CN114044490B - Device and method for preparing hydrogen-rich gas based on double fluidized bed pyrolysis gas conversion - Google Patents
Device and method for preparing hydrogen-rich gas based on double fluidized bed pyrolysis gas conversion Download PDFInfo
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- C01B3/388—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the heat being generated by superheated steam
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- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
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- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
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Abstract
The invention discloses a device and a method for preparing hydrogen-rich gas based on double fluidized bed pyrolysis gas conversion. The invention adopts a process route for preparing hydrogen-rich gas by catalytic reforming of tar water vapor under high temperature and carries out waste heat recovery by a combined mode of a superheater and a waste heat boiler, avoids the mode of ammonia spraying water quenching and electric tar catching, solves the problems of waste of sensible heat of high-temperature pyrolysis gas, pipeline blockage due to condensation and precipitation of tar, less pyrolysis gas amount and less hydrogen content, and realizes the optimal purposes of energy utilization and substance utilization of the whole device because the required heat and the high-temperature water vapor required by reforming reaction come from the side of the circulating fluidized bed boiler without externally supplementing steam or energy.
Description
Technical Field
The invention relates to a process for preparing hydrogen-rich gas by converting and purifying coal gas, belongs to the fields of clean energy technology and coal chemical industry, and particularly relates to a device and a method for preparing hydrogen-rich gas by converting pyrolysis gas based on a double fluidized bed.
Background
The active development of new energy and the efficient and clean utilization of traditional energy are the current energy patterns in China. The new energy sources currently in use and research mainly include: solar energy, wind energy, biomass energy, nuclear energy, hydrogen energy and the like. Hydrogen energy has excellent properties of large storage capacity, high calorific value, multiple purposes and no pollution, and occupies an important position in new energy. At present, the preparation method of hydrogen energy mainly comprises natural gas hydrogen production, water electrolysis hydrogen production, coal gasification hydrogen production and the like. Coal in the traditional energy is always the main body of an energy production and consumption structure, and the main idea of high-efficiency clean utilization of the coal is to achieve the aim of multilevel gradient utilization by carrying out graded conversion and gradual extraction on various effective components in the coal. Coal grading utilization technology based on pyrolysis is used for upgrading coal under the condition of high temperature and oxygen insulation to obtain coal gas, tar and semicoke, wherein the coal gas and the tar can be used as high-quality fuel and can also be used for producing chemical products; the char may be used as coke or further combusted or gasified. The micromolecule gas contained in the pyrolysis gas mainly comprises hydrogen, methane, carbon monoxide, carbon dioxide and the like. At present, the hydrogen production from pyrolysis gas is not the mainstream hydrogen production technology, mainly because the total amount of pyrolysis gas generated by each ton of coal is not large and the hydrogen concentration is not high, for medium and low temperature pyrolysis, each ton of coal generates 200-300 parts of pyrolysis gas, the volume fraction of hydrogen is about 20-30%, the high temperature pyrolysis of each ton of coal generates 350-450 parts of pyrolysis gas, and the volume fraction of hydrogen is about 50-60%. Hydrogen production from pyrolysis gas alone is not competitive with hydrogen production from steam reforming of methane. However, the coal grading utilization technology based on pyrolysis has the advantages that target products not only include pyrolysis gas, but also semicoke, electricity, steam and the like, so that the method for preparing the hydrogen-rich gas by using the pyrolysis gas still has practical significance.
In a plurality of pyrolysis technologies, the double fluidized bed pyrolysis technology organically couples pyrolysis of coal and semicoke combustion together, the coal is subjected to medium-low temperature pyrolysis in a pyrolysis furnace to generate pyrolysis gas containing gaseous tar, a pyrolysis heat source is high-temperature ash separated from cyclone of a circulating fluidized bed boiler, and the semicoke generated after pyrolysis and the cooled high-temperature ash are fed into the circulating fluidized bed boiler together to be combusted and heated to generate high-temperature ash and high-temperature flue gas. The double fluidized bed pyrolysis process has the advantages of wide fuel adaptability, low requirements on process parameters, low equipment investment, direct combustion and utilization of semicoke at a high temperature state, easiness in realization of large-scale production and good pollutant emission control characteristic, and is a technology with a very good application prospect in the field of efficient clean utilization of coal in the future.
