CN113293283A - Reduction method of vanadium titano-magnetite - Google Patents
Reduction method of vanadium titano-magnetite Download PDFInfo
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- CN113293283A CN113293283A CN202110609184.1A CN202110609184A CN113293283A CN 113293283 A CN113293283 A CN 113293283A CN 202110609184 A CN202110609184 A CN 202110609184A CN 113293283 A CN113293283 A CN 113293283A
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- magnetite
- pellets
- vanadium
- vanadium titano
- reducing agent
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 61
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 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 49
- 238000000034 method Methods 0.000 title claims abstract description 39
- 230000009467 reduction Effects 0.000 title claims abstract description 21
- 239000008188 pellet Substances 0.000 claims abstract description 77
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052742 iron Inorganic materials 0.000 claims abstract description 21
- 239000011230 binding agent Substances 0.000 claims abstract description 19
- 239000010936 titanium Substances 0.000 claims abstract description 19
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002893 slag Substances 0.000 claims abstract description 18
- 239000000654 additive Substances 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002844 melting Methods 0.000 claims abstract description 8
- 230000008018 melting Effects 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000000605 extraction Methods 0.000 claims abstract description 6
- 238000007598 dipping method Methods 0.000 claims description 18
- 238000010791 quenching Methods 0.000 claims description 16
- 230000000171 quenching effect Effects 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 14
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000571 coke Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000012141 concentrate Substances 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- 239000003245 coal Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 150000003682 vanadium compounds Chemical class 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract description 3
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 abstract description 3
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000166 zirconium phosphate Inorganic materials 0.000 abstract description 3
- 238000007654 immersion Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 8
- 238000003723 Smelting Methods 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000005453 pelletization Methods 0.000 description 4
- 238000011946 reduction process Methods 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- JCDAAXRCMMPNBO-UHFFFAOYSA-N iron(3+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Ti+4].[Fe+3].[Fe+3] JCDAAXRCMMPNBO-UHFFFAOYSA-N 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- -1 titanium metals Chemical class 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
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- 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
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0006—Making spongy iron or liquid steel, by direct processes obtaining iron or steel in a molten state
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0066—Preliminary conditioning of the solid carbonaceous reductant
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0086—Conditioning, transformation of reduced iron ores
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/12—Making spongy iron or liquid steel, by direct processes in electric 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
- C22B1/02—Roasting processes
-
- 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
- C22B1/242—Binding; Briquetting ; Granulating with binders
-
- 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
- C22B1/26—Cooling of roasted, sintered, or agglomerated ores
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
-
- 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
- C22B34/10—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
- C22B34/1213—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 wet processes, e.g. using leaching methods or flotation techniques
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- 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
- C22B34/1218—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 obtaining titanium or titanium compounds from ores or scrap by dry processes
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- 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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- 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
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for reducing vanadium titano-magnetite, and relates to the technical field of vanadium titano-magnetite. The vanadium titano-magnetite is evenly mixed with a reducing agent, an additive and a binder, then the mixture is pelletized and then is oxidized and roasted to oxidize low-valence vanadium compounds which are insoluble in water in the vanadium titano-magnetite to become high-valence vanadate (sodium vanadate) which is easily dissolved in water, and the roasting slag is obtained by water leachingVanadium-containing solution, vanadium extraction and calcination to obtain V2O5And (4) finishing, namely treating the pellets after water immersion, putting the pellets into reduction equipment again, and performing direct reduction-electric furnace melting separation. The molten iron and the titanium slag are separated, so that the recovery and the utilization of three valuable metals of iron, titanium and vanadium are realized.
Description
Technical Field
The invention relates to the technical field of vanadium titano-magnetite, in particular to a reduction method of vanadium titano-magnetite.
Background
Vanadium titano-magnetite is a kind of complex symbiotic ore of many metallic elements, besides iron, it also contains more than 30 valuable elements of titanium, vanadium, antimony, tin, nickel, copper, cadmium, cobalt, etc., it is an important iron-containing resource, and at the same time, most vanadium products are also smelted from vanadium titano-magnetite. Therefore, the development and the reduction utilization of the vanadium titano-magnetite have great economic value.
