.
The technical solution provided by the present invention is further explained below according to specific embodiments.
Cotton stalks were used as biomass raw materials, and their industrial analysis and elemental analysis are shown in table 1. The reforming furnace catalyst adopts a biochar catalyst, and oxygen does not need to be introduced into a heating chamber of the reforming furnace to eliminate carbon deposition of the catalyst. The technological indexes are shown in Table 2, wherein the gasification efficiency can reach 91.1% at most, and H 2 The concentration is as high as 43.4%.
TABLE 1 Industrial and elemental analysis of Cotton stalks
Note: a: ash content; v: volatilizing; FC: fixing carbon; db: drying the substrate; * : obtained by differential subtraction
TABLE 2 Biomass gasification Process index
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A system for producing hydrogen rich gas by staged gasification of biomass, comprising a pyrolysis reactor (200), a gasification reactor (300), a reforming reactor (500), and a combustion reactor (400), wherein:
the pyrolysis reactor (200) is respectively connected with the gasification reactor and the reforming reactor and is used for pyrolyzing biomass and respectively sending coke and pyrolysis gas generated by pyrolysis into the gasification reactor (300) and the reforming reactor (500);
a funnel-shaped baffle plate (304) is arranged in the gasification reactor (300), the surface of the funnel-shaped baffle plate (304) is provided with an opening, an annular air chamber (305) is arranged below the funnel-shaped baffle plate, so that the gasification reactor (300) is divided into a purification area and a gasification area, the purification area and the gasification area are connected through a central channel by a conical opening of the funnel-shaped baffle plate (304) so as to send coke from the purification area to the gasification area for gasification, and meanwhile, exhaust pipes (306) are arranged around the annular air chamber (305) so as to communicate gas spaces of the purification area and the gasification area; in addition, a first gas outlet (301) is arranged at the top of the gasification reactor (300), an overflow port (307) is arranged at the bottom of the gasification reactor, the first gas outlet (301) is used for outputting the prepared hydrogen-rich gas, and the overflow port (307) is used for conveying coke to the combustion reactor (400);
a first air inlet (511) of the reforming reactor (500) is connected with the pyrolysis reactor, and a second air outlet (514) of the reforming reactor is connected with the annular air chamber (305) so as to carry out catalytic reforming on the pyrolysis gas to obtain reformed gas, send the reformed gas into a purification zone for purification, and mix the reformed gas with the purified gasified gas to obtain hydrogen-rich gas;
the combustion reactor (400) is disposed at the lower portion of the reforming reactor (500) and separated from the reforming reactor (500) by an intermediate partition, and the bottom of the combustion reactor (400) is connected to an overflow port (307) to combust coke to heat the reforming reactor (500).
2. The system for preparing the hydrogen-rich gas through the graded gasification of the biomass as claimed in claim 1, wherein a preset number of impellers (530) which rotate coaxially are arranged in the reforming reactor (500), catalysts are arranged in spaces of adjacent blades in the impellers (530), and porous baffles are arranged above and below the impellers (530) to prevent the catalysts from falling off; the reforming reactor (500) is symmetrically divided into a reforming chamber (510) and a heating chamber (520) by a vertical partition plate between adjacent impellers (530), the top of the reforming chamber (510) is provided with a first air inlet (511) for connecting with the pyrolysis reactor to send pyrolysis gas into the reforming chamber (510) for catalytic reforming, and the bottom of the reforming chamber (510) is provided with a second air outlet (514) for connecting with the annular air chamber (305) to send the reforming gas into a purification area for purification; the bottom of the heating chamber (520) is connected with the combustion reactor (400) and used for introducing flue gas to heat, when the combustion reactor works, the impeller (530) rotates in a circulating mode in the reforming chamber and the heating chamber, the temperature of the catalyst is increased on one side of the heating chamber, and heat is released on one side of the reforming chamber.
3. The system for preparing hydrogen-rich gas through biomass staged gasification according to claim 1, wherein a first cyclone (210) is disposed above the pyrolysis reactor (200), the pyrolysis reactor (200) adopts a fluidized bed operation mode for pyrolyzing biomass raw materials, and an air outlet of the pyrolysis reactor (200) is connected to the first cyclone (210) for separating pyrolysis gas and coke generated by pyrolysis; the first cyclone (210) is connected to the gasification reactor and the reforming reactor, respectively, to feed the char and the pyrolysis gas into the gasification reactor and the reforming reactor, respectively.
