CN109295304A - A method of Titanium and iron oxide red are prepared using ilmenite concentrate - Google Patents
A method of Titanium and iron oxide red are prepared using ilmenite concentrate Download PDFInfo
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- CN109295304A CN109295304A CN201811172267.3A CN201811172267A CN109295304A CN 109295304 A CN109295304 A CN 109295304A CN 201811172267 A CN201811172267 A CN 201811172267A CN 109295304 A CN109295304 A CN 109295304A
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- titanium
- iron oxide
- ilmenite
- oxide red
- salt
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- 238000000034 method Methods 0.000 title claims abstract description 84
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 73
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000010936 titanium Substances 0.000 title claims abstract description 61
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000012141 concentrate Substances 0.000 title claims abstract description 15
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 43
- 238000002360 preparation method Methods 0.000 claims abstract description 41
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 30
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000706 filtrate Substances 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims description 36
- 150000003608 titanium Chemical class 0.000 claims description 26
- 239000011777 magnesium Substances 0.000 claims description 21
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 20
- 229910052749 magnesium Inorganic materials 0.000 claims description 20
- 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 description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 18
- 238000005868 electrolysis reaction Methods 0.000 claims description 17
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 16
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 16
- 230000007062 hydrolysis Effects 0.000 claims description 16
- 238000006460 hydrolysis reaction Methods 0.000 claims description 16
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 11
- 239000001110 calcium chloride Substances 0.000 claims description 10
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- VYOZKLLJJHRFNA-UHFFFAOYSA-N [F].N Chemical compound [F].N VYOZKLLJJHRFNA-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 229910019985 (NH4)2TiF6 Inorganic materials 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 8
- 238000003682 fluorination reaction Methods 0.000 claims description 8
- 230000003301 hydrolyzing effect Effects 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000000748 compression moulding Methods 0.000 claims description 4
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims description 4
- 238000009434 installation Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 230000004927 fusion Effects 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 4
- 238000002242 deionisation method Methods 0.000 claims 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical group [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 238000010926 purge Methods 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000006227 byproduct Substances 0.000 abstract description 6
- 239000002893 slag Substances 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000010586 diagram Methods 0.000 description 5
- -1 fluorine ammonia iron Salt Chemical compound 0.000 description 5
- 239000011435 rock Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910003074 TiCl4 Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 235000019580 granularity Nutrition 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 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 description 1
- 240000000233 Melia azedarach Species 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002699 waste material Substances 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
- 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
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- 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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical 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
- 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
- C22B34/1263—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 metallic titanium from titanium compounds, e.g. by reduction
-
- 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
- C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/66—Hue (H*)
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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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The present invention relates to a kind of methods for preparing Titanium and iron oxide red using ilmenite concentrate, and the preparation of the decomposition iron oxide red including ilmenite, filtrate processing and Titanium prepare four steps of lamp.Requirement of the present invention to raw material be not it is very high, raw material range of choice is wide；Step rationally utilizes the by-product of each process, and the feature of environmental protection is good；Green, low cost obtain the quality raw materials of upgrading titanium sponge, and compared with titanium slag, power consumption declines to a great extent, and compared with synthetic rutile, by-product is rationally utilized, and recycle at low cost；Simultaneously compared with conventional sponges titanium method, the short, low power consumption and other advantages with production procedure.
Description
Technical field
The present invention relates to a kind of methods for preparing Titanium and iron oxide red using ilmenite concentrate, belong to chemical industry metallurgical field.
Background technique
High titanium slag, synthetic rutile and natural rutile are the common raw materials for producing titanium sponge, with natural rutile
Increasingly depleted, high titanium slag has become the main production raw material of titanium sponge with synthetic rutile.There are energy consumption height, granularities point for high titanium slag
In place of the deficiencies of cloth is wide；Existing Production of Artificial Rutile method is there is also more deficiency, such as Reductive leaching, and there is no obtain for iron
It is utilized to effective, there are the series of problems such as equipment seriously corroded, HCl recovery be at high cost for hydrochloric acid leaching process, develop high-quality, valence
The preparation process of Lian Haimian titanium material is very necessary.