At present, a more mature process for smelting vanadium-titanium magnetite is a blast furnace process, the method comprises the steps of selecting concentrate from the vanadium-titanium magnetite by a mineral separation method, pelletizing, sintering and other procedures to obtain vanadium-titanium magnetite pellets, finally sending the pellets into a blast furnace for smelting, reducing most of vanadium into molten iron in a high-temperature reduction state to form vanadium-containing molten iron, almost all titanium enters blast furnace slag, pouring the vanadium-containing molten iron into a converter for blowing, so that most of vanadium is oxidized into slag phase to obtain semisteel and vanadium-containing steel slag, decarburizing the semisteel in the converter again to form molten steel, and the molten steel can be used for manufacturing products such as alloy steel and the like, and the vanadium-containing steel slag can be processed into vanadium-containing products. The main advantages of the blast furnace method for processing the vanadium-titanium magnetite ore are high production efficiency and large scale; the main disadvantages are two-fold: firstly, generating a large amount of high titanium blast furnace slag; secondly, the production process flow is long, coke is required to be used as a reducing agent, the coking environment pollution is serious, and the production cost is increased, so that the development of a blast furnace method is limited. Meanwhile, other problems exist in the smelting process of the blast furnace method, slag becomes sticky, iron is carried in the slag, and the like, and the utilization of the vanadium titano-magnetite is more or less hindered under the conditions. The vanadium-titanium magnetite smelting in blast furnace has high production efficiency and large scale, but blast furnace titanium slag (TiO)2Grade of 22% -25%), the titanium resource in the vanadium titano-magnetite is not available because of low activity after high temperature treatment, so the comprehensive utilization rate of the vanadium titano-magnetite treated by the process is not high. Therefore, the efficient non-blast furnace smelting technology is provided for efficiently and comprehensively utilizing iron, vanadium and titanium resources in the vanadium-titanium magnetite concentrate to reduce the vanadium-titaniumResearch focus on magnetite concentrates.
Disclosure of Invention
The invention aims to provide a method for reducing vanadium-titanium magnetite, which comprises the steps of uniformly mixing the vanadium-titanium magnetite with a reducing agent, an additive and a binder, pelletizing, oxidizing and roasting in a microwave reactor to oxidize low-valence water-insoluble vanadium compounds in the vanadium-titanium magnetite to obtain high-valence vanadate (sodium vanadate) which is easily dissolved in water, leaching roasted slag with water to obtain a vanadium-containing solution, extracting vanadium, calcining and the like to obtain V2O5And (4) finishing, namely treating the pellets after water immersion, putting the pellets into reduction equipment again, and performing direct reduction-electric furnace melting separation. The molten iron and the titanium slag are separated, so that the recovery and the utilization of three valuable metals of iron, titanium and vanadium are realized.
A method for reducing vanadium titano-magnetite comprises the following steps:
(1) uniformly mixing a reducing agent, vanadium-titanium magnetite, an additive and a binder, adding water to prepare pellets, and then carrying out microwave oxidation roasting;
(2) transferring the pellets subjected to microwave oxidation roasting into water for quenching and dipping to obtain dipping liquid and pellets;
(3) carrying out vanadium extraction and conventional calcination on the steeped steeping liquor after quenching and steeping to obtain a vanadium pentoxide finished product;
(4) the pellets after quenching and dipping are divided into two parts, the first part of pellets are dried, ground and crushed, and then are made into slurry with a reducing agent and a binder added with water, and the second part of pellets are subjected to heat treatment after being wrapped again to obtain secondary pellets;
(5) and separating molten iron and titanium slag from the secondary pellets by direct reduction-electric furnace melting.
Further, in the step (1): the mixing mass ratio of the vanadium titano-magnetite, the reducing agent, the additive and the binder is 100 to (5-10) to (10-15) to (2-5).
Further, the vanadium titano-magnetite in the step (1) is vanadium titano-magnetite concentrate, the reducing agent is coal powder, the additive is sodium hydroxide, and the binder is one or more of bentonite, polyvinyl alcohol and starch solution; pellet size: an ellipsoid with a major diameter of 10-20mm and a minor diameter of 8-15 mm.
Further, the reducing agent, the vanadium titano-magnetite, the additive and the binder in the step (1) are mixed uniformly and then ball-milled to be below 100 meshes, and water is added to prepare the pellets.
