CN114107591A - Heating-pure hydrogen reduction cooling system and method - Google Patents
Heating-pure hydrogen reduction cooling system and method Download PDFInfo
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- CN114107591A CN114107591A CN202111424537.7A CN202111424537A CN114107591A CN 114107591 A CN114107591 A CN 114107591A CN 202111424537 A CN202111424537 A CN 202111424537A CN 114107591 A CN114107591 A CN 114107591A
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- 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
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0046—Making spongy iron or liquid steel, by direct processes making metallised agglomerates or iron oxide
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- 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
Abstract
The invention relates to a heating-pure hydrogen reduction cooling system and a method, belongs to the technical field of shaft furnace reduction in a metallurgical process, and solves the problem of low hydrogen utilization rate in the prior art. The heating-pure hydrogen reduction cooling system comprises a heating section, an isobaric section and a reduction cooling section which are sequentially communicated from top to bottom; the heating section is provided with an oxidized pellet inlet, a hot flue gas inlet and a flue gas outlet, the oxidized pellets from the oxidized pellet inlet are contacted with the hot flue gas from the hot flue gas inlet in the heating section, the contacted flue gas is discharged from the flue gas outlet, and the contacted oxidized pellets enter the isobaric section; the reduction cooling section is provided with a hydrogen inlet and a gas outlet, the oxidized pellets in the isobaric section and the hydrogen from the hydrogen inlet are reduced and cooled in the reduction cooling section, and the gas generated in the reduction and cooling process is discharged from the gas outlet. The invention improves the utilization rate of hydrogen.
Description
The invention relates to the technical field of shaft furnace reduction, in particular to a heating-pure hydrogen reduction cooling system and a method.
Background
The hydrogen metallurgy is the inevitable choice for realizing carbon reduction and zero carbon in the steel industry, and can be divided into low-hydrogen metallurgy, hydrogen-rich metallurgy and pure-hydrogen metallurgy according to the carbon reduction effect. The low hydrogen metallurgy mainly adopts hydrogen-rich or pure hydrogen gas to partially replace coke as a reducing agent in a blast furnace, and the carbon reduction limit is lower than 20 percent; the hydrogen-rich metallurgy mainly comprises shaft furnace hydrogen-rich reduction and hydrogen-rich melting reduction, and the carbon reduction effect can reach 50-80%; pure hydrogen metallurgy is still in a test development stage, and generally a shaft furnace is used as a reactor, and pure hydrogen gas is used as reducing gas. From the viewpoint of carbon reduction effect, shaft furnace pure hydrogen reduction is the development trend of hydrogen metallurgy in the future.
The hydrogen-rich gas is generally synthesized and heated in a converter by natural gas or industrial by-product gas, and is H2、CO、CH4、CO2Or H2The heating temperature of the mixed gas of O and the synthesis gas is generally not higher than 900 ℃. The pure hydrogen reduction is a strong endothermic reaction, so the required reduction temperature is higher, but the specific heat coefficient of the hydrogen is lower, the corrosion to the heat exchange tube bundle is stronger, the heating difficulty of the hydrogen is higher, no mature equipment for heating the pure hydrogen gas exists at present, and the heating problem of the hydrogen becomes the bottleneck of pure hydrogen metallurgy; meanwhile, the pellet is reduced by adopting a normal-temperature oxidation-hot hydrogen mode, the heat required by reduction is completely provided by the physical heat of the hydrogen, the circulation quantity of the hydrogen is large, the once utilization rate of the hydrogen is generally not more than 30%, and the utilization rate is lower.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a heating-pure hydrogen reduction cooling system and method to solve the problem of low hydrogen utilization rate due to limited hydrogen heating limit temperature in the existing pure hydrogen shaft furnace reduction system.
In one aspect, an embodiment of the present invention provides a heating-pure hydrogen reduction cooling system, which includes a heating section, an isobaric section, and a reduction cooling section, which are sequentially connected from top to bottom;
the heating section is provided with an oxidized pellet inlet, a hot flue gas inlet and a flue gas outlet, the oxidized pellets from the oxidized pellet inlet are contacted with the hot flue gas from the hot flue gas inlet in the heating section, the contacted flue gas is discharged from the flue gas outlet, and the contacted oxidized pellets enter the isobaric section; the reduction cooling section is provided with a hydrogen inlet and a gas outlet, the oxidized pellets in the isobaric section and the hydrogen from the hydrogen inlet are reduced and cooled in the reduction cooling section, and the gas generated in the reduction and cooling process is discharged from the gas outlet.
In a further improvement of the method, the oxidized pellet inlet is arranged at the top of the heating section, the hot flue gas inlet is arranged at the junction of the heating section 1 and the isobaric section, the flue gas outlet is arranged at a position close to the upper part of the heating section, the hydrogen gas inlet is arranged at a position close to the lower part of the reduction cooling section, and the gas outlet is arranged at the junction of the isobaric section and the reduction cooling section.
Preferably, the heating-pure hydrogen reduction cooling system further comprises a pressure equalizing charging system, a combustion furnace and a hydrogen supply device, wherein the pressure equalizing charging system is connected with the oxidized pellet inlet, the combustion furnace is communicated with the hot flue gas inlet, and the hydrogen supply device is communicated with the hydrogen inlet.
Preferably, the heating-pure hydrogen reduction cooling system further comprises a flue gas purification system, and the flue gas purification treatment system is communicated with the flue gas outlet.
Preferably, the heating-pure hydrogen reduction cooling system further comprises a waste heat recovery system and a gas purification system, an inlet of the gas purification system is connected with the gas outlet, an outlet of the gas purification system is connected with the hydrogen inlet, and the waste heat recovery system is arranged between the gas outlet and the gas purification system.