In the dual fluidized bed pyrolysis process, pyrolysis gas from the fluidized bed pyrolysis furnace contains high-concentration dust, gaseous tar, small molecule combustible gas and a large amount of physical sensible heat. Traditional purification process is the mode of spouting ammonia quench under the high temperature state with electric tar, and this purification mode can waste a large amount of sensible heats that pyrolysis gas carried, and tar and dust are simultaneously appeared in the in-process of cooling in the lump, and the mobility of dust-laden tar is poor, blocks up the pipeline easily, has also reduced the quality of retrieving tar.
The patent CN103013583A discloses a pyrolysis gas cooling dust removal and tar recovery process, which comprises a superheater, a high-temperature dust remover, an accident quench tower, a waste heat recovery boiler, an intercooler and an electric tar precipitator which are connected in sequence, wherein the process comprises the steps of firstly introducing pyrolysis gas into the superheater for cooling to 400 ℃ and 700 ℃, then introducing the pyrolysis gas into the high-temperature dust remover for dust removal, then introducing the waste heat recovery boiler for cooling to 50-100 ℃, simultaneously condensing and separating out water and tar, and finally introducing the electric tar precipitator for recovering carried tar fog drops and water mist. The high-temperature dust remover adopted by the process is an electric dust remover or a filtering type dust remover, the performance and the stability are poor under the high-temperature condition, meanwhile, when the waste heat boiler cools the coal gas, most of tar is condensed and separated out, the separated tar can form a layer of film on the surface of the heat exchanger, when the liquid tar is gasified again by the high-temperature pyrolysis gas, the tar is reformed and gradually forms a graphite-like structure due to hydrogen loss and cross-linking reaction, and coking is adhered to the surface of the heat exchanger, so that the heat exchange efficiency is influenced, and the risk of blocking the pipeline is caused.
Patent CN104495749A discloses a device and method for preparing hydrogen by using coke oven crude gas, which comprises a reforming hydrogen production reactor, an adsorbent regenerator, a gas-solid separator, a storage bin, a steam reheater, a feeding device, a waste heat boiler, a gas storage cabinet and a pressure swing adsorption device; in the reforming hydrogen production reactor, the high-temperature coke oven crude gas and water vapor generate reforming hydrogen production reaction under the action of a catalyst, and CO2Sorbent and CO produced by reforming reactions2The solid adsorbent enters an adsorbent regenerator for regeneration to obtain CO2The hydrogen-rich gas is sequentially stored in the H after passing through the waste heat boiler and the drying tower2A gas storage cabinet. The steam required by the process comes from an external steam pipeline, the heat required by the reforming reaction is sensible heat carried by high-temperature pyrolysis gas, and the process is mainly suitable for high-temperature pyrolysis coke oven gas and is not suitable for double fluidized bed-based medium-low temperature pyrolysis gasThe reason is that the temperature required by the reforming reaction is 800-900 ℃, the temperature of the coke oven gas is high, but the double-fluidization pyrolysis process is typical medium-low temperature pyrolysis and is limited by the maximum pyrolysis gas temperature of the circulating ash of about 750 ℃, so that additional heat supplement is required, and the patent depends on CaO and CO2The reaction supplements part of heat, which is suitable for high-temperature pyrolysis gas, but absolutely insufficient for medium-low temperature pyrolysis gas. Meanwhile, the reforming reactor adopted by the patent is a fluidized bed, the catalyst and the absorbent are carried out of the reforming reactor by the pyrolysis gas, enter an adsorbent regenerator after gas-solid separation and then return to the reforming reactor, and in the continuous circulating process, the particle sizes of the catalyst and the absorbent are continuously abraded and reduced until the catalyst and the absorbent cannot be trapped by the gas-solid separator, so that the catalyst and the absorbent are carried to the tail end waste heat boiler by the pyrolysis gas. When the system operates, the catalyst and the adsorbent need to be continuously supplemented, so that the operating cost is increased; furthermore, the catalyst adopted by the invention is a nickel-based catalyst, the sulfur-containing substances in the pyrolysis gas can cause catalyst poisoning and inactivation, and the system tar reforming efficiency is difficult to ensure.