Further, the microwave oxidizing roasting temperature is 700-.
Furthermore, the water temperature in the quenching and dipping process in the step (2) is not more than 50 ℃, and the quenching and dipping time is 1-3 h.
Further, in the step (3), the mass ratio of the first part of pellets to the second part of pellets is (3-5) to (10-12).
Further, the grinding and crushing in the step (3) is specifically ultra-fine grinding and crushing to a particle size of less than 20 μm.
Further, in the step (3), the mixing mass ratio of the first part of pellets to the reducing agent to the binder is 100: 5-10: 1-2, and the reducing agent is coke; the wrapping thickness is 3-5 mm.
Further, the heat treatment in the step (3) is heat treatment at 500 ℃ for 1-2h and 300-.
Compared with the prior art, the invention has the beneficial effects that:
the invention mixes the sodium salt and the vanadium-titanium magnetite concentrate obtained after mineral dressing evenly, then carries out microwave oxidation roasting in a microwave reactor after pelletizing and sintering, oxidizes the low-valence vanadium compound which is not soluble in water in the vanadium-titanium magnetite to become high-valence vanadate (sodium vanadate) which is easily soluble in water, carries out water leaching on the roasting slag to obtain vanadium-containing solution, and then carries out the steps of vanadium extraction, calcination and the like to obtain V2O5And (4) putting the soaked residual balls into reduction equipment again, and melting and separating the residual balls through a direct reduction-electric furnace. The molten iron and the titanium slag are separated, so that the recovery and the utilization of three valuable metals of iron, titanium and vanadium are realized.
However, in the process, the pellets need to be subjected to water leaching to obtain a vanadium solution and then reduced, so that the mechanical strength of the leached pellets is reduced, and the pellets are likely to be crushed and formed into rings when reduced again in a furnace. Furthermore, the invention also supplies reducing agent and adhesive again after drying and grinding a part of the rest pellets and adds water to make slurry, and wraps the second part pellets again to make secondary pellets, the dried and crushed pellet material can fill up the pore structure generated in the pellet in the oxidation process, the secondary pellets can be well bonded with the crushed pellet material after heat treatment at 300 ℃ and 500 ℃ for 1-2h, further the strength and the adhesiveness of the pellet material are enhanced, the layering phenomenon in the reduction process is avoided, and the technical problems of pellet crushing, ring formation and the like in the reduction process are fundamentally avoided.
Meanwhile, in the preferred technical scheme of the invention, coal powder is further limited to be used as a reducing agent in the pellet preparation process in the step (1), coke is used as a reducing agent in the secondary pellet preparation process in the step (3), so that the reducing agent in the reduced pellet is distributed in a core-shell structure, volatile components generated when coal powder is used as the reducing agent in the pellet as a propping agent are discharged through micropores based on the characteristics of high porosity and high strength of the coke, the surface of the pellet reaches the reduction temperature for reduction reaction at first in the reduction process, the internal temperature of the pellet is relatively low, organic matters such as tar and alkane in the coal powder start to volatilize and separate out and seep out along the pores of the coke on the outer shell layer of the pellet, and pyrolysis reaction is generated along with the increase of the temperature in the process to generate products such as active carbon and hydrogen with strong reducibility, the iron titanate which is attached to the pores of the pellets and participates in the reduction reaction of metal oxides in the pellets, and the iron titanate which is difficult to reduce can be directly reduced at the temperature of 900-1000 ℃ based on the generation of hydrogen in the pellet structure, so that the formation of an iron titanate liquid phase caused by the high reduction temperature of ilmenite in the reduction process is avoided, and the technical purpose of efficiently and quickly reducing the vanadium titano-magnetite to recover iron, titanium and vanadium therein is realized.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The steps of vanadium extraction from the impregnation liquid and calcination, and the reduction-electric furnace melting separation steps in the following examples of the present invention all employ conventional operations in the art, which are conventional technical means of those skilled in the art, and are not described herein again.