In another aspect, an embodiment of the present invention provides a heating-pure hydrogen reduction cooling method, where the heating-pure hydrogen reduction cooling system according to the present invention is adopted, and the heating-pure hydrogen reduction cooling method includes: and the oxidized pellets from the oxidized pellet inlet and the hot flue gas from the hot flue gas inlet are in countercurrent contact in the heating section, the flue gas after the countercurrent contact is discharged from a flue gas outlet, the oxidized pellets after the countercurrent contact enter the isobaric section for isobaric transition and then enter the reduction cooling section, the oxidized pellets from the isobaric section and the hydrogen gas from the hydrogen gas inlet are synchronously reduced and cooled in the reduction cooling section, and the gas generated in the reduction and cooling process is discharged from a gas outlet to obtain a solid product, namely the sponge iron.
Preferably, the temperature of the hot flue gas is 1150-1350 ℃, and the temperature of the oxidized pellets is 1000-1100 ℃ due to the countercurrent contact.
Preferably, in the hot flue gas, H2And CO in an amount of 5 to 10% by volume, O2Is less than 1% by volume.
Preferably, the pressure of the hot flue gas at the hot flue gas inlet is equal to the pressure of the gas at the gas outlet.
Preferably, the flue gas discharged from the flue gas outlet is discharged after being purified; and the gas discharged from the gas outlet returns to the reduction cooling section after being subjected to waste heat recovery and purification treatment.
Compared with the prior art, the invention can realize at least one of the following beneficial effects:
(1) the invention adopts the reduction form of thermal oxidation pellets-normal temperature hydrogen (firstly, the oxidation pellets are heated by flue gas, and then the heated oxidation pellets are mixed with the hydrogen) to replace the traditional reduction form of normal temperature pellets-hot hydrogen (the normal temperature oxidation pellets are mixed with the heated hydrogen). When the traditional normal-temperature pellet-hot hydrogen reduction mode is adopted, a heat source required by reduction is provided by hot hydrogen, the hot hydrogen not only needs to meet the chemical consumption of iron oxide reduction, but also needs to provide heat required by reduction, so that the circulating hydrogen amount is large, and the primary utilization rate of hydrogen is lower than 30%. When the thermal oxidation pellet-normal temperature hydrogen reduction form is adopted, the heat required in the hydrogen reduction process is provided by the physical heat of the thermal oxidation pellet, the hydrogen circulation volume is greatly reduced, the hydrogen utilization rate is obviously improved, and the one-time utilization rate can be improved to more than 50%;
(2) according to the invention, the normal-temperature hydrogen is adopted to synchronously carry out the reduction and cooling processes on the thermally oxidized pellets, so that the finally obtained sponge iron is not required to be cooled independently, the use of cooling gas is avoided, the physical heat of the sponge iron is directly used for reduction, and the heat efficiency is improved;
(3) the method has the advantages that the hot flue gas is adopted to directly heat the oxidized pellets to provide heat for the subsequent reduction process, the mode of heating hydrogen by adopting hot flue gas and heating the reduced oxidized pellets by hot hydrogen in the traditional process is replaced, the heating efficiency is improved, a hydrogen heat exchanger for heating hydrogen in the traditional process is not needed, the process is simplified, the temperature limit of the hydrogen heat exchanger for heating hydrogen in the traditional process is eliminated, and the upper limit of the reduction temperature is improved;
(4) in a preferred embodiment of the invention, the reducing gas (H) in the heating flue gas is controlled2CO) and oxygen, avoids the combustion explosion of the heated flue gas and the reduced gas (reducing gas) after being mixed in the isobaric section, and meanwhile, in the heating section, the hot flue gas plays a pre-reduction effect on the oxidized pellets, so that the pure hydrogen reduction burden is reduced, the hydrogen consumption is reduced, and the hydrogen utilization rate is further improved.
In the invention, the technical schemes can be combined with each other to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, wherein like reference numerals are used to designate like parts throughout.
FIG. 1 is a heating-pure hydrogen reduction cooling system of the present invention;
FIG. 2 is a graph showing the effect of oxidized pellet temperature on hydrogen utilization;
FIG. 3 is a graph showing the effect of different oxidized pellet temperatures on hydrogen gas circulation;
FIG. 4 is a graph of the change in hot flue gas demand at different hot flue gas temperatures;
FIG. 5 is a graph of the effect of oxygen enrichment on hot flue gas temperature when blast furnace gas is used as a fuel;
FIG. 6 is a graph of the effect of preheated air on hot flue gas temperature when blast furnace gas is used as fuel;
FIG. 7 is a graph showing changes in flue gas demand at different flue gas temperatures when coke oven gas is used as a fuel;
FIG. 8 is a prior art pure hydrogen shaft furnace reduction system of comparative example 1;
FIG. 9 is a graph showing the effect of hot hydrogen temperature on hydrogen utilization in comparative examples 1 to 4.
Reference numerals:
1-a heating section; 2-isobaric section; 3-reduction cooling section; 4-oxidizing pellet inlet; 5-hot flue gas inlet; 6-a flue gas outlet; 7-a hydrogen inlet; 8-a gas outlet; 9-pressure equalizing charging system; 10-a combustion furnace; 11-a hydrogen supply; 12-a flue gas purification system; 13-a waste heat recovery system; 14-a gas purification system; 15-a hydrogen pressurization device; 16-a reduction section; 17-a cooling section; 18-a heat exchanger device; 19-a washing device; 20-a pressurizing device; 21-cooling gas supply means.
Detailed Description
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate preferred embodiments of the invention and together with the description, serve to explain the principles of the invention and not to limit the scope of the invention.
