CN116768154A - Large-scale pure hydrogen preparation method and system for hydrogen metallurgy - Google Patents
Large-scale pure hydrogen preparation method and system for hydrogen metallurgy Download PDFInfo
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- CN116768154A CN116768154A CN202310564182.4A CN202310564182A CN116768154A CN 116768154 A CN116768154 A CN 116768154A CN 202310564182 A CN202310564182 A CN 202310564182A CN 116768154 A CN116768154 A CN 116768154A
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 131
- 239000001257 hydrogen Substances 0.000 title claims abstract description 105
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 238000005272 metallurgy Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 239000000571 coke Substances 0.000 claims abstract description 30
- 238000002309 gasification Methods 0.000 claims abstract description 27
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002028 Biomass Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 12
- 230000009467 reduction Effects 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 83
- 239000008188 pellet Substances 0.000 claims description 47
- 229910052742 iron Inorganic materials 0.000 claims description 31
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000010802 sludge Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000003034 coal gas Substances 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 2
- 238000009834 vaporization Methods 0.000 claims description 2
- 230000008016 vaporization Effects 0.000 claims description 2
- 238000011031 large-scale manufacturing process Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 9
- 238000004064 recycling Methods 0.000 abstract description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 16
- 238000006722 reduction reaction Methods 0.000 description 15
- 238000007084 catalytic combustion reaction Methods 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000000446 fuel Substances 0.000 description 7
- 239000002910 solid waste Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Abstract
The application relates to a large-scale pure hydrogen preparation method and a system for hydrogen metallurgy, which belong to the technical field of new energy and metallurgy, can realize the preparation of chemical chain pure hydrogen and be used for metallurgy, and realize H by using metallurgical gas in the process 2 Recycling CO, reducing carbon emission; the system comprises: two fixed beds for converting CO and H in converter/coke oven gas 2 Oxidation to CO 2 And H 2 O mixture or H to be introduced therein 2 Reduction of O to H 2 The method comprises the steps of carrying out a first treatment on the surface of the A converter/coke oven for supplying gas to the fixed bed; biomass gasification furnace for realizing carbon and CO 2 And H 2 O reacts to obtain CO and H 2 The method comprises the steps of carrying out a first treatment on the surface of the A steam generator for supplying H to be reacted to the fixed bed 2 O; a gas-liquid separator for condensing H obtained by reaction in the fixed bed 2 Treating and separating out surplus water; a blast furnace/hydrogen-based shaft furnace connected with the gas-liquid separator forReceive H 2 Hydrogen metallurgy is performed.
Description
Technical Field
The application relates to the technical field of new energy and metallurgy, in particular to a large-scale pure hydrogen preparation method and system for hydrogen metallurgy.
Background
Conventional coke metallurgy produces large carbon dioxide emissions, which present a significant challenge to carbon neutralization. For this reason, the metallurgical industry has introduced hydrogen metallurgy, i.e. the use of hydrogen instead of coke for metallurgy. At present, about 60% of hydrogen in coke oven gas used in the coke oven gas metallurgy technology is a good hydrogen source, but the coke oven gas also contains about 22% of methane, 7.3% of carbon monoxide and 3% of carbon dioxide, and a large amount of carbon dioxide emission can still be generated when the coke oven gas is directly used in the hydrogen metallurgy technology. The purity of hydrogen adopted by the green hydrogen metallurgy technology is very high, and the hydrogen is limited by wind and light resources, so that the cost is high. The nuclear energy-hydrogen production-metallurgy coupling technology based on the I-S circulation and three-step pyrolysis of water for hydrogen production can realize ultralow emission and green production of carbon dioxide in the steel industry, but is also limited by the geographic position of the ultra-high temperature gas cooled reactor nuclear power station, and has the problems of complex system, material corrosion and the like. Therefore, hydrogen metallurgy is a hot spot in the current global technical development of the iron and steel industry, and development of novel low-cost pure hydrogen preparation technology is urgently needed to meet the hydrogen consumption requirement and carbon reduction requirement of hydrogen metallurgy.
Accordingly, there is a need to develop a method and system for large-scale pure hydrogen production for hydrogen metallurgy to address the deficiencies of the prior art and to solve or mitigate one or more of the problems described above.
