CN114525373B - Method for desulfurizing and phosphorus by reducing iron ore powder with microwave hydrogen - Google Patents
Method for desulfurizing and phosphorus by reducing iron ore powder with microwave hydrogen Download PDFInfo
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- CN114525373B CN114525373B CN202210068380.7A CN202210068380A CN114525373B CN 114525373 B CN114525373 B CN 114525373B CN 202210068380 A CN202210068380 A CN 202210068380A CN 114525373 B CN114525373 B CN 114525373B
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 240
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 104
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 65
- 239000001257 hydrogen Substances 0.000 title claims abstract description 65
- 239000000843 powder Substances 0.000 title claims abstract description 61
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 56
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 40
- 239000011574 phosphorus Substances 0.000 title claims abstract description 39
- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 16
- 230000009467 reduction Effects 0.000 claims abstract description 77
- 239000007789 gas Substances 0.000 claims abstract description 41
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000002844 melting Methods 0.000 claims abstract description 22
- 230000008018 melting Effects 0.000 claims abstract description 22
- 239000012071 phase Substances 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 13
- 239000011593 sulfur Substances 0.000 claims abstract description 13
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 11
- 230000023556 desulfurization Effects 0.000 claims abstract description 11
- 230000000694 effects Effects 0.000 claims abstract description 10
- 239000007791 liquid phase Substances 0.000 claims abstract description 10
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 9
- 238000007885 magnetic separation Methods 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 5
- 230000000750 progressive effect Effects 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052595 hematite Inorganic materials 0.000 claims description 2
- 239000011019 hematite Substances 0.000 claims description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 230000035699 permeability Effects 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims description 2
- 235000013980 iron oxide Nutrition 0.000 claims 2
- 239000002817 coal dust Substances 0.000 claims 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims 1
- 238000003723 Smelting Methods 0.000 abstract description 19
- 238000005272 metallurgy Methods 0.000 abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 11
- 229910000831 Steel Inorganic materials 0.000 abstract description 8
- 239000010959 steel Substances 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000002309 gasification Methods 0.000 abstract description 4
- 230000003749 cleanliness Effects 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 description 58
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 25
- 229910052799 carbon Inorganic materials 0.000 description 25
- 235000019580 granularity Nutrition 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 239000003638 chemical reducing agent Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000571 coke Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000003245 coal Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 230000002349 favourable effect Effects 0.000 description 5
- 239000003345 natural gas Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 239000003034 coal gas Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000011946 reduction process Methods 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002551 biofuel Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/004—Making spongy iron or liquid steel, by direct processes in a continuous way by reduction from ores
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/10—Reduction of greenhouse gas [GHG] emissions
- Y02P10/143—Reduction of greenhouse gas [GHG] emissions of methane [CH4]
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Furnace Details (AREA)
Abstract
The invention provides a method for desulfurizing and phosphorus by reducing iron ore powder with microwave hydrogen, which relates to the technical field of hydrogen metallurgy and microwave metallurgy, and comprises the following steps: grinding the iron ore into iron ore powder with preset granularity; obtaining the temperature and the melting state of a metal phase in the iron ore powder; controlling the microwave irradiation power according to the temperature and the melting state, carrying out microwave irradiation on the iron ore powder to ensure that no liquid phase is generated in the reduced metallic iron phase, and introducing reducing gas to carry out gradual reduction of iron oxide; introducing protective gas into the reduced metal iron phase, and recovering to room temperature to obtain reduced iron powder; and carrying out magnetic separation on the reduced iron powder to obtain the target reduced iron powder. The invention can promote the reduction effect of hydrogen and the gasification dephosphorization and desulfurization effects. The method realizes high-efficiency reduction at lower temperature, realizes the control of sulfur and phosphorus content from raw materials, is beneficial to improving the cleanliness of steel, can reduce the difficulty of desulfurization and dephosphorization in the subsequent molten metal smelting process, can reduce iron ore powder to directly produce iron powder, and shortens the smelting process.
Description
Technical Field
The invention relates to the technical field of hydrogen metallurgy and microwave metallurgy, in particular to a method for desulfurizing and phosphor by reducing iron ore powder by microwave hydrogen.