The industrial production of titanium sponge starts from 1948, and DuPont Corporation realized the work of titanium sponge for the first time in the world at that time
Industry production.Using natural rutile, synthetic rutile and titanium slag as waste titanium sponge possible approaches, overview, which is got up, mainly four
Kind method: the reduction of titanium oxide, the reduction method of halogenated titanium, the electrolysis method of titaniferous compound and the thermal decomposition method of halogenated titanium.Comprehensively consider
The factors such as the quality of production cost and titanium sponge, only two methods realize industrialized production.First is that gram of magnesium-reduced TiCl4
Raul's method, another kind are the hunt's methods of sodium reduction TiCl4.Since Mg ratio Na is safer, and reduzate (titanium sponge) is by broken
For granularity after broken more suitable for melting, C 1 content is lower, therefore Kroll method gradually replaces the hunt's method developed in advance, becomes and works as
The leading industry method of preceding titanium sponge production, but that there are still processes is tediously long for the method, and equipment investment is costly, and the production cycle is long, power consumption
Greatly, the disadvantages of environmental pollution is serious, although world titanium industry is after decades of development, Kroll method passes through a series of improvement, only
It is limited only to the small improvement of serialization, enlargement, automation etc., the price of titanium is not greatly reduced.Based on production
The high-quality vision with inexpensive titanium sponge, it is very necessary for developing new Titanium production new technique.
Summary of the invention
The object of the invention, which is that, overcomes above-mentioned deficiency, provides a kind of side that Titanium and iron oxide red are prepared using ilmenite concentrate
Method.Used technical solution is the present invention to solve above-mentioned technical problem:
To achieve the above object, the present invention is to be achieved through the following technical solutions:
A method of Titanium and iron oxide red are prepared using ilmenite concentrate, comprising the following steps:
S1, the decomposition of ilmenite carry out resolution process to concentrated ilmenite using ammonium fluoride, then to the solidliquid mixture after decomposition
It is filtered, filter residue and filtrate is stored respectively respectively, wherein wherein concentrated ilmenite TiO2Content is 40 ~ 60wt%, ammonium fluoride
Concentration is 15 ~ 35wt%；
S1 step is obtained filter residue and fluorine ammonia molysite carries out pyrohydrolysis, can obtain iron oxide red product by S2, the preparation of iron oxide red；Its
The ammonium fluoride generated in middle hydrolytic process returns in S1 step, and hydrolysis temperature is 600 ~ 800 DEG C, hydrolyzes the filter residue and fluorine when operation
Ammonia molysite ratio is 1:1-10.
S3, filtrate processing carry out secondary filter to the filtrate of S1 preparation, to (NH after filtering4)2TiF6Solution is collected
It is spare；
S4, Titanium preparation, (NH after the filter obtained with S3 step4)2TiF6Solution is that raw material carries out Titanium preparation.
Further, it in the S4 step, in carrying out Titanium preparation, can be prepared by Raul's method, magnesium-based legal system
It is prepared by any one in standby and electrolysis method.
Further, when Raul's method prepares Titanium, specific preparation process is as follows:
The first step prepares titanium dioxide, to filtrate (NH4)2TiF6It is hydrolyzed, generates titanium salt, the product separation of hydrolysising titanium salt
Afterwards, the solution of fluorine-containing ammonia salt is re-used for titanium salt decomposition, after filtering hydrolysising titanium salt, is carrying out pyrohydrolysis, hydrolysis temperature control
At 850 ~ 950 DEG C, TiO is obtained2；
Second step prepares Titanium, with the TiO prepared in the first step2S2Raw material can be obtained using current conventional Kroll process
Obtain finished metal titanium products.