Disclosure of Invention
In view of the above, the present application provides a method and a system for preparing pure hydrogen on a large scale for hydrogen metallurgy, which can realize the preparation of pure hydrogen with chemical chains and be used for metallurgy, and in the process, H is realized by using converter/coke oven gas, iron-containing solid waste, carbon-containing sludge/biomass, etc 2 And the circulation of CO, and the carbon emission is reduced.
In one aspect, the present application provides a large scale pure hydrogen production system for hydrogen metallurgy, the system comprising:
fixed bed A and fixed bed B for converting CO and H in converter/coke oven gas 2 Oxidation to CO 2 And H 2 O mixture, or H to be introduced therein 2 Reduction of O to H 2 ；
The converter/coke oven gas is respectively connected with the fixed bed A and the fixed bed B and is used for supplying gas to be reacted into the fixed bed A or the fixed bed B;
the biomass gasification furnace is respectively connected with the fixed bed A and the fixed bed B,for achieving carbon and CO 2 And H 2 O reacts to obtain CO and H 2 ；
Steam generators respectively connected with the fixed bed A and the fixed bed B for supplying H to be reacted into the fixed bed A or the fixed bed B 2 O；
A gas-liquid separator for condensing H obtained by the reaction in the fixed bed A or the fixed bed B 2 Treating and separating out surplus water;
a blast furnace/hydrogen-based shaft furnace connected with the gas-liquid separator for receiving H 2 Hydrogen metallurgy is performed.
Aspects and any one of the possible implementations as described above, further providing an implementation, the system further includes:
a purifier connected with the biomass gasification furnace and used for generating CO and H 2 And (5) purifying.
Aspects and any one of the possible implementations as described above, further providing an implementation, the system further includes:
in the aspect and any possible implementation manner as described above, there is further provided an implementation manner, wherein the purifier is connected with a pipeline for conveying gas to the fixed bed A or the fixed bed B, and is used for purifying the CO and the H after purification 2 Is fed into a fixed bed A or a fixed bed B to participate in the reaction.
In aspects and any one of the possible implementations described above, there is further provided an implementation in which the purifier is connected to a gas line for other uses.
In the aspect and any possible implementation manner described above, there is further provided an implementation manner, wherein the lower bed layer of the fixed bed a carries oxidized pellets, and the upper bed layer carries an iron-based catalyst;
the lower bed layer of the fixed bed B carries the reduced pellets, and the upper bed layer carries the iron-based catalyst.
In the aspects and any possible implementation manner described above, there is further provided an implementation manner, wherein the upper bed layers of the fixed bed a and the fixed bed B are connected with an oxygen supply pipeline.
As described aboveAspects and any possible implementation manner, further provides an implementation manner, where the system further includes: the heat exchanger is arranged in front of the steam generator and is used for realizing the reaction in the fixed bed A or the fixed bed B to obtain H 2 And H pre-fed to fixed bed A or B 2 O exchanges heat to finish H 2 Condensation and H of (2) 2 Vaporization of O.
Aspects and any one of the possible implementations as described above, further providing an implementation, the system further includes:
the water tank is connected with the gas-liquid separator and is used for storing water separated by the gas-liquid separator.
In the aspects and any possible implementation manner described above, there is further provided an implementation manner, wherein biomass and carbon-containing sludge particles are arranged in the biomass gasification furnace and are used for supplying organic matters required by the reaction in the biomass gasification furnace.
In the aspects and any possible implementation manner, there is further provided an implementation manner, after the pellets in the fixed bed are sintered or have reduced performance, the pellets are refilled, and the replaced pellets are sent to a blast furnace or a hydrogen-based shaft furnace for direct reduction iron making.
