CN116200565A - Electro-hydrogen efficient conversion reduction smelting device and method - Google Patents
Electro-hydrogen efficient conversion reduction smelting device and method Download PDFInfo
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Abstract
The invention discloses an electro-hydrogen efficient conversion reduction smelting device and method, which belong to the technical field of metallurgy, and adopt pure hydrogen as a reducing agent to perform functional partition on prereduction and deep reduction so as to obtain high-purity molten iron. The electro-hydrogen high-efficiency conversion reduction smelting device comprises a multi-zone induction furnace, wherein the multi-zone induction furnace comprises a first zone, a second zone and a third zone; the second area and the third area are positioned at two sides of the first area, the second area is positioned at the middle lower part of the first area, and the second area is directly communicated with the first area; the third area is communicated with the bottom of the first area through a sliding water gap; in the reduction smelting process, the second zone is used as a slag-iron layer melting zone, and the first zone is divided into a pre-reduced iron water layer, a slag-iron layer reduction zone and a slag layer from bottom to top; the slag-iron layer melting zone is connected with the slag-iron layer reducing zone; the third zone is divided into a deep reduced iron water layer and a refining slag layer from bottom to top. The device provided by the invention is adopted for reduction smelting, so that high-purity molten iron can be obtained.
Description
Technical Field
The invention relates to the technical field of metallurgy, in particular to an electro-hydrogen efficient conversion reduction smelting device and method.
Background
Development of hydrogen metallurgy with "carbon hydride" is one of the most effective ways to achieve carbon reduction in the steel industry.
The existing hydrogen metallurgy process comprises a shaft furnace and a fluidized bed direct reduction process, wherein the shaft furnace mainly takes oxidized pellets as raw materials, the raw material treatment process is longer, the energy consumption is higher, molten iron cannot be directly obtained by the two processes, further melting treatment is needed, and the equipment investment is increased.
Disclosure of Invention
In view of the above, the invention aims to provide an electro-hydrogen efficient conversion reduction smelting device and method, which adopt pure hydrogen as a reducing agent to perform functional partition on pre-reduction and deep reduction so as to obtain high-purity molten iron.
The aim of the invention is mainly realized by the following technical scheme:
in one aspect, the invention provides an electro-hydrogen efficient conversion reduction smelting device, which comprises a multi-zone induction furnace, wherein the multi-zone induction furnace comprises a first zone, a second zone and a third zone; the second area and the third area are positioned at two sides of the first area, the second area is positioned at the middle lower part of the first area, and the second area is directly communicated with the first area; the third area is communicated with the bottom of the first area through a sliding water gap; in the reduction smelting process, the second zone is used as a slag-iron layer melting zone, and the first zone is divided into a pre-reduced iron water layer, a slag-iron layer reduction zone and a slag layer from bottom to top; the slag-iron layer melting zone is connected with the slag-iron layer reducing zone; the third zone is divided into a deep reduced iron water layer and a refining slag layer from bottom to top.
Further, the electro-hydrogen high-efficiency conversion reduction smelting device also comprises a batching system and a blowing system connected with the batching system, and after the batching system is used for batching materials, the materials are blown to the second zone through the blowing system.
Further, the electro-hydrogen high-efficiency conversion reduction smelting device further comprises a first spray gun, wherein the first spray gun is positioned at the side edge of the second zone, and the first spray gun is used for spraying hydrogen to the second zone.
Further, the electro-hydrogen high-efficiency conversion reduction smelting device also comprises a second spray gun, wherein the second spray gun is positioned at the side edge of the third zone, and the second spray gun is used for spraying hydrogen to the third zone.
Further, the electro-hydrogen high-efficiency conversion reduction smelting device also comprises a vacuum granulating chamber, and the vacuum granulating chamber is positioned below the third zone.
Further, the electro-hydrogen high-efficiency conversion reduction smelting device also comprises a waste heat recovery system, a high-temperature dust removal device, an oxygen-blowing combustion system and a high-temperature electrolysis device which are connected in sequence.
