CN101871031B - Method and equipment for preparing reducing gas from coke oven gas to produce sponge iron - Google Patents
Method and equipment for preparing reducing gas from coke oven gas to produce sponge iron Download PDFInfo
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Abstract
The invention relates to a method and equipment for preparing reducing gas from coke oven gas to produce sponge iron. The method comprises the following steps: obtaining mixed gas through mixing conventionally purified coke oven gas with one kind or two kinds of gas in converter gas, blast furnace gas, converted reducing tail gas and supplementary CO2; carrying out coarse desulfurization treatment; carrying out fine desulfurization treatment on the mixed gas after the coarse desulfurization treatment so that the total sulfur content of the mixed gas is lower than 3 ppm; then, carrying out heat exchange and temperature rising; making the gas enter a coke oven gas conversation furnace so that hydrocarbon and CO2 in the mixed gas can be converted into CO and hydrogen gas; making the gas obtained after the conversation directly enter a vertical furnace for producing DRI; using a part of converted reducing tail gas after cooling and dust removal as fuel through air discharge; and returning the other part of the converted reducing tail gas after cooling and dust removal into a coarse desulfurization work section inlet. The invention also provides equipment for realizing the method. The method provided by the invention has the advantages of simplicity, high efficiency and low energy consumption, and belongs to the method of efficiently utilizing the coke oven gas.
Description
Technical field
The present invention relates to a kind ofly utilize coke(oven)gas production to synthesize reducing gas, utilize direct reducing gas base method to produce the method and apparatus of sponge iron (DRI), more particularly, relate to a kind of method and apparatus that utilizes reducing gas prepared from coke oven gas to produce sponge iron.
Background technology
Direct-reduced iron (DRI) claim sponge iron again, is a kind of metallic iron that obtains without blast-furnace smelting, and the technology of producing DRI is non-blast furnace ironmaking technology.The production technique of DRI is divided coal-based gentle basic two classes.Wherein gas base method accounts for 90% of DRI output at present, typical process is pot type method (HyL method) and shaft furnace process (Midrex method), shaft furnace process adopts perpendicular type moving-bed reduction reactor, it is mainly in two sub-sections: the reduction zone, reducing gas circulation in this district at high temperature, hydrogen more than 800 ℃ and carbon monoxide reducing iron oxides generate DRI, and hydrogen and carbon monoxide generate water and carbonic acid gas; And the cold-zone that is positioned at the bottom, reduction zone, before the DRI discharging, the DRI of cooling zone is cooled to envrionment temperature through the cooling gas of round-robin hydrogen and carbon monoxide in a cooling loop.
The used reductive agent of gas base method mainly is a Sweet natural gas, produces synthetic gas CO+H through steam reforming or partial oxidation
2, and Chinese Gas Prices costliness, more coastal regional Gas Prices have reached 5 yuan/m in the east
3, and adopt refining synthetic gas price that big type coal gasification produces also at 0.8 yuan/m
3More than, therefore seek a low-cost reducing gas raw material channel and be greatly develop Chinese DRI produce the problem that must face.
In state-owned a large amount of coke(oven)gas (COG) resource, except that a part be used for the generating, produce pure hydrogen, heating fuel and the production methyl alcohol, about 1/3rd resources are put into torch and are burnt; And in iron and steel enterprise, exist a large amount of fuel gas with low heat value more than needed, the blast furnace gas of emptying and converter gas etc.Along with the progress of power-saving technology, two preheating technologies of hotblast stove, accumulation of heat process furnace technology etc. continue to bring out, and a large amount of fuel gas with low heat value are utilized, and having more than needed of coke-oven gas is indubitable.With the Anshan iron and steel plant is example, predicts blast furnace gas 460,000 m more than needed in 2006
3/ h, coke-oven gas 4-6 ten thousand m that have more than needed
3/ h.
The coke-oven gas main component is H
2(55-66%), CH
4(24-26%), CO (6-8%), all the other are carbonic acid gas, nitrogen and C
2 +Hydrocarbon and a small amount of oxygen and sulphur impurity are fine DRI reducing gas raw materials, but because sulfur impurity complicated component wherein contains carbonylsulfide and thiophene sulphur compound, make the methane conversion nickel catalyzator be easy to inactivation; Simultaneously a small amount of C
2 +During according to the operation of system DRI reducing gas processing condition, carbon distribution causes methane conversion nickel catalyzator inactivation to hydrocarbon easily under the high temperature of methane conversion; Owing to making the industrial production of coke(oven)gas system DRI reducing gas, this two aspects reason is difficult to the economy operation; Also owing to be subjected to the influence of coke oven tolerance, scale operation DRI is restricted on the other hand, and therefore maximally utilising coke(oven)gas production reducing gas also is to want one of top-priority problem.