On one hand, the invention discloses a heating-pure hydrogen reduction cooling system, as shown in fig. 1, wherein the heating-pure hydrogen reduction cooling system comprises a heating section 1, an isobaric section 2 and a reduction cooling section 3 which are sequentially communicated from top to bottom; the heating section 1 is provided with an oxidized pellet inlet 4, a hot flue gas inlet 5 and a flue gas outlet 6, the oxidized pellets from the oxidized pellet inlet 4 are contacted with the hot flue gas from the hot flue gas inlet 5 in the heating section 1, the contacted flue gas is discharged from the flue gas outlet 6, and the contacted oxidized pellets enter the constant pressure section 2; the reduction cooling section 3 is provided with a hydrogen inlet 7 and a gas outlet 8, the oxidized pellets from the isobaric section 2 and the hydrogen from the hydrogen inlet 7 are reduced and cooled in the reduction cooling section 3, and the gas generated in the reduction and cooling process is discharged from the gas outlet 8.
In the invention, in the heating section 1, hot flue gas heats oxidized pellets, the oxidized pellets are heated into thermal oxidized pellets, and meanwhile, the hot flue gas has a pre-reduction effect on the oxidized pellets:
3Fe2O3+CO＝2Fe3O4+CO2formula (1);
3Fe2O3+H2＝2Fe3O4+H2o formula (2).
In the invention, in the reduction cooling section 3, hydrogen and oxidized pellets are subjected to reduction reaction:
3Fe2O3+H2＝2Fe3O4+H2o formula (2);
Fe3O4+H2＝3FeO+H2o formula (3);
FeO+H2＝Fe+H2o formula (4).
It should be noted that, in the present invention, the hydrogen in the hydrogen inlet 7 refers to hydrogen which has not been subjected to temperature treatment, i.e. normal temperature hydrogen.
The pure hydrogen shaft furnace reduction system in the prior art sequentially comprises a reduction section, an isobaric section and a cooling section from top to bottom, wherein normal-temperature oxidized pellets and heated hydrogen are subjected to reduction reaction in the reduction section, and then enter the cooling section for cooling after passing through the isobaric section for isobaric transition, namely, the normal-temperature oxidized pellets-hot hydrogen reduction mode.
In the invention, the heating section 1 plays a role in heating the oxidized pellets, the hot oxidized pellets can provide the required heat for the subsequent hydrogen reduction process, and the oxidized pellets are pre-reduced in the heating section 1; the heated oxidized pellets are subjected to isobaric transition in the isobaric section 2 and then enter the reduction cooling section 3 to synchronously carry out reduction and cooling processes, namely a reduction mode of thermal oxidized pellets-normal temperature hydrogen.
In the existing pure hydrogen shaft furnace reduction system, a heat source required by reduction is provided by hot hydrogen, the hot hydrogen not only needs to meet the chemical consumption of iron oxide reduction, but also needs to provide heat required by reduction, so that the circulating hydrogen amount is large, and the primary utilization rate of hydrogen is lower than 30%; meanwhile, the heat exchanger is required for heating hydrogen, the heating limit temperature of the heat exchanger to the hydrogen is not higher than 950 ℃, the heat required by pure hydrogen reduction cannot be met, and the utilization rate of the hydrogen is greatly reduced; and a process of using a heat exchanger and a cooling section after the reduction section is needed, so that the process is complicated.
In the heating-pure hydrogen reduction cooling system, the reduction form of thermal oxidation pellets and normal-temperature hydrogen is carried out, the heat required in the hydrogen reduction process is provided by the physical heat of the thermal oxidation pellets, the hydrogen circulation quantity is greatly reduced, the hydrogen utilization rate is obviously improved, and the one-time utilization rate can be improved to more than 50%; the method has the advantages that the hot flue gas is adopted to directly heat the oxidized pellets to provide heat for the subsequent reduction process, the mode of heating hydrogen by adopting hot flue gas and heating the reduced oxidized pellets by hot hydrogen in the traditional process is replaced, the heating efficiency is improved, a hydrogen heat exchanger for heating hydrogen in the traditional process is not needed, the process is simplified, the temperature limit of the hydrogen heat exchanger for heating hydrogen in the traditional process is eliminated, and the upper limit of the reduction temperature is improved; the finally obtained sponge iron does not need to be cooled separately, so that the use of cooling gas is avoided, the physical heat of the sponge iron is directly used for reduction, and the heat efficiency is improved; in addition, in the heating section 1, the hot flue gas can play a pre-reduction effect on the oxidized pellets, so that the reduction burden of pure hydrogen in the reduction cooling section 3 is reduced, and the consumption of hydrogen is reduced.
In order to sufficiently improve the heat utilization rate and the hydrogen utilization rate, preferably, the oxidized pellet inlet 4 is arranged at the top of the heating section 1, the hot flue gas inlet 5 is arranged at the junction of the heating section 1 and the isobaric section 2, the flue gas outlet 6 is arranged at a position close to the upper part of the heating section 1, the hydrogen inlet 7 is arranged at a position close to the lower part of the reduction cooling section 3, and the gas outlet 8 is arranged at the junction of the isobaric section 2 and the reduction cooling section 3.
