CN111676341A - Smelting system and smelting method of vanadium-titanium magnetite concentrate - Google Patents
Smelting system and smelting method of vanadium-titanium magnetite concentrate Download PDFInfo
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- CN111676341A CN111676341A CN202010754297.6A CN202010754297A CN111676341A CN 111676341 A CN111676341 A CN 111676341A CN 202010754297 A CN202010754297 A CN 202010754297A CN 111676341 A CN111676341 A CN 111676341A
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- vanadium
- smelting
- magnetite concentrate
- titanium magnetite
- reduction
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- 238000003723 Smelting Methods 0.000 title claims abstract description 198
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 105
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000012141 concentrate Substances 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 92
- 230000009467 reduction Effects 0.000 claims abstract description 119
- 239000007789 gas Substances 0.000 claims abstract description 111
- 230000001590 oxidative effect Effects 0.000 claims abstract description 80
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 63
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 63
- 230000006698 induction Effects 0.000 claims abstract description 59
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- 239000002184 metal Substances 0.000 claims abstract description 46
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims description 54
- 239000002893 slag Substances 0.000 claims description 50
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 46
- 239000010936 titanium Substances 0.000 claims description 46
- 229910052719 titanium Inorganic materials 0.000 claims description 46
- 239000011230 binding agent Substances 0.000 claims description 36
- 239000000047 product Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000002994 raw material Substances 0.000 claims description 32
- 229910001868 water Inorganic materials 0.000 claims description 32
- 230000003647 oxidation Effects 0.000 claims description 23
- 238000007254 oxidation reaction Methods 0.000 claims description 23
- 230000002829 reductive effect Effects 0.000 claims description 23
- 238000002844 melting Methods 0.000 claims description 21
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- 238000002156 mixing Methods 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 9
- 238000005453 pelletization Methods 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000002485 combustion reaction Methods 0.000 claims description 7
- 239000000567 combustion gas Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 229910000882 Ca alloy Inorganic materials 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- 239000000440 bentonite Substances 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000013589 supplement Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 2
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 36
- 239000008188 pellet Substances 0.000 description 36
- 229910052742 iron Inorganic materials 0.000 description 14
- 230000009286 beneficial effect Effects 0.000 description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 238000001465 metallisation Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000010405 reoxidation reaction Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000011946 reduction process Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 235000010215 titanium dioxide Nutrition 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- 239000004484 Briquette Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- MRHSJWPXCLEHNI-UHFFFAOYSA-N [Ti].[V].[Fe] Chemical compound [Ti].[V].[Fe] MRHSJWPXCLEHNI-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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Classifications
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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
- C21B13/08—Making spongy iron or liquid steel, by direct processes in rotary furnaces
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/006—Starting from ores containing non ferrous metallic oxides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/16—Sintering; Agglomerating
- C22B1/216—Sintering; Agglomerating in rotary furnaces
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1204—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent
- C22B34/1209—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent by dry processes, e.g. with selective chlorination of iron or with formation of a titanium bearing slag
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a smelting system and a smelting method of vanadium-titanium magnetite concentrate. This vanadium titanium magnetite concentrate's smelting system includes: an oxidizing roasting device, a reduction smelting device and an induction smelting device. The oxidizing roasting device is provided with a first charging hole, an oxidizing gas inlet and an oxidizing roasting product outlet; the reduction smelting device is provided with a second charging hole, a reducing gas inlet and a metallized material outlet, and the second charging hole is communicated with the oxidizing roasting product outlet through a first charging pipeline; and the induction smelting device is provided with a third charging hole, a non-carbon-based reducing agent inlet, a shielding gas inlet and vanadium-containing metal, wherein the shielding gas inlet is used for introducing inert gas, and the third charging hole is communicated with the metalized material outlet and is used for further reducing the metalized material discharged by the reduction smelting device. The smelting system has the advantages of high vanadium recovery rate, low recovery cost, small recovery difficulty, simple equipment and the like.
Description
Technical Field
The invention relates to the field of ore smelting, in particular to a vanadium-titanium magnetite concentrate smelting system and a vanadium-titanium magnetite concentrate smelting method.
Background
At present, the more mature process in the field of vanadium-titanium magnetite concentrate smelting is a blast furnace process, but the process can only recover iron and partial vanadium, and titanium can not be extracted and applied at all. Titanium-containing blast furnace slag TiO 22The non-blast furnace process only carries out experimental research on production scale by the pre-reduction-electric furnace method, and other researches basically stay in the laboratory research and enlarged test research stage The ore grinding cost is high, the production scale is small, and the economical efficiency is far lower than that of a pre-reduction-electric furnace method; the sodium roasting-prereduction-electric furnace method has the advantages of high vanadium-titanium recovery rate, but has the problems of large sodium modifier addition amount, long treatment process, large sewage treatment capacity and the like, and has poor feasibility.
The prior document (CN110484720) provides a process for comprehensively utilizing vanadium titano-magnetite by using a grate-gas-based shaft furnace-electric furnace deep reduction. And (3) producing oxidizing pellets by using a grate, reducing the pellets into metallized pellets with the metallization rate of about 88 percent in a gas-based shaft furnace, feeding the obtained metallized pellets into an electric furnace, adding reducing agent carbon for deep reduction, and producing vanadium-containing iron water and titanium slag. The process adopts carbon as a reducing agent in the subsequent deep reduction stage, and still fails to solve the problems of difficult smelting and low vanadium recovery rate in the deep reduction stage.