4. The system for preparing the hydrogen-rich gas through the biomass staged gasification according to claim 1, wherein the combustion reactor (400) is provided with a built-in second cyclone separator (410) at the upper part, the air outlet of the second cyclone separator (410) is connected with the second air inlet (521) of the reforming reactor (500) so as to lead the flue gas generated by the combustion of the combustion reactor (400) to the heating chamber (520), and the ash outlet (411) of the second cyclone separator (410) is positioned outside the combustion reactor (400).
5. The system for preparing the hydrogen-rich gas through the biomass staged gasification according to claim 1, further comprising a flue gas waste heat boiler (620) and a gas waste heat boiler (610), wherein an air inlet of the flue gas waste heat boiler (620) is connected with a third air outlet (523) of the heating chamber, and a first steam preheater (621) and a first oxygen preheater (622) are arranged inside the flue gas waste heat boiler (620) to preheat steam and oxygen or air by using the flue gas waste heat of the heating chamber; the gas inlet of the gas waste heat boiler is connected with a third gas outlet (301) of the gasification reactor (300), and meanwhile, a second steam preheater (611) and a second oxygen preheater (612) are arranged inside the gas waste heat boiler to preheat steam and oxygen or air by using the hydrogen-rich gas waste heat of the gasification reactor (300).
6. The system for preparing hydrogen rich gas through biomass staged gasification according to claim 1, further comprising a feeding unit (100), wherein the feeding unit (100) comprises a screw feeder (120) and a silo (110), one end of the screw feeder (120) is connected with the silo (110), and the other end of the screw feeder is connected with the pyrolysis reactor, so as to provide biomass raw material to the pyrolysis reactor.
7. The system for preparing the hydrogen-rich gas through the graded gasification of the biomass as claimed in any one of claims 1 to 6, wherein the number of the exhaust pipes (306) in the gasification reactor (300) is 6 to 12, the upper end of the exhaust pipe (306) is higher than the lower end of the ash falling pipe of the first cyclone separator (210), 3 to 5 layers of rotating impellers (530) are arranged in the reforming reactor (500), each layer of rotating impellers (530) comprises 20 to 30 blades, and the vertical partition plate is in an I shape.
8. A method for preparing hydrogen-rich gas by biomass staged gasification, which is characterized in that the method adopts the system for preparing hydrogen-rich gas by biomass staged gasification according to any one of claims 1 to 7, and comprises the following steps:
(1) Biomass is pyrolyzed in a pyrolysis reactor (200), and generated coke and pyrolysis gas are respectively sent into a gasification reactor (300) and a reforming reactor (500);
(2) The coke firstly falls into a purification area of a gasification reactor (300) and falls into a gasification area through a central channel, the coke is gasified in the gasification area, generated gasification gas is discharged to the upper part of the purification area through an exhaust pipe (306), and the coke at the bottom layer of the gasification area is sent into a combustion reactor (400) through an overflow port (307);
(3) Burning coke in a combustion reactor (400), and introducing the generated flue gas into a reforming reactor (500) to heat the flue gas;
(4) The pyrolysis gas is catalytically reformed in a reforming reactor (500) to generate reformed gas, and the reformed gas is sent into a purification zone through an annular air chamber (305) for purification and is mixed with the gasified gas to obtain hydrogen-rich gas, so that the preparation of the hydrogen-rich gas by biomass fractional gasification is completed.
9. The method for producing hydrogen-rich gas by staged gasification of biomass according to claim 8, wherein the temperature of the pyrolysis reactor (200) is 700 to 850 ℃, the temperature of the gasification reactor (300) is 800 to 900 ℃, and the temperature of the reforming reactor (500) is 900 to 1000 ℃.
10. The method for preparing the hydrogen-rich gas through the biomass staged gasification according to claim 8 or 9, wherein the molar ratio of steam to oxygen in the pyrolysis reactor (200) is 1.1; in the gasification reactor (300), the molar ratio of steam to oxygen is 0.5.
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