Background
The steel industry has huge yield scale and excellent history contribution, and has great significance for supporting the future development strategy of national economy and society. Meanwhile, the carbon emission environment and policy pressure are becoming more and more severe, and zero or low carbon breakthrough technology has become an epoch proposition in the field of steel manufacturing. Therefore, the leading edge technology of carbon reduction and carbon resource recycling is being developed greatly at home and abroad. The blast furnace ironmaking productivity is high, the efficiency is high, but the reality of high coke ratio and high energy consumption of the blast furnace is increasingly outstanding with the environment green development. Blast furnace ironmaking is under study including a series of technologies of replacing coke with natural gas or biofuel, replacing coal injection with hydrogen-rich gas injection, etc., but the skeleton of coke, the dominant position of reduction and heat source are not changed. Because of the steep increase of energy efficiency, the process technology is nearly perfect from the point of energy efficiency, and the improvement space is limited in the prior art.
The structure of the ironmaking energy source is examined from the perspective of ternary relation of carbon-electricity-hydrogen, and the current carbon metallurgy gradually develops towards the electro-hydrogen combination metallurgy. With the rapid development of the hydrogen production capacity of industrial scale, a new hydrogen metallurgy iron-making or direct steelmaking method which can basically replace carbon metallurgy is explored and developed, the high-efficiency supply of non-carbon heat energy in the hydrogen metallurgy process is solved, the comparable high-efficiency production capacity is obtained in the technical level, and the method is one of main paths for getting rid of carbon emission pressure.
Therefore, the following technical problems exist in the current hydrogen iron making: 1. the hydrogen reduction process is a strong endothermic reaction, the hydrogen metallurgy process needs a continuous heat source, and the mainstream hydrogen-rich smelting at present mainly relies on natural gas, biological and other fuels to provide the heat source, and carbon dioxide emission still exists; 2. in the reduction smelting process, harmful elements such as sulfur, phosphorus and the like enter molten iron, the liquid iron has high dephosphorization difficulty, and the phenomenon of sulfur recovery and phosphorus recovery is easy to occur.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for desulfurizing and phosphorus by reducing iron ore powder with microwave hydrogen, which can solve the problems that the hydrogen reduction process is a strong endothermic reaction, the hydrogen metallurgy process needs a continuous heat source, and the main stream hydrogen-rich smelting at present mainly depends on natural gas, biological fuel and other fuels to provide the heat source and still has carbon dioxide emission; in the reduction smelting process, harmful elements such as sulfur, phosphorus and the like enter molten iron, so that the liquid iron has high dephosphorization difficulty and is easy to generate the phenomenon of sulfur recovery and phosphorus recovery.
In order to solve the technical problems, the invention provides the following technical scheme:
the technical scheme of the invention has the following beneficial effects:
a method for desulfurizing and phosphor by reducing iron ore powder with microwave hydrogen, which comprises the following steps:
grinding the iron ore into iron ore powder with preset granularity;
acquiring the temperature and the melting state of a metal phase in the iron ore powder;
controlling the microwave irradiation power according to the temperature and the melting state, carrying out microwave irradiation on the iron ore powder to ensure that no liquid phase is generated in the reduced metallic iron phase, and introducing reducing gas to carry out gradual reduction of iron oxide;
introducing protective gas into the reduced metal iron phase, and recovering to room temperature to obtain reduced iron powder;
and carrying out magnetic separation on the reduced iron powder to obtain the target reduced iron powder.
In an alternative embodiment, the progressive reduction of iron oxide comprises a first stage reduction: fe (Fe) 2 O 3 Reduction to Fe 3 O 4 Second stage reduction: fe (Fe) 3 O 4 Reduction to FeO, third stage reduction: feO is reduced to metallic iron;
the control of the microwave irradiation power according to the temperature and the melting state comprises the steps of obtaining the temperature required by each stage of reduction, obtaining the melting state of phosphorus in each stage of reduction, and controlling the microwave irradiation power according to the temperature required by each stage of reduction and the melting state of phosphorus in each stage of reduction.
In an alternative embodiment, the method further comprises obtaining the time required for each stage of reduction, and controlling the power of microwave irradiation according to the time required for each stage of reduction.
In an alternative embodiment, the method further comprises obtaining a desired reducing gas content for each stage of reduction, and introducing a specific amount of reducing gas to each stage based on the desired reducing gas content for each stage of reduction.
In an alternative embodiment, the microwave irradiation has a power of 1-3 kw, a frequency of 2GHZ-2.45GHZ and a magnetic field strength of 110KA/cm-120KA/cm.