In the above preferred embodiment, the oxidized pellets entering from the top of the heating section 1 and the hot flue gas from the hot flue gas inlet 5 are in sufficient countercurrent contact for a long time, so that the oxidized pellets and the hot flue gas are subjected to sufficient heat exchange and pre-reduction, thereby improving the heat utilization rate and reducing the subsequent hydrogen consumption in the reduction cooling section 3; in the reduction cooling section 3, the temperature of the oxidized pellets from the constant-pressure section 2 is gradually reduced from top to bottom, the metallization rate is gradually increased, the oxidized pellets are discharged from the bottom of the shaft furnace system after reduction is completed, the temperature and the oxidation degree of the hydrogen from the hydrogen inlet 7 are gradually increased from bottom to top, and the oxidized pellets are discharged from the gas outlet 8 after reduction is completed, so that the oxidized pellets and the hydrogen are subjected to long-time component countercurrent contact, the oxidized pellets and the hydrogen are subjected to sufficient reduction and cooling in the reduction cooling section 3, and the heat utilization rate, the hydrogen utilization rate and the metallization rate are improved; in addition, the hot flue gas inlet 5 is arranged at the junction of the heating section 1 and the isobaric section 2, the gas outlet 8 is arranged at the junction of the isobaric section 2 and the reduction cooling section 3, and the isobaric section 2 plays a role of isolating hot flue gas from gas (reduction coal gas) discharged from the gas outlet 8 besides playing a role of heating the oxidized pellets by isobaric transition, and enables the pressure of the hot flue gas inlet 5 to be equal to the outlet pressure of the gas outlet 8.
Specifically, the heating-pure hydrogen reduction cooling system further comprises a pressure equalizing charging system 9, a combustion furnace 10 and a hydrogen supply device 11, wherein the pressure equalizing charging system 9 is connected with the oxidized pellet inlet 4, the combustion furnace 10 is communicated with the hot flue gas inlet 5, and the hydrogen supply device 11 is communicated with the hydrogen inlet 7. The pressure equalizing charging system 9 enables the pressure of the oxidized pellets entering the oxidized pellet inlet 4 to be equal, so that the heat absorbed by the oxidized pellets in the heating section 1 is more uniform; the combustion furnace 10 provides hot flue gas by combusting fuel, and the fuel of the combustion furnace 10 can be gas fuel commonly used in the art and can be used for providing hot flue gas to heat the oxidized pellets, and preferably, the fuel is one or more of natural gas, coke oven gas and blast furnace gas. When blast furnace gas is used as a fuel for the combustion furnace 10 and normal temperature air is used as combustion-supporting gas, the temperature of hot flue gas can only reach 956 ℃, so that the temperature of hot flue gas needs to be adjusted by oxygen enrichment, preheated gas or air and the like.
In the present invention, in order to accelerate the flow of hydrogen and accelerate the reduction and cooling speed of hydrogen and oxidized pellets in the reduction cooling section 3, thereby improving the hydrogen utilization rate, it is preferable to provide a hydrogen pressurizing device 15 between the hydrogen supply device 11 and the hydrogen inlet 7.
In the present invention, in order to improve the environmental protection performance of the heating-pure hydrogen reduction cooling system, preferably, the heating-pure hydrogen reduction cooling system further includes a flue gas purification system 12, and the flue gas purification treatment system is communicated with the flue gas outlet 6. And the waste flue gas discharged from the flue gas outlet 6 is treated by the flue gas purification system 12 to reach the emission standard and then is discharged, so that the environmental pollution is reduced, and the environmental protection performance of the heating-pure hydrogen reduction cooling system is improved. The arrangement of the flue gas purification system 12 is not particularly limited, and may be a flue gas purification system commonly used in the art, such as a flue gas purification system for cyclone dust removal, SDS desulfurization, bag dust removal, and the like, which can be implemented by those skilled in the art by referring to the prior art, and therefore, the flue gas purification system 12 of the present invention is not described in detail.
In the present invention, in consideration of the problems of energy saving and emission reduction and recycling of the heating-pure hydrogen reduction cooling system, it is preferable that the heating-pure hydrogen reduction cooling systemThe system further comprises a waste heat recovery system 13 and a coal gas purification system 14, wherein an inlet of the coal gas purification system 14 is connected with the gas outlet 8, an outlet of the coal gas purification system 14 is connected with the hydrogen inlet 7, and the waste heat recovery system 13 is arranged between the gas outlet 8 and the coal gas purification system 14. In the preferred embodiment, the reduced coal gas discharged from the gas outlet 8 is subjected to waste heat recovery by the waste heat recovery system 13, and the recovered heat is used for the heating process of other systems, so that waste of heat is avoided; the reduced coal gas treated by the waste heat recovery system 13 enters the coal gas purification system 14 again for coal gas purification treatment, and the residual hydrogen is recovered for cyclic utilization, so that H is obtained2The primary utilization rate of the catalyst reaches 50-55%. In the present invention, the waste heat recovery system 13 and the gas purification system 14 may be conventional means in the art, as long as the technical effects of the present invention can be achieved, and a person skilled in the art can determine the waste heat recovery system 13 and the gas purification system 14 through the prior art, which is not described herein again.
On the other hand, the invention discloses a heating-pure hydrogen reduction cooling method, which adopts the heating-pure hydrogen reduction cooling system, and comprises the following steps: the oxidized pellets from the oxidized pellet inlet 4 and the hot flue gas from the hot flue gas inlet 5 are in countercurrent contact in the heating section 1, the flue gas after the countercurrent contact is discharged from the flue gas outlet 6, the oxidized pellets after the countercurrent contact enter the isobaric section 2 to be in isobaric transition and then enter the reduction cooling section 3, the oxidized pellets from the isobaric section 2 and the hydrogen from the hydrogen inlet 7 are synchronously reduced and cooled in the reduction cooling section 3, and the gas generated in the reduction and cooling process is discharged from the gas outlet 8 to obtain the solid product sponge iron.
In the invention, in the heating section 1, hot flue gas heats oxidized pellets, the oxidized pellets are heated into thermal oxidized pellets, and meanwhile, the hot flue gas has a pre-reduction effect on the oxidized pellets:
3Fe2O3+CO＝2Fe3O4+CO2formula (1);
3Fe2O3+H2＝2Fe3O4+H2o formula (2).