The prior document (CN105925743) provides a method for preparing ultra-pure iron by directly reducing ultra-high-grade iron ore concentrate in a gas-based shaft furnace, which takes the ultra-high-grade iron ore concentrate as a raw material, adds an organic binder, pelletizing and oxidizing roasting to prepare oxidized pellets, then places the oxidized pellets of the ultra-high-grade iron ore concentrate in the gas-based shaft furnace to be directly reduced by adopting reducing gas, and then sends metallized pellets obtained by gas-based reduction to a medium-frequency induction furnace to be melted and separated in vacuum or argon atmosphere to obtain the ultra-pure iron with TFe more than or equal to 99.98% and C less than or equal to 0.005%. The process flow is short and compact in connection, and each process parameter is easy to control, but the process is only suitable for smelting by taking iron ore concentrate with higher grade as a raw material, and is not suitable for smelting iron vanadium titanium magnetite ore concentrate.
In view of the above problems, there is a need to provide a smelting method for vanadium-titanium magnetite concentrate, which has high vanadium recovery rate, low cost and low difficulty.
Disclosure of Invention
The invention mainly aims to provide a smelting system and a smelting method of vanadium-titanium magnetite concentrate, and aims to solve the problems that the existing smelting method of vanadium-titanium magnetite concentrate cannot simultaneously meet the requirements of high vanadium recovery rate, low cost and low difficulty.
In order to achieve the above object, an aspect of the present invention provides a vanadium-titanium magnetite concentrate smelting system, including: the device comprises an oxidation roasting device, a reduction smelting device and an induction smelting device, wherein the oxidation roasting device is provided with a first charging hole, an oxidizing gas inlet and an oxidation roasting product outlet, and the first charging hole is used for adding a mixture of vanadium-titanium magnetite concentrate, a binder and water; the reduction smelting device is provided with a second charging hole, a reducing gas inlet and a metallized material outlet, and the second charging hole is communicated with the oxidizing roasting product outlet through a first charging pipeline; and the induction smelting device is provided with a third charging hole, a non-carbon-based reducing agent inlet, a shielding gas inlet and a vanadium-containing metal outlet, wherein the shielding gas inlet is used for introducing inert gas, and the third charging hole is communicated with the metalate material outlet and is used for further reducing the metalate material discharged by the reduction smelting device.
Further, the smelting system of above-mentioned vanadium titanium magnetite concentrate still includes the balling device, and the balling device is provided with raw materials entry and raw materials ball export, and the raw materials ball export communicates through the second feeding tube way with first charge door, and the raw materials entry is used for adding vanadium titanium magnetite concentrate, binder and water.
Furthermore, the reduction smelting device is a rotary kiln or a shaft furnace, and the induction smelting device is a medium-frequency induction furnace.
Further, the reduction smelting device is a fluidized bed reactor.
Further, the smelting system of the vanadium-titanium magnetite concentrate comprises a CO detection device, wherein the CO detection device is used for detecting the volume percentage content of CO in the reduction smelting device in real time so as to ensure that the volume percentage content of CO in the reduction smelting device is 10-50%.
Furthermore, the reduction smelting device is also provided with a reduction tail gas outlet, the oxidation roasting device is also provided with a heat supplementing port, the heat supplementing port is provided with a combustor, and the reduction tail gas outlet can be communicated with an inlet end of the combustor and is used for supplementing heat for the oxidation roasting device through combustion.
Further, the smelting system of the vanadium-titanium magnetite concentrate also comprises a temperature detection device, and the temperature detection device is used for monitoring the temperature in the induction smelting device in real time.
Further, the smelting system of vanadium titanium magnetite concentrate still includes drying device, and drying device sets up on the second charging pipeline.
Further, the smelting system of vanadium titanium magnetite concentrate still includes sieving mechanism, and sieving mechanism sets up on first charging conduit.
Another aspect of the present application also provides a method for smelting vanadium-titanium magnetite concentrate, where the method for smelting vanadium-titanium magnetite concentrate includes: mixing the vanadium-titanium magnetite concentrate, a binder and water, and then carrying out oxidizing roasting on the mixture and oxidizing gas to obtain an oxidizing roasting product; carrying out reduction smelting on the oxidation roasting product and reducing gas in a reducing atmosphere to obtain a metalized material; and in the presence of protective gas, carrying out induction smelting on the metal material and the non-carbon-based reducing agent in an induction smelting device to obtain vanadium-containing metal and titanium slag.
Further, the feeding temperature in the oxidizing roasting process is 110-200 ℃, and the discharging temperature is 900-1100 ℃; the temperature of reduction smelting is 700-800 ℃; the reaction temperature in the induction smelting device is 1600-1800 ℃, and the power is 60-10000 Hz.
Further, the content of the binder is 0.5-3% and the content of water is 5-10% in percentage by weight of the vanadium-titanium magnetite concentrate; preferably, the binder is selected from one or more of bentonite, organic binders and composite binders.
Further, the smelting method of the vanadium-titanium magnetite concentrate further comprises the following steps: mixing vanadium-titanium magnetite concentrate, a binder and water to form a raw material ball; oxidizing and roasting the raw material balls and oxidizing gas to obtain an oxidized and roasted product; preferably, the particle size of the oxidation ball is 10-30 mm; preferably, the oxidizing gas is selected from air or oxygen-enriched air.
Further, the reducing gas is one or more of hydrogen, CO and water gas.
Further, the non-carbon-based reducing agent is selected from metal simple substances and/or alloys; preferably, the elemental metal is selected from one or more of the group consisting of Si, Ca, Al, Mg, K, and Na; preferably, the alloy is selected from one or more of the group consisting of ferrosilicon, silicocalcium, magnesium aluminum, sodium-containing alloys or potassium-containing alloys; preferably, the amount of the non-carbon-based reducing agent is 2-10% of the vanadium-titanium magnetite concentrate by weight percentage.