Further, the solution usage ratio of the titanium salt and fluorine-containing ammonia salt are as follows: 1:3-5, fluorination ammonium concentration be 15 ~
35wt%。
Further, when the magnesium-based method prepares Titanium, specific preparation process is as follows:
Step A: magnesium pretreatment, by magnesium in closed container, heating is fused into liquid under vacuum and inert gas shielding；
Step B: filtrate crystallisation obtains solid (NH after filtrate crystallisation after two sections of filterings4)2TiF6, then by solid (NH4)2TiF6
It is sealed storage in reactor, and reactor constant-speed heating is warming up to 700 DEG C in 10-30 minutes；
Step C: material mixing, to (the NH in reactor under 50-300 revs/min of revolving speeds4)2TiF6At the uniform velocity stirred, and
In whipping process by the molten state magnesium liquid prepared in step A be at the uniform velocity added in reactor and with (NH4)2TiF6Uniformly mixing,
Middle molten state magnesium liquid adding speed be 0.1-0.9 meter per second, carry out molten state magnesium liquid addition when, temperature of reactor it is constant
700~900℃；
Step D: obtaining finished product, after completing step C operation, opens reactor cap, the NH on purge reactor upper layer4F and MgF2Afterwards
Titanium sponge final metal product can be obtained；Add deionization, one side NH4F dissolution into NH4F and the MgF2 mixture of removing simultaneously
It is re-used for the decomposition of ilmenite afterwards, another aspect MgF2 drying is stand-by, and wherein deionization total amount is NH4F and MgF2 mixture
3-10 times of total amount；
Further, in the step B and step C, no more than 1%, and in reactor, air pressure is oxygen content in reactor
0.1-10 times of standard atmospheric pressures.
Further, when the electrolysis method prepares Titanium, specific preparation process is as follows:
Step I: preparing cathode, to filtrate (NH4)2TiF6It is hydrolyzed, generates titanium salt, it is fluorine-containing after the product separation of hydrolysising titanium salt
The solution of ammonia salt is re-used for titanium salt decomposition, after filtering hydrolysising titanium salt, is carrying out pyrohydrolysis, hydrolysis temperature control 850 ~
950 DEG C, obtain TiO2, then to the TiO of acquisition2Sinter cathode after compression moulding into；
Step II: preparing electrolyte, by MgF2With CaF2、CaCl2It is mixed according to 10 ratio of 1:1-3:1-, then through high-temperature fusion
Manufactured MgF2、CaF2、CaCl2Molten salt system；
Step III: electrolysis operation, the MgF that step II is obtained2With CaF2、CaCl2Molten salt system is as electrolyte, with step I system
Standby TiO2Cathode as in electrolysis installation, carries out electrolysis operation by electrolysis installation together, so that finished metal titanium is obtained,
Temperature control is at 900-1100 DEG C when middle electrolysis；
Compared with the prior art, the advantages of the present invention are as follows:
1. using ilmenite concentrate as raw material, the requirement to raw material be not it is very high, raw material range of choice is wide；
2. step rationally utilizes the by-product of each process, the feature of environmental protection is good；
3. green, low cost obtain the quality raw materials of upgrading titanium sponge, compared with titanium slag, power consumption declines to a great extent, with artificial golden red
Stone is compared, and by-product is rationally utilized, and is recycled at low cost；
4. compared with conventional sponges titanium method, the short, low power consumption and other advantages with production procedure.
Detailed description of the invention
Fig. 1 is integrated artistic flow diagram of the present invention；
Fig. 2 is the method for the present invention flow diagram；
Fig. 3 is that Raul's method prepares Titanium method flow schematic diagram；
Fig. 4 is that magnesium-based method prepares Titanium method flow schematic diagram；
Fig. 5 is that electrolysis method prepares Titanium method flow schematic diagram.
Specific embodiment
Embodiment 1: Titanium and iron oxide red are prepared using the present invention
Ilmenite in embodiment can be rock mine ilmenite also optional placer ilmenite.