Therefore, for associating iron and steel enterprise, can make full use of other suitable coal gas resource, as coal gas of converter and blast furnace gas etc.Be exactly to make full use of existing coke-oven gas on the other hand, in production process, avoid coke-oven gas to serve as fuel and emptying as far as possible, only in the circulation reducing gas for avoiding nitrogen accumulation that a part of coke(oven)gas is burnt.
Produce in the DRI process, effectively reducing gas content is high more, and the temperature of producing DRI is just low more, therefore for energy-conservation and enhance productivity, should become CO and H to the methane conversion in the reducing gas as far as possible
2, make the coke oven reducing gas that very high iron reduction ratio and reduction rate just be arranged about 800 ℃.
Chinese patent application CN1995402A discloses a kind of method of utilizing coke(oven)gas ferric oxide directly to be reduced into metallic iron.The disclosed technical scheme special concern of this application remove heavy hydrocarbon, tar among the COG with the DRI of cooling/material discharge region, to avoid the fouling of gas heating and miscellaneous equipment.And hydrogen sulfide that generates during to organosulfur in the coke(oven)gas and reducing gas reducing iron ore etc. does not remove, total sulfur in these gases maximum sulfur 1ppm that catalyzer requires during much larger than conversion of natural gas, to cause the methane reforming catalyst rapid deactivation in the technical process, and make production not have economy, in the carbonic acid gas scheme in removing reduction reaction tail gas, only put down in writing by chemical absorption or physical absorption and can remove carbonic acid gas effectively, how a large amount of hydrogen sulfide that do not have explanation to remove when removing carbonic acid gas in the reduction tail gas are handled, and these hydrogen sulfide enter with carbonic acid gas and do not meet environmental requirement in the atmosphere.
U.S. Pat 4270739, US4333761, US4351513 disclose and have utilized reducing gas prepared from coke oven gas to carry out direct reducing process, remove organosulfur among the COG by top, reduction zone at reduction furnace, but a large amount of hydrogen sulfide that do not have consideration in removing conversion process, to exist in the reduction tail gas, actual production can reach 300ppm, and these hydrogen sulfide easily make the methane reforming catalyst rapid deactivation and actually operating can't be carried out.
U.S. Pat 4900356 discloses a kind of sulfur method that reduces in the tail gas, make sulfide be converted into solid with quenched water washing reduction tail gas, thereby realize reducing the sulphur content in the reduction tail gas, reduce the purpose that methane reforming catalyst is poisoned, improved process efficiency to reach, but the sulfur-containing waste water that produces needs further to handle, and desulfurization precision is worth discussion.
Summary of the invention
For solving the problems of the technologies described above, the method that the object of the present invention is to provide a kind of reducing gas of utilizing coke(oven)gas to make to produce sponge iron by coke(oven)gas is carried out desulfurization and conversion processing, improves H
2With H
2The ratio of O and CO and CO
2Ratio, make it satisfy the requirement that shaft furnace process is produced sponge iron, have characteristics such as technology is simple, energy consumption is low.
The present invention also aims to provide the above-mentioned reducing gas of utilizing coke(oven)gas to make of realization to produce the equipment of the method for sponge iron.
For achieving the above object, the present invention at first provides a kind of method of utilizing reducing gas prepared from coke oven gas to produce sponge iron, and it may further comprise the steps:
Reduction tail gas after coke(oven)gas after will purifying by routine and coal gas of converter, blast furnace gas, the conversion and the CO that replenishes
2In one or both mix after, obtain gas mixture, and gas mixture carried out thick desulfurization handle, remove the hydrogen sulfide in the gas mixture, the hydrogen sulfide in the gas mixture is reduced to below the 10ppm;
The gas mixture of handling through thick desulfurization is carried out smart desulfurization handle, make total sulfur content in the gas mixture less than 3ppm;
The gas mixture of handling through smart desulfurization is carried out entering the coke(oven)gas converter after heat exchange heats up, make the hydro carbons in the gas mixture (comprise methane and C2
+Hydrocarbon) and CO
2Be converted into CO and hydrogen under the nickel catalyst effect, the gas that obtains after the conversion directly enters shaft furnace and produces DRI, and the reduction tail gas after the conversion is used as fuel through a part of emptying behind the cooling and dedusting, and another part returns thick desulfurization workshop section inlet.In aforesaid method provided by the invention, preferably, described thick desulfurization is handled and is adopted the ammonia process of desulfurization or the desulfurization of sulfonation phthalein mountain valley with clumps of trees and bamboo cobalt.