Aspects and any one of the possible implementations as described above, further providing an implementation, the system further includes:
a gas using device and/or a gas storage tank connected with the purifier for using and/or storing the purified CO and H 2 。
In another aspect, the present application provides a method for large scale pure hydrogen production for hydrogen metallurgy, the method being implemented using a novel chemical-looping pure hydrogen production system for hydrogen metallurgy as described in any one of the above; the method comprises the following steps:
the fixed bed A and the fixed bed B are used for receiving the coal gas conveyed from the converter/coke oven and converting CO and H in the coal gas 2 Oxidation to CO 2 And H 2 O, another fixed bed receives the steam state H from the steam generator 2 Reduction of O to H 2 ；
For H generated by reduction 2 Condensing and separating gas from liquid, purifying H 2 Delivering the mixture to a blast furnace/hydrogen-based shaft furnace for hydrogen metallurgy;
for CO produced by oxidation 2 And H 2 O is firstly conveyed to a biomass gasification furnace to react with carbon in the biomass gasification furnace to obtain CO and H 2 And after the mixed gas serving as a main component is purified, one part of the mixed gas is mixed with gas for reaction in a fixed bed, and the other part of the mixed gas is connected with pipelines for other gas purposes.
Compared with the prior art, one of the technical schemes has the following advantages or beneficial effects: pure hydrogen is prepared by efficiently utilizing products in the existing steel industry process, and the limitation of resources and geographic positions is avoided; the iron-based oxygen carrier and the catalyst adopted by the chemical chain hydrogen production can be obtained locally, and iron ores, pellets and iron-containing solid waste resources (sintering and pellet dust mud, blast furnace gas stucco, steelmaking dust mud, cold and hot rolling sludge, iron oxide scale and other iron-containing solid waste resources with the iron content of 30-70 percent) are reasonably utilized; after the sintering or performance of the iron-based oxygen carrier and the catalyst is reduced, the iron-based oxygen carrier and the catalyst are sent into a blast furnace or a hydrogen-based shaft furnace to directly reduce iron, so that the material utilization rate is improved; tail gas in the fuel reactor is catalytically combusted to realize chemical looping self-heating hydrogen production, and simultaneously the utilization rate of fuel is improved; chemical looping hydrogen production and high temperature CO produced by catalytic combustion 2 And H 2 O is used as gasification gas of biomass and carbon-containing sludge particles to generate hydrogen-rich gas, thus realizing CO 2 Is used for recycling; the novel chemical chain pure hydrogen preparation technology and system for hydrogen metallurgy have the advantages of high efficiency, low carbon and low cost.
Of course, it is not necessary for any of the products embodying the application to achieve all of the technical effects described above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a large-scale pure hydrogen production system for hydrogen metallurgy according to one embodiment of the present application.
Detailed Description
For a better understanding of the technical solution of the present application, the following detailed description of the embodiments of the present application refers to the accompanying drawings.
It should be understood that the described embodiments are merely some, but not all, embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Aiming at the defects of the prior art, the application provides a large-scale pure hydrogen preparation technology and a system for hydrogen metallurgy as a solution. The system mainly comprises a fixed bed A, a fixed bed B, a converter/coke oven (for gas supply), a biomass gasification furnace, a blast furnace/hydrogen-based shaft furnace and the like, can realize the preparation of pure hydrogen by reasonably and efficiently utilizing various gases, iron-based minerals and smelting byproducts generated in the steel industry process, is used for directly reducing and ironmaking the blast furnace or the hydrogen-based shaft furnace, and is used for directly reducing and smelting generated CO 2 And carrying out resource utilization.
In order to achieve the above purpose, the present application adopts the following technical scheme: gas (in CO and H) produced in converter/coke oven 2 Predominantly) and oxidized pellets (in Fe 2 O 3 And Fe (Fe) 3 O 4 Mainly) to produce reduced pellets (mainly FeO and Fe), and the fixed bed A is a fuel reactor. In particular, the converter/coke oven gas tail gas produced (with excess CO and H 2 ) With O 2 Catalytic combustion reaction takes place under the catalysis of iron-based catalyst, and the heat of reaction evolution is used for the reduction reaction of oxidation state pellet ore. Tail gas (mainly CO) produced after catalytic combustion reaction 2 And steam) enters a gasification furnace as gasification medium of sludge, biomass and the like, and is decomposed and converted into hydrogen-rich gas (in CO and H at high temperature) 2 Mainly). Part of the hydrogen-rich gas is mixed with the converter/coke oven gas and then is fed intoThe mixture enters a fixed bed A to react with oxidized pellets, and the other part of the mixture can be connected with gas pipelines of other purposes to realize CO 2 Is used for recycling. While the converter/coke oven gas reacts with the oxidized pellet ore, water vapor is introduced into the fixed bed B to react with the reduced pellet ore arranged in the fixed bed B to generate oxidized pellet ore and H 2 (containing surplus H 2 O vapor), in which case fixed bed B is a vapor reactor. Prepared H 2 (containing surplus H 2 O vapor) is fed into a blast furnace or a hydrogen-based shaft furnace to directly reduce iron after condensation and a gas-liquid separator.