As shown in Fig. 1-5, specific preparation process is as follows:
(1) decomposition of ilmenite: decomposing concentrated ilmenite using ammonium fluoride, and the solution after decomposition enters next process filtering,
In, concentrated ilmenite TiO used in step (1)2Content is 40wt%, and fluorination ammonium concentration is 15wt%；
(2) it the preparation of iron oxide red: carries out one section of filtering first to previous process material, removes filter residue (MgF2, CaF2) and fluorine ammonia iron
Salt (NH4FeF3, (NH4)3FeF6), pyrohydrolysis then is carried out to filter residue and fluorine ammonia molysite, obtains iron oxide red product, in hydrolytic process
The ammonium fluoride of generation returns to ilmenite decomposition process, wherein hydrolysis temperature described in step (2) is controlled at 600 DEG C；
(3) preparation of Titanium: filtrate carries out second of filtering, the filtrate (NH filtered to two sections after one section of filtering4)2TiF6Into
Row hydrolysis generates titanium salt, and after the product separation of hydrolysising titanium salt, the solution of fluorine-containing ammonia salt is re-used for the decomposition of ilmenite, filtering
After hydrolysising titanium salt, pyrohydrolysis is being carried out, hydrolysis temperature is controlled at 850 DEG C, obtains TiO2, then according still further to conventional Ke Laoer
Method produces Titanium；
Embodiment 2: Titanium and iron oxide red are prepared using the present invention
Ilmenite in embodiment can be rock mine ilmenite also optional placer ilmenite.
As shown in Fig. 1-5, specific preparation process is as follows:
(1) decomposition of ilmenite: decomposing concentrated ilmenite using ammonium fluoride, and the solution after decomposition enters next process filtering,
In, concentrated ilmenite TiO used in step (1)2Content is 60wt%, and fluorination ammonium concentration is 35wt%；
(2) it the preparation of iron oxide red: carries out one section of filtering first to previous process material, removes filter residue (MgF2, CaF2) and fluorine ammonia iron
Salt (NH4FeF3, (NH4)3FeF6), pyrohydrolysis then is carried out to filter residue and fluorine ammonia molysite, obtains iron oxide red product, in hydrolytic process
The ammonium fluoride of generation returns to ilmenite decomposition process, wherein hydrolysis temperature described in step (2) is controlled at 800 DEG C；
(3) preparation of Titanium: filtrate carries out second of filtering, the filtrate (NH filtered to two sections after one section of filtering4)2TiF6Into
Row hydrolysis generates titanium salt, and after the product separation of hydrolysising titanium salt, the solution of fluorine-containing ammonia salt is re-used for the decomposition of ilmenite, filtering
After hydrolysising titanium salt, pyrohydrolysis is being carried out, hydrolysis temperature is controlled at 950 DEG C, obtains TiO2, then according still further to conventional Ke Laoer
Method produces Titanium；
Embodiment 3: Titanium and iron oxide red are prepared using the present invention
Ilmenite in embodiment can be rock mine ilmenite also optional placer ilmenite.
As shown in Fig. 1-5, specific preparation process is as follows:
(1) decomposition of ilmenite: decomposing concentrated ilmenite using ammonium fluoride, and the solution after decomposition enters next process filtering,
In, concentrated ilmenite TiO used in step (1)2Content is 50wt%, and fluorination ammonium concentration is 20wt%；
(2) it the preparation of iron oxide red: carries out one section of filtering first to previous process material, removes filter residue (MgF2, CaF2) and fluorine ammonia iron
Salt (NH4FeF3, (NH4)3FeF6), pyrohydrolysis then is carried out to filter residue and fluorine ammonia molysite, obtains iron oxide red product, in hydrolytic process
The ammonium fluoride of generation returns to ilmenite decomposition process, wherein hydrolysis temperature described in step (2) is controlled at 700 DEG C；
(3) preparation of Titanium: filtrate carries out second of filtering after one section of filtering.
Step A: by magnesium in closed container, heating is fused into liquid under vacuum and inert gas shielding；
Solid (NH is obtained after filtrate crystallisation after B: two sections of step filterings4)2TiF6, take a certain amount of ammonium hexa-fluorotitanate in reactor
In, after covering reactor cap, leak detection in vacuum and inert gas shielding, is heated to 700 DEG C；
Step C: under certain mixing speed, the adding liquid magnesium into reactor, reaction temperature is controlled at 700 DEG C；
Step D: opening reactor cap, removes agitating device, understands the NH on upper layer4F and MgF2, titanium sponge is obtained, then to NH4F
With MgF2Add water, NH in mixture4The decomposition of ilmenite, MgF are re-used for after F dissolution2Drying is stand-by；
Embodiment 4: Titanium and iron oxide red are prepared using the present invention
Ilmenite in embodiment can be rock mine ilmenite also optional placer ilmenite.