In aforesaid method provided by the invention, the sulphur Tai Gaoyi in the gas mixture makes the conversion catalyst inactivation, and a certain amount of sulphur can slow down the carbon distribution of catalyzer, preferably, handles by smart desulfurization, makes the total sulfur content in the gas mixture be controlled to be 2-3ppm.
In aforesaid method provided by the invention, preferably, described smart desulfurization is handled to adopt fixed-bed desulfurization or transform the absorption sulfur removal technology and is carried out.Wherein, in fixed-bed desulfurization, the desulfurizing agent that is adopted can be one or more the combination in gac, ferric oxide and the zinc oxide etc.; In transforming the absorption sulfur removal technology, the carrier of the desulfurizing agent that is adopted is a zinc oxide, binding agent is aluminum oxide and/or diatomite etc., active ingredient is one or more the combination in oxide compound of iron, cobalt and nickel etc., and auxiliary agent is one or more the combination in tungsten, molybdenum and the rare earth (comprising rare earth simple substance and mishmetal) etc.More preferably, in transform absorbing sulfur removal technology, the carrier of the desulfurizing agent that is adopted is a zinc oxide, and active ingredient is one or more the combination in the oxide compound of iron, cobalt and nickel etc., and auxiliary agent is tungsten and/or molybdenum etc.
In aforesaid method provided by the invention, preferably, above-mentioned conversion absorbs the conversion absorption sulfur removal technology that sulfur removal technology can be a super regeneration, adopt the mode of two or three above smart desulphurization reactor serial or parallel connection operations to carry out, in reaction process, at least one reactor on-line operation, remaining reaction device are in sweetening agent regeneration or the wait process.Wherein, temperature of reaction is controlled to be 120-500 ℃, and pressure-controlling is 0.01-0.5MPa, and volume space velocity is 200-500H
-1Can use air to cooperate nitrogen to regenerate, wherein, the content of oxygen is 1-15V/V%, and regeneration temperature is 300-600 ℃, and pressure-controlling is a normal pressure, and volume space velocity is 200-500H
-1
In aforesaid method provided by the invention, preferably, smart desulfurization processing also can absorb sulfur removal technology by hydrocracking to be carried out, and it may further comprise the steps: at first utilize hydrogenation catalyst that the organosulfur hydrocracking in the coke(oven)gas is H
2S, the H that utilizes high temperature desulfuration agent that hydrogenation is generated then
2S absorbs.Wherein, the hydrogenation catalyst that is adopted is preferably Fe-Mo/Al
2O
3Hydrogenation catalyst, the high temperature desulfuration agent that is adopted can be that manganese is high temperature desulfuration agent and/or Zinc oxide high temperature desulfuration agent etc.
In aforesaid method provided by the invention, in the coke(oven)gas converter, under the effect of nickel catalyst, hydro carbons and CO such as methane in the coke oven gas mixture
2Reaction is converted into CO and hydrogen, and preferably, the invert point in the coke(oven)gas converter is controlled to be 400-950 ℃, and transfer pressure is controlled to be 0.1-0.5MPa.The carrier of the nickel series conversion catalyzer that is adopted is α-Al
2O
3(can add the binding agent of a small amount of routine), active ingredient are nickel, and auxiliary agent can be rare earth and/or alkaline-earth metal, for example La, Ce, Mg, Ca or its mixture.Catalyzer will be reduced to metallic nickel to nickel oxide before use.
The temperature of converter outlet is that 800-950 ℃ reducing gas directly enters shaft furnace (perpendicular type moving-burden bed reactor) production reduced iron, fuel is done in reduction tail gas a part of emptying after waste heat recovery, dedusting after the conversion that shaft furnace is discharged, as being used as the fuel in the coke(oven)gas converter, most of thick desulfurization workshop section inlet that returns after pressurization and carries out thick desulfurization after coke(oven)gas etc. mixes.CO and H in the reduction tail gas had so both been made full use of
2, simultaneously also the CO in the reduction tail gas
2Also make full use of, with methane reaction generation CO and the H in the coke(oven)gas
2, reduce and replenish CO
2Amount.
