CN114807591A - Method for preparing high-quality titanium-rich material by deeply removing impurities from ilmenite - Google Patents
Method for preparing high-quality titanium-rich material by deeply removing impurities from ilmenite Download PDFInfo
- Publication number
- CN114807591A CN114807591A CN202210258697.7A CN202210258697A CN114807591A CN 114807591 A CN114807591 A CN 114807591A CN 202210258697 A CN202210258697 A CN 202210258697A CN 114807591 A CN114807591 A CN 114807591A
- Authority
- CN
- China
- Prior art keywords
- leaching
- ilmenite
- rich material
- titanium
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 53
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000010936 titanium Substances 0.000 title claims abstract description 46
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 30
- 239000012535 impurity Substances 0.000 title claims abstract description 28
- 238000002386 leaching Methods 0.000 claims abstract description 71
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 55
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 36
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052742 iron Inorganic materials 0.000 claims abstract description 23
- 238000005260 corrosion Methods 0.000 claims abstract description 20
- 230000007797 corrosion Effects 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 238000006722 reduction reaction Methods 0.000 claims abstract description 15
- 239000002893 slag Substances 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 238000001465 metallisation Methods 0.000 claims abstract description 8
- 238000004064 recycling Methods 0.000 claims abstract description 6
- 239000002002 slurry Substances 0.000 claims abstract description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 28
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 230000005484 gravity Effects 0.000 claims description 4
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 abstract 1
- 239000012141 concentrate Substances 0.000 description 18
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 16
- 229910052749 magnesium Inorganic materials 0.000 description 16
- 239000011777 magnesium Substances 0.000 description 16
- 239000002994 raw material Substances 0.000 description 15
- 238000005660 chlorination reaction Methods 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 229910004298 SiO 2 Inorganic materials 0.000 description 10
- 239000004408 titanium dioxide Substances 0.000 description 9
- 238000009835 boiling Methods 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 4
- 229910001634 calcium fluoride Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 4
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 238000013459 approach Methods 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910004261 CaF 2 Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 2
- 229910004762 CaSiO Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017625 MgSiO Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
-
- 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
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
- C22B3/14—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions containing ammonia or ammonium salts
-
- 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
-
- 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
- C22B34/1236—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 wet processes, e.g. by leaching
- C22B34/124—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 wet processes, e.g. by leaching using acidic solutions or liquors
- C22B34/1245—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 wet processes, e.g. by leaching using acidic solutions or liquors containing a halogen ion as active agent
-
- 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
- C22B34/1236—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 wet processes, e.g. by leaching
- C22B34/1254—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 wet processes, e.g. by leaching using basic solutions or liquors
-
- 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases
Abstract
The invention discloses a method for preparing a high-quality titanium-rich material by deeply removing impurities from ilmenite, which belongs to the technical field of titanium resource utilization and comprises the following steps: s1, carrying out reduction reaction on ilmenite to convert the ilmenite into metallic iron and rutile, wherein the metallization rate of the iron is more than 90%; s2, carrying out a corrosion reaction on the reduced ilmenite obtained in the step S1, and reselecting and separating a corrosion product through a table concentrator to obtain a primary titanium-rich material and hydrated iron oxide red mud for preparing iron red; s3, carrying out ammonium fluoride leaching reaction on the primary titanium-rich material obtained in the step S2, carrying out solid-liquid separation on leached slurry to obtain leaching slag and leaching liquid, and recycling the leaching liquid after impurity removal; s4, carrying out hydrochloric acid leaching reaction on the leaching residue obtained in the step S3, carrying out solid-liquid separation on the leached slurry to obtain leaching residue and leaching liquid, and recycling the leaching liquid after impurity removal; s5, calcining the leached slag obtained in the step S4 to obtain a high-quality titanium-rich material product. The invention has reasonable process flow design, simple operation and no environmental pollution.
Description
Technical Field
The invention belongs to the technical field of titanium resource utilization, and relates to a method for preparing a high-quality titanium-rich material by deeply removing impurities from ilmenite.