Example 1
(1) Uniformly mixing vanadium-titanium magnetite (concentrate), a reducing agent (coal powder), an additive (sodium hydroxide) and a binder (polyvinyl alcohol) according to the mass ratio of 100: 8: 12: 4, adding water to prepare pellets (an ellipsoid type with the length diameter of about 15mm and the short diameter of about 10 mm), and then carrying out microwave oxidation roasting for 2 hours at the temperature of 900 ℃;
(2) transferring the pellets subjected to microwave oxidation roasting into water for quenching and dipping for 2 hours, wherein the water temperature is not higher than 50 ℃ in the process;
(3) carrying out vanadium extraction and calcination on the steeped dipping solution after quenching dipping to obtain a vanadium pentoxide finished product;
the pellets subjected to quenching impregnation are divided into two parts, wherein the first part of pellets (30 percent of the total mass) are dried, ground and crushed, then are uniformly mixed with a reducing agent (coke) and a binder (polyvinyl alcohol) according to the mass ratio of 100: 10: 2, then water is added to prepare slurry, the slurry is put into the second part of pellets, the second part of pellets are recoated (the coating thickness is 5mm), and then the temperature is increased to 500 ℃ at the speed of 10 ℃/min for heat treatment for 1h to prepare secondary pellets;
(4) and separating molten iron and titanium slag from the secondary pellets by direct reduction-electric furnace melting.
Example 2
The difference from the example 1 is that after the raw materials in the step (1) are mixed uniformly, ball milling and 100-mesh sieving are carried out before ball making.
Example 3
The difference from example 2 is that the first part of the pellets in step (3) is finely ground to a particle size of 20 μm or less after being uniformly mixed with the reducing agent and the binder.
Example 4
The difference from example 3 is that the quenching and dipping process is carried out under ultrasonic conditions.
Example 5
The difference from example 3 is that, in step (3), the process of recoating the second pellet after the first pellet is dried, ground and crushed and is made into slurry with a reducing agent and a binder and water is repeated for 3 times, and the specific process is as follows:
and (3) placing the second part of pellets into the slurry, dipping for 10s, taking out, drying at 60 ℃, dipping again for 10s, taking out, drying at 60 ℃, heating to 500 ℃ at 10 ℃/min after drying at 60 ℃, and carrying out heat treatment for 1h to obtain the secondary pellets.
Example 6
The difference from example 3 is that coke is used as the reducing agent in both step (1) and step (2).
Example 7
The difference from example 1 is that coal dust is used as the reducing agent in both step (1) and step (2).
Example 8
The difference from example 1 is that the heat treatment step in step (3) is omitted and baking at 60 ℃ is carried out instead.
Example 9
The difference from example 1 is that the pellets dipped in the quenching step (3) are dried, ground and crushed, then mixed with a reducing agent (coke) and a binder (polyvinyl alcohol) uniformly according to the mass ratio of 100: 10: 2, added with water to prepare pellets again, and heated to 500 ℃ at a speed of 10 ℃/min for heat treatment for 1h to prepare secondary pellets.
Example 10
The difference from the example 1 is that the ball milling and crushing treatment of the residual pellets in the step (3) is not carried out, and the residual pellets after quenching and dipping are directly subjected to reduction-electric furnace melting to separate molten iron and titanium slag.
Effect verification
The performance low-temperature reduction degradation performance of the secondary pellets prepared in the examples 1 to 10 is determined according to the standard GB/T13242-2017, and the specific method is as follows: statically reducing the samples of examples 1-10 in a fixed bed at 500 ℃ by using a reducing gas consisting of carbon monoxide, carbon dioxide and nitrogen in a volume ratio of 2: 6, reducing the samples at a constant temperature for 60min, cooling the samples, transferring the samples into a rotary drum after 300 turns, taking out the samples, classifying the samples by using a square-hole sieve with the diameter of 6.3mm, 3.15mm and 0.5mm, respectively calculating the content of each fraction, and expressing the low-temperature reduction degradation performance of the iron ore by using RDI (RDI), wherein the experimental results are shown in Table 1;
wherein:
RDI+6.3＝mD1/mD0×100％；
RDI+3.15＝(mD1+mD2)/mD0×100％；
RDI+0.5＝[mD0-(mD1+mD2+mD3)]/mD0×100％；
wherein m isD0The mass of the sample before the rotary drum is reduced;
mD1the mass of the sample left on the 6.30mm sieve;
mD2the mass of the sample left on the 3.15mm sieve;
mD3the mass of the sample left on the 0.5mm sieve.