The present invention also provides a kind of above-mentioned equipment that utilizes reducing gas prepared from coke oven gas to produce the method for sponge iron that is used for, it mainly comprises: thick desulphurization reactor, first interchanger, smart desulphurization reactor, second interchanger, coke(oven)gas converter and perpendicular type moving-bed reduction reactor (shaft furnace), wherein, the outlet of thick desulphurization reactor is connected with the inlet of described smart desulphurization reactor through first interchanger, the outlet of smart desulphurization reactor is connected through the inlet of second interchanger with the coke(oven)gas converter, the outlet of coke(oven)gas converter is connected with the inlet of perpendicular type moving-burden bed reactor, and, the coke(oven)gas converter also has an exhanst gas outlet, this exhanst gas outlet and second interchanger, first interchanger connects successively.
In aforesaid device provided by the invention, preferably, smart desulphurization reactor comprises two or three above reactors in series or in parallel with each other; In reaction process, at least one reactor on-line operation, the remaining reaction device is regenerated or is waited for, and the conversion that is suitable for super regeneration absorbs sulfur removal technology.
In aforesaid device provided by the invention, preferably, smart desulphurization reactor comprises a hydrogenator and a high temperature desulfurizing reactor, and the two is connected mutually, is suitable for the hydrocracking sulfur removal technology.
In aforesaid device provided by the invention, preferably, the coke(oven)gas converter has a fuel inlet, perpendicular type moving-bed reduction reactor has a reduction tail gas outlet, and this reduction tail gas outlet is connected with the fuel inlet of coke(oven)gas converter and the gas inlet of thick desulphurization reactor respectively by pipeline.By above-mentioned pipeline can be respectively with as the reduction tail gas of fuel and deliver to respectively as the reduction tail gas of gas mixture composition in the corresponding inlet of the corresponding inlet of coke(oven)gas converter and thick desulphurization reactor.
The method for preparing sponge iron provided by the invention is to utilize the hydrogen-rich advantage of coke(oven)gas, makes total sulfur content in the coke(oven)gas less than 3ppm through fine desulfurizing technology, and additional proper C O
2, under the nickel catalyzator effect, make CO then
2Generate CO and H with the hydrocarbon reactions such as CH4 in the coke(oven)gas
2, improve H
2With H
2The ratio of O and CO and CO
2Ratio, make it satisfy the requirement that shaft furnace process is produced sponge iron, directly enter in the coke(oven)gas converter.The technical process of aforesaid method provided by the invention is simply efficient, and energy consumption is low, has both consumed certain CO
2Being used for producing, can producing qualified DRI reducing gas at low cost again, is a kind of method of efficiently utilizing coke(oven)gas.
Description of drawings
The following drawings only is intended to the present invention done and schematically illustrates and explain, not delimit the scope of the invention.Wherein:
The process flow sheet that Fig. 1 is adopted for embodiment 1;
The process flow sheet that Fig. 2 is adopted for embodiment 2;
The process flow sheet that Fig. 3 is adopted for embodiment 3.
The drawing reference numeral explanation:
Thick desulphurization reactor 1 first interchanger 2 smart desulphurization reactor 3 second interchanger 4 coke(oven)gas converters 5 perpendicular type moving-bed reduction reactor 6 hydrogenators 7 high temperature desulfurizing reactors 8
Embodiment
Understand for technical characterictic of the present invention, purpose and beneficial effect being had more clearly, technical scheme of the present invention is carried out following detailed description, but but can not be interpreted as qualification practical range of the present invention referring now to Figure of description.
Embodiment 1
The method that present embodiment provides a kind of reducing gas of utilizing coke(oven)gas to make to produce sponge iron, its technical process as shown in Figure 1.