The invention also provides an electro-hydrogen efficient conversion reduction smelting method, which adopts the electro-hydrogen efficient conversion reduction smelting device and comprises the following steps:
step 1, at the beginning, adding industrial pure iron or sponge iron into a first zone to serve as an induction heating medium and melting to form a pre-reduced iron water layer;
step 3, adding the mixture of the iron concentrate powder and the quicklime powder into a second zone through a blowing system, wherein the blowing system takes oxygen as a conveying medium gas of the mixture; the hydrogen generated by the high-temperature electrolysis device is sprayed into the second area from the first spray gun to generate combustion heat release, so that heat is provided for melting materials, and the melted materials are conveyed to the slag-iron layer reduction area;
and 5, opening a sliding water gap, enabling molten iron in the pre-reduced molten iron layer to enter a third area, closing the sliding water gap after the molten iron layer in the third area reaches a specified height, and performing deep reduction smelting, wherein after the deep reduction smelting, the oxygen and sulfur contents in the molten iron are controlled below 10ppm.
Further, the reduced gas in the step 4 firstly meets the tolerance temperature of the high-temperature dust removing device after being subjected to heat recovery and temperature reduction, and the mixed gas of the hydrogen and the water vapor obtained by dust removal is subjected to oxygen blowing combustion for temperature elevation, and finally the hydrogen is generated through electrolysis.
Further, the method further comprises the following steps:
and 6, allowing the deeply reduced molten iron to enter a vacuum granulating chamber, dispersing into fine molten iron particles under the action of a granulator, and deeply removing gas impurities in the molten iron by greatly increasing the surface area of the molten iron.
Further, in the step 3, the binary alkalinity of the iron concentrate powder and the quicklime powder is controlled to be 3.0-3.5.
Further, in the step 4, the FeO content in the slag is controlled to be 5% -8% in the reduction process.
Compared with the prior art, the invention has the following beneficial effects:
a) The electro-hydrogen high-efficiency conversion reduction smelting device adopts a unique multi-zone induction furnace as a reduction smelting device, and when the electro-hydrogen high-efficiency conversion reduction smelting device is implemented, materials enter a slag-iron layer reduction zone after premelting in the slag-iron layer reduction zone, so that the heat loss and melting time of the slag-iron layer reduction zone are reduced, and the reduction rate and efficiency are improved; the slag-iron layer melting zone forms an independent strong oxidizing atmosphere, and dephosphorization efficiency is improved. The melted materials enter a slag-iron layer reduction zone, molten iron undergoes melting reduction and desulfurization reaction, slag-iron separation occurs, slag floats upwards to enter a slag layer, and molten iron sinks to enter a pre-reduced iron layer; the pre-reduced molten iron enters a third zone through a siphon effect to carry out deep reduction smelting, and oxygen and sulfur in the molten iron are deeply removed. The second area is communicated with the third area through a siphon principle, so that reduction smelting integration is realized.
b) The induction furnace in the electro-hydrogen efficient conversion reduction smelting device adopts an eccentric injection feeding mode to divide a melting zone and a reduction zone, the melting zone directly heats materials through hydrogen combustion, the heating efficiency and the melting rate of the materials are improved, and meanwhile, oxygen has a powder conveying effect and hydrogen has a melt conveying effect.
c) The method realizes the accurate control of the atmosphere from oxidizing property to reducing property through the functional partitions of the slag-iron layer melting zone, the slag-iron layer reducing zone and the deep reducing zone, realizes the graded deep removal of phosphorus, sulfur and oxygen, and improves the removal limit of impurity components. Can realize partition dephosphorization and desulfurization, improves the treatment efficiency and the quality of molten iron, and obtains high-purity molten iron.
d) The method adopts a vacuum granulating mode to replace the conventional argon blowing mode to deeply remove hydrogen in the molten iron, avoids the use of argon and the temperature drop of the molten iron, can further promote the reaction of oxygen and hydrogen in the molten iron, and simultaneously promotes the overflow of hydrogen. Further improves the purity of molten iron particles, ensures that the oxygen content in the molten iron is reduced to below 5ppm and the hydrogen content is reduced to below 1 ppm.
e) According to the method, the reduction gas is cooled to meet the tolerance temperature of the high-temperature dust collector, the electrolysis temperature of the reduction gas is controlled by heating, the electrolysis efficiency of the system can reach more than 43%, the energy consumption of electrolysis hydrogen production is reduced, meanwhile, high-temperature hydrogen meeting the reduction requirement is directly obtained, the use of a hydrogen heating device is avoided, and the use safety of each device can be ensured.
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 claims thereof as well as the appended drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, like reference numerals being used to refer to like parts throughout the several views.
FIG. 1 is a schematic diagram of an electro-hydro high efficiency conversion reduction smelting device of the present invention;
FIG. 2 is a schematic diagram of the electro-hydro high efficiency conversion reduction smelting process of the present invention.