Background
More than 90% of titanium resources exist in the Panxi area in Sichuan, and mainly exist in the form of vanadium titano-magnetite. At present, two titanium-containing products of vanadium-titanium magnetite concentrate and ilmenite concentrate can be obtained after beneficiation treatment, wherein 48% of titanium enters the ilmenite concentrate. At present, vanadium-titanium magnetite concentrate can only be smelted by a blast furnace method after being matched with common ore, and titanium element can not be directly utilized when entering blast furnace titanium slag. The contents of calcium and magnesium impurities in the Panxi ilmenite concentrate are high, the concentrate can only be used as a sulfuric acid process titanium dioxide raw material at present, and two approaches are mainly provided, wherein one approach is that the ilmenite concentrate is directly used as a sulfuric acid process titanium dioxide raw material, and the other approach is that the acid-soluble titanium slag is obtained after the ilmenite concentrate is smelted and separated from iron by an electric furnace and is used as the sulfuric acid process titanium dioxide raw material.
The sulfuric acid process titanium dioxide belongs to a medium and low-end titanium product, a large amount of copperas and waste acid generated in the production process of the sulfuric acid process titanium dioxide are difficult to solve, serious pollution is caused to the environment, the capacity of the sulfuric acid process titanium dioxide in China accounts for about 95% of the capacity of the titanium dioxide in China, and the production of the titanium dioxide in China becomes a serious pollution industry. Titanium dioxide produced by chlorination process belongs to high-end titanium products, and the main chlorination processes at present mainly comprise a boiling chlorination process and a molten salt chlorination process. The waste residue amount of the molten salt chlorination method is large, the waste salt recovery process is complex and can cause environmental pollution, and although the impurity content of the raw materials is not specified clearly, the impurity content of the raw materials is high, the waste residue amount is large. Calcium and magnesium impurities are formed and are difficult to volatilize in the boiling chlorination processThe generated calcium chloride and magnesium chloride are easy to cause the blockage of a boiling chlorination bed, so the boiling chlorination method adopts high-quality titanium-rich materials as raw materials and requires TiO 2 >90％，(CaO+MgO)<1.5 percent. Although the electric furnace smelting method can effectively recover the iron element in the ilmenite concentrate, a large amount of magnesium, aluminum and iron impurities are dissolved in the black titanium ore in a solid solution manner in the electric furnace smelting process, and the complex black titanium ore solid solution structure is stable and not easy to decompose, so that the impurity elements in the titanium slag are difficult to effectively remove, and therefore, the electric furnace titanium slag cannot be directly used as a raw material for a chlorination process. The ilmenite concentrate contains a large amount of iron elements, and the generation of a titanium black phase is avoided while the iron elements are recovered, so that the titanium-rich material obtained after the separation of the ilmenite is subjected to deep impurity removal and then is used as a raw material for a chlorination process.
Disclosure of Invention
Aiming at the problem that ilmenite concentrate can not be directly used as a raw material in a chlorination process, the invention aims to provide a method for preparing a high-quality titanium-rich material by deeply removing impurities from ilmenite, and the method has the advantages of reasonable process flow design, simplicity in operation and no environmental pollution.
The invention provides the following technical scheme: a method for preparing a high-quality titanium-rich material by deeply removing impurities from ilmenite comprises the following steps:
s1, carrying out reduction reaction on ilmenite to obtain reduced ilmenite;
s2, carrying out a rust reaction on the reduced ilmenite obtained in the step S1, and carrying out gravity separation on a rust product through a table concentrator to obtain a primary titanium-rich material and hydrated iron oxide red mud for preparing iron oxide red;
s3, performing ammonium fluoride leaching reaction on the primary titanium-rich material obtained in the step S2, performing solid-liquid separation on leached slurry to obtain leaching slag and leaching liquid, and recycling the leaching liquid after impurity removal;
s4, carrying out hydrochloric acid leaching reaction on the leaching residue obtained in the step S3, carrying out solid-liquid separation on the leached slurry to obtain leaching residue and leaching liquid, and recycling the leaching liquid after impurity removal;
s5, calcining the leached slag obtained in the step S4 to obtain a high-quality titanium-rich material product.
In the reduction reaction, the main phases in the reduced ilmenite are metallic iron, magnesium-containing ilmenite, rutile and silicate.
In the corrosion reaction, the metallic iron is oxidized and converted into iron oxide, and the iron oxide is separated by gravity separation of a table concentrator. The main phases of the iron ore concentrate are iron oxide, and the main phases of the primary titanium-rich material are magnesium-containing ilmenite, rutile and silicate.