In the invention, in the reduction cooling section 3, hydrogen and oxidized pellets are subjected to reduction reaction:
3Fe2O3+H2＝2Fe3O4+H2o formula (2);
Fe3O4+H2＝3FeO+H2o formula (3);
FeO+H2＝Fe+H2o formula (4).
It should be noted that, in the present invention, the hydrogen gas from the hydrogen inlet 7 refers to hydrogen gas that has not been subjected to temperature treatment, i.e., normal-temperature hydrogen gas.
The pure hydrogen shaft furnace reduction method in the prior art is carried out in a system sequentially comprising a reduction section, an isobaric section and a cooling section from top to bottom, firstly, hydrogen is heated, then, the hydrogen and normal-temperature oxidized pellets are subjected to reduction reaction in the reduction section, and then, the hydrogen enters the cooling section for cooling after passing through the isobaric section for isobaric transition, namely, the normal-temperature oxidized pellets-hot hydrogen reduction method.
In the invention, the oxidized pellet is heated, and the heated oxidized pellet enters the reduction cooling section 3 after passing through the isobaric section 2 for isobaric transition to synchronously carry out reduction and cooling processes, namely a reduction method of the thermal oxidized pellet-normal temperature hydrogen.
In the existing pure hydrogen shaft furnace reduction method, a heat source required by reduction is provided by hot hydrogen, the hot hydrogen not only needs to meet the chemical consumption of iron oxide reduction, but also needs to provide heat required by reduction, so that the circulating hydrogen amount is large, and the primary utilization rate of hydrogen is lower than 30%; meanwhile, the heat exchanger is required for heating hydrogen, the heating limit temperature of the heat exchanger to the hydrogen is not higher than 950 ℃, the heat required by pure hydrogen reduction cannot be met, and the utilization rate of the hydrogen is greatly reduced; and a process of a heat exchanger and a cooling section after the reduction section is needed, so that the process is complicated.
In the thermal oxidation pellet-normal temperature hydrogen reduction method, the heat required in the hydrogen reduction process is provided by the physical heat of the thermal oxidation pellet, the hydrogen circulation volume is greatly reduced, the hydrogen utilization rate is obviously improved, and the one-time utilization rate can be improved to more than 50%; the method has the advantages that the hot flue gas is adopted to directly heat the oxidized pellets to provide heat for the subsequent reduction process, the mode of heating hydrogen by adopting hot flue gas and heating the reduced oxidized pellets by hot hydrogen in the traditional process is replaced, the heating efficiency is improved, a hydrogen heat exchanger for heating hydrogen in the traditional process is not needed, the process method is simplified, the temperature limit of the hydrogen heat exchanger for heating hydrogen in the traditional process is eliminated, and the upper limit of the reduction temperature is improved; the finally obtained sponge iron does not need to be cooled separately (the temperature of the sponge iron is less than 120 ℃), the use of cooling gas is avoided, the physical heat of the sponge iron is directly used for reduction, and the heat efficiency is improved; in addition, in the heating section 1, the hot flue gas can play a pre-reduction effect on the oxidized pellets, so that the reduction burden of pure hydrogen in the reduction cooling section 3 is reduced, and the consumption of hydrogen is reduced.
According to a preferred embodiment of the present invention, the temperature of the hot flue gas is 1150-1350 ℃, and the temperature of the oxidized pellets is 1000-1100 ℃ due to the countercurrent contact.
In the present invention, the hydrogen circulation amount is 1025-1087m3/DRI。
In the invention, the oxidized pellet is directly heated by hot flue gas, the temperature of the oxidized pellet can easily reach above 1300 ℃, the inventor of the invention finds that the required circulating hydrogen quantity is larger when the temperature of the oxidized pellet is higher, so that the utilization rate of hydrogen is reduced, and when the heating temperature of the oxidized pellet is controlled within 1100 ℃, the utilization rate of hydrogen can reach above 50%, and the utilization rate of hydrogen is greatly improved compared with the prior art; meanwhile, when the heating temperature of the oxidized pellets reaches more than 1000 ℃, the metallization rate of the reduced pellets can reach more than 93 percent. Therefore, the heating temperature of the oxidized pellet is preferably 1000-1100 ℃ in combination with the influence of the temperature of the oxidized pellet on the hydrogen utilization rate and the metallization rate of the pellet after reduction.
Regarding the temperature of hot flue gas, generally, under the requirement of a certain heating temperature of oxidized pellets, the flue gas amount required is smaller when the flue gas temperature is higher, the inventor of the present invention also finds in research that the pellet adhesion is caused by the too high temperature of hot flue gas, when the flue gas temperature is higher than 1400 ℃, the local adhesion rate of the oxidized pellets is higher than 20%, and when the flue gas temperature is lower than 1350 ℃, the adhesion rate is below 10%; considering that the oxidized pellets are in a dynamic process in actual production, the temperature difference between the oxidized pellets and the hot flue gas is larger, and the temperature of the hot flue gas is controlled below 1350 ℃, so that the oxidized pellets can be prevented from being bonded in the heating process, and therefore, the temperature of the hot flue gas is preferably 1150-1350 ℃.
In the invention, the temperature of the flue gas after the countercurrent contact is 200-250 ℃.
In order to prevent deflagration of hot flue gases, in which H is present, mixed with the reducing gas from the reduction cooling stage 3 in the isobaric stage 22And CO in an amount of 5 to 10% by volume, O2Is less than 1% by volume.
The hot flue gas of the present invention is obtained by burning a fuel, which may be a gas fuel commonly used in the art that can be used to provide hot flue gas to heat the oxidized pellets, preferably, the fuel is one or more of natural gas, coke oven gas, and blast furnace gas. It should be noted that when blast furnace gas is used as fuel and normal temperature air is used as combustion-supporting gas, the temperature of hot flue gas can only reach 956 ℃, so the temperature of the heated flue gas needs to be adjusted by oxygen enrichment, preheated gas or air.
Meanwhile, in order to reduce the atmospheric pollution of the hot flue gas, the volume percentage of NOx in the flue gas can be controlled to be less than 80ppm by adopting the conventional low-nitrogen combustion technology in the field.
In the present invention, preferably, the pressure of the hot flue gas at the hot flue gas inlet 5 is equal to the pressure of the gas at the gas outlet 8. In this preferred embodiment, the hot flue gases can be further prevented from mixing with the reducing gas from the reduction cooling stage 3 in the isobaric stage 2.
In the invention, in order to accelerate the flow of hydrogen and accelerate the reduction and cooling speed of hydrogen and oxidized pellets in the reduction cooling section 3, thereby improving the utilization rate of hydrogen, preferably, the hydrogen is pressurized before entering the reduction cooling section 3.
In consideration of the problems of environmental protection, energy conservation, emission reduction and recycling of the heating-pure hydrogen reduction cooling method, the flue gas discharged from the flue gas outlet 6 is preferably purified and discharged; and the gas discharged from the gas outlet 8 is returned to the reduction cooling section 3 after being subjected to waste heat recovery and purification treatment.
In the preferred embodiment, the flue gas is discharged after being purified to reach the discharge standard, so as to reduce environmental pollution, the purification treatment method is not particularly limited, and can be a common method in the field, such as a flue gas purification method of cyclone dust removal, SDS desulfurization, bag dust removal and the like, and the flue gas purification treatment method can be implemented by a person skilled in the art by referring to the prior art, so that the purification treatment is not described again; the gas (reducing gas) discharged from the gas outlet 8 is used for the heating process of other systems by recovering waste heat, the heat is prevented from being wasted, the gas is purified and treated, and the residual hydrogen is recovered for cyclic utilization, so that H is enabled to be generated2The primary utilization rate of the waste heat recovery gas reaches 50-55%, in the invention, the waste heat recovery gas purification can be a conventional means in the field, as long as the technical effect of the invention can be achieved, and a person skilled in the art can determine the method for the waste heat recovery and the gas purification through the prior art, and details are not repeated herein.
The technical scheme and technical effect of the invention are further illustrated by the following specific examples.
In the following examples, the properties of the oxidized pellets are shown in table 1:
TABLE 1
| Composition (I) | TFe | FeO | Fe2O3 | Al2O3 | CaO | MgO | SiO2 | P2O5 | S |
| Content (a) of | 68.66 | 0.87 | 97.12 | 0.86 | 0.23 | 0.58 | 1.32 | 0.28 | 0.002 |
Example 1
In the heating-pure hydrogen reduction cooling system shown in figure 1, 10kg of oxidized pellets in a pressure equalizing charging system 9 enter a heating section 1 through an oxidized pellet inlet 4, and a combustion furnace 10 takes natural gas as fuel to heat hot flue gas (H) with the temperature of 1150 DEG C2And CO in an amount of 7% by volume2Volume percent ofThe content of 0.4 percent) enters the heating section 1 through the hot flue gas inlet 5, the oxidized pellets and the hot flue gas are in countercurrent contact in the heating section 1, the oxidized pellets are heated to 1000 ℃, the flue gas (the temperature is 200 ℃) after the countercurrent contact is discharged into the flue gas purification system 12 from the flue gas outlet 6 to be treated and discharged after reaching the discharge standard, the oxidized pellets after the countercurrent contact enter the isobaric section 2 to be in isobaric transition and then enter the reduction cooling section 3, the hydrogen provided by the hydrogen supply device 11 is pressurized by the hydrogen pressurizing device 15 and then passes through the hydrogen inlet 7 (the pressure ensures that the hydrogen circulation volume is 1025 m)3the/DRI) enters a reduction cooling section 3, the oxidized pellets and hydrogen are synchronously reduced and cooled for 4 hours in the reduction cooling section 3, gas (reduced coal gas) generated in the reduction and cooling process is discharged from a gas outlet 8, sequentially enters a waste heat recovery system 13 to recover waste heat, enters a coal gas purification system 14 to be purified, residual hydrogen is recovered, the residual hydrogen is introduced into the reduction cooling section 3 through a hydrogen inlet 7 to be recycled, and sponge iron (with the temperature of 90 ℃) obtained after the reduction and cooling process is discharged from the lower part of the reduction cooling section 3.
Example 2
The procedure is as in example 1, except that the oxidized pellets are heated to 1050 ℃ in the heating zone 1 and the circulation of hydrogen is 1062m3/DRI。
Example 3
The procedure is as in example 1, except that the oxidized pellets are heated to 1100 ℃ in the heating zone 1 and the circulation of hydrogen is 1087m3/DRI。
Example 4
The procedure is as in example 1, except that the oxidized pellets are heated to 950 ℃ in the heating zone 1 and the circulation of hydrogen is 988m3/DRI。
In examples 1 to 4, the hydrogen utilization rate was obtained by calculating the heat balance. As shown in fig. 2, it can be seen from fig. 2 that the hydrogen utilization rate is reduced when the temperature of the oxidized pellet is increased, the heating temperature of the oxidized pellet is controlled within 1100 ℃, and the hydrogen utilization rate can reach more than 50%. Compared with the results of comparative example 1, it can be seen that the utilization rate of hydrogen is greatly improved by adopting the heating-pure hydrogen reduction cooling system and method.
In examples 1-4, the effect of different oxidized pellet temperatures on the hydrogen recycle is shown in fig. 3, and it can be seen that the higher the oxidized pellet temperature, the greater the amount of recycle hydrogen required.