Reference numerals
1-first area, 2-second area, 3-third area, 4-sliding gate, 5-feed proportioning system, 6-jetting system, 7-vacuum granulating chamber, 8-waste heat recovery system, 9-high temperature dust collector, 10-oxygen-blowing combustion system, 11-high temperature electrolyzer, and 12-slag outlet.
Detailed Description
Preferred embodiments of the present invention are described in detail below with reference to the attached drawing figures, which form a part of the present invention and are used in conjunction with embodiments of the present invention to illustrate the principles of the present invention.
The invention provides an electro-hydrogen efficient conversion reduction smelting device, which comprises a multi-zone induction furnace, wherein the multi-zone induction furnace comprises a first zone 1, a second zone 2 and a third zone 3; the second zone 2 and the third zone 3 are positioned at two sides of the first zone 1, the second zone 2 is positioned at the middle lower part of the first zone 1, and the second zone 2 is directly communicated with the first zone 1; the third zone 3 is communicated with the bottom of the first zone 1 through a sliding gate valve 4; in the reduction smelting process, the second zone 2 is used as a slag-iron layer melting zone, and the first zone 1 is divided into a pre-reduced iron water layer, a slag-iron layer reduction zone and a slag layer from bottom to top; the slag-iron layer melting zone is connected with the slag-iron layer reducing zone; the third zone 3 is divided into a deep reduced iron water layer and a refining slag layer from bottom to top.
Specifically, the first region 1 may be cylindrical.
Specifically, the upper part of the first zone 1 is provided with a slag outlet 12.
Specifically, the electro-hydrogen high-efficiency conversion reduction smelting device further comprises a batching system 5 and a blowing system 6 connected with the batching system 5, and after the batching system 5 is used for batching materials, the materials are blown to the second zone 2 through the blowing system 6.
Specifically, the electro-hydrogen high-efficiency conversion reduction smelting device further comprises a first spray gun, wherein the first spray gun is positioned at the side edge of the second zone 2 and is used for spraying hydrogen to the second zone 2.
Specifically, the electro-hydrogen high-efficiency conversion reduction smelting device further comprises a second spray gun, wherein the second spray gun is positioned at the side edge of the third zone 3 and is used for spraying hydrogen to the third zone 3.
Specifically, the electro-hydrogen high-efficiency conversion reduction smelting device further comprises a vacuum granulating chamber 7, and the vacuum granulating chamber 7 is positioned below the third zone 3.
Specifically, the electro-hydrogen high-efficiency conversion reduction smelting device also comprises a waste heat recovery system 8, a high-temperature dust removal device 9, an oxygen-blowing combustion system 10 and a high-temperature electrolysis device 11 which are connected in sequence.
Specifically, during implementation, the mixture of the iron concentrate powder and the lime powder is added into the second zone 2 (slag-iron layer melting zone) through the injection system 6, oxygen is used as a conveying medium gas of the mixture by the injection system 6, and hydrogen is injected into the second zone 2 from the side surface of the second zone 2 to generate combustion heat release to provide heat for material melting, and simultaneously, the melted material is conveyed to the slag-iron layer reduction zone, so that an independent strong oxidizing atmosphere is formed in the slag-iron layer melting zone, dephosphorization efficiency is improved, and dephosphorization is realized. The materials enter the slag-iron layer reduction zone after being premelted in the slag-iron layer melting zone, so that the heat loss and melting time of the slag-iron layer reduction zone are reduced, and the reduction rate and efficiency are improved. The melted materials enter a slag-iron layer reduction zone, undergo fusion reduction and desulfurization reaction with molten iron brought by 'spring surge' of reducing gas, slag-iron separation occurs, slag floats upwards and enters a slag layer, and molten iron sinks and enters a pre-reduced molten iron layer; the pre-reduced molten iron enters the third zone 3 through a siphon effect and is subjected to deep reduction smelting with hydrogen entering from the bottom of the third zone 3, so that oxygen and sulfur in the molten iron are deeply removed. The invention realizes the accurate control of the atmosphere from oxidizing property to reducing property through the functional partitions of the slag-iron layer melting zone, the slag-iron layer reducing zone and the deep reducing zone, realizes the graded deep removal of phosphorus, sulfur and oxygen, and improves the removal limit of impurity components.