In the ammonium fluoride leaching process, silicate reacts with ammonium fluoride, silicon element enters leaching liquid, and elements such as calcium, magnesium, aluminum and the like are left in leaching slag in the form of fluoride. The main phases of the leaching slag comprise magnesium-containing ilmenite, rutile, calcium fluoride, magnesium fluoride, ammonium fluoroaluminate and the like.
In the hydrochloric acid leaching reaction, magnesium-containing ilmenite, calcium fluoride, magnesium fluoride, ammonium fluoroaluminate and the like react with hydrochloric acid, and elements such as calcium, magnesium, aluminum and the like are dissolved and then enter the leaching solution.
Preferably, in step S1, the reduction reaction uses a mixed gas of carbon monoxide and hydrogen as a reducing agent, the concentration of carbon monoxide is 0-40%, the concentration of hydrogen is 60-100%, the reduction temperature is 500-1150 ℃, the reduction time is 30-180 min, the reduction reaction only generates metallic iron and rutile phase, the metallization rate of iron is greater than 90%, wherein the oxidation degree of carbon monoxide (CO) is higher than 90% 2 /CO+CO 2 ) Less than 6%, degree of oxidation (H) of hydrogen 2 O/H 2 +H 2 O) is less than 10 percent.
Preferably, in step S2, the corrosion inhibitor used in the corrosion reaction is ammonium chloride or ferric chloride, and the concentration is 0-3 wt%. The corrosion temperature is 20-100 ℃, the stirring speed is 50-800 r/min, the liquid-solid ratio is 0-20: 1, and the oxygen introduction speed is 0-1 multiplied by 10 5 L·m -3 ·min -1 The rusting time is 30-180 min.
In a preferable scheme, in the step S3, the concentration of the ammonium fluoride is 1-30 wt%, the liquid-solid ratio is 0-10: 1, the leaching temperature is 20-200 ℃, and the leaching time is 10-180 min.
In a preferable scheme, in the step S4, the concentration of the hydrochloric acid is 5-30 wt%, the liquid-solid ratio is 0-10: 1, the leaching temperature is 20-200 ℃, and the leaching time is 10-180 min.
Preferably, in step S5, the calcination temperature is 200 to 1000 ℃, and the calcination time is 10 to 180 min.
The principle of the technical scheme of the invention is as follows:
the pre-oxidized ilmenite reduction process of the present invention aims to convert ilmenite to the metallic iron, rutile phase. The main phases in the obtained reduced ilmenite are metallic iron, magnesium-containing ilmenite, rutile and silicate. Reaction taking place during reduction of ilmenite:
FeTiO 3(s) +2CO (g) ＝Fe (s) +TiO 2(s) +2CO 2(g) (1)
FeTiO 3(s) +2H 2(g) ＝Fe (s) +TiO 2(s) +2H 2 O (g) (2)
the invention aims to reduce the corrosion of ilmenite, namely, oxidize metal iron into iron oxide, and separate the iron oxide by gravity separation of a shaking table. The main phases of the iron ore concentrate are iron oxide, and the main phases of the primary titanium-rich material are magnesium-containing ilmenite, rutile and silicate. Reaction taking place during the rust process of reducing ilmenite:
2Fe (s) ＝2Fe 2+ (aq) +4e - (3)
O 2(g) +2H 2 O+4e - ＝4OH - (aq) (4)
Fe 2+ (aq) +2OH - (aq) ＝Fe(OH) 2(s) (5)
4Fe(OH) 2(s) +O 2(g) +2H 2 O＝4Fe(OH) 3(s) (6)
4Fe 2+ (aq) +8OH - (aq) +O 2(g) ＝2Fe 2 O 3(s) +4H 2 O (7)
2FeOOH (s) ＝Fe 2 O 3(s) +H 2 O (8)
6Fe 2+ (aq) +12OH - (aq) +O 2(g) ＝2Fe 3 O 4(s) +6H 2 O (9)
Fe(OH) 2(s) +2Fe(OH) 3(s) ＝Fe 3 O 4(s) +4H 2 O (10)
the ammonium fluoride leaching process aims to react silicate with ammonium fluoride, silicon element enters leaching liquid, and elements such as calcium, magnesium, aluminum and the like are left in leaching slag in the form of fluoride. The main phases of the leaching slag comprise magnesium-containing ilmenite, rutile, calcium fluoride, magnesium fluoride, ammonium fluoroaluminate and the like. Reaction taking place during ammonium fluoride leaching:
CaSiO 3(s) +8F - (aq) +6H + (aq) ＝CaF 2(s) +SiF 6 2- (aq) +3H 2 O (aq) (11)
MgSiO 3(s) +8F - (aq) +6H + (aq) ＝MgF 2(s) +SiF 6 2- (aq) +3H 2 O (aq) (12)
Al 2 (SiO 3 ) 3(s) +30F - (aq) +18H + (aq) +6NH 4+(aq) ＝2(NH 4 ) 3 AlF 6(s) +3SiF 6 2- (aq) +9H 2 O (aq) (13)
the hydrochloric acid leaching process aims to react magnesium-containing ilmenite, calcium fluoride, magnesium fluoride, ammonium fluoroaluminate and the like with hydrochloric acid, and calcium, magnesium, aluminum and other elements are dissolved and then enter the leaching solution. Reaction occurring during hydrochloric acid leaching:
CaF 2(s) +2HCl (aq) ＝CaCl 2(aq) +2HF (aq) (14)
MgF 2(s) +2HCl (aq) ＝MgCl 2(aq) +2HF (aq) (15)
(NH 4 ) 3 AlF 6(s) +6HCl (aq) ＝AlCl 3(aq) +6HF (aq) +3NH 4 Cl (aq) (16)
FeTiO 3(s) +4HCl (aq) ＝FeCl 2(aq) +TiOCl 2(aq) +2H 2 O (aq) (17)
the invention has the beneficial technical effects that:
according to the invention, the reduction process can be effectively controlled without forming a black titanium ore phase, only the ilmenite is reduced and converted into metallic iron and rutile phases, and iron and titanium elements in the ilmenite can be separated, the metallic iron element is separated by a corrosion method and recovered in the form of iron oxide, the impurity elements in the obtained primary titanium-rich material are mainly enriched in the magnesium-containing ilmenite which is separated by leaching, and the impurity elements in the obtained titanium-rich material are leached and removed to prepare a high-quality titanium-rich material which is used as a chlorination method raw material; the leached filtrate can be recycled after impurity removal and concentration. The process has reasonable design, simple operation and no environmental pollution.
Drawings
FIG. 1 is a process flow diagram of example 1 of the present invention.
Detailed Description
The following examples further illustrate embodiments of the present invention, but the embodiments of the present invention are not limited to the following examples.
In the examples of the present invention, unless otherwise specified, the means employed are those conventional in the art, and the reagents employed are commercially available in a conventional manner.
The technical solution of the present invention is explained in detail by the following embodiments and the accompanying drawings.
Example 1
Ilmenite concentrate (47.76% TiO) 2 、31.60％TFe、1.45％SiO 2 、1.33％Al 2 O 3 0.68% CaO and 5.60% MgO) as raw materials, the concentration of hydrogen in reducing gas is 80%, the concentration of carbon monoxide is 20%, the reducing temperature is 850 ℃, the reducing time is 60min, and the metallization rate of the obtained reduced ilmenite iron is 93.1%, wherein the oxidation degree of carbon monoxide (CO) 2 /CO+CO 2 ) 4% degree of oxidation of hydrogen (H) 2 O/H 2 +H 2 O) is 2 percent. The concentration of ammonium chloride in the corrosion process is 1.6 percent, the corrosion temperature is 70 ℃, the stirring speed is 400r/min, the liquid-solid ratio is 10:1, and the oxygen introduction speed is 15 multiplied by 10 3 L·m -3 ·min -1 The rusting time is 120 min. Ammonium fluoride leaching processThe concentration is 10%, the liquid-solid ratio is 10:1, the leaching temperature is 30 ℃, and the leaching time is 120 min. In the hydrochloric acid leaching process, the hydrochloric acid concentration is 20%, the liquid-solid ratio is 10:1, the leaching temperature is 80 ℃, and the leaching time is 120 min. The calcining temperature of the filter residue after filtration is 900 ℃, and the calcining time is 30 min.
Example 1 TiO is finally obtained 2 94.43% of CaO, 0.25% of CaO, 0.34% of MgO, and SiO 2 2.67% of a boiling chlorinated charge. The specific process flow is shown in figure 1.