In conclusion, the double-fluidized-bed-based medium-low temperature pyrolysis technology is a technology with a good application prospect in the field of efficient clean utilization of coal in the future. As the medium-low temperature pyrolysis gas has the characteristics of small gas amount, low hydrogen content, high dust content and high tar content, no process report for preparing the rich hydrogen by adopting the medium-low temperature pyrolysis gas is found.
Disclosure of Invention
Aiming at the defects of low energy utilization efficiency, pipeline blockage due to tar condensation and precipitation, low tar recovery quality, low pyrolysis gas amount and low hydrogen content in the traditional medium-low temperature pyrolysis gas treatment, the invention discloses a device and a method for preparing hydrogen-rich gas based on double fluidized bed pyrolysis gas conversion.
In order to solve the technical problem, the invention provides a device for preparing hydrogen-rich gas based on the conversion of pyrolysis gas of a double fluidized bed, which comprises:
the catalytic reactor, the pyrolysis gas side superheater, the high-temperature dust remover, the waste heat boiler, the intercooler, the fan and the hydrogen-rich gas storage tank are sequentially connected with a pyrolysis gas outlet of the pyrolysis furnace of the double fluidized bed pyrolysis process;
the flue gas side superheater is connected with a flue gas outlet of a cyclone dust collector of the double fluidized bed pyrolysis process, a cold end medium of the flue gas side superheater is superheated steam, and the superheated steam is heated by the flue gas side superheater and then partially or completely enters the catalytic reactor; and
and the high-temperature heat exchanger is connected with the flue gas outlet of the cyclone dust collector, surrounds the catalytic reactor, provides reaction heat for the catalytic reactor, and allows the flue gas subjected to heat exchange by the high-temperature heat exchanger to enter a flue gas shell of the flue gas side superheater.
Furthermore, the pyrolysis furnace adopts a bubbling fluidized bed, the fluidized medium is hydrogen-rich gas from a hydrogen-rich gas storage tank, an overflow port is formed in the bottom of the pyrolysis furnace and is used as a channel for allowing pyrolyzed semicoke and circulating ash to enter the circulating fluidized bed, and the operating temperature of the pyrolysis furnace is between 500 ℃ and 800 ℃.
Further, the circulating fluidized bed boiler is a circulating fluidized bed for burning high-temperature semicoke, the fluidizing medium is air, and the operating temperature is between 900 ℃ and 1000 ℃; the cyclone dust collector connected with the circulating fluidized bed boiler is a heat-insulating cyclone dust collector with an inner lining made of wear-resistant refractory materials.
Further, the high-temperature heat exchanger is a tubular heat exchanger, the medium at the hot end is high-temperature flue gas, and the temperature is 900-; the catalytic reactor is a fixed bed reactor, the temperature in the catalytic reactor is 800-900 ℃, and coal tar and steam in pyrolysis gas in the catalytic reactor are subjected to reforming reaction under the action of a catalyst to prepare hydrogen-rich gas.
Furthermore, the flue gas side superheater and the pyrolysis gas side superheater both adopt coiled tube type heating surfaces, the medium at the cold end of the flue gas side superheater and the medium at the pyrolysis gas side superheater are superheated steam with the temperature of more than 350 ℃, the steam flows through a tube pass, and the flue gas and the pyrolysis gas flow through a shell pass.
Furthermore, the waste heat boiler adopts a coiled pipe type heating surface, the medium at the cold end of the waste heat boiler is liquid water, water flows through a pipe pass, and hydrogen-rich gas flows through a shell pass.
Further, the intercooler is internally provided with a heat exchange tube array, circulating cooling water flows in the tube, hydrogen-rich gas flows out of the tube, and the intercooler further cools the hydrogen-rich gas and condenses and separates out liquid water.
On the other hand, the invention also provides a method for preparing hydrogen-rich gas based on the conversion and purification of the double fluidized bed pyrolysis gas, which comprises the following steps:
coal enters a pyrolysis furnace and is pyrolyzed under the heating of high-temperature ash to generate pyrolysis gas containing gaseous tar and semicoke, the cooled high-temperature ash and semicoke are sent into a circulating fluidized bed through a material returning mechanism, and semicoke is combusted to generate high-temperature flue gas and heat circulating ash;
mixing pyrolysis gas discharged from the pyrolysis furnace with high-temperature steam, feeding the mixed steam-rich pyrolysis gas into a catalytic reactor, and carrying out a reforming reaction on coal tar and the steam in the pyrolysis gas under the action of a catalyst to generate a hydrogen-rich gas;
the hydrogen-rich gas enters a pyrolysis gas side superheater to be cooled; then the hydrogen-rich gas enters a high-temperature dust remover to remove dust; then the hydrogen-rich gas enters a waste heat boiler for cooling and is condensed to produce water; then the water enters an intercooler for further condensation and water outlet, and finally enters a hydrogen-rich gas storage tank for temporary storage under the action of a fan;
after cyclone dust removal is carried out on high-temperature flue gas discharged from the circulating fluidized bed boiler through a cyclone dust collector, one stream of the high-temperature flue gas is introduced into a high-temperature heat exchanger to serve as a hot end medium of the high-temperature heat exchanger, the flue gas after heat exchange and the flue gas which does not exchange heat are used as the hot end medium of a flue gas side superheater to heat superheated steam, and part or all of the superheated steam after temperature rise is decompressed through a steam pressure reducing valve and then is mixed with pyrolysis gas from a pyrolysis furnace.
Further, the high-temperature heat exchanger is a tubular heat exchanger, the medium at the hot end is high-temperature flue gas, and the temperature is 900-. Further, the catalytic reactor is a fixed bed reactor, the temperature in the catalytic reactor is 800-900 ℃, and coal tar and steam in the pyrolysis gas in the catalyst reactor are subjected to reforming reaction under the action of the catalyst to prepare hydrogen-rich gas. Further, the high temperature heat exchanger is enclosed outside the catalyst reactor.
Furthermore, the introduction amount of high-temperature water vapor is controlled according to the amount of gaseous tar in the pyrolysis gas, so that the water-carbon ratio of the mixed gas is ensured to be between 5 and 10 when the mixed gas enters the catalytic reactor.
Furthermore, the amount of the high-temperature flue gas introduced into the high-temperature heat exchanger is determined according to the temperature and the flow of the pyrolysis gas containing steam entering the catalytic reactor, so that the temperature of the catalytic reactor is ensured to be 800-900 ℃. Furthermore, the catalyst in the catalytic reactor is calcined dolomite which is ground into powder.
Further, the temperature of the hydrogen-rich gas after entering the pyrolysis gas side superheater and being cooled is 400-500 ℃. Further, the temperature of the hydrogen-rich gas after entering the waste heat boiler for cooling is 80-150 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts the process route of catalytically reforming tar water vapor under high temperature to prepare hydrogen-rich gas and carries out waste heat recovery by the combined mode of a superheater and a waste heat boiler, avoids the mode of spraying ammonia water for quenching and electrically trapping tar under high temperature state adopted in the prior pyrolysis gas purification technology, and solves the problems of waste of sensible heat of high-temperature pyrolysis gas, pipeline blockage due to condensation and precipitation of tar, less pyrolysis gas amount and less hydrogen content, thereby obtaining the pyrolysis gas with large flow and high hydrogen content.
The anti-sticking and anti-blocking array type high-temperature multi-pipe cyclone dust removal device is adopted to directly remove dust under the high-temperature condition, and the defect that the dust is removed by spraying in the existing pyrolysis gas purification technology is overcome, so that high-quality hydrogen-rich pyrolysis gas is obtained, the condition that a large amount of dust is separated out together with condensate water of a waste heat boiler in the process is avoided, and the stable operation of the waste heat boiler is facilitated.
The invention is suitable for the pyrolysis process based on the double fluidized beds, raw material steam required for catalytic reaction in the process is completely from heating superheated steam of a flue gas side superheater, and high-temperature steam is not required to be supplemented externally; the heat required by the reaction in the catalytic reactor is from the high-temperature heat exchanger, the heat of the high-temperature heat exchanger is completely from the flue gas at the outlet of the circulating fluidized bed boiler, and the whole process does not need external energy supplement.
Drawings
FIG. 1 is a schematic view of the process flow of the invention for preparing hydrogen-rich gas by dust removal, waste heat recovery and catalytic reforming of tar and steam;
wherein: 1-circulating fluidized bed boiler, 2-pyrolysis furnace, 3-cyclone dust collector, 4-flue gas side superheater, 5-steam pressure reducing valve, 6-high temperature heat exchanger, 7-catalytic reactor, 8-pyrolysis gas side superheater, 9-high temperature dust collector, 10-waste heat boiler, 11-intercooler, 12-fan, 13-hydrogen-rich gas storage tank and 14-wastewater disposal pool. A-high-temperature flue gas, B-superheater cold end medium, C-high-temperature water vapor, D-flue gas, E-pyrolysis gas, F-rich water vapor pyrolysis gas, G-superheater cold end medium, H-high-temperature ash, I-waste heat boiler cooling medium, J-intercooler cooling medium, K-dewatered hydrogen-rich gas and L-waste water.
Detailed Description
The invention will be further illustrated and described with reference to specific embodiments. The technical features of the embodiments of the present invention can be combined correspondingly without mutual conflict.
As shown in fig. 1, a device for preparing hydrogen-rich gas based on double fluidized bed pyrolysis gas conversion, comprises a catalytic reactor 7, a pyrolysis gas side superheater 8, a high-temperature dust remover 9, a waste heat boiler 10, an intercooler 11, a fan 12, a hydrogen-rich gas storage tank 13, a cyclone dust remover 3, a high-temperature heat exchanger 6, a flue gas side superheater 4 and a steam pressure reducing valve 5, wherein the cyclone dust remover 3 is sequentially connected with the circulating fluidized bed boiler 1, a flue gas outlet is also provided with a branch which is directly connected with a hot end inlet of the flue gas side superheater 4, and the proportion of flue gas at the outlet of the cyclone dust remover entering the flue gas side superheater 4 and entering the high-temperature heat exchanger 6 can be adjusted according to actual working conditions.
The pyrolysis furnace 2 adopts a bubbling fluidized bed, the fluidized medium is the hydrogen-rich gas from the hydrogen-rich gas storage tank 13, the bottom of the pyrolysis furnace 2 is provided with an overflow port which is used as a channel for the semicoke and the circulating ash after pyrolysis to enter the circulating fluidized bed boiler 1, and the operation temperature of the pyrolysis furnace 2 is between 500 ℃ and 800 ℃, which is a typical medium-low temperature pyrolysis process.
The circulating fluidized bed boiler 1 is a circulating fluidized bed for burning high-temperature semicoke, the fluidizing medium is air, the operating temperature is between 900 ℃ and 1000 ℃, the cyclone dust collector 3 connected with the circulating fluidized bed boiler 1 is an adiabatic cyclone dust collector with an inner lining of wear-resistant refractory materials, part of high-temperature ash separated by the cyclone dust collector 3 is sent into the pyrolysis furnace 2 to be used as a heat source for coal pyrolysis, and the rest part of high-temperature ash is returned to the circulating fluidized bed boiler 1.
The flue gas side superheater 4 and the pyrolysis gas side superheater 8 adopt coiled pipe type heating surfaces, a cold end medium B, G of the coiled pipe type heating surfaces is superheated steam with the temperature of more than 350 ℃, the steam flows through a pipe pass, and flue gas and pyrolysis gas flow through a shell pass.
The high-temperature heat exchanger 6 is a tubular heat exchanger, the medium at the hot end is high-temperature flue gas A, the temperature is 900-.
The catalytic reactor 7 is a fixed bed reactor, and coal tar and steam in the pyrolysis gas inside the catalytic reactor 7 are subjected to reforming reaction under the action of a catalyst to prepare hydrogen-rich gas. The catalyst is calcined dolomite which is ground into powder.
The high-temperature dust remover 9 is self-developed equipment of the applicant, has a detailed structure disclosed in publication No. CN112156900A, and is an anti-sticking and anti-blocking array type high-temperature multi-pipe cyclone dust removal device, the dust remover has high dust removal efficiency and high stability, and the dust removal efficiency of dust carried in typical bubbling fluidized bed pyrolysis gas can reach 95%.
The exhaust-heat boiler 10 adopts a coiled pipe type heating surface, the cooling medium I is liquid water, the water flows through a pipe pass, and the hydrogen-rich gas flows through a shell pass. Meanwhile, a large amount of liquid water is condensed and separated out in the hydrogen-rich cooling process, and a layer of water film is formed on the outer wall of the pipeline, so that a large contamination coefficient is considered in the design of the waste heat boiler.
The intercooler 11 is internally provided with a heat exchange tube array, circulating cooling water flows in the tube, and hydrogen-rich gas flows out of the tube, and the intercooler is used for further cooling the hydrogen-rich gas and condensing to separate out liquid water.
The waste water tank 14 temporarily stores liquid water condensed and separated from the waste heat boiler 10 and the intercooler 11.
The fan 12 provides power for pyrolysis gas delivery.
The hydrogen rich gas storage tank 13 is a place for temporarily storing the hydrogen rich gas.
The working principle of the process is as follows:
the pyrolysis furnace 2 and the circulating fluidized bed boiler 1 form a double fluidized bed pyrolysis and semicoke combustion process section, coal enters the fluidized bed pyrolysis furnace 2 to be pyrolyzed under the heating of high-temperature ash to generate pyrolysis gas E containing gaseous tar and semicoke, the cooled high-temperature ash and semicoke are sent into the circulating fluidized bed boiler 1 through a material returning mechanism, and the semicoke is combusted to generate high-temperature flue gas A and heat circulating ash;
pyrolysis gas E discharged from the pyrolysis furnace enters a catalytic reactor 7 from water-rich steam pyrolysis gas F mixed with high-temperature steam C, and coal tar and steam in the pyrolysis gas are subjected to reforming reaction under the action of a catalyst to generate hydrogen-rich gas;
then the hydrogen-rich gas enters a pyrolysis gas side superheater 8 and is cooled to 400-500 ℃;
then the hydrogen-rich gas enters a high-temperature dust remover 9 to remove dust;
further, the hydrogen-rich gas enters the waste heat boiler 10 and is cooled to 80-150 ℃, and simultaneously a large amount of water is separated out;
then enters an intercooler 11 for further condensation to obtain water;
finally, the hydrogen-rich gas enters a hydrogen-rich gas storage tank 13 for temporary storage under the action of a fan 12;
one stream of high-temperature flue gas A which is discharged from the circulating fluidized bed boiler 1 is introduced into a high-temperature heat exchanger 6 after cyclone dust removal and is used as a hot end medium of the high-temperature heat exchanger, the flue gas after heat exchange and the flue gas without heat exchange are used as the hot end medium of a flue gas side superheater 4 to heat superheated steam, one stream of the superheated steam after temperature rise is decompressed by a steam pressure reducing valve 5 and then mixed with pyrolysis gas E from a pyrolysis furnace, and the flue gas D which passes through the flue gas side superheater 4 enters a downstream heat exchanger.
The introduction amount of the high-temperature water vapor C is related to the amount of the gaseous tar in the pyrolysis gas E, so that the water-carbon ratio of the mixed gas is ensured to be between 5 and 10.
The amount of the high-temperature flue gas A introduced into the high-temperature heat exchanger 6 is determined according to the temperature and the flow of the pyrolysis gas F rich in water vapor at the front end, and the temperature of the reactor is ensured to be 800-900 ℃ so as to ensure that the catalyst is always in a high-activity temperature window; the steam pressure after being decompressed by the decompression valve is micro-positive pressure.
Example 1
The temperature of pyrolysis gas at the outlet of the pyrolysis furnace is 650 ℃, the dust content is 12g/Nm3, the water vapor content is 26 percent, and the tar content is 115g/Nm3And the temperature of the flue gas at the outlet of the circulating fluidized bed boiler is 950 ℃. The pyrolysis gas is mixed with high-temperature steam generated by the flue gas side superheater processed by the pressure reducing valve, the content of the mixed steam is 73%, and the water-carbon ratio is about 6. And introducing the mixed steam-rich pyrolysis gas into a catalytic reactor, and carrying out a reforming reaction on tar and steam in the pyrolysis gas under the action of a catalyst to generate a hydrogen-rich gas. The outside of the reforming reactor is surrounded by a high-temperature heat exchanger, the medium at the hot end of the high-temperature heat exchanger is high-temperature flue gas, the inlet temperature is 950 ℃, the outlet temperature is 850 ℃, and the catalytic reaction temperature is basically maintained at 830 ℃. The flue gas after heat exchange and the flue gas without heat exchange are mixed and enter a flue gas side superheater to generate high-temperature high-pressure steam. The high-temperature hydrogen-rich gas enters a pyrolysis gas side superheater to be cooled to 450 ℃, and then enters a high-temperature dust remover, wherein the dust removal efficiency is 96%; then the waste heat water enters a waste heat boiler to be cooled to about 80 ℃, and liquid water is condensed and separated out; then introducing the mixture into an intercooler to be cooled to 25 ℃, and further separating out liquid water; and finally, the hydrogen-rich gas enters a hydrogen-rich gas storage tank for temporary storage under the driving of a fan.
The gas in the hydrogen-rich gas storage tank is sampled and analyzed, the volume fraction of the hydrogen-rich gas obtained by the process flow is 76%, the total waste heat recovery efficiency is 91%, the tar-containing gas is converted and purified under the condition of high energy utilization efficiency, and the whole process does not need to supplement heat and steam externally, so that the process has the characteristics of high energy utilization efficiency and excellent material utilization.
Example 2
The temperature of pyrolysis gas at the outlet of the pyrolysis furnace is 700 ℃, the dust content is 15g/Nm3, the water vapor content is 13%, the tar content is 76g/Nm3, and the temperature of flue gas at the outlet of the circulating fluidized bed boiler is 950 ℃. The pyrolysis gas is mixed with high-temperature steam generated by the flue gas side superheater processed by the pressure reducing valve, the content of the mixed steam is 65%, and the water-carbon ratio is about 7. And introducing the mixed steam-rich pyrolysis gas into a catalytic reactor, and carrying out a reforming reaction on tar and steam in the pyrolysis gas under the action of a catalyst to generate a hydrogen-rich gas. The outside of the reforming reactor is surrounded by a high-temperature heat exchanger, the medium at the hot end of the high-temperature heat exchanger is high-temperature flue gas, the inlet temperature is 950 ℃, the outlet temperature is 850 ℃, and the catalytic reaction temperature is basically maintained at 850 ℃. The flue gas after heat exchange and the flue gas without heat exchange are mixed and enter a flue gas side superheater to generate high-temperature high-pressure steam. The high-temperature hydrogen-rich gas enters a pyrolysis gas side superheater to be cooled to 450 ℃, and then enters a high-temperature dust remover, wherein the dust removal efficiency is 97%; then the waste heat water enters a waste heat boiler to be cooled to about 80 ℃, and liquid water is condensed and separated out; then introducing the mixture into an intercooler to be cooled to 25 ℃, and further separating out liquid water; and finally, the hydrogen-rich gas enters a hydrogen-rich gas storage tank for temporary storage under the driving of a fan.
The gas in the hydrogen-rich gas storage tank is sampled and analyzed, the volume fraction of the hydrogen-rich gas obtained by the process flow is 72%, the total waste heat recovery efficiency is 90%, the tar-containing gas is converted and purified under the condition of high energy utilization efficiency, and the whole process does not need to supplement heat and steam externally, so that the process has the characteristics of high energy utilization efficiency and excellent material utilization.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the appended claims.
Claims (5)
1. A method for preparing hydrogen-rich gas based on double fluidized bed pyrolysis gas conversion is characterized in that,
a pyrolysis gas outlet of a pyrolysis furnace of the double fluidized bed pyrolysis process is sequentially connected with a catalytic reactor, a pyrolysis gas side superheater, a high-temperature dust remover, a waste heat boiler, an intercooler, a fan and a hydrogen-rich gas storage tank;
a flue gas outlet of a cyclone dust collector of the double fluidized bed pyrolysis process is connected with a flue gas side superheater, a cold end medium of the flue gas side superheater is superheated steam, and the superheated steam is heated by the flue gas side superheater and then partially or completely enters the catalytic reactor;
the flue gas outlet of the cyclone dust collector is connected with a high-temperature heat exchanger, the high-temperature heat exchanger surrounds the catalytic reactor and provides reaction heat for the catalytic reactor, and the flue gas subjected to heat exchange by the high-temperature heat exchanger enters a flue gas shell of the flue gas side superheater;
the method comprises the following steps:
the coal enters a pyrolysis furnace and is pyrolyzed under the heating of high-temperature ash to generate pyrolysis gas containing gaseous tar and semicoke, the operating temperature of the pyrolysis furnace is between 500 ℃ and 800 ℃, the cooled high-temperature ash and semicoke are sent into a circulating fluidized bed through a material returning mechanism, and the semicoke is combusted to generate high-temperature flue gas and heat the circulating ash;
mixing pyrolysis gas discharged from the pyrolysis furnace with high-temperature steam, and controlling the introduction amount of the high-temperature steam according to the amount of gaseous tar in the pyrolysis gas to ensure that the water-carbon ratio of the mixed gas is between 5 and 10 when the mixed gas enters a catalytic reactor;
the mixed steam-rich pyrolysis gas enters a catalytic reactor, and coal tar and steam in the pyrolysis gas undergo a reforming reaction under the action of a catalyst to generate a hydrogen-rich gas; the high-temperature heat exchanger surrounds the outside of the catalytic reactor, the high-temperature heat exchanger is a tubular heat exchanger, the hot end medium is high-temperature flue gas, the temperature is 900-,
the hydrogen-rich gas enters a pyrolysis gas side superheater to be cooled; then the hydrogen-rich gas enters a high-temperature dust remover to remove dust; then the hydrogen-rich gas enters a waste heat boiler for cooling and is condensed to produce water; then the water enters an intercooler for further condensation and water outlet, and finally enters a hydrogen-rich gas storage tank for temporary storage under the action of a fan;
after cyclone dust removal is carried out on high-temperature flue gas discharged from the circulating fluidized bed boiler through a cyclone dust collector, one stream of the high-temperature flue gas is introduced into a high-temperature heat exchanger to serve as a hot end medium of the high-temperature heat exchanger, the flue gas after heat exchange and the flue gas which does not exchange heat are used as the hot end medium of a flue gas side superheater to heat superheated steam, and part or all of the superheated steam after temperature rise is decompressed through a steam pressure reducing valve and then is mixed with pyrolysis gas from a pyrolysis furnace.
2. The method for preparing hydrogen-rich gas by converting pyrolysis gas as claimed in claim 1, wherein the amount of the high-temperature flue gas introduced into the high-temperature heat exchanger is determined according to the temperature and flow rate of the pyrolysis gas containing steam entering the catalytic reactor, so as to ensure that the temperature of the catalytic reactor is 800-900 ℃.
3. The process for producing hydrogen-rich gas by the conversion of pyrolysis gas as claimed in claim 1, wherein the catalyst in the catalytic reactor is dolomite which is pulverized after calcination.
4. The method for preparing hydrogen-rich gas by converting pyrolysis gas as claimed in claim 1, wherein the temperature of the cooled hydrogen-rich gas entering the superheater at the pyrolysis gas side is 400-500 ℃.
5. The method for producing hydrogen-rich gas by converting pyrolysis gas according to claim 1, wherein the temperature of the cooled hydrogen-rich gas entering the exhaust-heat boiler is 80-150 ℃.
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