The invention also provides an electro-hydrogen efficient conversion reduction smelting method, which adopts the electro-hydrogen efficient conversion reduction smelting device and comprises the following steps:
step 1, at the beginning, adding industrial pure iron or sponge iron into a first zone 1 as an induction heating medium and melting to form a pre-reduced iron water layer;
step 3, adding the mixture of the iron concentrate powder and the quicklime powder into a second zone 2 (namely a slag-iron layer melting zone) through a blowing system 6, wherein the blowing system 6 takes oxygen as a conveying medium gas of the mixture; the hydrogen generated by the electrolysis device 11 is sprayed into the second zone 2 from the first spray gun to generate combustion heat release, so as to provide heat for melting materials, and simultaneously, the melted materials are conveyed to a slag-iron layer reduction zone;
and 5, opening a sliding water gap 4, enabling molten iron of the pre-reduced molten iron layer to enter a third region 3 through a siphon effect, closing the sliding water gap 4 after the molten iron layer in the third region 3 reaches a specified height, spraying hydrogen from the bottom of the third region 3 to perform deep reduction smelting, wherein the adding amount of refining slag is 8-10% of the mass of the molten iron, and controlling the oxygen and sulfur content in the molten iron to be below 10ppm after the deep reduction smelting.
Specifically, in the step 1, the temperature of the pre-reduced iron water layer is controlled to 1600-1650 ℃.
Specifically, in the step 2, in the continuous production process, high-temperature reducing gas from the third zone 3 may be injected from the middle of the pre-reduced iron water layer to drive the iron water into the slag-iron layer reduction zone.
Specifically, in the step 3, the binary alkalinity is too high, so that the slag phase has high melting temperature and high viscosity, and the diffusion rate of sulfur into the slag phase is reduced; too low results in a reduced distribution of sulfur in the slag phase, affecting the desulfurization limit. Therefore, the binary alkalinity of the iron concentrate powder and the quicklime powder is controlled to be 3.0-3.5.
Specifically, in the step 3, oxidation reaction of sulfur and phosphorus occurs in the second zone 2 (i.e., slag-iron layer melting zone), specifically as follows:
O 2 +2H 2 ＝2H 2 O (1)
11Fe 2 O 3 +2Fe 3 P+3CaO＝28FeO+Ca 3 (PO 4 ) 2 (2)
4Fe 2 O 3 +FeS+CaO＝9FeO+CaSO 4 (3)
specifically, in the step 4, the reaction in the slag-iron layer reduction zone is specifically as follows:
Fe 2 O 3 +Fe＝3FeO (5)
Fe 3 O 4 +Fe＝4FeO (6)
FeO+H 2 ＝Fe+H 2 O (7)
CaO+FeSO 4 +5H 2 ＝CaS+Fe+5H 2 O (8)
specifically, in the step 4, the FeO content in the slag is controlled to be 5% -8% in the reduction process, so that the 'back phosphorus' phenomenon is avoided, and meanwhile, calcium sulfate is reduced into calcium sulfide to enter the slag layer.
Specifically, in the step 4, the phosphorus content of the reduced molten iron is less than 10ppm.
Specifically, in the above step 5, the reaction in the third zone 3 is specifically as follows:
[O]+H 2 ＝H 2 O (9)
CaO+FeS+H 2 ＝CaS+Fe+H 2 O (10)
specifically, the step 5 further includes:
and 6, allowing the deeply reduced molten iron to enter a vacuum granulating chamber 7, dispersing into fine molten iron particles under the action of a granulator, and deeply removing gas impurities in the molten iron by greatly increasing the surface area of the molten iron, so that on one hand, the reaction of oxygen and hydrogen in the molten iron is promoted, and meanwhile, the overflow of hydrogen is promoted.
Specifically, in the step 6, in order to ensure that the hydrogen content in the molten iron is lower than 3ppm, the vacuum degree is controlled to be 20-30 Pa, the oxygen content in the molten iron is ensured to be reduced to below 5ppm, and the hydrogen content is ensured to be reduced to below 1 ppm.
Specifically, the reaction in the above step 6 is specifically as follows:
[O]+2[H]＝H 2 O (11)
2[H]＝H 2 (12)
specifically, slag of the slag layer is discharged in an eccentric overflow mode.
Specifically, in the step 4, the temperature of the reduced gas generated by pre-reduction is reduced to about 600 ℃ after the waste heat recovery of the waste heat recovery system 8, the mixed gas of hydrogen and water vapor obtained after the heat exchange of the reduced gas is dedusted by the high-temperature dedusting device 9 is heated to 900-950 ℃ by the oxygen-blowing combustion system 10, and finally the high-temperature hydrogen is generated for recycling by the electrolysis of the high-temperature oxide solid electrolytic cell of the high-temperature electrolysis device 11. The invention can ensure that the electrolysis efficiency of the system can reach more than 43 percent by controlling the process parameters, and reduces the energy consumption of the electrolytic hydrogen production. In this way, a separate hydrogen heating device is not required in the present invention.
Specifically, in consideration of the fact that the corrosiveness of hydrogen to the electrode plate material is increased after the temperature is higher than 950 ℃, the electrolysis temperature is optimally controlled within the range of 900-950 ℃. In consideration of the fact that the tolerance temperature of the high-temperature dust remover is not higher than 600 ℃, the temperature of the reduced gas before dust removal is controlled to be about higher than 600 ℃, the temperature of the reduced gas after dust removal is raised by adopting an oxygen-blowing combustion mode, and the temperature is controlled to be regulated by the oxygen-blowing amount.
In particular, hydrogen produced by the electrolyzer 11 can be used for the reactions in the second zone 2 and the third zone 3.
Compared with the prior art, the electro-hydrogen high-efficiency conversion reduction smelting device adopts a unique multi-zone induction furnace as a reduction smelting device, can realize zoned dephosphorization and desulfurization, improves the treatment efficiency and the quality of molten iron, and realizes reduction smelting integration by communicating the second zone with the third zone through a siphon principle.
The induction furnace in the electro-hydrogen efficient conversion reduction smelting device adopts an eccentric injection feeding mode to divide a melting zone and a reduction zone, the melting zone directly heats materials through hydrogen combustion, the heating efficiency and the melting rate of the materials are improved, and meanwhile, oxygen has a powder conveying effect and hydrogen has a melt conveying effect.
The method realizes the accurate control of the atmosphere from oxidizing property to reducing property through the functional partitions of the slag-iron layer melting zone, the slag-iron layer reducing zone and the deep reducing zone, realizes the graded deep removal of phosphorus, sulfur and oxygen, and improves the removal limit of impurity components. Can realize partition dephosphorization and desulfurization, improves the treatment efficiency and the quality of molten iron, and obtains high-purity molten iron.
The method adopts a vacuum granulating mode to replace the conventional argon blowing mode to deeply remove hydrogen in the molten iron, avoids the use of argon and the temperature drop of the molten iron, can further promote the reaction of oxygen and hydrogen in the molten iron, and simultaneously promotes the overflow of hydrogen. Further improves the purity of molten iron particles, ensures that the oxygen content in the molten iron is reduced to below 5ppm and the hydrogen content is reduced to below 1 ppm.
According to the method, the reduction gas is cooled to meet the tolerance temperature of the high-temperature dust collector, the electrolysis temperature of the reduction gas is controlled by heating, the electrolysis efficiency of the system can reach more than 43%, the energy consumption of electrolysis hydrogen production is reduced, meanwhile, high-temperature hydrogen meeting the reduction requirement is directly obtained, the use of a hydrogen heating device is avoided, and the use safety of each device can be ensured.
Example 1
The embodiment provides an electro-hydrogen efficient conversion reduction smelting device, which comprises a multi-zone induction furnace, as shown in fig. 1, wherein the multi-zone induction furnace comprises a first zone 1, a second zone 2 and a third zone 3; the second zone 2 and the third zone 3 are positioned at two sides of the first zone 1, the second zone 2 is positioned at the middle lower part of the first zone 1, and the second zone 2 is directly communicated with the first zone 1; the third zone 3 is communicated with the bottom of the first zone 1 through a sliding gate valve 4; in the reduction smelting process, the second zone 2 is used as a slag-iron layer melting zone, and the first zone 1 is divided into a pre-reduced iron water layer, a slag-iron layer reduction zone and a slag layer from bottom to top; the slag-iron layer melting zone is connected with the slag-iron layer reducing zone; the third zone 3 is divided into a deep reduced iron water layer and a refining slag layer from bottom to top.
Specifically, the first region 1 has a cylindrical shape.
Specifically, the upper part of the first zone 1 is provided with a slag outlet 12.
Specifically, the electro-hydrogen high-efficiency conversion reduction smelting device further comprises a batching system 5 and a blowing system 6 connected with the batching system 5, and after the batching system 5 is used for batching materials, the materials are blown to the second zone 2 through the blowing system 6.
Specifically, the electro-hydrogen high-efficiency conversion reduction smelting device further comprises a first spray gun, wherein the first spray gun is positioned at the side edge of the second zone 2 and is used for spraying hydrogen to the second zone 2.