Further, the product of the reduction smelting process also comprises a reduction tail gas, and the smelting method of the vanadium-titanium magnetite concentrate also comprises the following steps: burning the reduction tail gas to obtain combustion gas; the combustion gas is conveyed back to the oxidizing roasting process for heat compensation.
By applying the technical scheme of the invention, in the smelting system, the mixture of the vanadium-titanium magnetite concentrate, the binder and the water and the oxidizing gas are subjected to oxidizing roasting in the oxidizing roasting device, so that the mineral structure of the vanadium-titanium magnetite can be damaged, and the reduction performance of the vanadium-titanium magnetite can be improved. The obtained oxidation roasting product and reducing gas are subjected to reduction smelting in a reduction device, so that higher metal recovery rate can be ensured; in the presence of protective gas, when a metal material and a non-carbon-based reducing agent are subjected to reduction smelting in an induction smelting device, the reduction products are metal oxides, can replace a flux to improve the property of titanium slag, and is beneficial to improving the grade of the titanium slag; meanwhile, the iron and vanadium oxides in the slag are more easily reduced to metal phase in the induction smelting device, so that the recovery rate of the iron and vanadium is improved; the reduction product has no gas in the induction smelting process, the smoke gas amount is greatly reduced, the sealing is convenient, and the reoxidation caused by the introduction of air is reduced; and less carbon is introduced into the system, less nitrogen is involved, the splashing of a molten pool in the smelting process is inhibited, the generation of titanium carbonitride with a high melting point in the slag can be inhibited, and the melting performance of the titanium slag is improved. In addition, the smelting system also has the advantages of simple equipment, low cost, short process flow, good process continuity and the like.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is a schematic structural diagram illustrating a vanadium-titanium magnetite concentrate smelting system according to an exemplary embodiment of the present invention; and
fig. 2 shows a schematic flow chart of a smelting method of vanadium-titanium magnetite concentrate provided in embodiments 1 to 9 of the present invention.
Wherein the figures include the following reference numerals:
10. an oxidizing roasting device; 101. a first feed inlet; 102. a heat supplementing port; 20. a reduction smelting device; 30. an induction melting device; 40. a pelletizing device; 50. a CO detection device; 60. a temperature detection device; 70. a drying device; 80. a screening device.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background art, the existing smelting method of vanadium-titanium magnetite concentrate has the problems that the vanadium recovery rate is high, the cost is low and the difficulty is low. In order to solve the above technical problem, the present application provides a vanadium-titanium magnetite concentrate smelting system, as shown in fig. 1, the vanadium-titanium magnetite concentrate smelting system includes: the device comprises an oxidizing roasting device 10, a reduction smelting device 20 and an induction smelting device 30, wherein the oxidizing roasting device 10 is provided with a first feed opening 101, an oxidizing gas inlet and an oxidizing roasting product outlet, and the first feed opening 101 is used for adding a mixture of vanadium-titanium magnetite concentrate, a binder and water; the reduction smelting device 20 is provided with a second charging hole, a reducing gas inlet and a metallized material outlet, and the second charging hole is communicated with the oxidizing roasting product outlet through a first charging pipeline; and the induction smelting device 30 is provided with a third charging hole, a non-carbon-based reducing agent inlet, a shielding gas inlet and vanadium-containing metal, wherein the shielding gas inlet is used for introducing inert gas, and the third charging hole is communicated with a metal material outlet and is used for further reducing the metal material discharged by the reduction smelting device 20.
In the smelting system, the mixture of the vanadium-titanium magnetite concentrate, the binder and the water and the oxidizing gas are subjected to oxidizing roasting in the oxidizing roasting device 10, so that the mineral structure of the vanadium-titanium magnetite can be destroyed, and the reduction performance of the vanadium-titanium magnetite can be improved. The obtained oxidation roasting product and reducing gas are subjected to reduction smelting in a reduction device, so that higher metal recovery rate can be ensured; when the metallized material (metallized pellet or reduced powder briquette product) and the non-carbon-based reducing agent are subjected to reduction smelting in the induction smelting device 30 in the presence of protective gas, the reduced product is metal oxide, can replace a flux to improve the property of titanium slag, and is beneficial to improving the grade of the titanium slag; meanwhile, the oxides of iron and vanadium in the slag are more easily reduced to a metal phase in the induction smelting device 30, so that the recovery rate of the iron and the vanadium is improved; the reduction product has no gas in the induction smelting process, the smoke gas amount is greatly reduced, the sealing is convenient, and the reoxidation caused by the introduction of air is reduced; and less carbon is introduced into the system, less nitrogen is involved, the splashing of a molten pool in the smelting process is inhibited, the generation of titanium carbonitride with a high melting point in the slag can be inhibited, and the melting performance of the titanium slag is improved. In addition, the smelting system also has the advantages of simple equipment, low cost, short process flow, good process continuity and the like.
In a preferred embodiment, as shown in fig. 1, the vanadium-titanium magnetite concentrate smelting system further comprises a pelletizing device 40, the pelletizing device 40 is provided with a raw material inlet and a raw material ball outlet, the raw material ball outlet is communicated with the first feeding port 101 through a second feeding pipeline, and the raw material inlet is used for feeding vanadium-titanium magnetite concentrate, a binder and water.