The equipment that present embodiment adopted mainly comprises: thick desulphurization reactor 1, first interchanger 2, smart desulphurization reactor 3, second interchanger 4, coke(oven)gas converter 5 and perpendicular type moving-bed reduction reactor 6, wherein, the outlet of thick desulphurization reactor 1 is connected with the inlet of smart desulphurization reactor 3 through first interchanger 2, the outlet of smart desulphurization reactor 3 is connected with the inlet of coke(oven)gas converter 5 through second interchanger 4, the outlet of coke(oven)gas converter 5 is connected with the inlet of perpendicular type moving-burden bed reactor 6, and, coke(oven)gas converter 5 also has an exhanst gas outlet, this exhanst gas outlet and second interchanger 4, first interchanger 3 connects successively; Above-mentioned smart desulphurization reactor 3 absorbs smart desulphurization reactor for transforming, and comprises the reactor of two parallel connections, and above-mentioned coke(oven)gas converter 5 is coke(oven)gas and CO
2The tubulation converter.
The method that the reducing gas of utilizing coke(oven)gas to make that present embodiment provides is produced sponge iron adopts the smart doctor treatment of conversion absorption to carry out smart desulfurization, and the concrete processing step of this method is as follows:
To flow is 10000Nm
3/ h's is 2500Nm through adding flow in the conventional coke(oven)gas that purifies (it is mainly formed and comprises: methane 20-25v%, hydrogen 50-60v%, total sulfur content are about 300ppm)
3The CO of/h
2, make it be pressurized to 0.6MPa, obtain gas mixture;
Gas mixture is entered carry out the thick desulfurization processing of ammonia process in the thick desulphurization reactor 1, absorb desulfurization to hydrogen sulfide content＜10ppm, wherein, the volumetric concentration of the ammoniacal liquor that is adopted is 17%;
Gas mixture heat exchange in first interchanger 2 that the thick desulfurization of process is handled is warming up to 200 ℃, enters then to transform to absorb to transform in the smart desulphurization reactor 3 to absorb smart desulfurization processing, and the total sulfur content of gas mixture is reduced to less than 3ppm; Adopt two reactors, one opens a regeneration, adorns 5m in each smart desulphurization reactor
3Transform the absorption desulfurizing agent, this conversion absorbs desulfurizing agent and contains the NiO of 20wt%, 5% molybdic oxide, and surplus is a zinc oxide;
Make gas mixture heat exchange in second interchanger 4 of handling through smart desulfurization be warming up to 500 ℃, enter coke(oven)gas and CO then
2React in the tubulation converter, make hydro carbons and CO
2Be converted into CO and H
2, wherein, load 5m in the converter
3Z413-HR type nickel catalyst, it consists of: the nickel oxide of 30wt%, surplus are α-Al
2O
3And small amount of binder; The temperature out of converter is controlled to be 850 ℃, and pressure-controlling is 0.4MPa, and mixed gas flow is about 17500Nm
3/ h;
The H of the gas mixture (reducing gas) that obtains after the process converter
2: H
2O and CO: CO
2Significantly, reach the requirement of U.S. Midrex synthetic gas, enter in the perpendicular type moving-burden bed reactor 6 and be used to produce sponge iron greater than 2.3.
The method that present embodiment provides a kind of reducing gas of utilizing coke(oven)gas to make to produce sponge iron, its technical process as shown in Figure 2.
In the equipment that present embodiment adopted, the smart desulphurization reactor that adopted 3 is placed in-line hydrogenator 7 in front and back and high temperature desulfurizing reactor 8, and other structures are identical with equipment among the embodiment 1.