Specifically, the electro-hydrogen high-efficiency conversion reduction smelting device further comprises a second spray gun, wherein the second spray gun is positioned at the side edge of the third zone 3 and is used for spraying hydrogen to the third zone 3.
Specifically, the electro-hydrogen high-efficiency conversion reduction smelting device further comprises a vacuum granulating chamber 7, and the vacuum granulating chamber 7 is positioned below the third zone 3.
Specifically, the electro-hydrogen high-efficiency conversion reduction smelting device also comprises a waste heat recovery system 8, a high-temperature dust removal device 9, an oxygen-blowing combustion system 10 and a high-temperature electrolysis device 11 which are connected in sequence.
Example 2
As shown in fig. 2, this embodiment provides an electro-hydrogen efficient conversion reduction smelting method, which adopts the electro-hydrogen efficient conversion reduction smelting apparatus of the above embodiment 1, and includes:
step 1, adding industrial pure iron into a first zone 1 as an induction heating medium and melting to form a pre-reduced iron water layer;
step 3, adding the mixture of the iron concentrate powder and the quicklime powder into a second zone 2 (namely a slag-iron layer melting zone) through a blowing system 6, wherein the blowing system 6 takes oxygen as a conveying medium gas of the mixture; the hydrogen generated by the high-temperature electrolysis device 11 is sprayed into the second zone 2 from the first spray gun to generate combustion heat release, so as to provide heat for melting materials, and simultaneously, the melted materials are conveyed to a slag-iron layer reduction zone;
and 6, feeding the molten iron subjected to deep reduction into a vacuum granulating chamber 7, and dispersing the molten iron into fine molten iron particles under the action of a granulator.
Specifically, in the step 3, the iron concentrate powder has the ingredients shown in the following table 1, and the total iron content is 67%, and the sulfur and phosphorus contents are 0.01%. The iron concentrate powder and the quicklime powder are mixed according to the binary alkalinity of 3.0.
TABLE 1 iron concentrate powder composition
| Composition of the components | TFe | FeO | Fe 2 O 3 | Al 2 O 3 | CaO | MgO | SiO 2 | P | S |
| Content of% | 67 | 1.04 | 94.6 | 0.64 | 0.89 | 0.68 | 2.61 | 0.03 | 0.01 |
Specifically, the specific process steps of the steps 1 to 4 are as follows: 10kg of industrial pure iron was charged into the first zone 1 of the multi-zone induction furnace having a capacity of 50kg as an induction heating medium and melted to form a pre-reduced iron water layer, and the induction heating temperature was controlled at 1600 ℃. Then 5kg of slag (without iron) is added into the first zone 1, hydrogen is synchronously sprayed from the bottom of the first zone 1, and a slag-iron mixed layer is formed above the pre-reduced iron water layer through the phenomenon of 'spring' caused by hydrogen stirring. 10kg of iron concentrate powder with binary alkalinity of 3.0 and quicklime powder mixed material are melted at 1600 ℃ and cooled to prepare powder, and the powder is sprayed into a second zone 2 through a spraying system 6 to simulate that the material is melted in a melting zone of a slag-iron mixed layer and then enters a reduction zone. The slag layer and the pre-reduced iron water layer were sampled by a sampler at intervals of 5min, and the FeO content in the slag and the sulfur, phosphorus and oxygen contents in the pre-reduced iron water were determined by chemical titration analysis, and the experimental results are shown in Table 2. It can be seen that in the pre-reduction dephosphorization stage, when the FeO content in the slag is controlled to be more than 5%, the phosphorus content in the molten iron can be removed to be less than 10ppm, and when the FeO content is more than 8%, the change is not large, and in order to reduce the damage of the iron, the FeO content of the slag is preferably controlled to be in the range of 5% -8%.
TABLE 2 variation of slag and molten iron compositions
| FeO content of slag,% | 3 | 5 | 8 | 10 |
| Sulfur content of molten iron, |
12 | 20 | 25 | 38 |
| Phosphorus content of molten iron, ppm | 17 | 7 | 5 | 4 |
| Molten iron oxygen content, ppm | 136 | 176 | 234 | 283 |
Specifically, in the step 5, molten iron with the FeO content of 5% is used, the molten iron enters the third zone 3 through a siphon effect, refining slag (the composition is similar to that of the ladle furnace reducing refining slag) with 3-10% of the molten iron mass is added into the third zone, and excessive hydrogen is introduced from the middle lower part of the molten iron layer for deep reduction and desulfurization, and the experimental results are shown in table 3. It can be seen that after deep reduction, the phosphorus content in the molten iron is slightly reduced, the sulfur and oxygen content is greatly reduced, but the hydrogen content is higher. Preferably, the adding proportion of the refining slag is 8-10% of the mass of the molten iron.