The metallized pellet reduced on the upper layer of the reduction cooling section is taken to be tested and analyzed to determine the metallization rate, and the experimental conditions and results are shown in table 2. It can be seen that when the heating temperature of the oxidized pellet reaches more than 1000 ℃, the metallization rate of the pellet after reduction reaches more than 93%.
TABLE 2
| Temperature of oxidized pellets,. |
950 | 1000 | 1050 | 1100 |
| Hydrogen flow rate, L/min | 29.96 | 31.08 | 32.10 | 33.01 |
| Reduced pellet metallization rate% | 86 | 93 | 95 | 96 |
In conclusion, when the temperature of the oxidized pellet is 1000-1100 ℃, higher hydrogen utilization rate and metallization rate can be achieved.
Example 5
The procedure is as in example 2, except that the temperature of the hot flue gases is 1150 ℃.
Example 6
The procedure is as in example 2, except that the temperature of the hot flue gases is 1200 ℃.
Example 7
The procedure is as in example 2, except that the temperature of the hot flue gases is 1250 ℃.
Example 8
The procedure is as in example 2, except that the temperature of the hot flue gases is 1300 ℃.
Example 9
The procedure is as in example 2, except that the temperature of the hot flue gases is 1350 ℃.
Example 10
The procedure is as in example 2, except that the temperature of the hot flue gases is 1400 ℃.
Examples 11 to 16
The procedure was followed as in examples 5 to 10, respectively, except that the flue gas temperature at the flue gas outlet was 250 ℃.
In examples 5-16, the variation in hot flue gas demand at different hot flue gas temperatures is shown in FIG. 4 by heat balance calculations. It can be seen that the higher the temperature of the hot flue gas, the smaller the amount of hot flue gas required.
In examples 5 to 16, after the heating process in the heating section 1 was completed, the pellets were taken out after they were completely cooled, the oxidized pellets in the lowermost layer (hot flue gas inlet) were taken out and weighed, the oxidized pellets that had been bonded were selected and weighed, and the mass ratio of the bonded pellets, that is, the bonding ratio, was determined by calculation.
The results are shown in Table 3.
Wherein: gamma is the bonding ratio,%; m is0The total mass of the lower layer oxidized pellet is g; m is1The mass of the oxidized pellets bonded in the lower layer, g.
TABLE 3
| Hot flue gas temperature,. |
1150 | 1200 | 1250 | 1300 | 1350 | 1400 |
| Flow of hot flue gas, L/min | 57.4 | 54.5 | 51.6 | 49.4 | 47.2 | 45.4 |
| The binding ratio of the oxidized pellets,% | 0 | 0 | 0 | 2 | 7 | 18.3 |
As can be seen from Table 3, the local bonding ratio of the oxidized pellets is close to 20% when the temperature of the hot flue gas is as high as 1400 ℃, and the bonding ratio is below 10% when the temperature of the hot flue gas is 1150-1350 ℃; meanwhile, the temperature difference between the oxidized pellets and hot flue gas is larger in consideration of the fact that the oxidized pellets are in a dynamic process in actual production, and the oxidized pellets can be prevented from being bonded in the heating process when the temperature of the hot flue gas is controlled below 1350 ℃. Therefore, the optimal range of the temperature of the heating flue gas is 1150-1350 ℃.
Examples 17 to 20
The process of example 1 was followed except that the furnace 10 was fueled with blast furnace gas and was fired in an oxygen-rich mode to produce hot flue gases. The oxygen enrichment rates are respectively 45%, 57.5%, 78% and 100%, and the achieved hot flue gas temperatures are respectively 1150 ℃, 1200 ℃, 1250 ℃ and 1280 ℃. The blast furnace gas composition is shown in table 4.
TABLE 4
| Composition of gas | CO | O2 | CO2 | H2 | N2 |
| Volume percent of% | 24.42 | 0.28 | 22.16 | 0.06 | 53.07 |
The effect of oxygen enrichment on hot flue gas is shown in figure 5. As can be seen from fig. 5, the maximum combustion temperature of the hot flue gas can only reach 1280 ℃ when oxygen enrichment is adopted.
Examples 21 to 25
The process of example 17 was followed except that the furnace 10 was fired with blast furnace gas and preheated air was used to generate hot flue gas. The air temperature is respectively 450 ℃, 560 ℃, 675 ℃, 775 ℃ and 900 ℃, and the hot smoke temperature is respectively 1150 ℃, 1200 ℃, 1250 ℃, 1300 ℃ and 1350 ℃.
The effect of the air temperature on the hot flue gas temperature is shown in fig. 6, and it can be seen from fig. 6 that the hot flue gas temperature can reach 1350 ℃ by preheating the air.
Examples 26 to 30
The process is carried out according to the method of example 2, except that coke oven gas is used as fuel of the combustion furnace 10, and normal temperature air is used as combustion-supporting gas, and the temperature of hot flue gas is adjusted by returning the flue gas because the combustion temperature of the hot flue gas can reach 1734 ℃. The hot flue gas temperature is 1150 deg.C, 1200 deg.C, 1250 deg.C, 1300 deg.C, 1350 deg.C respectively. The coke oven gas composition is shown in table 5.
TABLE 5
| Composition of gas | H2 | CH4 | CO | CO2 | N2 | O2 |
| Percent by weight% | 56.54 | 24.74 | 7.5 | 4.5 | 4.12 | 0.3 |
Examples 31 to 35
The process was carried out as in examples 26 to 30, respectively, except that the flue gas temperature at the flue gas outlet was 250 ℃.
In examples 26 to 35, the change of the required amount of the hot flue gas at different hot flue gas temperatures is shown in FIG. 7 by the heat balance calculation, and compared with FIG. 4, it can be seen that the hot flue gas is generated by burning coke oven gas and natural gas, and the required flue gas amount is similar when the hot flue gas temperatures are the same.