When the reaction is finished, the fixed beds A and B change the switching valve. At this time, the fixed bed A is a steam reactor, and oxidation reaction of the reduced pellets occurs. The fixed bed B is a fuel reactor, and the reduction reaction of the oxidized pellets occurs.
And when the pellets are sintered or the performance is reduced, the pellets are refilled, and the replaced reduced pellets are sent into a blast furnace or a hydrogen-based shaft furnace to directly reduce iron.
As a specific embodiment, FIG. 1 is a schematic structural diagram of a hydrogen metallurgy-chemical looping pure hydrogen production system according to the embodiment, wherein V1-V10 in the drawing represent valves. The system comprises two fixed beds (fixed beds A and B), a converter/coke oven, a blast furnace, a gasification furnace, a gas-liquid separator, a heat exchanger, a purifier and a water tank. When the device works, the fixed bed has two working processes, one is the reduction reaction aiming at the oxidized pellets, the other is the oxidation reaction aiming at the reduced pellets, any fixed bed alternately carries out the two working processes, and the working processes of the two fixed beds are different at the same time.
The equipment setting mode aiming at the reduction reaction is as follows: the converter/coke oven is respectively connected with the two fixed beds through gas pipelines, valves are arranged on the two connecting pipelines, a valve V1 is arranged on the connecting pipeline with the fixed bed A, and a valve V2 is arranged on the connecting pipeline with the fixed bed B. The fixed bed A and the fixed bed B are respectively connected with the gasification furnace through pipelines, valves are arranged on the two connecting pipelines, a valve V9 is arranged on the connecting pipeline of the fixed bed A and the gasification furnace, and a valve V10 is arranged on the connecting pipeline of the fixed bed B and the gasification furnace. Gas outlet of gasification furnaceThe pipeline is divided into two paths, one path is connected with pipelines for other gas purposes, the other path is connected with the converter/coke oven and the pipelines connected with the two fixed beds in a combined way, and the gas output by the gasification furnace is input into the fixed beds to participate in the oxidation reaction. Preferably, a purifier is arranged on the output pipeline of the gasification furnace and is used for purifying the gas output by the gasification furnace so as to ensure the purity of the gas entering the pipeline of other gas applications and the gas re-participating in the oxidation reaction. To ensure that the excess CO and H in the reduction reaction process 2 Can be totally reacted into CO 2 And H 2 O, O is required to be introduced into a fixed bed 2 To undergo a catalytic combustion reaction; the oxygen pipeline is respectively connected with the two fixed beds, and is respectively provided with a valve, a valve V7 is arranged on the pipeline connected with the fixed bed A, and a valve V8 is arranged on the pipeline connected with the fixed bed B.
The equipment setting mode aiming at the oxidation reaction is as follows: the steam generator is respectively connected with the two fixed beds through pipelines, valves are arranged on the two connecting pipelines, a valve V6 is arranged on the connecting pipeline with the fixed bed A, and a valve V5 is arranged on the connecting pipeline with the fixed bed B. The fixed bed A and the fixed bed B are respectively connected with condensing equipment through pipelines, and the condensing equipment is connected with a gas-liquid separator; a valve V4 is arranged on a connecting pipeline between the fixed bed A and the condensing equipment, and a valve V3 is arranged on a connecting pipeline between the fixed bed B and the condensing equipment. The liquid outlet of the gas-liquid separator is connected with the water tank through a pipeline, and the gas outlet is connected with the blast furnace through a pipeline. As a preferred embodiment, the above-mentioned condensing device may be implemented by a heat exchanger for implementing heat exchange between the high-temperature gas outputted after the fixed bed oxidation reaction and the vapor line of the pre-inputted fixed bed, on the one hand, condensation of vapor in the high-temperature gas is implemented, on the other hand, the temperature of vapor in the vapor line is increased, and cooling and liquefying in the line are avoided.
Initially, oxidized pellets are carried on a lower bed layer of a fixed bed A, an iron-based catalyst is carried on an upper bed layer, the lower bed layer is subjected to reduction reaction of the oxidized pellets, and the upper bed layer is subjected to catalytic combustion reaction of tail gas; the upper bed layer of the fixed bed B carries the reduced pellet ore, the lower bed layer carries the iron-based catalyst, and the upper bed layer generates oxidation reaction of the reduced pellet ore; in the reaction process, the fixed bed A is arranged by a reduction reaction device, and the fixed bed B is arranged by an oxidation reaction device. After the reaction is finished, the fixed beds A and B change working states, and the valves are switched; in this case, the fixed bed a is installed using an oxidation reaction apparatus, and the oxidation reaction of the reduced pellets occurs as a steam reactor. The fixed bed B is provided using a device for reduction reaction, and as a fuel reactor, reduction reaction of oxidized pellets and catalytic combustion reaction occur. Alternating in this way. Specifically:
valves V1, V3, V5, V7 and V9 are opened and valves V2, V4, V6, V8 and V10 are closed. Converter/coke oven gas (CO and H) 2 Mainly) is fed into a fixed bed A, and oxidized pellets (Fe is used as 2 O 3 And Fe (Fe) 3 O 4 Mainly) into reduced pellets (mainly FeO and Fe), and the reacted converter/coke oven gas (containing rich CO and H 2 ) With O 2 Catalytic combustion reaction takes place in the upper bed layer of fixed bed A under the catalysis of iron-based catalyst, and the heat of reaction evolution is used for supplying heat to the reaction of fixed bed A lower bed layer. Tail gas (in CO) produced by catalytic combustion reaction 2 And water vapor mainly) enters a gasification furnace to react with organic matters (from biomass, carbon-containing sludge particles and the like) in the gasification furnace to generate CO and H 2 And hydrogen-rich gas.
The hydrogen-rich gas is dedusted by a purifier, desulfurized/nitrogen and water, one part of the hydrogen-rich gas and converter/coke oven gas are mixed and sent to a chemical-looping hydrogen production reaction bed (fixed bed A or fixed bed B), and the other part of the hydrogen-rich gas can be connected with pipelines for other gas purposes.
At the same time, the water vapor is introduced into the upper bed layer of the fixed bed B (in the process, the catalyst of the lower bed layer of the fixed bed B does not participate in the reaction) to react with the reduced pellets to generate H 2 (containing surplus water vapor) and oxidized pellets, and the generated high temperature H 2 And H is 2 O path exchanges heat and makes water gasified and flow into upper bed layer of fixed bed B, H after heat exchange 2 And the waste water is removed in the gas-liquid separator and then is sent into a blast furnace or a hydrogen-based shaft furnace to participate in reduction iron making.
After the pellets in the fixed beds A and B react, oxidation-reduction states of the pellets carried by the fixed beds A and B are changed, then the valves V1, V3, V5, V7 and V9 are closed, and the valves V2, V4, V6, V8 and V10 are opened. Converter/coke oven gas (CO and H) 2 Mainly) is introduced into a fixed bed B, and oxidized pellets (Fe) 2 O 3 And Fe (Fe) 3 O 4 Mainly) into reduced pellets (mainly FeO and Fe), and the reacted converter/coke oven gas (with surplus CO and H 2 ) With O 2 Catalytic combustion reaction occurs in the lower bed layer of the fixed bed B under the catalysis of the iron-based catalyst, and the heat released by the reaction is used for supplying heat to the reaction of the upper bed layer of the fixed bed B. Tail gas (in CO) produced by catalytic combustion reaction 2 And water vapor is the main component) and biomass, carbon-containing sludge particles and the like to generate CO and H 2 And hydrogen-rich gas. The hydrogen-rich gas is dedusted by a purifier, desulfurized/nitrogen and water, one part of the hydrogen-rich gas and converter/coke oven gas are mixed and sent to a chemical-looping hydrogen production reaction bed, and the other part of the hydrogen-rich gas can be connected with pipelines for other gas uses.