TABLE 3 variation of molten iron composition with different addition amounts of refining slag
| Refining slag addition ratio, percent | 3 | 5 | 8 | 10 |
| Sulfur content of molten iron, |
11 | 8 | 4 | 3 |
| Phosphorus content of molten iron, |
5 | 4 | 3 | 3 |
| Molten iron oxygen content, ppm | 18 | 16 | 12 | 14 |
| Hydrogen content of molten iron, ppm | 30 | 34 | 32 | 35 |
Specifically, in the step 6, molten iron with the adding ratio of 8% of the refining slag is introduced into the vacuum granulating chamber 7 for granulating and degassing, the rotating speed of the granulating rotary table is set to 2500r/min, and the hydrogen content in the molten iron after degassing under different vacuum degrees is shown in table 4. According to the requirement, the hydrogen content in the molten iron is lower than 3ppm, so that the quality is not affected, and the vacuum degree can be controlled within the range of 20-30 Pa, and the oxygen content in the molten iron can be lower than 5ppm.
TABLE 4 variation of molten iron composition at different vacuum degrees
| Vacuum degree, pa | 20 | 30 | 40 | 50 |
| Molten iron oxygen content, |
4 | 5 | 7 | 9 |
| Hydrogen content of molten iron, ppm | 1 | 1 | 2 | 3 |
Specifically, in the step 4, the reduced gas component generated by pre-reduction is 50% H 2 -50％H 2 In the conventional electrolytic water hydrogen production process, the reduced gas is firstly reduced to below 200 ℃ through waste heat recovery under the condition that the O and outlet temperature is 1500-1600 ℃, then the hydrogen is separated through dust removal and spray cooling dehydration, and the hydrogen consumed is supplemented through electrolytic water hydrogen production. The thermal efficiency of electric energy generated by electrolysis hydrogen production through steam power generation is set to be 40%, the electrolytic efficiency of hydrogen production through normal-temperature water electrolysis is set to be 71%, and the thermal efficiency of the whole system for hydrogen production through electrolysis is set to be 28.37%.
Under the condition of the gas, in the process, the temperature of the reduced gas is reduced to about 600 ℃ through a waste heat recovery system, and the reduced gas is subjected to high-temperature dust removal and then is subjected to hydrogen production by high-temperature solid electrolyte electrolysis for recycling. The thermal efficiency of electric energy generated by electrolysis hydrogen production through steam generation is set to be 40%, the electrolytic efficiency of high-temperature steam is set to be 90%, the thermal efficiency of physical heat of steam is set to be 90%, and the thermal efficiency of a system for producing hydrogen by a high-temperature solid oxide electrolytic cell at different temperatures is shown in table 5. It can be seen that the higher the temperature is, the higher the electrolysis thermal efficiency is, and the electrolysis temperature is controlled to be in the range of 900-950 ℃ optimally in consideration of the increased corrosiveness of hydrogen to the electrode plate material after the temperature is higher than 950 ℃.
Because the tolerant temperature of the high-temperature dust remover is not higher than 600 ℃, the reduced gas after dust removal can be heated in a mode of oxygen-blowing combustion, and the temperature is controlled to be regulated by the oxygen-blowing amount. The invention can ensure that the electrolysis efficiency of the system can reach more than 43 percent by controlling the process parameters, and reduces the energy consumption of the electrolytic hydrogen production.
TABLE 5 high temperature electrolytic Hydrogen production efficiency
| Electrolysis temperature, DEG C | 600 | 700 | 800 | 900 | 950 | 1000 |
| System efficiency% | 41.78 | 42.36 | 42.96 | 43.58 | 43.89 | 44.21 |
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.
Claims (10)
1. The electro-hydrogen efficient conversion reduction smelting device is characterized by comprising a multi-zone induction furnace, wherein the multi-zone induction furnace comprises a first zone (1), a second zone (2) and a third zone (3); the second zone (2) and the third zone (3) are positioned at two sides of the first zone (1), the second zone (2) is positioned at the middle lower part of the first zone (1), and the second zone (2) is directly communicated with the first zone (1); the third zone (3) is communicated with the bottom of the first zone (1) through a sliding water gap (4); in the reduction smelting process, the second zone (2) is used as a slag-iron layer melting zone, and the first zone (1) is divided into a pre-reduced iron water layer, a slag-iron layer reduction zone and a slag layer from bottom to top; the slag-iron layer melting zone is connected with the slag-iron layer reduction zone; the third zone (3) is divided into a deep reduced iron water layer and a refining slag layer from bottom to top.
2. The electro-hydrogen efficient conversion reduction smelting device according to claim 1, further comprising a batching system (5) and a blowing system (6) connected with the batching system (5), wherein after batching by the batching system (5), materials are blown to the second zone (2) by the blowing system (6).
3. The electro-hydrogen efficient conversion reduction smelting device according to claim 1, further comprising a first lance located at a side of the second zone (2) for injecting hydrogen gas towards the second zone (2).
4. The electro-hydrogen efficient conversion reduction smelting device according to claim 1, further comprising a second lance located at a side of the third zone (3) for injecting hydrogen gas into the third zone (3).
5. The electro-hydrogen efficient conversion reduction smelting device according to claim 1, further comprising a vacuum granulation chamber (7), the vacuum granulation chamber (7) being located below the third zone (3).
6. The electro-hydrogen efficient conversion reduction smelting device according to claim 1, further comprising a waste heat recovery system (8), a high-temperature dust removal device (9), an oxygen-blowing combustion system (10) and a high-temperature electrolysis device (11) which are connected in sequence.
7. An electro-hydrogen efficient conversion reduction smelting method, characterized in that the electro-hydrogen efficient conversion reduction smelting device according to any one of claims 1 to 6 is adopted, comprising:
step 1, at the beginning, adding industrial pure iron or sponge iron into a first zone (1) as an induction heating medium and melting to form a pre-reduced iron water layer;
step 2, forming a slag-iron mixed layer above the pre-reduced iron water layer; the slag-iron mixed layer is used as a slag-iron layer reduction zone in continuous production;
step 3, adding the mixture of the iron concentrate powder and the quicklime powder into the second zone (2) through a blowing system (6), wherein the blowing system (6) takes oxygen as a conveying medium gas of the mixture; the hydrogen generated by the high-temperature electrolysis device (11) is sprayed into the second zone (2) from the first spray gun to generate combustion heat release, so as to provide heat for melting materials, and simultaneously, the melted materials are conveyed to the slag-iron layer reduction zone;
step 4, the melted materials enter a slag-iron layer reduction zone, and undergo a melting pre-reduction reaction with molten iron brought by 'spring surge' at the lower part to form low-valence iron oxide, and meanwhile, the low-valence iron oxide is reduced into metallic iron by high-temperature hydrogen, slag-iron separation occurs, slag floats upwards and enters a slag layer, and molten iron sinks and enters a pre-reduction iron layer;
and 5, opening a sliding water gap (4), enabling molten iron of the pre-reduced molten iron layer to enter a third area (3), closing the sliding water gap (4) after the molten iron layer in the third area (3) reaches a specified height, and carrying out deep reduction smelting, wherein after the deep reduction smelting, the oxygen and sulfur contents in the molten iron are controlled below 10ppm.
8. The method for high-efficiency electro-hydrogen conversion reduction smelting according to claim 7, wherein the reduced gas in the step 4 is firstly subjected to waste heat recovery and temperature reduction to meet the tolerance temperature of a high-temperature dust removal device, and the mixed gas of the hydrogen and the water vapor obtained by dust removal is subjected to oxygen blowing combustion and temperature elevation, and finally is subjected to electrolysis to generate the hydrogen.
9. The electro-hydro efficient conversion reduction smelting process according to claim 7, further comprising:
and 6, allowing the deeply reduced molten iron to enter a vacuum granulating chamber (7), dispersing into fine molten iron particles under the action of a granulator, and deeply removing gas impurities in the molten iron by increasing the surface area of the molten iron.
10. The electro-hydrogen efficient conversion reduction smelting method according to any one of claims 7 to 9, wherein in step 4, the FeO content in slag is controlled to be 5% -8% during the reduction process.
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Effective date of registration: 20230703 Address after: 100081 No. 76 South College Road, Beijing, Haidian District Applicant after: CHINA IRON & STEEL RESEARCH INSTITUTE Group Applicant after: Metallurgical Automation Research and Design Institute Co.,Ltd. Address before: 100081 No. 76 South College Road, Beijing, Haidian District Applicant before: CHINA IRON & STEEL RESEARCH INSTITUTE Group Applicant before: CISRI SUNWARD TECHNOLOGY Co.,Ltd. |