The method that the reducing gas that present embodiment provides utilizes coke(oven)gas to make is produced sponge iron adopts hydrocracking to absorb smart doctor treatment to carry out smart desulfurization, and the concrete processing step of this method is as follows:
To flow is 20000Nm
3/ h's is 5000Nm through adding flow in the conventional coke(oven)gas that purifies (it is mainly formed and comprises: methane 20-25v%, hydrogen 55-60v%, total sulfur content are about 200ppm)
3The CO of/h
2, make it be pressurized to 0.5MPa, obtain gas mixture;
Make gas mixture enter in the sulfonation phthalein mountain valley with clumps of trees and bamboo cobalt liquid in the thick desulphurization reactor 1 desulfurization and handle, absorb desulfurization to hydrogen sulfide content＜10ppm;
Make gas mixture heat exchange in first interchanger 2 of handling through thick desulfurization be warming up to 250 ℃, enter then and carry out hydrocracking in the hydrodesulphurisatioreactors reactors 7, making the organosulfur hydrocracking is hydrogen sulfide, wherein, in the hydrodesulphurisatioreactors reactors 7 15m is housed
3Industrial Fe-Mo/Al
2O
3Hydrogenation catalyst, its composition comprises: 5% Fe
2O
3, 15% MoO
3, surplus is aluminum oxide; Gas mixture is entered carry out the high temperature desulfurizing processing in the high temperature desulfurizing reactor 8, wherein, the sweetening agent that is adopted is 30m
3High temperature manganese fimily desulfurizing agent is reduced to less than 3ppm the total sulfur content of gas mixture;
Make gas mixture heat exchange in second interchanger 4 of handling through smart desulfurization be warming up to 550 ℃, enter coke(oven)gas and CO then
2React in the tubulation converter, make hydro carbons and CO such as methane
2Be converted into CO and H
2, wherein, load 12m in the converter
3Z413-HR type catalyzer, it is formed with embodiment 1; The temperature out of converter is controlled to be 900 ℃, and pressure-controlling is 0.3MPa, and mixed gas flow is about 35000Nm
3/ h;
The H of the gas mixture (reducing gas) that obtains after the process converter
2: H
2O and CO: CO
2Significantly greater than 2.3, H
2: CO ≈ 1.5: 1, reach the requirement of U.S. Midrex synthetic gas, enter in the perpendicular type moving-burden bed reactor 6 and be used to produce sponge iron.
Present embodiment replenishes CO by adjusting processing parameter and change on the basis of embodiment 1
2Amount, the quality of the reducing gas that is obtained is better than the reducing gas that embodiment 1 is obtained.
The method that present embodiment provides a kind of reducing gas of utilizing coke(oven)gas to make to produce sponge iron, its technical process as shown in Figure 3.The structure of the equipment that present embodiment adopted is identical with equipment among the embodiment 1.
The method that the reducing gas of utilizing coke(oven)gas to make that present embodiment provides is produced sponge iron adopts the smart doctor treatment of conversion absorption to carry out smart desulfurization, and the concrete processing step of this method is as follows:
To flow is 20000Nm
3/ h's is 2000Nm through adding flow in the conventional coke(oven)gas that purifies (it is mainly formed and comprises: methane 20-25v%, hydrogen 55-60v%, total sulfur content are about 250ppm)
3The CO of/h
2, and mix with reduction tail gas after the shaft furnace of 2/3 volume transforms, be pressurized to 0.4MPa, obtain gas mixture;
Gas mixture is entered carry out the thick desulfurization processing of ammonia process in the thick desulphurization reactor 1, absorb desulfurization to hydrogen sulfide content＜10ppm, wherein, the volumetric concentration of the ammoniacal liquor that is adopted is 17%; Gas mixture heat exchange in first interchanger 2 that the thick desulfurization of process is handled is warming up to 300 ℃, enters then to transform to absorb to transform in the smart desulphurization reactor 3 to absorb smart desulfurization processing, and the total sulfur content of gas mixture is reduced to less than 3ppm; Adopt two reactors, one opens a regeneration, adorns 15m in each smart desulphurization reactor
3Transform the absorption desulfurizing agent, it is Co-Mo/ZnO that this conversion absorbs desulfurizing agent, and it contains 5% CoO, 20% MoO
3, surplus is ZnO;
Make gas mixture heat exchange in second interchanger 4 of handling through smart desulfurization be warming up to 550 ℃, enter coke(oven)gas and CO then
2React in the tubulation converter, make hydro carbons and CO
2Be converted into CO and H
2, wherein, load 15m in the converter
3Z413-HR type nickel catalyst, it is formed with embodiment 1; The temperature out of converter is controlled to be 950 ℃, and pressure-controlling is 0.2MPa;
The H of the gas mixture (reducing gas) that obtains after the process converter
2: H
2O and CO: CO
2Significantly greater than 2.3, H
2: CO ≈ I.5: 1, reach the requirement of U.S. Midrex synthetic gas, enter in the perpendicular type moving-burden bed reactor 6 and be used to produce sponge iron.
Reduction tail gas after the conversion is discharged by perpendicular type moving-burden bed reactor 6, the reduction tail gas of wherein about 1/3 volume enters coke(oven)gas converter 5 use that acts as a fuel, the reduction tail gas of about in addition 2/3 volume enter thick desulphurization reactor 1 ingress with through the conventional coke(oven)gas that purifies, additional CO
2Mix, between perpendicular type moving-burden bed reactor 6 and thick desulphurization reactor 1, be provided with waste-heat recovery device and cleaning apparatus.
Above-described specific embodiment; purpose of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the above only is specific embodiments of the invention; and be not intended to limit the scope of the invention; within the spirit and principles in the present invention all, any modification of being made, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (15)
1. method of utilizing reducing gas prepared from coke oven gas to produce sponge iron, it may further comprise the steps:
Reduction tail gas after coke(oven)gas after will purifying by routine and coal gas of converter, blast furnace gas, the conversion and the CO that replenishes
2In one or both mix after, obtain gas mixture, and gas mixture carried out thick desulfurization handle;
The gas mixture of handling through thick desulfurization is carried out smart desulfurization handle, make total sulfur content in the gas mixture less than 3ppm;
The gas mixture of handling through smart desulfurization is carried out entering the coke(oven)gas converter after heat exchange heats up, make hydro carbons and CO in the gas mixture
2Under the nickel catalyst effect, be converted into CO and hydrogen, the gas that obtains after the conversion directly enters perpendicular type moving-bed reduction reactor and produces sponge iron, reduction tail gas after the conversion is used as fuel through a part of emptying behind the cooling and dedusting, and another part returns thick desulfurization workshop section inlet.
2. the method for claim 1, wherein described thick desulfurization is handled and is adopted the ammonia process of desulfurization or the desulfurization of sulfonation phthalein mountain valley with clumps of trees and bamboo cobalt.
3. it is to handling through the gas mixture of thick desulfurization processing, the total sulfur content in the gas mixture being controlled to be more than or equal to 2ppm, less than 3ppm that the method for claim 1, wherein described smart desulfurization is handled.
4. as claim 1 or 3 described methods, wherein, described smart desulfurization is handled to adopt fixed-bed desulfurization or transform the absorption sulfur removal technology and is carried out.
5. method as claimed in claim 4, wherein, the desulfurizing agent that is adopted in the described fixed-bed desulfurization is one or more the combination in gac, ferric oxide and the zinc oxide.
6. method as claimed in claim 4, wherein, absorb in the sulfur removal technology in described conversion, the carrier of the desulfurizing agent that is adopted is a zinc oxide, binding agent is aluminum oxide and/or diatomite, active ingredient is one or more the combination in the oxide compound of the oxide compound of oxide compound, cobalt of iron and nickel, and auxiliary agent is one or more the combination among tungsten, molybdenum and the rare earth three.
7. method as claimed in claim 6, wherein, the carrier that described conversion absorbs the desulfurizing agent that is adopted in the sulfur removal technology is a zinc oxide, and active ingredient is one or more the combination in the oxide compound of the oxide compound of oxide compound, cobalt of iron and nickel, and auxiliary agent is tungsten and/or molybdenum.
8. method as claimed in claim 4, wherein, described conversion absorbs sulfur removal technology and adopts the mode of two or three above smart desulphurization reactor serial or parallel connection operations to carry out, wherein, temperature of reaction is controlled to be 120-500 ℃, and pressure-controlling is 0.01-0.5MPa, and volume space velocity is 200-500H
-1
9. as claim 1 or 3 described methods, wherein, described smart desulfurization is handled by hydrocracking absorption sulfur removal technology and is undertaken, and it may further comprise the steps: at first utilize hydrogenation catalyst that the organosulfur hydrocracking in the coke(oven)gas is H
2S, the H that utilizes high temperature desulfuration agent that hydrogenation is generated then
2S absorbs.
10. method as claimed in claim 9, wherein, described hydrogenation catalyst is Fe-Mo/Al
2O
3Hydrogenation catalyst, described high temperature desulfuration agent are that manganese is high temperature desulfuration agent and/or Zinc oxide high temperature desulfuration agent.
11. the invert point in the method for claim 1, wherein described coke(oven)gas converter is controlled to be 400-950 ℃, transfer pressure is controlled to be 0.1-0.5MPa.
12. one kind is used for each described equipment that utilizes reducing gas prepared from coke oven gas to produce the method for sponge iron of claim 1-11, it mainly comprises: thick desulphurization reactor, first interchanger, smart desulphurization reactor, second interchanger, coke(oven)gas converter and perpendicular type moving-bed reduction reactor, wherein, the outlet of described thick desulphurization reactor is connected with the inlet of described smart desulphurization reactor through described first interchanger, the outlet of described smart desulphurization reactor is connected with the inlet of described coke(oven)gas converter through described second interchanger, the outlet of described coke(oven)gas converter is connected with the inlet of described perpendicular type moving-bed reduction reactor, and, described coke(oven)gas converter also has an exhanst gas outlet, this exhanst gas outlet and described second interchanger, described first interchanger connects successively.