Example 2
With ilmenite concentrate (47.76% TiO) 2 、31.60％TFe、1.45％SiO 2 、1.33％Al 2 O 3 0.68 percent of CaO and 5.60 percent of MgO) as raw materials, the concentration of hydrogen in reducing gas is 90 percent, the concentration of carbon monoxide is 10 percent, the reducing temperature is 800 ℃, the reducing time is 60min, and the metallization rate of the obtained reduced ilmenite iron is 94.2 percent, wherein the oxidation degree of carbon monoxide (CO) 2 /CO+CO 2 ) 5% degree of oxidation of hydrogen (H) 2 O/H 2 +H 2 O) is 3 percent. The concentration of ammonium chloride in the corrosion process is 1.6 percent, the corrosion temperature is 70 ℃, the stirring speed is 400r/min, the liquid-solid ratio is 10:1, and the oxygen introduction speed is 15 multiplied by 10 3 L·m -3 ·min -1 The rusting time is 120 min. In the ammonium fluoride leaching process, the concentration of ammonium fluoride is 15%, the liquid-solid ratio is 10:1, the leaching temperature is 30 ℃, and the leaching time is 120 min. In the hydrochloric acid leaching process, the hydrochloric acid concentration is 15%, the liquid-solid ratio is 10:1, the leaching temperature is 90 ℃, and the leaching time is 120 min. The calcining temperature of the filter residue after filtration is 900 ℃, and the calcining time is 30 min.
Example 2 TiO is finally obtained 2 94.21 percent of CaO, 0.18 percent of CaO, 0.45 percent of MgO and SiO 2 Is 2.13 percent of boiling chlorination charge.
Example 3
With ilmenite concentrate (47.76% TiO) 2 、31.60％TFe、1.45％SiO 2 、1.33％Al 2 O 3 0.68% of CaO, 5.60% of MgO) as raw materials. The reducing gas has hydrogen concentration of 80%, carbon monoxide concentration of 20%, reduction temperature of 850 deg.C, and reduction time of 60min, wherein the oxidation degree of carbon monoxide (CO) 2 /CO+CO 2 ) 5% degree of oxidation of hydrogen (H) 2 O/H 2 +H 2 O) is 5 percent. The concentration of ferric trichloride is 2.0 percent in the corrosion process, the corrosion temperature is 70 ℃, the stirring speed is 400r/min, the liquid-solid ratio is 10:1, and the oxygen introduction speed is 0.5 multiplied by 10 3 L·m -3 ·min -1 The rusting time is 120 min. In the ammonium fluoride leaching process, the concentration of ammonium fluoride is 10%, the liquid-solid ratio is 10:1, the leaching temperature is 30 ℃, and the leaching time is 120 min. In the hydrochloric acid leaching process, the hydrochloric acid concentration is 15%, the liquid-solid ratio is 10:1, the leaching temperature is 90 ℃, and the leaching time is 120 min. The calcining temperature of the filter residue after filtration is 900 ℃, and the calcining time is 30 min. Finally obtaining TiO 2 91.21%, CaO 0.31%, MgO 0.52%, SiO 2 3.21% of a boiling chlorination charge.
Comparative example 1
With ilmenite concentrate (47.76% TiO) 2 、31.60％TFe、1.45％SiO 2 、1.33％Al 2 O 3 0.68% CaO and 5.60% MgO) as raw materials, the concentration of hydrogen in reducing gas is 80%, the concentration of carbon monoxide is 20%, the reducing temperature is 850 ℃, the reducing time is 60min, and the metallization rate of the obtained reduced ilmenite iron is 90.1%, wherein the oxidation degree of carbon monoxide (CO) 2 /CO+CO 2 ) 6% degree of oxidation of hydrogen (H) 2 O/H 2 +H 2 O) is 5 percent. The concentration of ammonium chloride in the corrosion process is 1.6 percent, the corrosion temperature is 70 ℃, the stirring speed is 400r/min, the liquid-solid ratio is 10:1, and the oxygen introduction speed is 15 multiplied by 10 3 L·m -3 ·min -1 The rusting time is 120 min. Finally obtaining TiO 2 73.40 percent of CaO, 1.25 percent of CaO, 8.57 percent of MgO and SiO 2 Is 2.73 percent of primary titanium-rich material.