As shown in Fig. 1-5, specific preparation process is as follows:
(1) decomposition of ilmenite: decomposing concentrated ilmenite using ammonium fluoride, and the solution after decomposition enters next process filtering,
In, concentrated ilmenite TiO used in step (1)2Content is 45wt%, and fluorination ammonium concentration is 25wt%；
(2) it the preparation of iron oxide red: carries out one section of filtering first to previous process material, removes filter residue (MgF2, CaF2) and fluorine ammonia iron
Salt (NH4FeF3, (NH4)3FeF6), pyrohydrolysis then is carried out to filter residue and fluorine ammonia molysite, obtains iron oxide red product, in hydrolytic process
The ammonium fluoride of generation returns to ilmenite decomposition process, wherein hydrolysis temperature described in step (2) is controlled at 750 DEG C；
(3) preparation of Titanium: filtrate carries out second of filtering after one section of filtering.
Step A: by magnesium in closed container, heating is fused into liquid under vacuum and inert gas shielding；
Solid (NH is obtained after filtrate crystallisation after B: two sections of step filterings4)2TiF6, take a certain amount of ammonium hexa-fluorotitanate in reactor
In, after covering reactor cap, leak detection in vacuum and inert gas shielding, is heated to 700 DEG C；
Step C: under certain mixing speed, the adding liquid magnesium into reactor, reaction temperature is controlled at 900 DEG C；
Step D: opening reactor cap, removes agitating device, understands the NH on upper layer4F and MgF2, titanium sponge is obtained, then to NH4F
With MgF2Add water, NH in mixture4The decomposition of ilmenite, MgF are re-used for after F dissolution2Drying is stand-by；
Embodiment 5: Titanium and iron oxide red are prepared using the present invention
Ilmenite in embodiment can be rock mine ilmenite also optional placer ilmenite.
As shown in Fig. 1-5, specific preparation process is as follows:
(1) decomposition of ilmenite: decomposing concentrated ilmenite using ammonium fluoride, and the solution after decomposition enters next process filtering,
In, concentrated ilmenite TiO used in step (1)2Content is 40wt%, and fluorination ammonium concentration is 35wt%；
(2) it the preparation of iron oxide red: carries out one section of filtering first to previous process material, removes filter residue (MgF2, CaF2) and fluorine ammonia iron
Salt (NH4FeF3, (NH4)3FeF6), pyrohydrolysis then is carried out to filter residue and fluorine ammonia molysite, obtains iron oxide red product, in hydrolytic process
The ammonium fluoride of generation returns to ilmenite decomposition process, wherein hydrolysis temperature described in step (2) is controlled at 800 DEG C；
(3) preparation of Titanium: filtrate carries out second of filtering after one section of filtering.
Step I: the TiO that will be obtained during the first preparation method2Sinter cathode after compression moulding into；
Step II: preparing electrolyte, by the by-product MgF in second of preparation method2With CaF2、CaCl2It mixes according to a certain percentage
It closes, the stable MgF of physicochemical properties is made through high-temperature fusion2With CaF2、CaCl2Step III: utilizing this molten salt system pair
TiO2It is electrolysed, temperature control is at 900 DEG C when electrolysis；
Step IV: it is cooling, obtain Titanium.
Embodiment 6: Titanium and iron oxide red are prepared using the present invention
Ilmenite in embodiment can be rock mine ilmenite also optional placer ilmenite.