13. equipment as claimed in claim 12, wherein, described smart desulphurization reactor comprises two or three above reactors in series or in parallel with each other.
14. equipment as claimed in claim 13, wherein, described smart desulphurization reactor comprises a hydrogenator and a high temperature desulfurizing reactor, and the two is connected mutually.
15. equipment as claimed in claim 12, wherein, described coke(oven)gas converter has a fuel inlet, described perpendicular type moving-bed reduction reactor has a reduction tail gas outlet, and this reduction tail gas outlet is connected with the fuel inlet of described coke(oven)gas converter and the gas inlet of described thick desulphurization reactor respectively by pipeline.
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| CN102206724B (en) * | 2011-05-03 | 2012-09-05 | 苏亚杰 | Method for coproducing directly reduced iron in process of coke dry quenching by coke oven gas |
| AT510955B1 (en) * | 2011-05-30 | 2012-08-15 | Siemens Vai Metals Tech Gmbh | REDUCTION OF METAL OXIDES USING A BOTH HYDROCARBONS AND HYDROGEN CONTAINING GAS STREAM |
| CN102304599A (en) * | 2011-09-22 | 2012-01-04 | 中冶赛迪上海工程技术有限公司 | Method and device for producing direct reduced iron by using gas-based reduction shaft furnace |
| CN102559980A (en) * | 2012-01-04 | 2012-07-11 | 中冶南方工程技术有限公司 | Method for producing sponge iron by using blast furnace gas |
| CN103525965B (en) * | 2013-10-08 | 2015-12-02 | 中国石油大学(北京) | Coke(oven)gas on-catalytic is utilized to transform the method and system of producing gas base directly reducing iron |
| CN103525964B (en) * | 2013-10-08 | 2016-05-25 | 中国石油大学(北京) | Utilize oven gas catalyzed conversion to produce the method and system of gas base directly reducing iron |
| CN103525966B (en) * | 2013-10-08 | 2016-05-25 | 中国石油大学(北京) | Utilize Catalytic Conversion of Natural Gas to produce the method and system of gas base directly reducing iron |
| CN106241736A (en) * | 2016-08-03 | 2016-12-21 | 西南化工研究设计院有限公司 | A kind of technique utilizing coke-stove gas extraction metallurgy reducing gases |
| CN113620240B (en) * | 2021-06-29 | 2022-08-19 | 东北大学 | Method for determining technological parameters for preparing hydrogen-based reducing gas |
| CN113845089B (en) * | 2021-08-13 | 2024-03-12 | 中国石油大学(北京) | Method for producing synthesis gas for reduced iron by using coke oven gas |
| CN114807486A (en) * | 2022-03-31 | 2022-07-29 | 中晋冶金科技有限公司 | CO (carbon monoxide) 2 Oxidative coupling of CH 4 Method and device for converting hydrogen production base shaft furnace reducing gas |
| CN114774611A (en) * | 2022-03-31 | 2022-07-22 | 中晋冶金科技有限公司 | Hydrogen rich gas CO2Method for producing iron by oxidation conversion and hydrogen-based shaft furnace direct reduction |
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| US4270739A (en) * | 1979-10-22 | 1981-06-02 | Midrex Corporation | Apparatus for direct reduction of iron using high sulfur gas |
| US20060027043A1 (en) * | 2004-08-03 | 2006-02-09 | Hylsa S.A. De C.V. | Method and apparatus for producing clean reducing gases from coke oven gas |
| CN1896286B (en) * | 2006-06-13 | 2010-04-21 | 苏亚杰 | Method for producing direct iron-reduction by iron-ore briquet self-production reproduced gas |
| CN100523228C (en) * | 2007-07-31 | 2009-08-05 | 张文慧 | Method and device for producing sponge iron by using reducing gas prepared from coke oven gas |
| CN101392192B (en) * | 2008-11-05 | 2012-08-01 | 江苏省冶金设计院有限公司 | Conversion of coke oven gas carbon dioxide and production method of gas-based shaft kiln directly reduced iron |
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