Comparative example 2
With ilmenite concentrate (47.76% TiO) 2 、31.60％TFe、1.45％SiO 2 、1.33％Al 2 O 3 0.68% CaO and 5.60% MgO) as raw materials, the concentration of hydrogen in reducing gas is 80%, the concentration of carbon monoxide is 20%, the reducing temperature is 850 ℃, the reducing time is 60min, and the metallization rate of the obtained reduced ilmenite iron is 90.1%, wherein the oxidation degree of carbon monoxide (CO) 2 /CO+CO 2 ) The content of the active carbon is 6%,degree of oxidation (H) of hydrogen 2 O/H 2 +H 2 O) is 5 percent. The concentration of ammonium chloride in the corrosion process is 1.6 percent, the corrosion temperature is 70 ℃, the stirring speed is 400r/min, the liquid-solid ratio is 10:1, and the oxygen introduction speed is 15 multiplied by 10 3 L·m -3 ·min -1 The rusting time is 120 min. In the hydrochloric acid leaching process, the hydrochloric acid concentration is 20%, the liquid-solid ratio is 10:1, the leaching temperature is 95 ℃, and the leaching time is 120 min. The calcining temperature of the filter residue after filtration is 900 ℃, and the calcining time is 30 min. Finally obtaining TiO 2 90.92%, CaO 1.21%, MgO 0.23%, SiO 2 Is 6.06 percent of titanium-rich material.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited to the above-described examples. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.
Claims (6)
1. The method for preparing the high-quality titanium-rich material by deeply removing impurities from ilmenite is characterized by comprising the following steps of:
s1, carrying out reduction reaction on ilmenite to obtain reduced ilmenite;
s2, carrying out a rust reaction on the reduced ilmenite obtained in the step S1, and carrying out gravity separation on a rust product through a table concentrator to obtain a primary titanium-rich material and hydrated iron oxide red mud for preparing iron oxide red;
s3, performing ammonium fluoride leaching reaction on the primary titanium-rich material obtained in the step S2, performing solid-liquid separation on leached slurry to obtain leaching slag and leaching liquid, and recycling the leaching liquid after impurity removal;
s4, carrying out hydrochloric acid leaching reaction on the leaching residue obtained in the step S3, carrying out solid-liquid separation on the leached slurry to obtain leaching residue and leaching liquid, and recycling the leaching liquid after impurity removal;
s5, calcining the leached slag obtained in the step S4 to obtain a high-quality titanium-rich material product.
2. The method for preparing high-quality titanium-rich material by deeply removing impurities from ilmenite according to claim 1, characterized in thatIn step S1, in the reduction reaction, a mixed gas of carbon monoxide and hydrogen is used as a reducing agent, the concentration of carbon monoxide is 0-40%, the concentration of hydrogen is 60-100%, the reduction temperature is 800-1150 ℃, the reduction time is 30-180 min, the reduction reaction only generates metallic iron and rutile phase, the metallization rate of iron is greater than 90%, and the oxidation degree of carbon monoxide (CO metallization rate) is higher than 90% 2 /CO+CO 2 ) Less than 6%, degree of oxidation (H) of hydrogen 2 O/H 2 +H 2 O) is less than 10 percent.
3. The method for preparing the high-quality titanium-rich material by deeply removing impurities from the ilmenite as claimed in claim 4, wherein in the step S2, the rust-removing agent adopted in the corrosion reaction is ammonium chloride or ferric chloride, the concentration is 0-3 wt%, the corrosion temperature is 20-100 ℃, the stirring speed is 50-800 r/min, the liquid-solid ratio is 0-20: 1, and the oxygen introduction speed is 0-1 x 10 5 L·m -3 ·min -1 The rusting time is 30-180 min.
4. The method for preparing the high-quality titanium-rich material through the deep impurity removal of the ilmenite as claimed in claim 1, wherein in the step S3, the concentration of the ammonium fluoride is 1-30 wt%, the liquid-solid ratio is 0-10: 1, the leaching temperature is 20-200 ℃, and the leaching time is 10-180 min.
5. The method for preparing the high-quality titanium-rich material through deep impurity removal of the ilmenite as claimed in claim 1, wherein in the step S4, the hydrochloric acid concentration is 5-30 wt%, the liquid-solid ratio is 0-10: 1, the leaching temperature is 20-200 ℃, and the leaching time is 30-180 min.