Comparative example 1
In a pure hydrogen shaft furnace reduction system shown in fig. 8, 10kg of oxidized pellets in a pressure equalizing charging system 9 enter a reduction section 16 through an oxidized pellet inlet 4, hydrogen provided by a hydrogen supply device 11 is heated to 800 ℃ through a heat exchanger device 18 heated by using natural gas as fuel and then enters the reduction section 16, the oxidized pellets and hot hydrogen are in countercurrent contact in the reduction section 16 for reduction reaction, and reduced coal gas (300 ℃) after the reduction reaction is discharged from the upper part of the reduction section 16 and enters a heat exchanger device 18 for recycling after being subjected to a washing device 19 and a pressurizing device 20; and the solid product after the reduction reaction enters an isobaric section 2 for isobaric transition and then enters a cooling section 17, and in the cooling section 17, the solid product after the reduction reaction is in contact with cooling gas provided by a cooling gas supply device 21 for cooling treatment to obtain cooled sponge iron.
Comparative examples 2 to 4
The procedure of comparative example was followed except that the hydrogen gas temperature was 850 deg.C, 900 deg.C, 950 deg.C, respectively.
In comparative examples 1 to 4, the utilization rate of hydrogen in the reduced gas by the heat balance calculation is shown in fig. 9. It can be seen that the utilization rate of hydrogen gradually increases as the heating temperature of hydrogen increases, but the utilization rate does not exceed 30%.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (10)
1. A heating-pure hydrogen reduction cooling system is characterized by comprising a heating section (1), an isobaric section (2) and a reduction cooling section (3) which are sequentially communicated from top to bottom;
the heating section (1) is provided with an oxidized pellet inlet (4), a hot flue gas inlet (5) and a flue gas outlet (6), oxidized pellets from the oxidized pellet inlet (4) are contacted with hot flue gas from the hot flue gas inlet (5) in the heating section (1), the contacted flue gas is discharged from the flue gas outlet (6), and the contacted oxidized pellets enter the isobaric section (2); the reduction cooling section (3) is provided with a hydrogen inlet (7) and a gas outlet (8), the oxidized pellets from the isobaric section (2) and the hydrogen from the hydrogen inlet (7) are reduced and cooled in the reduction cooling section (3), and the gas generated in the reduction and cooling process is discharged from the gas outlet (8).
2. The heating-pure hydrogen reduction cooling system according to claim 1, wherein the oxidized pellet inlet (4) is disposed at the top of the heating section (1), the hot flue gas inlet (5) is disposed at the intersection of the heating section (1) and the isobaric section (2), the flue gas outlet (6) is disposed at a position near the upper portion of the heating section (1), the hydrogen gas inlet (7) is disposed at a position near the lower portion of the reduction cooling section (3), and the gas outlet (8) is disposed at the intersection of the isobaric section (2) and the reduction cooling section (3).
3. The heating-pure hydrogen reduction cooling system according to claim 1 or 2, further comprising a pressure equalizing charging system (9), a combustion furnace (10) and a hydrogen supply device (11), wherein the pressure equalizing charging system (9) is connected with the oxidized pellet inlet (4), the combustion furnace (10) is communicated with the hot flue gas inlet (5), and the hydrogen supply device (11) is communicated with the hydrogen inlet (7).
4. The heating-pure-hydrogen reduction cooling system according to claim 1 or 2, further comprising a flue gas cleaning system (12) in communication with the flue gas outlet (6).
5. The heating-pure hydrogen reduction cooling system according to claim 3, further comprising a waste heat recovery system (13) and a gas purification system (14), wherein an inlet of the gas purification system (14) is connected with the gas outlet (8), an outlet of the gas purification system (14) is connected with the hydrogen inlet (7), and the waste heat recovery system (13) is disposed between the gas outlet (8) and the gas purification system (14).
6. A heating-pure hydrogen reduction cooling method, characterized in that the heating-pure hydrogen reduction cooling system according to any one of claims 1 to 5 is used, and the heating-pure hydrogen reduction cooling method comprises: the method comprises the steps that oxidized pellets from an oxidized pellet inlet (4) and hot flue gas from a hot flue gas inlet (5) are in countercurrent contact in a heating section (1), the flue gas after countercurrent contact is discharged from a flue gas outlet (6), the oxidized pellets after countercurrent contact enter an isobaric section (2) and enter a reduction cooling section (3) after isobaric transition, the oxidized pellets from the isobaric section (2) and hydrogen from a hydrogen inlet (7) are synchronously reduced and cooled in the reduction cooling section (3), and gas generated in the reduction and cooling process is discharged from a gas outlet (8) to obtain solid product sponge iron.
7. The heating-pure hydrogen reduction cooling method as claimed in claim 6, wherein the temperature of the hot flue gas is 1150-1350 ℃, and the temperature of the oxidized pellet is 1000-1100 ℃ by the countercurrent contact.
8. The heating-pure hydrogen reduction cooling method according to claim 6 or 7, wherein in the hot flue gas, H2And CO in an amount of 5 to 10% by volume, O2Is less than 1% by volume.
9. The heating-pure hydrogen reduction cooling method according to claim 6 or 7, characterized in that the pressure of the hot flue gas at the hot flue gas inlet (5) is equal to the pressure of the gas at the gas outlet (8).
10. The heating-pure hydrogen reduction cooling method according to claim 6 or 7, wherein the flue gas discharged from the flue gas outlet (6) is purified and discharged;
and the gas discharged from the gas outlet (8) is returned to the reduction cooling section (3) after being subjected to waste heat recovery and purification treatment.
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