In an alternative embodiment, the reaction temperature is controlled between 900 ℃ and 1400 ℃ during microwave irradiation.
In an alternative embodiment, the method further comprises drying the iron ore fines ground to a predetermined particle size at a temperature of 100 ℃ to 120 ℃ for a time period of 2 hours to 4 hours.
In an alternative embodiment, the method further includes obtaining a phosphorus content in the iron ore fines, and adding a reference amount of pulverized coal to the iron ore fines when the phosphorus content is greater than a predetermined content.
In an alternative embodiment, the pressure of the hydrogen gas or hydrogen-rich gas is not less than 0.1MPa.
In an alternative embodiment, the flow rate of the hydrogen gas or hydrogen-rich gas is 5L/min to 10L/min.
The method provided by the embodiment of the invention has at least the following beneficial effects:
the iron ore powder in the embodiment of the invention is very favorable for reduction and gasification removal of sulfur and phosphorus under microwave irradiation, and the iron ore is heated by microwave irradiation while smelting the iron ore, so that the hydrogen reduction effect and gasification dephosphorization and desulfurization effects can be promoted. The adoption of the microwave radiation hydrogen as the reducing gas can greatly reduce the reducing smelting temperature, realize high-efficiency reduction at lower temperature, realize the control of the sulfur and phosphorus content from the source of raw materials, be favorable for improving the cleanliness of steel, not only reduce the difficulty of desulfurization and dephosphorization in the subsequent molten metal smelting process, but also reduce the iron ore powder to directly produce iron powder, and shorten the smelting flow. The invention eliminates the sintering and coking processes which are necessary for blast furnace smelting, does not need solid carbon or coal gas as a reducing agent in the reaction process, does not depend on the solid carbon or coal gas as a fuel to provide a heat source, takes hydrogen as the reducing agent, realizes the reduction of iron ore under microwave irradiation, mainly generates water vapor in the reaction process, can realize zero carbon emission, and greatly reduces the emission of sulfur dioxide, nitrogen oxides, dust, dioxin and the like.
Drawings
FIG. 1 is a schematic flow chart of a method according to an embodiment of the present invention;
fig. 2 is a schematic flow chart of a method according to an embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved more apparent, the following detailed description will be given with reference to the accompanying drawings and specific embodiments.
The steel industry has huge yield scale and excellent history contribution, and has great significance for supporting the future development strategy of national economy and society. Meanwhile, the carbon emission environment and policy pressure are becoming more and more severe, and zero or low carbon breakthrough technology has become an epoch proposition in the field of steel manufacturing. Therefore, the leading edge technology of carbon reduction and carbon resource recycling is being developed greatly at home and abroad. The blast furnace ironmaking productivity is high, the efficiency is high, but the reality of high coke ratio and high energy consumption of the blast furnace is increasingly outstanding with the environment green development. Blast furnace ironmaking is under study including a series of technologies of replacing coke with natural gas or biofuel, replacing coal injection with hydrogen-rich gas injection, etc., but the skeleton of coke, the dominant position of reduction and heat source are not changed. Because of the steep increase of energy efficiency, the process technology is nearly perfect from the point of energy efficiency, and the improvement space is limited in the prior art. The structure of the ironmaking energy source is examined from the perspective of ternary relation of carbon-electricity-hydrogen, and the current carbon metallurgy gradually develops towards the electro-hydrogen combination metallurgy. With the rapid development of the hydrogen production capacity of industrial scale, a new hydrogen metallurgy iron-making or direct steelmaking method which can basically replace carbon metallurgy is explored and developed, the high-efficiency supply of non-carbon heat energy in the hydrogen metallurgy process is solved, the comparable high-efficiency production capacity is obtained in the technical level, and the method is one of main paths for getting rid of carbon emission pressure.
Therefore, the following technical problems need to be overcome in the current hydrogen ironmaking: 1. the hydrogen reduction process is a strong endothermic reaction, the hydrogen metallurgy process needs a continuous heat source, and the mainstream hydrogen-rich smelting at present mainly relies on natural gas, biological and other fuels to provide the heat source, and carbon dioxide emission still exists; 2. in the reduction smelting process, harmful elements such as sulfur, phosphorus and the like enter molten iron, the liquid iron has high dephosphorization difficulty, and the phenomenon of sulfur recovery and phosphorus recovery is easy to occur. In view of the above, the embodiment of the invention provides a method for desulfurizing and phosphorus by reducing iron ore powder with microwave hydrogen, which aims to solve the technical problems.
Referring to fig. 1, fig. 1 is a schematic flow chart of a method for desulfurizing and phosphorus by reducing iron ore powder with microwave hydrogen, which includes:
s101, grinding the iron ore into iron ore powder with preset granularity.
S102, acquiring the temperature and the melting state of a metal phase in the iron ore powder.
And S103, controlling the microwave irradiation power according to the temperature and the melting state, carrying out microwave irradiation on the iron ore powder, enabling the reduced metallic iron phase not to generate a liquid phase, and introducing reducing gas to carry out gradual reduction of the iron oxide.
And S104, introducing protective gas into the reduced metal iron phase, and recovering to room temperature to obtain reduced iron powder.
S105, magnetically separating the reduced iron powder to obtain target reduced iron powder.
The method provided by the embodiment of the invention has at least the following beneficial effects:
according to the method provided by the embodiment of the invention, the iron ore is ground into the iron ore powder with the preset granularity, so that the iron ore powder can be conveniently and fully contacted with the reducing gas, and can be heated uniformly when microwave radiation is carried out, and the temperature and the melting state of a metal phase in the iron ore powder are obtained; controlling the microwave irradiation power according to the temperature and the melting state, carrying out microwave irradiation on the iron ore powder to ensure that no liquid phase is generated in the reduced metallic iron phase, and introducing reducing gas to carry out gradual reduction of iron oxide; introducing protective gas into the reduced metal iron phase, and recovering to room temperature to obtain reduced iron powder; and carrying out magnetic separation on the reduced iron powder to obtain the target reduced iron powder.
The iron ore powder in the embodiment of the invention is very favorable for reducing and gasifying and removing sulfur and phosphorus under microwave irradiation, and the microwave irradiation is utilized to heat the iron ore while smelting the iron ore, so that the hydrogen reduction effect and gasifying dephosphorization and desulfurization effects can be promoted.
Compared with the traditional blast furnace smelting process, the invention omits the sintering and coking processes which are necessary for blast furnace smelting, does not need solid carbon or coal gas as a reducing agent in the reaction process, does not depend on the solid carbon or the coal gas as a fuel to provide a heat source, takes hydrogen as the reducing agent, realizes the reduction of iron ore under the irradiation of microwaves, mainly generates water vapor in the reaction process, can realize zero carbon emission, and greatly reduces the emission of sulfur dioxide, nitrogen oxides, dust, dioxin and the like.
Microwave treatment is fundamentally different from other heating sources in which heat is applied externally to the surface of the material and is conducted or radiated into cooler interior regions, thereby creating a gradient field. Microwave radiation penetrates and uniformly heats in the volume range simultaneously, so that a reverse temperature gradient exists in the material, the temperature can be quickly raised, surface overheating can not occur, the reaction absorption heat can cause energy dissipation in the reactant, heat transfer is not needed by utilizing microwave irradiation, the material is directly heated in the form of light waves accurately, and the raw materials can be quickly, accurately and uniformly heated. Conventional heating may cause the surface reactions to complete before the interior is fully reacted, and the surface pores may close prematurely, preventing substantial transport of gaseous reactants to the interior center. The microwave heated material allows the reactant gas to permeate into the sample and diffuse to the thermal center until it is fully reacted.
The method provided by the embodiments of the present invention will be further explained and illustrated by alternative embodiments.
S101, grinding the iron ore into iron ore powder with preset granularity.
In an alternative embodiment, the iron ore-containing raw materials in S101 include: one or more of iron concentrate, high-phosphorus iron ore, high-sulfur iron ore, hematite, magnetite, manganese ore and dephosphorizing converter slag.
The preset particle size may be 1.2cm to 1.60cm, and for example, the particle size of the iron ore may be 1.2cm, 1.21cm, 1.22cm, 1.25cm, 1.3cm, 1.35cm, 1.36cm, 1.4cm, 1.44cm, 1.46cm, 1.5cm, 1.51cm, 1.52cm, 1.6cm, etc. The grinding granularity of the iron ore powder is in the range, so that the iron ore powder can be ensured to fully receive microwave irradiation and be heated uniformly.
S102, acquiring the temperature and the melting state of a metal phase in the iron ore powder.
In an alternative embodiment, the progressive reduction of iron oxide comprises a first stage reduction: fe (Fe) 2 O 3 Reduction to Fe 3 O 4 Second stage reduction: fe (Fe) 3 O 4 Reduction to FeO, third stage reduction: feO is reduced to metallic iron;
controlling the power of microwave irradiation according to the temperature and the melting state, including obtaining the temperature required by each stage of reduction, obtaining the melting state of phosphorus in each stage of reduction, and controlling the power of microwave irradiation according to the temperature required by each stage of reduction and the melting state of phosphorus in each stage of reduction.
It will be appreciated that iron oxide reduction includes the above-described different three-stage reduction reactions, and that the temperature required for each stage of reaction and the time required for the reaction are different, and that by obtaining the temperature required for each stage of reduction, the molten state of phosphorus in each stage of reduction is obtained, and the power of microwave irradiation is controlled in accordance with the temperature required for each stage of reduction. Therefore, the efficiency of microwave irradiation can be improved, the melting state of phosphorus in the iron ore powder is obtained, the microwave irradiation power is reduced when the phosphorus is observed to be close to the melting state, the phosphorus is prevented from melting into the metallic iron phase, and the reduced metallic iron phase is ensured not to generate a liquid phase.
In an alternative embodiment, the method further comprises obtaining the time required for each stage of reduction, and controlling the power of the microwave irradiation according to the time required for each stage of reduction.
It can be appreciated that Fe 2 O 3 Reduction to Fe 3 O 4 ，Fe 3 O 4 The reaction time of each stage of reduction of FeO into metallic iron is different, and the power and time of microwave irradiation can be better controlled by obtaining the reaction time of each stage, so that the efficient implementation of each stage of reduction reaction is ensured.
In an alternative embodiment, the method further comprises obtaining a desired reducing gas content for each stage of reduction, and introducing a specific amount of reducing gas to each stage based on the desired reducing gas content for each stage of reduction.
It can be understood that after the content of the iron ore powder is determined, the content of the reducing gas required by each stage of reaction can be determined, and the cost is saved and the efficient reaction is ensured by obtaining the content of the reducing gas required by each stage of reduction and introducing a specific amount of the reducing gas into each stage according to the content of the reducing gas required by each stage of reduction.
In an alternative embodiment, the microwave irradiation has a power of 1 kw-3 kw, a frequency of 2GHZ-2.45GHZ and a magnetic field strength of 110KA/cm-120KA/cm.
As an example, the microwave irradiation power may be 1kw, 1.5kw, 1.8kw, 2kw, 2.2kw, 2.5kw, 2.8kw, 3kw, etc., the microwave irradiation frequency may be 2GHZ, 2.2GHZ, 2.25GHZ, 2.45GHZ, etc., and the magnetic field strength may be 110KA/cm, 111KA/cm, 112.37KA/cm115KA/cm, 119.37KA/cm, 120KA/cm, etc. It should be noted that the above is only an example of the embodiment of the present invention, and the embodiment of the present invention is not limited to the microwave irradiation power, frequency and magnetic field strength.
In an alternative embodiment, the reaction temperature is controlled between 900 ℃ and 1400 ℃ during microwave irradiation.
As an example, the reaction temperature is controlled at 900 ℃, 950 ℃, 1000 ℃, 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃, 1380 ℃, 1400 ℃ and the like when irradiated with microwaves.
In an alternative embodiment, the method further comprises drying the iron ore fines ground to a predetermined particle size at a temperature of 100 ℃ to 120 ℃ for a time period of 2 hours to 4 hours.
As an example, the drying temperature may be 100 ℃, 105 ℃, 110 ℃, 111 ℃, 115 ℃, 116 ℃, 120 ℃, etc., and the drying time may be 2 hours, 2.5 hours, 2.8 hours, 3 hours, 3.5 hours, 4 hours, etc.
In an alternative embodiment, the method further includes obtaining a phosphorus content in the iron ore fines, and adding a reference amount of pulverized coal to the iron ore fines when the phosphorus content is greater than a predetermined content. By adding pulverized coal, the removal of phosphorus can be promoted by taking the pulverized coal as a reducing agent.
In an alternative embodiment, the pressure of the hydrogen gas or hydrogen-rich gas is not less than 0.1MPa.
In an alternative embodiment, the flow rate of the hydrogen gas or hydrogen-rich gas is 5L/min to 10L/min.
As an example, the flow rate of the hydrogen gas or hydrogen-rich gas may be 5L/min, 5.5L/min, 6L/min, 6.5L/min, 7L/min, 8L/min, 9L/min, 10L/min, etc.
The method provided by the embodiments of the present invention will be further explained and described below by alternative embodiments.
Step 1, preprocessing iron ore-containing raw materials, crushing and screening the raw materials, and selecting the granularity according to the reaction time and the required desulfurization and dephosphorization effects, wherein the smaller the granularity is, the shorter the required reaction time is, and the better the desulfurization and dephosphorization effects are; the granularity of the iron ore provided by the embodiment of the invention is 1.2cm.
And 2, adding the pretreated raw material obtained in the step 1 into microwave heating, carrying out microwave irradiation, and introducing hydrogen or hydrogen-rich gas to reduce iron oxide, reduce, gasify, desulfurize and dephosphorize.
And 3, cooling the iron powder obtained by microwave hydrogen reduction to room temperature in a cooling area in an atmosphere furnace, removing most of impurities from the obtained directly reduced iron powder by strong magnetic separation, and directly smelting the iron powder obtained by magnetic separation into steel in an electric furnace.
Wherein, because the phosphorus obtained by reduction is easy to enter liquid-phase iron, in the method step 2 provided by the embodiment of the invention, the reaction temperature in the furnace is controlled by adjusting the microwave irradiation power in real time, so that the metallic iron is reducedThe phase does not generate liquid phase so as to ensure that phosphorus in the furnace charge cannot dissolve into metal and P remains in the solid phase 2 O 5 And (5) removing the waste water by strong magnetic separation. The method provided by the embodiment of the invention is applicable to the gasification desulfurization and dephosphorization of most types of ore raw materials in the prior iron and steel smelting, and has wide application range.
The microwave irradiation power is continuously adjusted according to the real-time monitoring reaction temperature in the reaction process, the temperature in the furnace is kept at 1400 ℃, the temperature setting is mainly based on the ore components, on the premise that the reduced metallic iron does not generate liquid phase, because the carbonaceous reducing agent is not adopted in the reaction process, the solid solution carbon content of the metallic iron phase is extremely low, the melting point is higher, the materials are kept in a full solid phase, the reduction temperature is raised to be favorable for gasifying and removing sulfur and phosphorus, meanwhile, the microwave can be used for catalyzing the reaction to a certain extent, the microwave is directly radiated to molecules, and the molecules are easier to enter an excited state after absorbing energy, so that the heterogeneous reaction of gas-solid is accelerated, and the reaction is accelerated.
In the embodiment of the invention, in order to ensure that the reduction reaction is carried out efficiently and continuously, the pressure of hydrogen is not lower than 0.1MPa (micro positive pressure), the flow is set to be 5L/min, and the gas introduced is not limited to hydrogen, but can be hydrogen-rich gas obtained by mixing hydrogen with industrial gas and the like. In the reduction process, solid carbon is not required to be added as a reducing agent, and the gas generated after the reaction is water vapor and gasified desulfurization dephosphorization products (H) 2 S、P 4 、PH 3 Etc.), the hydrogen molecules react more fully with the solid minerals, not only without carbon emissions, but also at a reaction rate far exceeding that of solid carbonaceous reducing agents, due to the minimal size of the hydrogen molecules compared to other molecules. The microwave irradiation is adopted to irradiate the reaction system, so that not only is coke replaced as a heat source, but also the clean production is realized, the microwave irradiation can enable the reaction materials to participate in the reaction in a higher excited state, and meanwhile, the activation energy of the chemical reaction can be reduced, the optimal reaction state is easier to achieve, and the production smelting efficiency is improved.
In an alternative embodiment, please refer to fig. 2, fig. 2 is a simplified flowchart of a method according to an embodiment of the present invention. The pretreated mineral raw materials are distributed by a material bin distributing deviceThe mixture is fed into a continuous reaction furnace with controllable microwave atmosphere for microwave irradiation, and reaction gas H is introduced at the same time 2 . Wherein the material layer in the reaction furnace is flatly paved on a breathable conveying belt, and the temperature is constant in a microwave heating field. Reaction gas is introduced from the lower part of the conveyor belt in the microwave heating field, and the gas generated by the reaction is led out of the reaction furnace from the smoke hood above the conveyor belt. The thickness of the material layer, the granularity of the raw material and the microwave power are all required in the reaction furnace, the microwave power ensures that microwaves penetrate through the whole material layer, and the granularity of the raw material and the thickness of the material layer ensure sufficient air permeability. The absorption and attenuation capabilities of microwave energy are different for different materials, depending on the dielectric properties of the materials. The attenuation state determines the penetration of microwaves into the medium. For example, the dielectric properties of vanadium titano-magnetite increase with decreasing particle size. The penetration depth is reduced along with the temperature rise between 20 and 800 ℃, and the larger the granularity is, the more favorable for the penetration of microwaves on ores, and the optimal material thickness for heating vanadium titano-magnetite by the microwaves is 1.28 to 1.60cm. The temperature of the vanadium titano-magnetite with different granularities in a microwave field is linearly increased along with the microwave heating time.
The foregoing is a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention and are intended to be comprehended within the scope of the present invention.
Claims (8)
1. A method for desulfurizing and phosphor by reducing iron ore powder with microwave hydrogen, which is characterized by comprising the following steps:
grinding iron ore into iron ore powder with preset granularity, wherein the granularity is selected according to the reaction time and the required desulfurization and dephosphorization effects, and the smaller the granularity is, the shorter the required reaction time is, and the better the desulfurization and dephosphorization effects are; the iron ore raw materials include: one or more of high-phosphorus iron ore, high-sulfur iron ore, hematite, magnetite, manganese ore and dephosphorization converter slag;
acquiring the temperature and the melting state of a metal phase in the iron ore powder;
the progressive reduction of iron oxides in the iron ore fines comprises a first stage reduction: fe (Fe) 2 O 3 Reduction to Fe 3 O 4 Second stage reduction: fe (Fe) 3 O 4 Reduction to FeO, third stage reduction: feO is reduced to metallic iron;
obtaining the temperature required by each stage of reduction, obtaining the time required by each stage of reduction, obtaining the melting state of phosphorus in each stage of reduction, controlling the microwave irradiation power to perform microwave irradiation on the iron ore powder according to the temperature required by each stage of reduction, the time required by each stage of reduction and the melting state of phosphorus in each stage of reduction, so that no liquid phase is generated in the reduced metallic iron phase, and introducing reducing gas to perform gradual reduction of iron oxide; the microwave irradiation power in the reaction process is continuously adjusted according to the reaction temperature monitored in real time, the temperature in the furnace is set according to the raw material components of the iron ore, and the premise is that no liquid phase is generated in the process of reducing the metallic iron; the microwave power should ensure that the microwaves penetrate through the whole material layer, and the granularity of the raw materials and the thickness of the material layer should ensure sufficient air permeability;
introducing protective gas into the reduced metal iron phase, and recovering to room temperature to obtain reduced iron powder;
and carrying out magnetic separation on the reduced iron powder to obtain the target reduced iron powder.
2. The method for desulfurizing and phosphorus by reducing iron ore powder with microwave hydrogen according to claim 1, further comprising obtaining the content of the reducing gas required by each stage of reduction, and charging a specific amount of reducing gas into each stage according to the content of the reducing gas required by each stage of reduction.
3. The method for desulfurizing and dephosphorizing iron ore powder by microwave hydrogen reduction according to claim 1, wherein the power of microwave irradiation is 1-3 kw, the frequency is 2GHZ-2.45GHZ, and the magnetic field strength is 110KA/cm-120KA/cm.
4. The method for desulfurizing and phosphating iron ore powder by reducing hydrogen with microwave according to claim 1, wherein the reaction temperature is controlled between 900 ℃ and 1400 ℃ during the microwave irradiation.
5. The method for desulfurizing and phosphating iron ore powder by microwave hydrogen reduction according to claim 1, further comprising the step of drying the iron ore powder ground into preset granularity at a drying temperature of 100-120 ℃ for 2-4 hours.
6. The method for desulfurizing and phosphorus-reducing iron ore powder by microwave hydrogen according to claim 1, further comprising obtaining the phosphorus content in the iron ore powder, and adding reference amount of coal dust into the iron ore powder when the phosphorus content is greater than a preset content.
7. The method for desulfurizing and dephosphorizing iron ore powder by microwave hydrogen reduction according to claim 1, wherein the pressure of the introduced hydrogen or hydrogen-rich gas is not lower than 0.1MPa.
8. The method for desulfurizing and dephosphorizing iron ore powder by microwave hydrogen reduction according to claim 1, wherein the flow rate of the introduced hydrogen or hydrogen-rich gas is 5L/min-10L/min.
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