6. The method for preparing the high-quality titanium-rich material by deeply removing impurities from the ilmenite according to claim 1, wherein in the step S5, the calcination temperature is 200-1000 ℃ and the calcination time is 10-180 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210258697.7A CN114807591B (en) | 2022-03-16 | 2022-03-16 | Method for preparing high-quality titanium-rich material by deep impurity removal of ilmenite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210258697.7A CN114807591B (en) | 2022-03-16 | 2022-03-16 | Method for preparing high-quality titanium-rich material by deep impurity removal of ilmenite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114807591A true CN114807591A (en) | 2022-07-29 |
| CN114807591B CN114807591B (en) | 2023-12-15 |
Family
ID=82529622
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210258697.7A Active CN114807591B (en) | 2022-03-16 | 2022-03-16 | Method for preparing high-quality titanium-rich material by deep impurity removal of ilmenite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114807591B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015081775A1 (en) * | 2013-12-05 | 2015-06-11 | 中国科学院过程工程研究所 | Method for comprehensively using high-chromium-content vanadium-titanium magnetite concentrate |
| CN109402415A (en) * | 2018-07-17 | 2019-03-01 | 宜宾天原集团股份有限公司 | A kind of preparation of low grade natural rutile can chlorination rich-titanium material method |
-
2022
- 2022-03-16 CN CN202210258697.7A patent/CN114807591B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015081775A1 (en) * | 2013-12-05 | 2015-06-11 | 中国科学院过程工程研究所 | Method for comprehensively using high-chromium-content vanadium-titanium magnetite concentrate |
| CN109402415A (en) * | 2018-07-17 | 2019-03-01 | 宜宾天原集团股份有限公司 | A kind of preparation of low grade natural rutile can chlorination rich-titanium material method |
Non-Patent Citations (2)
| Title |
|---|
| 周育生等: "改性电炉钛渣矿相解构法制备富钛料新工艺研究", 《过程工程学报》 * |
| 郭宇峰: "钒钛磁铁矿固态还原强化及综合利用研究", 《中国博士学位论文全文数据库（工程科技Ⅰ辑）》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114807591B (en) | 2023-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2837426A (en) | Cyclic process for the manufacture of titanium-aluminum alloys and regeneration of intermediates thereof | |
| US3929962A (en) | Titanium purification process | |
| CN111534706A (en) | Method for preparing titanium-rich material from Panxi titanium concentrate | |
| CN110683580B (en) | Method for preparing high-purity vanadium pentoxide from high-calcium high-phosphorus vanadium slag through low-temperature chlorination | |
| CN110484712B (en) | Process for comprehensively utilizing vanadium-titanium magnetite by prereduction-electric furnace deep reduction-fluorination method | |
| CN110468285B (en) | Method for preparing TiO from titanium-containing furnace slag2Method for producing powder | |
| US20140308197A1 (en) | Production of titanium compounds and metal by sustainable Methods | |
| JPH08500393A (en) | Titanium iron material quality improvement | |
| Kothari | Recent developments in processing ilmenite for titanium | |
| CN110453093B (en) | Method for selectively leaching titanium from titanium-containing slag | |
| US2912320A (en) | Process for treating materials containing titanium and iron | |
| WO1995007366A1 (en) | Upgrading titaniferous materials | |
| CN114807591B (en) | Method for preparing high-quality titanium-rich material by deep impurity removal of ilmenite | |
| CN111534699A (en) | Method for recovering valuable substances from cemented carbide scrap | |
| CN109868370A (en) | The recovery method of valuable metal in a kind of vanadium chromium slag | |
| CN116287737A (en) | Method for realizing cyclic utilization of titanium, vanadium, iron, calcium, silicon, sulfur and nitrogen | |
| CN114480882B (en) | Method for fully utilizing ferrotitanium and vanadium resources in vanadium titano-magnetite | |
| CN113416847B (en) | Method for recycling, reducing and harmlessly treating vanadium extraction tailings | |
| CN114790517B (en) | Method for preparing high-quality titanium-rich material by using ilmenite | |
| CN115637305A (en) | Method for acid leaching of iron element in iron ore or steel slag and application thereof | |
| CN110482601B (en) | Preparation of TiO from rutile ore2Method for producing powder | |
| Pong et al. | A novel fluoride process for producing TiO2 from titaniferous ore | |
| CN109252057B (en) | Molten salt chlorination extraction method of low-grade zirconium concentrate | |
| CN110482597B (en) | Preparation process of titanium white by fluorination method | |
| CN114752772A (en) | Method for preparing fluidized chlorination furnace charge by upgrading titanium slag |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |