CN113816337A - Device and method for preparing hydrogen by reforming natural gas steam based on sensible heat of liquid metallurgical slag - Google Patents
Device and method for preparing hydrogen by reforming natural gas steam based on sensible heat of liquid metallurgical slag Download PDFInfo
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- C01B3/42—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 using moving solid particles
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- C01B3/40—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 characterised by the catalyst
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- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—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
- C01B3/34—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
- C01B3/48—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 followed by reaction of water vapour with carbon monoxide
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- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
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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
A device for preparing hydrogen by reforming natural gas steam based on sensible heat of liquid metallurgical slag comprises a heat-preservation slag tank, wherein the heat-preservation slag tank is connected with a granulating device through a water gap, the granulating device is communicated with a reforming furnace, the bottom of the reforming furnace is provided with a gas supply device and a slag discharge device, the top of the reforming furnace is communicated with a catalytic reactor, one side of the top of the catalytic reactor is communicated with a reformed gas waste heat boiler through a horizontal gas passage, a reformed gas outlet of the reformed gas waste heat boiler is sequentially communicated with a medium-temperature shift reactor and a pressure swing adsorption device, and a desorption tail gas outlet of the pressure swing adsorption device is communicated with the granulating device through a pipeline. The natural gas is heated by the high-temperature metallurgical slag, and the gas-liquid flow and the superheated steam of the metallurgical slag are subjected to conversion reaction, so that a complicated combustion device is omitted, a pipeline is not required, and the cost of expensive materials is saved; meanwhile, the heat provided by the liquid metallurgical slag also avoids burning a large amount of natural gas, and the use amount of the natural gas is greatly reduced, so that the carbon dioxide emission is reduced.
Description
Technical Field
The invention relates to the field of hydrogen production devices by utilizing metallurgical solid wastes and adopting energy and chemical technology, in particular to a device and a method for producing hydrogen by reforming natural gas steam based on sensible heat of liquid metallurgical slag.
Background
The method is carried out in a high temperature range around 1160 ℃ in a converter, has complex equipment structure, high cost and harsh working conditions, and generally burns methane to provide heat for the converter at present.
The ferrous metallurgy process generates a large amount of high-temperature waste slag, the discharge temperature of the high-temperature waste slag is 1400-1650 ℃, 1750MJ heat is contained in each ton of slag, the liquid metallurgical slag is a high-quality waste heat resource, the mode of treating the liquid metallurgical slag in the prior art is mainly a water quenching method, and the water quenching method not only wastes a large amount of water resources but also causes environmental pollution.
Therefore, the heat energy of the liquid metallurgical slag can be recovered and acted on the natural gas steam reforming, and the heat energy of the liquid metallurgical slag is used for providing heat supply for the converter, so that the waste of the heat energy of the metallurgical slag is reduced, and a large amount of carbon dioxide generated by burning methane is avoided.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a device and a method for preparing hydrogen by reforming natural gas steam based on the sensible heat of liquid metallurgical slag.
In order to achieve the purpose, the invention is realized by the following technical scheme: the utility model provides a device of natural gas vapour steam reforming hydrogen production based on liquid metallurgical sediment sensible heat, includes the heat preservation sediment jar, the heat preservation sediment jar passes through the mouth of a river and connects the granulation device, granulation device intercommunication reborner, the reborner stove bottom is provided with air feeder and row's sediment device, reborner top intercommunication catalytic reactor, catalytic reactor top one side communicates reborner gas exhaust-heat boiler through horizontal air flue, reborner gas exhaust-heat boiler's reborner gas outlet communicates medium temperature shift reactor, pressure swing adsorption equipment in proper order, pressure swing adsorption equipment's desorption tail gas export communicates the granulation device through the pipeline.
The granulating device consists of a gas nozzle with a Laval structure and an expansion channel, a communication port of the water gap is positioned between the gas nozzle and the expansion channel, and the granulating device is arranged on the upper furnace wall on the side surface of the converter through the expansion channel.
The expansion channel is of a sandwich structure, and ventilation spray holes are formed in the inner wall of the sandwich.
The reformed gas waste heat boiler and the water-cooled wall of the reforming furnace are communicated with the steam pocket, the generated saturated steam is sent to the gas supply device at the bottom of the reforming furnace, and the surplus steam is sent out.
And a gas-solid separation device is arranged in the horizontal air passage.
The gas supply device is communicated with the start-up steam pipeline.
A natural gas steam reforming hydrogen production method based on sensible heat of liquid metallurgical slag comprises the following steps:
s1, before the system is started, the heat-preservation slag pot, the water gap and the granulating device are dried and preheated, when the preheating temperature reaches 1000 ℃, liquid metallurgical slag is guided into the heat-preservation slag pot, the fluidity of slag liquid is kept, and the slag liquid with high fluidity flows between the gas nozzle and the expansion channel of the granulating device through the water gap;
s2, natural gas and a proper amount of oxygen enter a gas nozzle of the granulating device, the mixed gas of the natural gas and the oxygen is accelerated through a Laval throat of the gas nozzle to form supersonic airflow, the supersonic airflow is sprayed out of the nozzle to transversely impact slag liquid flowing out of a water gap, and the surface tension and viscosity constraint of the slag liquid are overcome, so that the liquid metallurgical slag is crushed into micro-liquid droplets; dispersing the mixed gas into a gas-liquid flow, wherein the natural gas and oxygen generate weak oxidation reaction to release heat during the process, so that the temperature of the gas-liquid flow is not lower than the melting temperature of metallurgical slag, the slag liquid is not solidified and bonded, tail gas is sprayed and desorbed on an expansion channel wall to form a gas film, and the gas-liquid mixed flow is sprayed into a furnace chamber of a converter through the expansion channel;
s3, introducing the start-up steam into the converter through the converter bottom gas supply device, mixing with the gas-liquid mixed flow in the converter, directly fusing and contacting, generating natural gas steam reforming reaction, absorbing heat strongly, and converting into H2、CO、CH4Transforming gas; the gas-liquid mixed flow is reformed and reactedAbsorbing heat, wherein the temperature of the mixed flow is reduced to be lower than the melting temperature of metallurgical slag, liquid drops in the mixed flow are solidified to form slag particles, the flow rate of the mixed flow is reduced, the slag particles are separated and settled from the air flow, the settled slag particles and steam rising at the bottom of the furnace perform countercurrent heat exchange, the slag particles are cooled and discharged out of the furnace from a slag discharge device at the bottom of the furnace, and the steam is heated to be higher than 500 ℃;
s4, rising the reformed gas generated by reforming reaction of natural gas steam from the reformer, accelerating the reformed gas through a contraction and expansion port at the connecting part of the furnace top and the catalytic reactor, entering a fluidized bed body of the catalytic reactor, generating violent turbulence and mixing of gas-solid phases of the reformed gas catalyst in the fluidized bed under the action of airflow, fully contacting, continuously forming agglomerates to return downwards in the rising process, continuously disintegrating the agglomerates in the violent turbulence and being lifted by the airflow again, and enabling the slip speed between the gas and the solid to be as high as tens of times of the slip speed of single particles;
s5, the converted gas after reforming reaction enters into the horizontal air passage through the top of the catalytic reactor, the converted gas decelerates in the horizontal air passage, the solid catalyst carried in the converted gas is settled by gravity, the sediment enters into the catalytic reactor through the dust collecting chute, the converted gas after dust removal enters into the converted gas waste heat boiler from the horizontal air passage, the converted gas after heat exchange of the waste heat boiler enters into the medium temperature shift reactor, and H in the converted gas is further converted by shift reaction2Conversion of O to H2While converting CO to CO2Thereby increasing the H of the product2The ratio of the converted gas after medium temperature conversion is cooled and then is introduced into a pressure swing adsorption device for H2Purification of (2), H2The purity reaches 99.9 percent.
Steam-water mixture generated by the heat exchange of the reformed gas waste heat boiler enters a steam drum, the steam-water mixture generated by the water-cooled wall of the reforming furnace also enters the steam drum, the steam-water mixture is subjected to steam-water separation in the steam drum, and steam enters a steam supply device at the bottom of the reforming furnace and is heated by the heat exchange of metallurgical slag to participate in the reforming of natural gas.
The temperature of liquid metallurgical slag in the heat-insulating slag pot is controlled at 1500-1650 ℃, the viscosity of slag liquid is 0.02-0.1 Pa.s, the surface tension is 0.3-0.6 N.m < -1 >, and the slag contains metal oxide with higher catalytic activity.
The molar ratio of steam to natural gas is 4: 1.
Compared with the prior art, the invention has the beneficial effects that:
1. the high-temperature liquid metallurgical slag is atomized into liquid drops to form a gas-liquid flow under the condition of blowing of natural gas mixed oxygen, the natural gas is heated to 1000 ℃, the high-temperature gas-liquid flow is in direct contact with steam overheated by solidified metallurgical slag, mixing and heat absorption are carried out, and a conversion reaction is carried out, so that a complicated combustion device is not arranged in a converter, a huge pipeline system is not needed, expensive high-temperature-resistant alloy materials with high chromium and nickel contents are saved, and a large amount of equipment investment is reduced.
2. Natural gas steam reforming is an energy-intensive endothermic process that requires high temperature heat input. In the traditional natural gas steam reforming method, natural gas is used as a reactant for hydrogen production and is combusted as a heat source for reaction, so that a large amount of natural gas is needed, and a large amount of carbon dioxide is discharged.
3. The metallurgical slag heat conductivity is low, the heat exchange is slow, the air is used for gas-solid heat exchange to recover high-temperature air at present, but the specific heat of the air is low, a huge amount of air is needed when the air is used for recovering the heat of the metallurgical slag, the recovery heat value is not against the input cost, the sensible heat of the liquid metallurgical slag is converted into chemical energy through the natural gas steam reforming conversion reaction, and the problems of large equipment loss, low effective energy recovery efficiency and the like generally existing in physical methods such as dry granulation of the metallurgical slag are solved.
4. The main chemical components of the metallurgical slag are CaO and SiO2、FeO、Fe2O3Some of the metal oxides include V, MgO, MnO and free CaO2O5、TiO2、Cr2O3The valuable metals are in a coexistence model of an ionic state, a molecular state or a combination of the ionic state and the molecular state, and have high fluidity and activity.Therefore, the liquid metallurgical slag not only plays a role of a heat transfer medium, but also is a good catalyst and can promote the decomposition reaction of natural gas. CaO and MgO in the liquid metallurgical slag are easy to absorb CO2Reaction to form CaCO3And MgCO3，CO2The reduction of (b) facilitates the conversion reaction to produce H2A higher content of hydrogen rich gas.
5. The catalyst is arranged after the reforming and conversion reaction of the liquid metallurgical slag, and further carries out fluidized conversion on part of the natural gas steam without reforming conversion, so that carbon deposition on the surface of the catalyst is less, the service life of the catalyst is greatly prolonged, the replacement times are reduced, the operation cost is reduced, the conversion rate is high and can reach more than 90 percent at most, and the catalyst has good environmental protection benefit and economic benefit.
Drawings
FIG. 1 is a schematic diagram of the overall structure of the present invention;
reference numerals shown in the drawings: 1. a heat-preservation slag tank; 2. a water gap; 3. a granulating device; 4. a water cooled wall; 5. a water wall lower header; 6. a header is arranged on the water wall; 7. a reformer; 8. a gas supply device; 9. a slag discharge device; 10. a belt conveyor; 11. a wind distribution plate; 12. a catalytic reactor; 13. a reformed gas waste heat boiler; 14. a steam drum; 15. a medium temperature shift reactor; 16. a pressure swing adsorption device.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the present application.
Example 1: hydrogen production device based on sensible heat of liquid metallurgical slag
A device for preparing hydrogen by reforming natural gas steam based on sensible heat of liquid metallurgical slag mainly comprises a heat-preservation slag tank 1, a granulation device 3, a reforming furnace 7, a catalytic reactor 12, a reformed gas waste heat boiler 13, a medium-temperature shift reactor 15 and a pressure swing adsorption device 16.
The heat-preservation slag pot is preferably provided with a heating device for keeping the fluidity of the metallurgical slag liquid and adjusting the viscosity of the slag liquid. The bottom of the heat-preservation slag pot 1 is provided with a slag liquid runner water gap 2, the upper part of the water gap 2 is communicated with the heat-preservation slag pot 1, the lower part is communicated with a granulating device 3,
the granulation device 3 consists of a gas nozzle with a Laval structure and an expansion channel, wherein the gas nozzle is connected with a liquefied gas supply pipeline and an oxygen gas supply pipeline and is provided with a stop valve and an adjusting valve; the communicating port of the water gap 2 is positioned between the gas nozzle and the expanding channel, the gas nozzle is designed into a shrinking and expanding nozzle, the straight pipe section in front of the expanding port is communicated with the water gap at the bottom of the heat-preservation slag pot, the straight pipe section is connected with the expanding channel, the expanding channel is of a sandwich structure, the inner wall of the sandwich layer is provided with a ventilation spray hole, and the granulating device 3 is arranged on the furnace wall at the upper part of the side surface of the converter 7 through the expanding channel, preferably arranged at two sides of the furnace wall;
the wall of the converter 7 is a light wall composed of water-cooled walls 4, the inner wall of the water-cooled wall is laid with wear-resistant refractory materials, the outer wall is laid with heat-insulating materials, and the wall is supported by a steel frame; the water-cooled wall 4 comprises a water-cooled wall lower header 5 and a water-cooled wall upper header 6, the water-cooled wall lower header 5 is communicated with the steam drum 14 through a downcomer, and the water-cooled wall upper header 6 is communicated into the steam drum 14 through an upcomer;
the converter bottom of the converter 7 is provided with an air supply device 8 and a slag discharge device 9, and the air supply device 8 consists of a blast cap, a cross air duct, an upper cone hopper and a lower cone hopper; the slag discharging device 9 consists of a flat gate, an electromagnetic vibration feeder, a rotary sealing valve, a trolley and a coke discharging chute, and quantitatively, continuously and hermetically discharges the cooled metallurgical slag onto the belt conveyor 10;
the top of the converter 7 is connected with the inlet at the bottom of the catalytic reactor 12, the connection part of the converter 7 and the catalytic reactor 12 is designed into a Venturi structure, the bottom of the catalytic reactor 12 is provided with an air distribution plate 11, the air distribution plate 11 is filled with a catalyst to form a fluidized bed, one side of the top of the catalytic reactor 12 is communicated with a converted gas waste heat boiler 13 through a horizontal air passage, the horizontal air passage is provided with a gas-solid separation device, and the gas-solid separation device can be cyclone separation or gravity separation; the reformed gas waste heat boiler 13 is communicated with a steam drum 14 through a down pipe and an up pipe, the reformed gas waste heat boiler 13 and the water-cooled wall 4 of the reformer share one steam drum, the generated saturated steam is sent to a gas supply device at the bottom of the reformer, and the surplus steam is sent out.
A reformed gas outlet of the reformed gas waste heat boiler 13 is communicated with the medium temperature shift reactor 15 and the pressure swing adsorption device 16 in sequence; the pressure swing adsorption device 16 is communicated with the expansion channel of the granulation device through a pipeline to supply air for the ventilation spray holes of the expansion channel.
Preferably, the gas supply device at the bottom of the reforming furnace is also connected with a start-up steam pipeline.
Example 2: natural gas steam reforming hydrogen production method based on sensible heat of liquid metallurgical slag
The hydrogen production method by reforming natural gas steam based on the sensible heat of liquid metallurgical slag comprises the following steps:
s1, before the system is started, the heat-preservation slag pot 1, the water gap 2 and the granulating device 3 are dried and preheated, when the preheating temperature reaches 1000 ℃, liquid metallurgical slag is guided into the heat-preservation slag pot 1, the fluidity of slag liquid is kept, and the slag liquid with high fluidity flows between the gas nozzle and the expansion channel of the granulating device 3 through the water gap 2;
s2, natural gas and a proper amount of oxygen enter a gas nozzle of the granulating device 3, the mixed gas of the natural gas and the oxygen is accelerated through a Laval throat of the gas nozzle to form supersonic airflow, the supersonic airflow is sprayed out of the nozzle to transversely impact slag liquid flowing out of the water gap 2, and the surface tension and viscosity constraint of the slag liquid are overcome, so that the liquid metallurgical slag is crushed into micro-liquid droplets; dispersing the mixed gas into a gas-liquid flow to form a gas-liquid flow, wherein the natural gas and the oxygen generate weak oxidation reaction to release heat during the process, so that the temperature of the gas-liquid flow is not lower than the melting temperature of metallurgical slag, the slag liquid is not solidified and bonded, tail gas is sprayed and desorbed on the wall of the expanded channel to form a gas film, and the gas-liquid mixed flow is sprayed into a furnace chamber of a converter 7 through the expanded channel;
s3, introducing start-up steam into the converter through the gas supply device 8 at the bottom of the converter 7, mixing with the gas-liquid mixed flow in the converter intensely, directly fusing and contacting, generating natural gas steam reforming reaction, absorbing heat intensely, and converting into H-containing steam2、CO、CH4Transforming gas; the gas-liquid mixed flow absorbs heat by reforming reaction, and the temperature of the mixed flow is reduced to be lower than that of the metallurgical slagMelting temperature, solidifying liquid drops in the mixed flow to form slag particles, reducing the flow velocity of the mixed flow, separating and settling the slag particles from the air flow, carrying out countercurrent heat exchange on the settled slag particles and steam rising from the furnace bottom, cooling the slag particles, discharging the cooled slag particles out of the furnace from a furnace bottom slag discharging device 9, and heating the steam to the temperature of more than 500 ℃;
s4, rising the reformed gas generated by reforming reaction of natural gas steam from the reformer 7, accelerating the reformed gas through a reducing and expanding port at the connecting part of the furnace top and the catalytic reactor 12, entering a fluidized bed body of the catalytic reactor 12, generating violent turbulence and mixing of gas-solid two phases of the reformed gas catalyst in the fluidized bed under the action of airflow, fully contacting, continuously forming agglomerates to return downwards in the rising process, continuously disintegrating the agglomerates in the violent turbulence and being lifted by the airflow again, and enabling the slip speed between the gas and the solid to be as high as tens of the single particle slip speed; the mechanism of gas-solid two-phase flow in the fluidized bed greatly strengthens the mass transfer and reforming among gas and solid, realizes high conversion rate, and ensures that unconverted natural gas steam in the converter completes the reforming conversion in the catalytic reactor.
S5, the reformed gas after reforming reaction enters into the horizontal air passage through the top of the catalytic reactor 12, the reformed gas decelerates in the horizontal air passage, the solid catalyst carried in the reformed gas is settled by gravity, the sediment enters into the catalytic reactor through the dust collecting chute, the reformed gas after dust removal enters into the reformed gas waste heat boiler 13 from the horizontal air passage, the reformed gas after heat exchange of the waste heat boiler enters into the medium temperature shift reactor 15, H in the reformed gas is further converted through shift reaction2Conversion of O to H2While converting CO to CO2Thereby increasing the H of the product2The ratio of the converted gas after the medium temperature shift is cooled and then is introduced into a pressure swing adsorption device 16 for H2Purification of (2), H2The purity reaches 99.9 percent.
Steam-water mixture generated by heat exchange of the reformed gas waste heat boiler 13 enters the steam drum 14, steam-water mixture generated by a water-cooled wall of the reformer 7 also enters the steam drum 14, the steam-water mixture is subjected to steam-water separation in the steam drum 14, and steam enters a steam supply device at the bottom of the reformer 7 and is subjected to heat exchange of metallurgical slag to heat up to participate in natural gas reforming.
The temperature of the liquid metallurgical slag in the heat-preserving slag tank 1 is controlled at 1500 DEG CAbout 1650 ℃, the viscosity of slag liquid is 0.02-0.1 pas, the surface tension is 0.3-0.6 Nm < -1 >, and the slag contains CaO and Al2O3、Fe2O3MgO, MnO and TiO2The metal oxides have high catalytic activity, and can promote the catalytic conversion of low-molecular hydrocarbons such as CH4 in natural gas.
The furnace temperature of the reformer is 1000-1200 ℃, and the temperature in the catalytic reactor is preferably more than or equal to 850 ℃; preferably the molar ratio of steam to natural gas is 4: 1; the pressure in the furnace is 2-3 MPa, and the catalyst is Ni/alpha-Al2O3And the airflow speed in the catalytic reactor is 0.1-3 m/s.
After the water is removed from the converted gas, the H2 content, the CO content and the CO content in the product gas are 97.3 percent and 0.5 percent respectively2The content is 2.0 percent, the conversion rate of natural gas is 95 percent, the average grain diameter of metallurgical slag is 2mm, and the glass phase is 96 percent.
In the invention, natural gas and partial oxygen are sprayed out from a nozzle at high speed and are mixed with liquid metallurgical slag violently, under the condition of high temperature and heat insulation, the cracking rate of methane under the condition of high temperature is high, CH4 is decomposed to generate carbon with strong activity, and the carbon reacts with water vapor in a converter to form C + H2O → CO ten H2Carbon and hydrogen are generated, the cracking carbon is digested in the converter, and the carbon deposition inactivation of the catalyst in the catalytic reactor is avoided; and the liquid metallurgical slag and the water vapor generate CaO-SiO2-FeO(l)+H20(g)＝CaO-SiO2-FeO-Fe2O3(l)+H2(g) The method realizes the comprehensive utilization of the waste heat of the liquid metallurgical slag, conforms to the waste heat gradient utilization principle, and can improve the yield of hydrogen.
Claims (10)
1. A device for preparing hydrogen by reforming natural gas steam based on sensible heat of liquid metallurgical slag is characterized in that: including heat preservation slag ladle (1), granulation device (3) is connected through mouth of a river (2) in heat preservation slag ladle (1), granulation device (3) intercommunication reborner (7), reborner (7) stove bottom is provided with air feeder (8) and row's sediment device (9), reborner (7) top intercommunication catalytic reactor (12), catalytic reactor (12) top one side is through horizontal air flue intercommunication reborned gas exhaust-heat boiler (13), the reborned gas export of reborned gas exhaust-heat boiler (13) communicates medium temperature shift reactor (15), pressure swing adsorption equipment (16) in proper order, desorption tail gas outlet of pressure swing adsorption equipment (16) passes through pipeline intercommunication granulation device (3).
2. The device for producing hydrogen by reforming natural gas steam based on the sensible heat of liquid metallurgical slag according to claim 1, wherein the device comprises: the granulating device (3) consists of a gas nozzle with a Laval structure and an expansion channel, a communication port of the water gap (2) is positioned between the gas nozzle and the expansion channel, and the granulating device (3) is arranged on the upper furnace wall of the side surface of the converter (7) through the expansion channel.
3. The device for preparing hydrogen by reforming natural gas steam based on the sensible heat of liquid metallurgical slag according to claim 2, which is characterized in that: the expansion channel is of a sandwich structure, and ventilation spray holes are formed in the inner wall of the sandwich.
4. The device for producing hydrogen by reforming natural gas steam based on the sensible heat of liquid metallurgical slag according to claim 1, wherein the device comprises: the reformed gas waste heat boiler (13) and the reformer (7) are both communicated with the steam drum (14), the generated saturated steam is sent to the gas supply device (8) at the bottom of the reformer (7), and the surplus steam is sent out.
5. The device for producing hydrogen by reforming natural gas steam based on the sensible heat of liquid metallurgical slag according to claim 1, wherein the device comprises: and a gas-solid separation device is arranged in the horizontal air passage.
6. The device for producing hydrogen by reforming natural gas steam based on the sensible heat of liquid metallurgical slag according to claim 1, wherein the device comprises: and the gas supply device (8) is communicated with the start-up steam pipeline.
7. A natural gas steam reforming hydrogen production method based on sensible heat of liquid metallurgical slag is characterized by comprising the following steps:
s1, before the system is started, the heat-preservation slag pot (1), the water gap (2) and the granulating device (3) are dried and preheated, when the preheating temperature reaches 1000 ℃, liquid metallurgical slag is guided into the heat-preservation slag pot (1), the fluidity of slag liquid is kept, and the slag liquid with high fluidity flows between a gas nozzle and an expansion channel of the granulating device (3) through the water gap (2);
s2, natural gas and a proper amount of oxygen enter a gas nozzle of a granulating device (3), the mixed gas of the natural gas and the oxygen is accelerated through a Laval throat of the gas nozzle to form supersonic airflow, the supersonic airflow is sprayed out of the nozzle to transversely impact slag liquid flowing out of a water gap (2), and the surface tension and viscosity constraint of the slag liquid are overcome, so that the liquid metallurgical slag is crushed into micro-liquid droplets; the gas-liquid mixed flow is dispersed in the mixed gas to form a gas-liquid flow, during which the natural gas and the oxygen are subjected to weak oxidation reaction to release heat, so that the temperature of the gas-liquid flow is not lower than the melting temperature of metallurgical slag, the slag liquid is not solidified and bonded, and the gas-liquid mixed flow is sprayed into a furnace chamber of a converter (7) through an expansion channel to desorb tail gas to form a gas film;
s3, introducing start-up steam into the converter through a converter (7) bottom gas supply device (8), violently mixing with the gas-liquid mixed flow in the converter, directly fusing and contacting to generate natural gas steam reforming reaction, strongly absorbing heat, and converting into H-containing steam2、CO、CH4Transforming gas; the gas-liquid mixed flow absorbs heat by reforming reaction, the temperature of the mixed flow is reduced to be lower than the melting temperature of metallurgical slag, liquid drops in the mixed flow are solidified to form slag particles, the flow rate of the mixed flow is reduced, the slag particles are separated and settled from the gas flow, the settled slag particles and steam rising at the bottom of the furnace perform countercurrent heat exchange, the slag particles are cooled and discharged out of the furnace from a slag discharge device (9) at the bottom of the furnace, and the steam is heated to the temperature of more than 500 ℃;
s4, rising the reformed gas generated by reforming reaction of natural gas steam from a reformer (7), accelerating the reformed gas through a contraction and expansion port at the connecting part of a furnace top and a catalytic reactor (12), entering a fluidized bed body of the catalytic reactor (12), generating violent turbulence and mixing of gas-solid phases of the reformed gas catalyst in the fluidized bed due to the action of airflow, fully contacting, continuously forming agglomerates returning downwards in the rising process, continuously disintegrating the agglomerates in the violent turbulence, and lifting by the airflow again, so that the slip speed between the gas and the solid is as high as tens of times of the single particle slip speed;
s5, the converted gas after finishing the reforming reaction enters a horizontal air passage through the top of a catalytic reactor (12), the converted gas decelerates in the horizontal air passage, the solid catalyst carried in the converted gas is settled by gravity, the sediment enters the catalytic reactor through a dust collecting chute, the converted gas after dust removal enters a converted gas waste heat boiler (13) from the horizontal air passage, the converted gas after heat exchange of the waste heat boiler enters a medium temperature shift reactor (15), and H in the converted gas is further converted through shift reaction2Conversion of O to H2While converting CO to CO2Thereby increasing the H of the product2The ratio of the converted gas after the medium temperature shift is cooled and then is introduced into a pressure swing adsorption device (16) for H2Purification of (2), H2The purity reaches 99.9 percent.
8. The method for preparing hydrogen by reforming natural gas steam based on the sensible heat of liquid metallurgical slag according to claim 7, characterized in that a steam-water mixture generated by heat exchange of a reformed gas waste heat boiler (13) enters a steam drum (14), the steam-water mixture generated by a water-cooled wall of the reforming furnace (7) also enters the steam drum (14), the steam-water mixture is subjected to steam-water separation in the steam drum (14), and the steam enters a steam supply device at the bottom of the reforming furnace (7) and is heated by heat exchange of metallurgical slag to participate in reforming natural gas.
9. The method for preparing hydrogen by reforming natural gas steam based on the sensible heat of liquid metallurgical slag according to claim 7, characterized in that the temperature of the liquid metallurgical slag in the heat-preserving slag tank (1) is controlled to be 1500-1650 ℃, the viscosity of the slag liquid is 0.02-0.1 pas, the surface tension is 0.3-0.6 n.m < -1 >, and the slag contains metal oxide with higher catalytic activity.
10. The method for preparing hydrogen by reforming natural gas steam based on the sensible heat of liquid metallurgical slag according to claim 7, which is characterized in that: the molar ratio of steam to natural gas is 4: 1.
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