At the same time of the above reaction, the steam is introduced into the lower bed layer of the fixed bed A (in the process, the iron-based catalyst of the upper bed layer of the fixed bed A does not participate in the reaction) to react with the reduced pellets to generate H 2 And oxidized pellets, high temperature H produced 2 Exchanges heat with water and gasifies the water to flow into the lower bed layer of the fixed bed A. H after heat exchange 2 And removing excessive water through a gas-liquid separator, and then introducing the water into a blast furnace or a hydrogen-based shaft furnace to participate in reducing iron.
After the reaction is completed, the above steps are repeated. And when the pellets are sintered or the performance is reduced, the pellets are refilled and the replaced reduced pellets are sent into a blast furnace or a hydrogen-based shaft furnace for reducing iron.
The oxygen carrier for preparing hydrogen by the chemical chain is pellet ore, but not limited to pellet ore, and can also comprise iron ore and iron-containing solid waste resources (sintering and pellet dust mud, blast furnace gas plaster, steelmaking dust mud, cold and hot rolling sludge, iron oxide scale and other iron-containing solid waste resources with the iron content of 30-70 percent).
The main chemical reactions involved in the hydrometallurgical-chemical chain pure hydrogen preparation process are as follows:
reaction of coal gas with oxidized pellets:
3Fe 2 O 3 (s)+H 2 (g)→2Fe 3 O 4 (s)+H 2 O(g)
Fe 3 O 4 (s)+H 2 (g)v3FeO(s)+H 2 O(g)
FeO(s)+H 2 (g)→Fe(s)+H 2 O(g)
3Fe 2 O 3 (s)+CO(g)→2Fe 3 O 4 (s)+CO 2 (g)
Fe 3 O 4 (s)+CO(g)→3FeO(s)+CO 2 (g)
FeO(s)+CO(g)→Fe(s)+CO 2 (g)
the water vapor reacts with the reduced pellets:
3Fe(s)+4H 2 O(g)→Fe 3 O 4 (s)+4H 2 (g)
3FeO(s)+H 2 O(g)→Fe 3 O 4 (s)+H 2 (g)
catalytic combustion reaction:
the reacted coke oven gas tail gas reacts with carbon:
CO 2 (g)+C(s)→2CO(g)
H 2 O(g)+C(s)→CO(g)+H 2 (g)
H 2 O(g)+CO(g)→CO 2 (g)+H 2 (g)
the system of the present application is a dual-bed reaction mode, but is not limited to a dual-bed reaction mode, such as a three-bed reaction mode, i.e., adding an air reaction bed on the basis of a fuel reaction bed and a vapor reaction bed. In the air reaction bed, fe generated by the steam reaction bed 3 O 4 Can further react with air to generate Fe 2 O 3 。Fe 2 O 3 Reacts with coal gas in a fuel reaction bed to generate FeO and Fe. The exothermic reaction in the air reaction bed can provide heat for the system:
4Fe 3 O 4 (s)+O 2 (g)→6Fe 2 O 3 (s)
the embodiment of the application provides a large-scale pure hydrogen preparation method and system for hydrogen metallurgy, which are described in detail. The above description of embodiments is only for aiding in the understanding of the method of the present application and its core ideas; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present application, the present description should not be construed as limiting the present application in view of the above.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a product or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such product or system. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a commodity or system comprising such elements. By "substantially" is meant that within an acceptable error range, a person skilled in the art is able to solve the technical problem within a certain error range, substantially achieving the technical effect.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. The term "and/or" as used in the present application is merely an association relation describing the association object, and means that three kinds of relations may exist, for example, a and/or B may mean: a exists alone, A and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship.