The final recovery rates of iron, vanadium and titanium in examples 1-10 were counted and the results are shown in Table 1.
TABLE 1
The data in table 1 show that the ball milling pulverization treatment of the raw materials before pelletizing is beneficial to improving the strength of the residual pellets, and meanwhile, the pulverized materials are more easily subjected to oxidation and reduction reactions, so that the final recovery rate of iron, vanadium and titanium metals is improved; meanwhile, the ultrasonic operation is supplemented in the cold water dipping process, so that the vanadium compound subjected to reaction is rapidly dissolved out, and the recovery rate of vanadium is improved. Furthermore, the thorny pellet is prepared by adopting a three-time impregnation wrapping mode, so that the materials are combined more tightly, the strength is higher, and the technical problem of pulverization of the pellet is avoided. And the two layers of the pellets respectively adopt different reducing agents, so that the mutual synergistic effect can be achieved, and the metal recovery rate is higher.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A method for reducing vanadium titano-magnetite is characterized by comprising the following steps:
(1) uniformly mixing a reducing agent, vanadium-titanium magnetite, an additive and a binder, adding water to prepare pellets, and then carrying out microwave oxidation roasting;
(2) transferring the pellets subjected to microwave oxidation roasting into water for quenching and dipping to obtain dipping liquid and dipped pellets;
(3) carrying out vanadium extraction and calcination on the steeped steeping liquor after quenching and steeping to obtain a vanadium pentoxide finished product;
(4) the pellets after quenching and dipping are divided into two parts, the first part of pellets are dried, ground and crushed, and then are made into slurry with a reducing agent and a binder added with water, and the second part of pellets are subjected to heat treatment after being wrapped again to obtain secondary pellets;
(5) and separating molten iron and titanium slag from the secondary pellets by direct reduction-electric furnace melting.
2. The reduction method of vanadium titano-magnetite according to claim 1, characterized in that in step (1): the mixing mass ratio of the vanadium titano-magnetite, the reducing agent, the additive and the binder is 100: (5-10): (10-15): (2-5).
3. The reduction method of the vanadium titano-magnetite according to claim 1, characterized in that the vanadium titano-magnetite in the step (1) is vanadium titano-magnetite concentrate, the reducing agent is coal powder, the additive is sodium hydroxide, and the binder is one or more of bentonite, polyvinyl alcohol and starch solution; pellet size: an ellipsoid with a major diameter of 10-20mm and a minor diameter of 8-15 mm.
4. The reduction method of vanadium titano-magnetite according to claim 1, characterized in that in step (1), the reducing agent, vanadium titano-magnetite, additive and binder are mixed uniformly, ball milled to below 100 mesh and then water is added to make into pellets.
5. The reduction method of vanadium titano-magnetite as claimed in claim 1, characterized in that microwave oxidation roasting temperature is 700-.
6. The reduction method of vanadium titano-magnetite according to claim 1, characterized in that the water temperature in the quenching and dipping process in the step (2) is not more than 50 ℃, and the quenching and dipping time is 1-3 h.
7. The reduction method of vanadium titano-magnetite according to claim 1, characterized in that the mass ratio of the first part of pellets to the second part of pellets in the step (3) is (3-5) to (10-12).
8. The reduction method of vanadium titano-magnetite according to claim 1, characterized in that the grinding pulverization in the step (3) is ultra-fine grinding to particle size of 20 μm or less.
9. The reduction method of vanadium titano-magnetite according to claim 1, characterized in that in the step (3), the mixing mass ratio of the first part of pellets to the reducing agent and the binder is 100: (5-10) to (1-2), wherein the reducing agent is coke.
10. The reduction method of vanadium titano-magnetite according to claim 1, characterized in that the heat treatment in step (3) is a heat treatment at 5-10 ℃/min up to 300-500 ℃ for 1-2 h.
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| CN102690944A (en) * | 2012-06-19 | 2012-09-26 | 北京神雾环境能源科技集团股份有限公司 | Method for comprehensively recovering vanadium, titanium and iron from high-vanadium vanadium titano-magnetite |
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