CN118545681B - Hydrogen production and metal reduction system and process thereof - Google Patents
Hydrogen production and metal reduction system and process thereof Download PDFInfo
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- CN118545681B CN118545681B CN202411018095.XA CN202411018095A CN118545681B CN 118545681 B CN118545681 B CN 118545681B CN 202411018095 A CN202411018095 A CN 202411018095A CN 118545681 B CN118545681 B CN 118545681B
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 47
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 35
- 239000002184 metal Substances 0.000 title claims abstract description 35
- 230000009467 reduction Effects 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000008569 process Effects 0.000 title claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 142
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- 239000002994 raw material Substances 0.000 claims abstract description 60
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 238000002485 combustion reaction Methods 0.000 claims abstract description 24
- 239000003345 natural gas Substances 0.000 claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 239000002737 fuel gas Substances 0.000 claims abstract description 9
- 238000002407 reforming Methods 0.000 claims abstract description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 61
- 239000003546 flue gas Substances 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000011084 recovery Methods 0.000 claims description 16
- 238000006477 desulfuration reaction Methods 0.000 claims description 14
- 230000023556 desulfurization Effects 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000011229 interlayer Substances 0.000 claims description 10
- 239000000779 smoke Substances 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims 2
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 229910000831 Steel Inorganic materials 0.000 description 11
- 239000010959 steel Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- 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
- C01B3/38—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
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0073—Selection or treatment of the reducing gases
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/02—Making spongy iron or liquid steel, by direct processes in shaft furnaces
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/063—Refinery processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
- C01B2203/0816—Heating by flames
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B2100/00—Handling of exhaust gases produced during the manufacture of iron or steel
- C21B2100/60—Process control or energy utilisation in the manufacture of iron or steel
- C21B2100/66—Heat exchange
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention belongs to the technical field of metal reduction, and relates to a hydrogen production and metal reduction system and a process thereof, wherein the hydrogen production and metal reduction system comprises a hydrogen production device and a shaft furnace device; the hydrogen production device comprises a reformer, a burner and a reforming pipeline; a plurality of groups of independently controlled burners are arranged on the side wall of the reformer, the outer ends of the burners are connected with a fuel gas pipeline and a natural gas pipeline, and the inner ends of the burners are communicated with a combustion chamber of the reformer; a conversion pipeline is arranged in the combustion chamber, an inlet of the conversion pipeline is connected with a raw material gas mixture pipeline, and an outlet of the conversion pipeline is connected with an inlet end of a reducing gas output pipe; the shaft furnace device comprises a furnace body and an oxygen pipeline; an oxygen pipeline is arranged in the middle of the furnace body, and comprises a plurality of oxygen pipes; the middle lower part of the furnace body is provided with a reducing gas inlet which is connected with the outlet end of the reducing gas output pipe. The invention has reasonable structural design, simple and convenient method, no pollution of the reduction product, low manufacturing cost, energy conservation, environmental protection and high reaction rate, and is suitable for direct reduction of various metal oxides.
Description
Technical Field
The invention belongs to the technical field of metal reduction, and particularly relates to a hydrogen production metal reduction system and a hydrogen production metal reduction process.
Background
The iron and steel industry is the basis of manufacturing industry and has irreplaceable functions in economic and social development; the annual output of the coarse steel in 2022 of China reaches 10.18 hundred million tons. The steel industry in China mainly uses the long process of a blast furnace-converter, and accounts for more than 90% of the yield of coarse steel. The steel industry is a typical high carbon emissions industry with emissions up to 1.8 tons per ton of steel. The CO2 emission sources comprise sintering, oxidized pellet production, coking process, blast furnace ironmaking, steelmaking, steel rolling and the like, wherein the blast furnace ironmaking is to reduce iron ore through coke, consume coal as fuel, are the links with the highest energy consumption and the highest CO2 emission, and can account for about 70% of the whole steel production flow.
The iron and steel industry is a key field for realizing green low-carbon development, so that carbon emission reduction in the iron and steel industry in China has important significance.
Hydrogen has a distinct advantage as a reducing agent over traditional metallurgical means of carbon reduction: the reduction product is water, no CO2 is generated, the molecular radius of hydrogen is small, the diffusion and permeation capacity is high, the reaction energy barrier for reducing iron oxide is small, and the reduction rate is 5-10 times of CO. The hydrogen metallurgy direct reduction metal has stable chemical components and less harmful elements, and is an ideal raw material for smelting high-quality steel. However, in the existing hydrogen production and metal reduction device, the reducing gas needs to be cooled and purified to obtain hydrogen, and the process is complex and tedious. There is a need for an efficient and energy efficient natural gas hydrogen production system wherein the hydrogen production unit is capable of producing reduced hydrogen for direct use in reducing metal for efficient reduction of metal in the shaft furnace unit.
Disclosure of Invention
Aiming at the problems that the reducing gas is used for reducing metal objects after being purified by complex procedures in the prior art, the heat of the high-temperature reducing gas generated by the hydrogen production furnace cannot be efficiently recycled, the reaction of the reaction furnace is insufficient, and the like, the hydrogen production reducing metal system and the process thereof are provided, the hydrogen production device can rapidly generate hydrogen for reducing materials, the hydrogen and the materials react fully, and the heat generated by hydrogen production can be efficiently recycled.
In order to achieve the above object, there is provided a hydrogen production reduction metal system comprising a hydrogen production device, a shaft furnace device;
the hydrogen production device comprises a reformer, a burner and a reforming pipeline;
a plurality of groups of independently controlled burners are arranged on the side wall of the reformer, the outer ends of the burners are connected with a fuel gas pipeline and a natural gas pipeline, and the inner ends of the burners are communicated with the combustion chamber of the reformer;
a conversion pipeline is arranged in the combustion chamber, an inlet of the conversion pipeline is connected with a raw material gas mixture pipeline, and an outlet of the conversion pipeline is connected with an inlet of a reducing gas output pipe;
the shaft furnace device comprises a furnace body and an oxygen pipeline;
an oxygen pipeline is arranged in the middle of the furnace body and comprises a plurality of oxygen pipes;
the middle lower part of the furnace body is provided with a reducing gas inlet;
the reducing gas inlet is connected with the outlet of the reducing gas output pipe.
Preferably, the conversion pipeline is provided with a conversion pipeline inlet pipe and a conversion pipeline outlet pipe, and a plurality of groups of Z-shaped conversion pipe groups are arranged between the conversion pipeline inlet pipe and the conversion pipeline outlet pipe;
The conversion tube group comprises straight tubes and U-shaped tubes, and the straight tubes are connected through the U-shaped tubes;
a transverse supporting plate is arranged in the middle of the conversion tube group;
the lower part of the conversion tube group is provided with a supporting plate for supporting.
Preferably, the near-inlet of the raw material gas mixture pipeline is connected with a steam pipe for conveying steam.
Preferably, an interlayer is arranged in the middle of the furnace body, and small holes for reducing gas to pass through are uniformly distributed in the interlayer.
Preferably, the upper part of the furnace body is provided with a feed inlet section and a smoke outlet section;
the feeding port section is provided with two discharge valves, and a buffer bin is formed between the two discharge valves;
an inert gas inlet is arranged on the buffer bin;
A flue gas flame arrester is arranged on the flue gas outlet section;
the lower part of the furnace body is provided with a discharge port section, and the discharge port section is provided with a discharge valve; the bottom of the discharge port section is connected with a discharge device.
Preferably, the hydrogen production reduction metal system further comprises a flue gas heat recovery device;
The flue gas heat recovery device comprises a flue gas pipeline, an air heat exchanger, a raw material gas preheater and a hot water heat exchanger; an inlet of the flue gas pipeline is arranged on the side wall of the reformer, and an air heat exchanger, a raw material gas preheater, a hot water heat exchanger and a smoke exhaust fan are sequentially arranged on the flue gas pipeline;
A desulfurization reactor is arranged on the feed gas mixture pipeline; the inlet of the raw material gas preheater is connected with a raw material gas conveying pipe for conveying raw material gas, and the outlet of the raw material gas preheater is connected with the desulfurization reactor; the desulfurization reactor is connected with a raw material gas mixture pipeline, and an outlet of the raw material gas mixture pipeline is connected with an inlet of the conversion pipeline;
an air heat exchanger is arranged near the inlet of the flue gas pipeline;
one end of the air heat exchanger is connected with a fuel gas assisting pipeline, the other end is connected with a combustion-supporting gas conveying pipe; the combustion-supporting gas conveying pipe is connected with the combustion-supporting fan.
A process for reducing metal using a hydrogen production reduction metal system, the process comprising the steps of:
S1, enabling combustion-supporting gas to sequentially enter a combustor through a combustion-supporting fan, a combustion-supporting gas conveying pipe, an air heat exchanger and a combustion-supporting gas pipeline, enabling natural gas conveyed by a natural gas pipeline to burn in a combustion chamber of a reformer, and providing heat for the reformer pipeline;
The raw material gas is mixed with steam conveyed by a steam pipe through a raw material gas conveying pipe, a raw material gas preheater, a desulfurization reactor and a raw material gas mixture pipeline, the raw material gas and steam mixture is input into a conversion pipeline through the raw material gas mixture pipeline and reacts with a catalyst in a conversion pipe group to generate high-temperature reducing gas;
S2, high-temperature reducing gas enters the furnace body through a reducing gas output pipe and a reducing gas inlet to react with materials in the furnace body;
s3, enabling high-temperature flue gas generated by the burner to enter a flue gas heat recovery device through a flue gas pipeline for flue gas heat recovery;
The high-temperature flue gas firstly heats combustion-supporting gas through an air heat exchanger, then enters a raw gas preheater to heat raw gas participating in conversion reaction, then enters a hot water heat exchanger to heat water, and the cooled fuel gas is discharged through a smoke exhaust fan.
Preferably, the raw material gas in the step 1 is natural gas.
Preferably, in the step 1, the temperature in the combustion chamber is not higher than 1000 ℃;
the temperature of the catalyst is not higher than 900 ℃.
Preferably, the temperature of the cooled flue gas in the step 3 is lower than 150 ℃.
The invention has the beneficial effects that:
1. In the hydrogen production device, the start and stop of the multiple groups of combustors can be independently controlled, the combustion intensity of the hearth can be effectively controlled, the control temperature is achieved, and the fuel and natural gas can be saved, and the cost is saved. The burners are uniformly distributed at the side of the reformer to provide heat sources for the combustion chamber of the reformer, the heat is uniformly distributed, the flame is dispersed, the combustion temperature is lower than 1000 ℃, and nitrogen oxides can not be generated. The reaction gas generated by the reformer does not need the measures of medium temperature conversion, SPA adsorption purification and the like, directly enters the furnace body to serve as a reducing agent, does not need to provide energy by additionally arranging a preheating device, can also ensure the reduction temperature, and effectively reduces the consumption of hydrogen production cost.
2. The high-temperature reducing gas of the shaft furnace device enters the interior through the interlayer of the furnace body, and small holes which are uniformly distributed are formed in the interlayer, so that the reducing gas and materials are uniformly mixed. And a plurality of oxygen inlets are uniformly distributed on the furnace body, if the reaction temperature is reduced, an oxygen valve group is opened, and pure oxygen is introduced into the shaft furnace device so as to ensure the reaction temperature of the furnace body.
The feeding port section is provided with a double cut-off valve, and the intermediate buffer bin is provided with an inert gas inlet for introducing inert gas to replace air in the furnace body, so that no air in the furnace body enters. The discharge device of the discharge port section has strong conveying capacity, and the variable frequency adjustment can control the discharge rate and ensure the reaction time of materials in the furnace body.
3. The flue gas heat recovery device recovers high-temperature flue gas heat generated by the combustion of the burner, the heat is used for heating combustion-supporting gas, raw gas required by a conversion pipeline and water in a hot water heat exchanger, and finally the flue gas temperature is reduced to 150 ℃ to be discharged out of the system, so that the flue gas heat is effectively utilized.
The invention has reasonable structural design, simple and convenient method, provides the reducing gas which directly enters the shaft furnace device with simple and reasonable structure without cooling and purification, is in direct contact with materials to generate full chemical reaction, has no pollution to the reducing substance, low manufacturing cost, energy conservation and environmental protection, high reaction rate and effectively utilizes the heat of the reducing gas; the high-temperature flue gas generated by combustion has high recycling rate, so that the investment of the whole system is reduced; the technical scheme is suitable for direct reduction of various metal oxides, and the types of materials are greatly improved.
Drawings
FIG. 1 is a schematic diagram of a hydrogen plant and a flue gas heat recovery device according to the present invention;
FIG. 2 is a front view of a conversion pipeline in the converter;
FIG. 3 is a schematic side view of a conversion circuit within a reformer;
FIG. 4 is a top view of the conversion piping in the converter;
FIG. 5 is a schematic view in section A-A of FIG. 4;
FIG. 6 is a schematic view of a shaft furnace apparatus according to the present invention.
In the figure: the device comprises a hydrogen production device 1, a shaft furnace device 2, a flue gas heat recovery device 3, a combustor 4, a reformer 5, a reducing gas output pipe 6, a reforming pipeline 7, a reforming pipeline inlet pipe 7-1, a reforming pipeline outlet pipe 7-2, a supporting plate 7-3, a supporting plate 7-4, a straight pipe 7-5, a U-shaped pipe 7-6, a reforming pipe group 7-7, a raw gas preheater 8, a desulfurization reactor 9, a furnace body 10, a reducing gas inlet 11, an oxygen pipeline 12, a buffer bin 13, a discharge valve 14, a feed inlet section 15, a flue gas outlet section 16, a flue gas flame arrester 17, a discharge port section 18, a discharge device 19, a flue gas pipeline 20, an air heat exchanger 21, a combustion-supporting fan 22, a hot water heat exchanger 23, a smoke exhaust fan 24, a combustion-supporting gas pipeline 25, a raw gas mixture pipeline 26, an inert gas inlet 27, a discharge valve 28, a combustion-supporting gas conveying pipe 29 and a water vapor pipe 30.
Detailed Description
The following description of the preferred embodiments of the present invention will be given in detail with reference to the accompanying drawings.
As shown in fig. 1-6, a hydrogen production reduction metal system comprises a hydrogen production device 1 and a shaft furnace device 2; the hydrogen production device 1 comprises a reformer 5, a combustor 4 and a reforming pipeline 7; a plurality of groups of independently controlled burners 4 are arranged on the side wall of the reformer 5, the outer ends of the burners 4 are connected with a fuel gas pipeline 25 and a natural gas pipeline, the inner ends of the burners are communicated with the combustion chamber of the reformer 5, and the natural gas pipeline is connected with natural gas storage equipment; a conversion pipeline 7 is arranged in the combustion chamber, the inlet of the conversion pipeline 7 is connected with a raw material gas mixture pipeline 26, and the outlet of the conversion pipeline 7 is connected with the inlet of the reducing gas output pipe 6; the shaft furnace device 2 comprises a furnace body 10 and an oxygen pipeline 12; an oxygen pipeline 12 is arranged in the middle of the furnace body 10, and the oxygen pipeline 12 comprises a plurality of oxygen pipes; the middle lower part of the furnace body 10 is provided with a reducing gas inlet 11; the reducing gas inlet 11 is connected to the outlet of the reducing gas outlet pipe 6.
The conversion pipeline 7 is provided with a conversion pipeline inlet pipe 7-1 and a conversion pipeline outlet pipe 7-2, and a plurality of groups of Z-shaped conversion pipe groups 7-7 are arranged between the conversion pipeline inlet pipe and the conversion pipeline outlet pipe; the conversion tube group 7-7 comprises straight tubes 7-5 and U-shaped tubes 7-6, and the straight tubes 7-5 are connected through the U-shaped tubes 7-6; the middle part of the conversion tube group 7-7 is provided with a transverse supporting plate 7-4; the lower part of the conversion tube group 7-7 is provided with a supporting plate 7-3 for supporting. The raw material gas mixture pipeline 26 is connected with a steam pipe 30 for conveying steam near the inlet, and the steam pipe 30 is connected with a steam generating device.
An interlayer is arranged in the middle of the furnace body 10, and small holes for reducing gas to pass through are uniformly distributed in the interlayer. The upper part of the furnace body 10 is provided with a feed inlet section 15 and a smoke outlet section 16; the feed inlet section 15 is provided with two discharge valves 14, and a buffer bin 13 is formed between the two discharge valves 14; the buffer bin 13 is provided with an inert gas inlet 27, and the inert gas is argon as a preferable scheme; a flue gas flame arrester 17 is arranged on the flue gas outlet section 16; the lower part of the furnace body 10 is provided with a discharge port section 18, and the discharge port section 18 is provided with a discharge valve 28; the bottom of the discharge port section 18 is connected with a discharge device 19.
The hydrogen production reduction metal system also comprises a flue gas heat recovery device 3; the flue gas heat recovery device 3 comprises a flue gas pipeline 20, an air heat exchanger 21, a raw material gas preheater 8 and a hot water heat exchanger 23; an inlet of the flue gas pipeline 20 is arranged on the side wall of the reformer 5, and an air heat exchanger 21, a raw material gas preheater 8, a hot water heat exchanger 23 and a smoke exhaust fan 24 are sequentially arranged on the flue gas pipeline 20; a desulfurization reactor 9 is arranged on the raw material gas mixture pipeline 26; the inlet of the raw material gas preheater 8 is connected with a raw material gas conveying pipe for conveying raw material gas, the raw material gas conveying pipe is connected with raw material gas storage equipment, and the outlet of the raw material gas preheater 8 is connected with the desulfurization reactor 9; the desulfurization reactor 9 is connected with a raw material gas mixture pipeline 26, and the outlet of the raw material gas mixture pipeline 26 is connected with the inlet of the conversion pipeline 7; an air heat exchanger 21 is arranged near the inlet of the flue gas pipeline 20; one end of the air heat exchanger 21 is connected with a combustion-supporting gas pipeline 25, and the other end is connected with a combustion-supporting gas conveying pipe 29; the combustion-supporting gas delivery pipe 29 is connected to the combustion-supporting blower 22.
A process for reducing metal using a hydrogen production reduction metal system, the process comprising the steps of:
S1, combustion-supporting gas sequentially enters the combustor 4 through the combustion-supporting fan 22, the combustion-supporting gas conveying pipe 29, the air heat exchanger 21 and the combustion-supporting gas pipeline 25, so that natural gas conveyed by the natural gas pipeline is combusted in a combustion chamber of the reformer 5, and heat is provided for the reformer pipeline 7;
The raw material gas is mixed with steam conveyed by a steam pipe 30 through a raw material gas conveying pipe, a raw material gas preheater 8 and a desulfurization reactor 9, and enters a raw material gas mixture pipeline 26, and the raw material gas and steam mixture is input into a conversion pipeline 7 through the raw material gas mixture pipeline 26 to react with the catalyst in the conversion pipe group 7-7 to generate high-temperature reducing gas; preferably, the catalyst is a nickel-based catalyst;
S2, high-temperature reducing gas enters the furnace body 10 through the reducing gas output pipe 6 and the reducing gas inlet 11 to react with materials in the furnace body 10;
s3, simultaneously enabling high-temperature flue gas generated by the burner 4 to enter the flue gas heat recovery device 3 through the flue gas pipeline 20 for flue gas heat recovery;
The high-temperature flue gas firstly heats combustion-supporting gas through the air heat exchanger 21, then enters the raw material gas preheater 8 to heat raw material gas which participates in conversion reaction, then enters the hot water heat exchanger 23 to heat water, and the cooled fuel gas is discharged through the smoke exhaust fan 24.
The raw material gas in the step 1 is alkane gas, and the raw material gas is natural gas as a preferable scheme. In the step 1, the temperature in the combustion chamber is not higher than 1000 ℃; the temperature of the catalyst is not higher than 900 ℃. The temperature of the cooled flue gas in the step 3 is lower than 150 ℃.
The working process of the invention comprises the following steps:
The heat of the reformer 5 is provided by the simultaneous combustion of a plurality of burners 4, the interior of the reformer 5 is entirely made of refractory materials and heat preservation modules, the heat storage capacity is strong, and the heat is not easy to lose. The heat generated by the burner 4 heats the reformer line 7 with the catalyst in the reformer 5, preferably at a temperature of 850 c for the nickel-based catalyst reaction. The nickel-based catalyst enables natural gas and water vapor to chemically react to generate high-temperature reducing gas at 800 ℃, the reducing gas comprises high-temperature pyrolysis gas products such as hydrogen, carbon monoxide and the like, the reducing gas is conveyed to a reducing gas inlet 11 through a reducing gas output pipe 6 to enter a furnace body 10 to contact materials for deoxidization reaction, the high-temperature reducing gas of a reformer 5 directly enters a shaft furnace device 2, and the heat of the reducing gas is utilized to the greatest extent. The reaction gas produced by the reformer 5 at 800 ℃ directly enters the furnace body 10 to serve as a reducing agent without the measures of medium temperature conversion, SPA adsorption purification and the like, and the reducing temperature can be ensured without providing energy by additionally installing a preheating device, so that the purposes of high efficiency and energy saving are achieved, and the consumption of hydrogen production cost is reduced.
In the shaft furnace device 2, the material enters the intermediate surge bin 13 through the opening of the first discharge valve 14, at which time the second discharge valve 14 is closed, and the inert gas ammonia of the surge bin 13 ensures that no air enters during feeding; the high-temperature reducing gas enters the interior through the interlayer of the furnace body 10, small holes are uniformly distributed in the interlayer, a plurality of DN15 oxygen inlets are uniformly distributed on the furnace body 10, if the reaction temperature is reduced, a switch valve group of an oxygen pipeline 12 is opened, and pure oxygen is introduced into the shaft furnace device 2. The discharging device 19 is a shaftless dragon discharging device, has strong conveying capacity, can control the discharging speed by frequency conversion adjustment, and ensures the reaction time of materials in the furnace body 10.
The burner 4 burns and supplies heat to the conversion pipeline 7, and meanwhile, high-temperature flue gas discharged from the conversion furnace 5 enters the gas heat recovery device 3. The high-temperature flue gas is firstly preheated by the air heat exchanger 21, and the preheated combustion-supporting gas is used for supporting combustion of the combustor 4 through the combustion-supporting gas pipeline 25. And secondly, heating the natural gas for conversion by the flue gas through a raw gas preheater 8, feeding the natural gas into a desulfurization reactor 9 after heating, removing impurity sulfur, mixing the natural gas with steam fed by a steam pipe 30, and feeding the mixed mixture into a conversion pipeline 7 in the conversion furnace 5 through a raw gas mixture pipeline 26. Finally, the flue gas heats pure water through the hot water heat exchanger 23, so that the temperature of the flue gas is reduced to 150 ℃ and the flue gas is discharged by the smoke exhaust fan 24. The multiple groups of burners 4 are uniformly distributed at the side part of the reformer 5 to provide heat sources for the reformer combustion chamber, the heat is uniformly distributed, the flames are dispersed, and the multiple groups of burners 4 can be independently controlled to start and stop, so that the fuel and the natural gas are saved, and the cost is saved. The combustion temperature of the burner 4 is lower than 1000 ℃, the generation of NOx is avoided, and the aim of 'controlling nitrate from source' and protecting environment is achieved by reasonably optimizing the mechanical structure.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that various changes and substitutions are possible within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (7)
1. A process for reducing metal in a hydrogen-producing metal-reducing system, comprising the steps of:
S1, enabling combustion-supporting gas to sequentially enter a combustor through a combustion-supporting fan, a combustion-supporting gas conveying pipe, an air heat exchanger and a combustion-supporting gas pipeline, enabling natural gas conveyed by a natural gas pipeline to burn in a combustion chamber of a reformer, and providing heat for the reformer pipeline;
the conversion pipeline is provided with a conversion pipeline inlet pipe and a conversion pipeline outlet pipe, and a plurality of groups of Z-shaped conversion pipe groups are arranged between the conversion pipeline inlet pipe and the conversion pipeline outlet pipe;
The raw material gas is mixed with steam conveyed by a steam pipe through a raw material gas conveying pipe, a raw material gas preheater, a desulfurization reactor and a raw material gas mixture pipeline, the raw material gas and steam mixture is input into a conversion pipeline through the raw material gas mixture pipeline and reacts with a catalyst in a conversion pipe group to generate high-temperature reducing gas;
S2, high-temperature reducing gas enters the furnace body through a reducing gas output pipe and a reducing gas inlet to react with materials in the furnace body;
s3, enabling high-temperature flue gas generated by the burner to enter a flue gas heat recovery device through a flue gas pipeline for flue gas heat recovery;
The high-temperature flue gas firstly heats combustion-supporting gas through an air heat exchanger, then enters a raw material gas preheater to heat raw material gas participating in conversion reaction, then enters a hot water heat exchanger to heat water, and the cooled flue gas is discharged through a smoke exhaust fan;
the hydrogen production and metal reduction system applied in the process comprises a hydrogen production device and a shaft furnace device;
the hydrogen production device comprises a reformer, a burner and a reforming pipeline;
a plurality of groups of independently controlled burners are arranged on the side wall of the reformer, the outer ends of the burners are connected with a fuel gas pipeline and a natural gas pipeline, and the inner ends of the burners are communicated with the combustion chamber of the reformer;
a conversion pipeline is arranged in the combustion chamber, an inlet of the conversion pipeline is connected with a raw material gas mixture pipeline, and an outlet of the conversion pipeline is connected with an inlet of a reducing gas output pipe;
the shaft furnace device comprises a furnace body and an oxygen pipeline;
an oxygen pipeline is arranged in the middle of the furnace body and comprises a plurality of oxygen pipes;
the middle lower part of the furnace body is provided with a reducing gas inlet which is connected with the outlet of the reducing gas output pipe;
The raw material gas is natural gas;
The temperature in the combustion chamber is not higher than 1000 ℃, the combustion temperature is lower than 1000 ℃, and nitrogen oxides can not be generated;
the temperature of the catalyst is not higher than 900 ℃.
2. The process for reducing metal by a hydrogen production metal reduction system according to claim 1, wherein the converting tube group comprises a straight tube and a U-shaped tube, and the straight tubes are connected by the U-shaped tube;
a transverse supporting plate is arranged in the middle of the conversion tube group;
the lower part of the conversion tube group is provided with a supporting plate for supporting.
3. A process for reducing metals in a hydrogen production and reduction metal system as described in claim 1, wherein said feed gas mixture conduit is connected to a steam pipe for transporting steam near the inlet.
4. The process for reducing metal by a hydrogen production and reduction metal system according to claim 1, wherein an interlayer is arranged in the middle of the furnace body, and small holes for reducing gas to pass through are uniformly distributed in the interlayer.
5. The process for reducing metal by a hydrogen production and reduction metal system according to claim 1, wherein a feed inlet section and a flue gas outlet section are arranged at the upper part of the furnace body;
the feeding port section is provided with two discharge valves, and a buffer bin is formed between the two discharge valves;
an inert gas inlet is arranged on the buffer bin;
A flue gas flame arrester is arranged on the flue gas outlet section;
the lower part of the furnace body is provided with a discharge port section, and the discharge port section is provided with a discharge valve; the bottom of the discharge port section is connected with a discharge device.
6. A process for reducing metal in a hydrogen production reducing metal system as defined in claim 1, further comprising a flue gas heat recovery device;
The flue gas heat recovery device comprises a flue gas pipeline, an air heat exchanger, a raw material gas preheater and a hot water heat exchanger; an inlet of the flue gas pipeline is arranged on the side wall of the reformer, and an air heat exchanger, a raw material gas preheater, a hot water heat exchanger and a smoke exhaust fan are sequentially arranged on the flue gas pipeline;
A desulfurization reactor is arranged on the feed gas mixture pipeline; the inlet of the raw material gas preheater is connected with a raw material gas conveying pipe for conveying raw material gas, and the outlet of the raw material gas preheater is connected with the desulfurization reactor; the desulfurization reactor is connected with a raw material gas mixture pipeline, and an outlet of the raw material gas mixture pipeline is connected with an inlet of the conversion pipeline;
an air heat exchanger is arranged near the inlet of the flue gas pipeline;
one end of the air heat exchanger is connected with a fuel gas assisting pipeline, the other end is connected with a combustion-supporting gas conveying pipe; the combustion-supporting gas conveying pipe is connected with the combustion-supporting fan.
7. The process for reducing metals according to claim 1, wherein the flue gas temperature after cooling in step S3 is lower than 150 ℃.
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| CN108439337A (en) * | 2018-03-16 | 2018-08-24 | 新地能源工程技术有限公司 | A kind of method of natural gas reforming hydrogen manufacturing |
| CN212109570U (en) * | 2020-03-23 | 2020-12-08 | 成都同创伟业新能源科技有限公司 | Sectional type flue heat utilization device for hydrogen production from natural gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108439337A (en) * | 2018-03-16 | 2018-08-24 | 新地能源工程技术有限公司 | A kind of method of natural gas reforming hydrogen manufacturing |
| CN212109570U (en) * | 2020-03-23 | 2020-12-08 | 成都同创伟业新能源科技有限公司 | Sectional type flue heat utilization device for hydrogen production from natural gas |
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