Claims (10)
1. A large scale pure hydrogen production system for hydrogen metallurgy, the system comprising:
fixed bed A and fixed bed B for converting CO and H in converter/coke oven gas 2 Oxidation to CO 2 And H 2 O mixture, or H to be introduced therein 2 Reduction of O to H 2 ；
The converter/coke oven is respectively connected with the fixed bed A and the fixed bed B and is used for supplying coal gas to be reacted into the fixed bed A or the fixed bed B;
the biomass gasification furnace is respectively connected with the fixed bed A and the fixed bed B and is used for realizing carbon and CO 2 And H 2 O reacts to obtain CO and H 2 ；
Steam generators respectively connected with the fixed bed A and the fixed bed B for supplying H to be reacted into the fixed bed A or the fixed bed B 2 O；
A gas-liquid separator for condensing H obtained by the reaction in the fixed bed A or the fixed bed B 2 Treating and separating out surplus water;
a blast furnace/hydrogen-based shaft furnace connected with the gas-liquid separator for receiving H 2 Hydrogen metallurgy is performed.
2. The large scale pure hydrogen production system for hydrogen metallurgy according to claim 1, further comprising:
a purifier connected with the biomass gasification furnace and used for generating CO and H 2 And (5) purifying.
3. The large-scale pure hydrogen production system for hydrogen metallurgy according to claim 2, wherein the purifier is connected to a pipe for feeding gas to the fixed bed a or the fixed bed B for purifying CO and H 2 Is fed into a fixed bed A or a fixed bed B to participate in the reaction.
4. The system for producing large-scale pure hydrogen for hydrogen metallurgy according to claim 1, wherein the lower bed layer of the fixed bed a carries oxidized pellets and the upper bed layer carries an iron-based catalyst;
the lower bed layer of the fixed bed B carries the reduced pellets, and the upper bed layer carries the iron-based catalyst.
5. The large-scale pure hydrogen production system for hydrogen metallurgy according to claim 4, wherein upper beds of the fixed bed a and the fixed bed B are each connected to an oxygen supply line.
6. The large scale pure hydrogen production system for hydrogen metallurgy according to claim 1, further comprising: the heat exchanger is arranged in front of the steam generator and is used for realizing the reaction in the fixed bed A or the fixed bed B to obtain H 2 And H pre-fed to fixed bed A or B 2 O exchanges heat to finish H 2 Condensation and H of (2) 2 Vaporization of O.
7. The large scale pure hydrogen production system for hydrogen metallurgy according to claim 1, further comprising:
the water tank is connected with the gas-liquid separator and is used for storing water separated by the gas-liquid separator.
8. The system for large scale production of pure hydrogen for hydrogen metallurgy according to claim 1, wherein biomass, carbon-containing sludge particles are provided in the biomass gasification furnace for supplying carbon required for the reaction in the biomass gasification furnace.
9. The large scale pure hydrogen production system for hydrogen metallurgy according to claim 1, further comprising:
a gas using device and/or a gas storage tank connected with the purifier for using and/or storing the purified CO and H 2 。
10. A process for the preparation of large-scale pure hydrogen for hydrogen metallurgy, characterized in that the process is carried out using the large-scale pure hydrogen preparation system for hydrogen metallurgy according to any one of claims 1 to 9; the method comprises the following steps:
the fixed bed A and the fixed bed B are used for receiving the coal gas conveyed from the converter/coke oven and converting CO and H in the coal gas 2 Oxidation to CO 2 And H 2 O, another fixed bed receives the steam state H from the steam generator 2 Reduction of O to H 2 ；
For H generated by reduction 2 Condensing and separating gas from liquid, purifying H 2 Delivering the mixture to a blast furnace/hydrogen-based shaft furnace for hydrogen metallurgy;
for CO produced by oxidation 2 And H 2 O is firstly conveyed to a biomass gasification furnace to react with carbon in the biomass gasification furnace to obtain CO and H 2 The mixed gas as main component is purified and mixed with gas for reaction in fixed bed, and the other part is connected with gas pipeline for other purposes.
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| CN202310564182.4A CN116768154A (en) | 2023-05-18 | 2023-05-18 | Large-scale pure hydrogen preparation method and system for hydrogen metallurgy |
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