As shown in Fig. 1-5, specific preparation process is as follows:
(1) decomposition of ilmenite: decomposing concentrated ilmenite using ammonium fluoride, and the solution after decomposition enters next process filtering,
In, concentrated ilmenite TiO used in step (1)2Content is 43wt%, and fluorination ammonium concentration is 31wt%；
(2) it the preparation of iron oxide red: carries out one section of filtering first to previous process material, removes filter residue (MgF2, CaF2) and fluorine ammonia molysite
(NH4FeF3, (NH4)3FeF6), pyrohydrolysis then is carried out to filter residue and fluorine ammonia molysite, iron oxide red product is obtained, is produced in hydrolytic process
Raw ammonium fluoride returns to ilmenite decomposition process, wherein hydrolysis temperature described in step (2) is controlled at 900 DEG C；
(3) preparation of Titanium: filtrate carries out second of filtering after one section of filtering.
Step I: the TiO that will be obtained during the first preparation method2Sinter cathode after compression moulding into；
Step II: preparing electrolyte, by the by-product MgF in second of preparation method2With CaF2、CaCl2It mixes according to a certain percentage
It closes, the stable MgF of physicochemical properties is made through high-temperature fusion2With CaF2、CaCl2Molten salt system；
Step III: using this molten salt system to TiO2It is electrolysed, temperature control is at 1000 DEG C when electrolysis；
Step IV: it is cooling, obtain Titanium.
Claims (7)
1. a kind of method for preparing Titanium and iron oxide red using ilmenite concentrate, it is characterised in that: described prepares gold using ilmenite concentrate
Belong to the method for titanium and iron oxide red the following steps are included:
S1, the decomposition of ilmenite carry out resolution process to concentrated ilmenite using ammonium fluoride, then to the solidliquid mixture after decomposition
It is filtered, filter residue and filtrate is stored respectively respectively, wherein wherein concentrated ilmenite TiO2Content is 40 ~ 60wt%, ammonium fluoride
Concentration is 15 ~ 35wt%；
S1 step is obtained filter residue and fluorine ammonia molysite carries out pyrohydrolysis, can obtain iron oxide red product by S2, the preparation of iron oxide red；Its
The ammonium fluoride generated in middle hydrolytic process returns in S1 step, and hydrolysis temperature is 600 ~ 800 DEG C, hydrolyzes the filter residue and fluorine when operation
Ammonia molysite ratio is 1:1-10；
S3, filtrate processing carry out secondary filter to the filtrate of S1 preparation, to (NH after filtering4)2TiF6Solution is collected spare；
S4, Titanium preparation, (NH after the filter obtained with S3 step4)2TiF6Solution is that raw material carries out Titanium preparation.
2. a kind of method for preparing Titanium and iron oxide red using ilmenite concentrate according to claim 1, which is characterized in that described
S4 step in, carry out Titanium preparation in, can by Raul's method prepare, magnesium-based method preparation and electrolysis method in any one into
Row preparation or three kinds of methods are prepared simultaneously.
3. a kind of method for preparing Titanium and iron oxide red using ilmenite concentrate according to claim 2, which is characterized in that described
Raul's method when preparing Titanium, specific preparation process is as follows:
The first step prepares titanium dioxide, to filtrate (NH4)2TiF6It is hydrolyzed, generates titanium salt, the product separation of hydrolysising titanium salt
Afterwards, the solution of fluorine-containing ammonia salt is re-used for titanium salt decomposition, after filtering hydrolysising titanium salt, is carrying out pyrohydrolysis, hydrolysis temperature control
At 850 ~ 950 DEG C, TiO is obtained2；
Second step prepares Titanium, with the TiO prepared in the first step2S2Raw material can be obtained using current conventional Kroll process
Obtain finished metal titanium products.
4. a kind of method for preparing Titanium and iron oxide red using ilmenite concentrate according to claim 3, which is characterized in that described
Titanium salt and fluorine-containing ammonia salt solution usage ratio are as follows: 1:3-5, fluorination ammonium concentration be 15 ~ 35wt%.
5. a kind of method for preparing Titanium and iron oxide red using ilmenite concentrate according to claim 2, which is characterized in that described
Magnesium-based method when preparing Titanium, specific preparation process is as follows:
Step A: magnesium pretreatment, by magnesium in closed container, heating is fused into liquid under vacuum and inert gas shielding；
Step B: filtrate crystallisation obtains solid (NH after filtrate crystallisation after two sections of filterings4)2TiF6, then by solid (NH4)2TiF6
It is sealed storage in reactor, and reactor constant-speed heating is warming up to 700 DEG C in 10-30 minutes；
Step C: material mixing, to (the NH in reactor under 50-300 revs/min of revolving speeds4)2TiF6At the uniform velocity stirred, and
In whipping process by the molten state magnesium liquid prepared in step A be at the uniform velocity added in reactor and with (NH4)2TiF6Uniformly mixing,
Middle molten state magnesium liquid adding speed be 0.1-0.9 meter per second, carry out molten state magnesium liquid addition when, temperature of reactor it is constant
700~900℃；
Step D: obtaining finished product, after completing step C operation, opens reactor cap, the NH on purge reactor upper layer4F and MgF2After be
Titanium sponge final metal product can be obtained；Simultaneously to the NH of removing4F and MgF2Add deionization, one side NH in mixture4After F dissolution again
The secondary decomposition for ilmenite, another aspect MgF2Drying is stand-by, and wherein deionization total amount is NH4F and MgF2Amount of the mixture
3-10 times.
6. a kind of method for preparing Titanium and iron oxide red using ilmenite concentrate according to claim 5, which is characterized in that described
Step B and step C in, in reactor oxygen content no more than 1%, and in reactor air pressure be 0.1-10 times of normal atmospheres
Pressure.
7. a kind of method for preparing Titanium and iron oxide red using ilmenite concentrate according to claim 2, which is characterized in that described
Electrolysis method when preparing Titanium, specific preparation process is as follows:
Step I: preparing cathode, to filtrate (NH4)2TiF6It is hydrolyzed, generates titanium salt, it is fluorine-containing after the product separation of hydrolysising titanium salt
The solution of ammonia salt is re-used for titanium salt decomposition, after filtering hydrolysising titanium salt, is carrying out pyrohydrolysis, hydrolysis temperature control 850 ~
950 DEG C, obtain TiO2, then to the TiO of acquisition2Sinter cathode after compression moulding into；
Step II: preparing electrolyte, by MgF2With CaF2、CaCl2It is mixed according to 10 ratio of 1:1-3:1-, then through high-temperature fusion
Manufactured MgF2、CaF2、CaCl2Molten salt system；
Step III: electrolysis operation, the MgF that step II is obtained2With CaF2、CaCl2Molten salt system is as electrolyte, with step I system
Standby TiO2Cathode as in electrolysis installation, carries out electrolysis operation by electrolysis installation together, so that finished metal titanium is obtained,
Temperature control is at 900-1100 DEG C when middle electrolysis.
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Citations (5)
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|---|---|---|---|---|
| US2042435A (en) * | 1934-09-27 | 1936-05-26 | Burgess Titanium Company | Treatment of titanium-bearing materials |
| EP0319857B1 (en) * | 1987-12-04 | 1993-03-17 | Nkk Corporation | Method for producing titanium fluoride |
| CN101111616A (en) * | 2005-01-27 | 2008-01-23 | 派鲁克（私人）有限公司 | A method of producing titanium |
| CN101111456A (en) * | 2005-01-24 | 2008-01-23 | 百利通有限公司 | A process for the production of titanium dioxide using aqueous fluoride |
| CN103025663A (en) * | 2010-08-06 | 2013-04-03 | 百利通有限公司 | Titanium dioxide doped with fluorine and process for the production thereof |
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| US2042435A (en) * | 1934-09-27 | 1936-05-26 | Burgess Titanium Company | Treatment of titanium-bearing materials |
| EP0319857B1 (en) * | 1987-12-04 | 1993-03-17 | Nkk Corporation | Method for producing titanium fluoride |
| CN101111456A (en) * | 2005-01-24 | 2008-01-23 | 百利通有限公司 | A process for the production of titanium dioxide using aqueous fluoride |
| CN101111616A (en) * | 2005-01-27 | 2008-01-23 | 派鲁克（私人）有限公司 | A method of producing titanium |
| CN103025663A (en) * | 2010-08-06 | 2013-04-03 | 百利通有限公司 | Titanium dioxide doped with fluorine and process for the production thereof |
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