The vanadium-titanium magnetite concentrate, the binder and water can be made into oxidizing acidic pellets by the pelletizing device 40, which is beneficial to improving the combustion efficiency of fuel and improving the reducible property of the raw material pellets.
In the above-described smelting system of vanadium-titanium magnetite concentrate, the reduction smelting device 20 and the induction smelting device 30 may be of the types commonly used in the art. In a preferred embodiment, the reduction smelting unit 20 is a rotary kiln or a shaft furnace and the induction smelting unit 30 is a medium frequency induction furnace. The reduction smelting devices 20 and the induction smelting device 30 are low in cost, and the process conditions of the reduction smelting process and the induction smelting process are not harsh, so that the selection of the devices is beneficial to further reducing the investment cost of a smelting system of vanadium-titanium magnetite concentrate, and meanwhile, higher metal recovery rate can be obtained. In another preferred embodiment, the above-mentioned reduction smelting unit 20 is a fluidized bed reactor. The fluidized bed reactor is adopted as the reduction smelting device 20, and the powder can be directly used for reaction, so that the pelletizing process is omitted. The reduced powder is discharged from the fluidized bed and then can be pressed into blocks and then enter the subsequent induction melting device 30.
In another preferred embodiment, the reduction smelting device 20 may be an electric reduction device, and the vanadium-titanium magnetite concentrate smelting system further includes a reducing agent supply device for supplying a reducing agent to the electric reduction device. The adoption of the electric reduction device as the reduction smelting device 20 is beneficial to improving the environmental protection of the process, and can more accurately control the temperature in the reduction process, thereby being beneficial to further improving the recovery efficiency of the vanadium element.
In order to further improve the recovery rate of the metal element, it is necessary to perform smelting in the reduction smelting device 20 in a reducing atmosphere. In order to ensure the smelting condition, preferably, as shown in fig. 1, the smelting system of the vanadium-titanium magnetite concentrate includes a CO detection device 50, and the CO detection device 50 is configured to detect the volume percentage content of CO in the reduction smelting device 20 in real time, so as to ensure that the volume percentage content of CO in the reduction smelting device 20 is 10% to 50%, such as 10%, 20%, 30%, and 40%.
When the heat source of the reduction smelting device 20 is provided for fuel combustion, the reducing gas is CO and H generated after natural gas or pulverized coal is not sufficiently combusted2Mainly, the off-gas of the reduction smelting unit 20 may be mixed with a part of the combustible gas. In order to better utilize the part of the tail gas, in a preferred embodiment, as shown in fig. 1, the reduction smelting device 20 is further provided with a reduction tail gas outlet, the oxidation roasting device 10 is further provided with a heat supplementing port 102, a burner is arranged at the heat supplementing port 102, and the reduction tail gas outlet can be communicated with an inlet end of the burner for supplementing heat to the oxidation roasting device 10 through combustion. The reduction tail gas outlet is communicated with the inlet end of the combustor, so that the reduction tail gas enters the oxidizing roasting device 10 after being combusted, and the chemical heat and the physical heat of the tail gas can be fully utilized, thereby improving the utilization rate of raw materials.
In a preferred embodiment, as shown in fig. 1, the vanadium-titanium magnetite concentrate smelting system further comprises a temperature detection device 60, and the temperature detection device 60 is used for monitoring the temperature in the induction smelting device 30 in real time. The temperature detection device 60 is arranged to detect the temperature in the induction melting device 30 in real time, so that the induction melting device can perform induction melting at a more appropriate temperature, the recovery rate of vanadium-containing metal is further improved, titanium carbonitride is further inhibited, and the grade of titanium slag is improved.
The reaction raw material may be dried and oxidatively roasted in the oxidizing roasting apparatus 10. In order to further improve the oxidized and burned efficiency of the oxidizing and roasting device 10, and thus further improve the recovery rate of the vanadium-containing metal, preferably, the smelting system of the vanadium-titanium magnetite concentrate further comprises a drying device 70, and the drying device 70 is arranged on the second feeding pipeline.
In a preferred embodiment, as shown in fig. 1, the vanadium-titanium magnetite concentrate smelting system further comprises a screening device 80, and the screening device 80 is arranged on the first feeding pipe. The screening device 80 is arranged on the first feeding pipeline and can screen the granularity of the raw material balls entering the oxidizing roasting unit so as to further improve the oxidizing roasting efficiency of the oxidizing roasting unit and further improve the recovery rate of vanadium-containing metal.
Another aspect of the present application also provides a method for smelting vanadium-titanium magnetite concentrate, where the method for smelting vanadium-titanium magnetite concentrate includes: mixing the vanadium-titanium magnetite concentrate, a binder and water, and then carrying out oxidizing roasting on the mixture and oxidizing gas to obtain an oxidizing roasting product; carrying out reduction smelting on the oxidation roasting product and reducing gas in a reducing atmosphere to obtain a metalized material; and in the presence of protective gas, carrying out induction smelting on the metal material and the non-carbon-based reducing agent in an induction smelting device 30 to obtain vanadium-containing metal and titanium slag.
In the smelting method, the mixture of the vanadium-titanium magnetite concentrate, the binder and the water and the oxidizing gas are subjected to oxidizing roasting, so that the mineral structure of the vanadium-titanium magnetite can be damaged, and the reduction performance of the vanadium-titanium magnetite can be improved. The obtained oxidation roasting product and reducing gas are subjected to reduction smelting, so that higher metal recovery rate can be ensured; in the presence of protective gas, when a metal material and a non-carbon-based reducing agent are subjected to induction melting in the induction melting device 30, the reduction products are metal oxides, can replace a flux to improve the property of titanium slag, and is beneficial to improving the grade of the titanium slag; meanwhile, the oxides of iron and vanadium in the slag are more easily reduced to a metal phase in the induction smelting device 30, so that the recovery rate of the iron and the vanadium is improved; the reduction product has no gas in the induction smelting process, the smoke gas amount is greatly reduced, the sealing is convenient, and the reoxidation caused by the introduction of air is reduced; and the carbon is introduced into the system less, the nitrogen is less involved, the splashing of a molten pool in the smelting process is inhibited, and the generation of titanium carbonitride with a high melting point in the slag can be inhibited, so that the melting performance of the titanium slag is improved. In addition, the smelting method also has the advantages of simple equipment, low cost, short process flow, good process continuity and the like.
Because the prior art does not record a treatment process combining the oxidation roasting, reduction smelting and induction smelting processes, the inventor finds that the process parameters of the three processes are respectively controlled in a certain range to be beneficial to improving the recovery rate of vanadium-containing metal and the grade of titanium slag through multi-angle grope, and in a preferred embodiment, the feeding temperature in the oxidation roasting process is 110-200 ℃, and the discharging temperature is 900-1100 ℃; the temperature of reduction smelting is 700-800 ℃; the reaction temperature in the induction melting device 30 is 1600-1800 ℃, and the power is 60-10000 Hz. Compared with other temperature ranges, the temperature of the oxidizing roasting process, the temperature of the reduction smelting and the temperature and power of the induction smelting are limited in the ranges, so that the recovery rate of the vanadium-containing metal is further improved.
Meanwhile, in the smelting process, the smelting time of each step can be adjusted according to the composition of the vanadium-titanium magnetite concentrate. Preferably, in the reduction smelting process, the time required for enabling the metallization rate of the metallization material to be 85-90% is taken as a standard; in the process of induction smelting, the time required for the content of the iron element in the titanium slag to be lower than 1 percent is taken as the standard.
The addition of the binder and the water is used for enabling the vanadium-titanium magnetite concentrate to form a blocky or spherical material so as to reduce dust pollution and improve the environmental protection property of the vanadium-titanium magnetite concentrate. In a preferred embodiment, the content of the binder is 0.5-3% and the content of the water is 5-10% by weight of the vanadium-titanium magnetite concentrate. Water can volatilize in the form of steam in the oxidizing roasting process, and most of the binder can be decomposed into CO and CO in the oxidizing roasting process2And water vapor, etc., so that the reaction raw material can form a porous substance at the point of addition. The use amount of the binder and the water is limited in the range, so that the roasting efficiency of the vanadium-titanium magnetite concentrate can be further improved, and the recovery rate of vanadium-containing metal is further improved.
The binder used in the above-mentioned smelting method may be one commonly used in the art. Preferably the binder is selected from one or more of bentonite, organic binders and composite binders.
In order to further improve the efficiency of oxidizing roasting, preferably, the method for smelting vanadium-titanium magnetite concentrate further comprises the following steps: mixing vanadium-titanium magnetite concentrate, a binder and water to form a raw material ball; and oxidizing and roasting the raw material balls and oxidizing gas to obtain an oxidizing and roasting product. More preferably, the granularity of the oxidation ball is 10-30 mm; the oxidizing gas is air or oxygen-enriched air.
In a preferred embodiment, the volume fraction of CO is 10-50% in the reduction smelting process. Compared with other ranges, the volume fraction of CO is beneficial to further improving the metal conversion rate in the reduction smelting process, thereby improving the recovery rate of vanadium-containing metal. The volume fraction of CO mentioned above is usually determined by measuring the volume fraction of CO in the reduced smelting off-gas.
The reducing gas used in the smelting process may be selected from the group commonly used in the art, for example, the reducing gas is one or more of hydrogen, CO and water gas.
In the smelting method of the vanadium-titanium magnetite concentrate, the used non-carbon-based reducing agent has the following characteristics: contains a component having a stronger reducibility than the simple substance carbon; the catalyst does not contain or contains lower carbon (less than 1 percent), and basically does not introduce carbon in the reduction process, so that the formation of titanium carbide in the deep reduction process can be avoided; the reduced product obtained after reduction by the reducing agent is a metal oxide, and the slag component can be adjusted. Components having the above characteristics may be used as the non-carbon based reducing agent in the present application. In a preferred embodiment, the metal elements include, but are not limited to, one or more of the group consisting of Si, Ca, Al, Mg, K, Na, and the like. In a preferred embodiment, the metal alloy includes, but is not limited to, one or more of the group consisting of silicon-iron alloy, silicon-calcium alloy, magnesium-aluminum alloy, sodium-containing alloy, or potassium-containing alloy. The metal simple substance can form metal oxide after being oxidized, including but not limited to CaO and SiO2、MgO、Al2O3、Na2O and K2O, or a combination thereof. The above oxides are directly introduced into the slag, and the slag components can be adjusted. Compared with carbon-based reducing agents, the reducing agents have stronger reducibility and better inhibiting effect on titanium carbonitride, thereby being beneficial to further improving the recovery of vanadium-containing metalThe rate and the grade of titanium slag. More preferably, the amount of the non-carbon-based reducing agent is 2-10% by weight of the vanadium-titanium magnetite concentrate.
In a preferred embodiment, the product of the reduction smelting process further comprises a reducing tail gas, and the smelting method of vanadium-titanium magnetite concentrate further comprises: burning the reduction tail gas to obtain combustion gas; the combustion gas is conveyed back to the oxidizing roasting process for heat compensation.
The reducing gas is CO and H generated after natural gas or pulverized coal is not fully combusted2The high-temperature mixed gas is mainly used, the tail gas enters the oxidizing roasting process after being combusted, and the chemical heat and the physical heat of the tail gas can be fully utilized, so that the utilization rate of the raw materials is improved.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
The composition of the vanadium-titanium magnetite concentrate used in the examples is shown in table 1 and the process flow is shown in figure 2.
TABLE 1
Example 1
Mixing and stirring vanadium titano-magnetite, bentonite and water according to the weight ratio of 100:0.5:5, and preparing into pellet particles with the particle size of 10-30 mm by using a pelletizer.
Drying, heating and roasting the green pellets in an oxidizing roasting device 10 (rotary kiln) to obtain raw material pellets (oxidizing pellets), wherein the temperature of a feed inlet of the rotary kiln is 200 ℃, the temperature of a discharge outlet of the rotary kiln is 1100 ℃, and the average residence time of the pellets in the oxidizing roasting device 10 is 30 min. The high-temperature reductive tail gas discharged by the reduction smelting device 20 (rotary kiln) is burnt to be used as a heat source, and a certain amount of natural gas is burnt to supplement heat. The oxidized pellets directly enter the reduction smelting device 20 of the next stage for reduction.
The reduction smelting device 20 used in the reduction stage is a rotary kiln, and the natural gas and the oxygen are insufficiently combusted according to the volume ratio of 2:1 to produceMainly with CO and H2Mainly, the metal is used as reducing gas to perform reduction smelting with the oxidizing pellets to obtain a metallized material, the metallization rate is 89.75%, wherein the temperature of a reducing gas inlet is 1100 ℃, the temperature of a reducing tail gas outlet is 800 ℃, the tail gas is reducing gas (the content of CO is 50%), and the tail gas returns to the previous stage of the oxidizing and roasting device 10 to be fully combusted for heat supply.
The metallized material and ferrosilicon (FeSi75-B) are placed in an induction smelting device 30 (induction furnace) together for further heating melting and deep reduction, the deep reduction temperature in the induction furnace is controlled to be 1600 ℃, the Fe content in the tailings is lower than 0.78 percent, vanadium-containing metal and titanium slag are obtained, the vanadium-containing metal contains 1.34 percent by weight, the silicon contains 2.97 percent by weight, the vanadium recovery rate is 80.78 percent by weight, and TiO in the titanium slag contains TiO2The content is 56.80 wt%, and the titanium slag can be further used as a raw material for preparing titanium dioxide by a sulfuric acid method.
790kg of metallized pellets can be produced by treating each ton of vanadium-titanium magnetite concentrate, 50kg of ferrosilicon alloy FeSi75-B is consumed, 588kg of vanadium-containing metal and 246kg of titanium slag are produced.
Example 2
Mixing and stirring vanadium titano-magnetite, an organic binder (sodium carboxymethylcellulose) and water according to a weight ratio of 100:3:10, and preparing into pellet particles with the particle size of 10-30 mm by using a pelletizer.
Drying, heating and roasting the green pellets in an oxidizing roasting device 10 (rotary kiln) to obtain raw material pellets (oxidizing pellets), wherein the temperature of a feed inlet of the rotary kiln is 150 ℃, the temperature of a discharge outlet of the rotary kiln is 1000 ℃, and the average residence time of the pellets in the oxidizing roasting device 10 is 60 min. The pulverized coal is combusted to supplement heat, and simultaneously, high-temperature tail gas discharged by the reduction smelting device 20 is introduced into the supplementary heat. The oxidized pellets directly enter the shaft furnace at the next stage for reduction.
The reduction smelting device 20 used in the reduction stage is a shaft furnace, high-temperature water gas produced by insufficient combustion of coal powder is used as reducing gas to perform reduction smelting with the oxidative pellets to obtain a metalized material, the metallization rate is 91.71%, the temperature of a reducing gas inlet is 1100 ℃, the temperature of a reduction tail gas outlet is 700 ℃, and the tail gas is reducing gas (wherein the content of CO is 10%). And the tail gas returns to the oxidation roasting device 10 at the previous section to be fully combusted for heat supply.
The metallized material and the silicon-calcium alloy (containing 30 percent of calcium) are placed in an induction smelting device 30 (an induction furnace) together for further heating melting and deep reduction, the deep reduction temperature in the induction furnace is controlled to be 1650-1700 ℃, the content of Fe in the tailings is lower than 0.5 percent, vanadium-containing metal and titanium slag are obtained, the vanadium-containing metal contains 1.47 weight percent of vanadium, the silicon contains 3.46 weight percent of vanadium, the recovery rate of vanadium is 87.18 weight percent, and TiO in the titanium slag contains TiO 78 weight percent2The content is 58.80 wt%, and the titanium slag can be further used as a raw material for preparing titanium dioxide by a sulfuric acid method.
780kg of metallized pellet can be produced by treating each ton of vanadium-titanium magnetite concentrate, 40kg of silicon-calcium alloy (containing 30 percent of calcium) is consumed, 578kg of vanadium-containing metal is produced, and 238kg of titanium slag is produced.
Example 3
Mixing and stirring vanadium titano-magnetite, an organic binder (sodium carboxymethylcellulose) and water according to a weight ratio of 100:3:10, and preparing into pellet particles with the particle size of 10-30 mm by using a pelletizer.
Drying, heating and roasting the green pellets in an oxidizing roasting device 10 (rotary kiln) to obtain raw material pellets (oxidizing pellets), wherein the temperature of a feed inlet of the rotary kiln is 200 ℃, the temperature of a discharge outlet of the rotary kiln is 900 ℃, and the average residence time of the pellets in the oxidizing roasting device 10 is 90 min. The coal dust is combusted to supplement heat, and simultaneously, the tail gas discharged by the reduction smelting device 20 is introduced into the supplementary heat. The oxidized pellets directly enter the reduction smelting device 20 of the next stage for reduction.
The reduction smelting device 20 used in the reduction stage is a shaft furnace, high-temperature water gas produced by insufficient combustion of coal powder is used as reduction gas and is subjected to reduction smelting with the oxidative pellets to obtain a metallized material, the metallization rate of the pellets is 85.21%, the temperature of a reducing gas inlet is 1100 ℃, the temperature of a reducing tail gas outlet is 700 ℃, and the tail gas is reducing gas (wherein the content of CO is 20%). The tail gas is introduced into the oxidation roasting device 10 at the previous section to be fully combusted for supplying heat.
The metallized material and aluminum particles are placed in an induction melting device 30 (induction furnace) together for further heating melting and deep reduction, and the induction furnace is controlledThe deep reduction temperature is 1750-1800 ℃, the content of Fe in the tailings is lower than 0.5 percent, vanadium-containing metal and titanium slag are obtained, the vanadium content in the vanadium-containing metal is 1.56 percent by weight, the recovery rate of vanadium is 89.23 percent by weight, and TiO in the titanium slag2The content is 54.37 wt%, and the titanium slag can be further used as a raw material for preparing titanium white by a sulfuric acid method.
795kg of metallized pellets can be produced by treating each ton of vanadium-titanium magnetite concentrate, 30kg of aluminum particles are consumed, 560kg of vanadium-containing metal is produced, and 260kg of titanium slag is produced.
Example 4
The differences from example 1 are: in the reduction smelting, the volume percentage of CO is 10 percent.
The vanadium contained in the vanadium-contained metal is 1.29wt percent, the recovery rate of the vanadium is 77.39wt percent, and TiO in the titanium slag2The content was 55.7 wt%.
Example 5
The differences from example 1 are: in the reduction smelting, the volume percentage of CO is 30 percent.
1.33 wt% of vanadium in the vanadium-containing metal, 79.79 wt% of vanadium recovery rate, and TiO in the titanium slag2The content was 56.1 wt%.
Example 6
The differences from example 1 are: in the reduction smelting, the volume percentage of CO is 20%.
1.31 wt% of vanadium in the vanadium-containing metal, the recovery rate of vanadium is 78.59 wt%, and TiO in the titanium slag2The content was 55.9 wt%.
Example 7
The differences from example 1 are: the usage amount of the ferrosilicon alloy is 1.5 percent based on the weight percentage of the vanadium-titanium magnetite concentrate.
1.25 wt% of vanadium in the vanadium-containing metal, the recovery rate of vanadium is 71.78 wt%, and TiO in the titanium slag2The content was 51.77 wt%.
Example 8
The differences from example 1 are: the non-carbon-based reducing agent accounts for 4 percent of the weight of the vanadium-titanium magnetite concentrate.
The vanadium contained in the vanadium-contained metal is 1.51wt percent, the recovery rate of the vanadium is 89.04wt percent, and TiO in the titanium slag2The content was 57.3 wt%.
Example 9
The differences from example 1 are: the non-carbon based reducing agent is 3% of metallic aluminum.
The vanadium contained in the vanadium-contained metal is 1.55 wt%, the recovery rate of the vanadium is 89.81 wt%, and TiO in the titanium slag2The content was 55.4 wt%.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
in the smelting system, the mixture of the vanadium-titanium magnetite concentrate, the binder and the water and the oxidizing gas are subjected to oxidizing roasting in the oxidizing roasting device, so that the mineral structure of the vanadium-titanium magnetite can be destroyed, and the reduction performance of the vanadium-titanium magnetite can be improved. The obtained oxidation roasting product and reducing gas are subjected to reduction smelting in a reduction device, so that higher metal recovery rate can be ensured; in the presence of protective gas, when the metallized material (metallized pellet or reduced powder briquetting product) and non-carbon-based reducing agent are subjected to reduction smelting in an induction smelting device, the reduced product is metal oxide, can replace a flux to improve the property of titanium slag, and is beneficial to improving the grade of the titanium slag; meanwhile, the iron and vanadium oxides in the slag are more easily reduced to metal phase in the induction smelting device, so that the recovery rate of the iron and vanadium is improved; the reduction product has no gas in the induction smelting process, the smoke gas amount is greatly reduced, the sealing is convenient, and the reoxidation caused by the introduction of air is reduced; and less carbon is introduced into the system, less nitrogen is involved, the splashing of a molten pool in the smelting process is inhibited, the generation of titanium carbonitride with a high melting point in the slag can be inhibited, and the melting performance of the titanium slag is improved. In addition, the smelting system also has the advantages of simple equipment, low cost, short process flow, good process continuity and the like.
It is noted that the terms first, second and the like in the description and in the claims of the present application are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments of the application described herein are, for example, capable of operation in sequences other than those described or illustrated herein.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (16)
1. The smelting system of vanadium-titanium magnetite concentrate is characterized by comprising the following components:
the device comprises an oxidizing roasting device (10), wherein the oxidizing roasting device (10) is provided with a first feeding hole (101), an oxidizing gas inlet and an oxidizing roasting product outlet, and the first feeding hole (101) is used for feeding a mixture of the vanadium-titanium magnetite concentrate, a binder and water;
the reduction smelting device (20), the reduction smelting device (20) is provided with a second charging hole, a reducing gas inlet and a metalized material outlet, and the second charging hole is communicated with the oxidizing roasting product outlet through a first charging pipeline; and
the induction smelting device (30) is provided with a third feed opening, a non-carbon-based reducing agent inlet, a protective gas inlet and a vanadium-containing metal outlet, wherein the protective gas inlet is used for introducing inert gas, and the third feed opening is communicated with the metal material outlet and used for further reducing the metal material discharged by the reduction smelting device (20).
2. The smelting system of vanadium-titanium magnetite concentrate according to claim 1, wherein the smelting system of vanadium-titanium magnetite concentrate further comprises a pelletizing device (40), the pelletizing device (40) is provided with a raw material inlet and a raw material ball outlet, the raw material ball outlet is communicated with the first charging port (101) through a second charging pipeline, and the raw material inlet is used for charging the vanadium-titanium magnetite concentrate, the binder and the water.
3. The smelting system of vanadium-titanium magnetite concentrate according to claim 1, wherein the reduction smelting device (20) is a rotary kiln or a shaft furnace, and the induction smelting device (30) is an intermediate frequency induction furnace.
4. The smelting system of vanadium-titanium magnetite concentrate according to claim 1, wherein the reduction smelting unit (20) is a fluidized bed reactor.
5. The smelting system of vanadium-titanium magnetite concentrate according to claim 3 or 4, wherein the smelting system of vanadium-titanium magnetite concentrate comprises a CO detection device (50), and the CO detection device (50) is used for detecting the volume percentage content of CO in the reduction smelting device (20) in real time so as to ensure that the volume percentage content of CO in the reduction smelting device (20) is 10-50%.
6. The smelting system of vanadium-titanium magnetite concentrate according to claim 5, wherein the reduction smelting device (20) is further provided with a reduction tail gas outlet, the oxidation roasting device (10) is further provided with a heat supplementing port (102), a burner is arranged at the heat supplementing port (102), and the reduction tail gas outlet can be communicated with an inlet end of the burner and used for supplementing heat to the oxidation roasting device (10) through combustion.
7. The smelting system of vanadium-titanium magnetite concentrate according to claim 1, further comprising a temperature detection device (60), wherein the temperature in the induction smelting device (30) is monitored in real time by the temperature detection device (60).
8. The smelting system of vanadium-titanium magnetite concentrate according to claim 2, wherein the smelting system of vanadium-titanium magnetite concentrate further comprises a drying device (70), and the drying device (70) is disposed on the second feeding line.
9. The smelting system of vanadium-titanium magnetite concentrate according to claim 1 or 2, further comprising a screening device (80), wherein the screening device (80) is disposed on the first charging line.
10. The smelting method of the vanadium-titanium magnetite concentrate is characterized by comprising the following steps:
mixing the vanadium-titanium magnetite concentrate, a binder and water, and then carrying out oxidizing roasting on the mixture and oxidizing gas to obtain an oxidizing roasting product;
in a reducing atmosphere, carrying out reduction smelting on the oxidation roasting product and reducing gas to obtain a metalized material; and
and in the presence of protective gas, the metal material and the non-carbon-based reducing agent are subjected to induction smelting in an induction smelting device (30) to obtain vanadium-containing metal and titanium slag.
11. The smelting method of the vanadium-titanium magnetite concentrate according to claim 10, wherein the feeding temperature in the oxidizing roasting process is 110 to 200 ℃, and the discharging temperature is 900 to 1100 ℃; the temperature of the reduction smelting is 700-800 ℃; the reaction temperature in the induction melting device (30) is 1600-1800 ℃, and the power is 60-10000 Hz.
12. The method for smelting vanadium-titanium magnetite concentrate according to claim 10 or 11, wherein the binder is used in an amount of 0.5 to 3% and the water is used in an amount of 5 to 10% by weight of the vanadium-titanium magnetite concentrate;
preferably, the binder is selected from one or more of bentonite, organic binders and composite binders.
13. The method for smelting vanadium-titanium magnetite concentrate according to claim 12, wherein the method for smelting vanadium-titanium magnetite concentrate further comprises:
mixing the vanadium-titanium magnetite concentrate, a binder and water to form a raw material ball;
oxidizing and roasting the raw material balls and the oxidizing gas to obtain an oxidized and roasted product;
preferably, the particle size of the oxidation ball is 10-30 mm;
preferably, the oxidizing gas is selected from air or oxygen-enriched air.
14. The method for smelting vanadium-titanium magnetite concentrate according to claim 10, wherein the reducing gas is one or more of hydrogen, CO and water gas.
15. The method for smelting vanadium-titanium magnetite concentrate according to any one of claims 10 to 14, wherein the non-carbon based reducing agent is selected from the group consisting of elemental metals and/or alloys;
preferably, the elemental metal is selected from one or more of the group consisting of Si, Ca, Al, Mg, K and Na;
preferably, the alloy is selected from one or more of the group consisting of silicon-iron alloy, silicon-calcium alloy, magnesium-aluminum alloy, sodium-containing alloy or potassium-containing alloy;
preferably, the amount of the non-carbon-based reducing agent is 2-10% by weight of the vanadium-titanium magnetite concentrate.
16. The method for smelting vanadium-titanium magnetite concentrate according to claim 15, wherein the product of the reductive smelting process further comprises a reductive tail gas, and the method for smelting vanadium-titanium magnetite concentrate further comprises: burning the reduction tail gas to obtain combustion gas; and conveying the combustion gas back to the oxidizing roasting process to supplement heat.
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