CN109626420A - A method of titanium dioxide and iron oxide are prepared using fluoride purification ferrotianium material - Google Patents
A method of titanium dioxide and iron oxide are prepared using fluoride purification ferrotianium material Download PDFInfo
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- CN109626420A CN109626420A CN201910035455.XA CN201910035455A CN109626420A CN 109626420 A CN109626420 A CN 109626420A CN 201910035455 A CN201910035455 A CN 201910035455A CN 109626420 A CN109626420 A CN 109626420A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 60
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 36
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 15
- 238000000746 purification Methods 0.000 title claims abstract description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 9
- 230000001376 precipitating effect Effects 0.000 claims abstract description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000010936 titanium Substances 0.000 claims abstract description 26
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 24
- VYOZKLLJJHRFNA-UHFFFAOYSA-N [F].N Chemical class [F].N VYOZKLLJJHRFNA-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000012535 impurity Substances 0.000 claims abstract description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 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 7
- 238000001556 precipitation Methods 0.000 claims abstract description 7
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 claims description 29
- 238000004140 cleaning Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 239000012141 concentrate Substances 0.000 claims description 7
- 239000002893 slag Substances 0.000 claims description 6
- 238000003682 fluorination reaction Methods 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 28
- 239000011575 calcium Substances 0.000 abstract description 15
- 229910052791 calcium Inorganic materials 0.000 abstract description 15
- 239000004615 ingredient Substances 0.000 abstract description 14
- 239000011777 magnesium Substances 0.000 abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 6
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000049 pigment Substances 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 29
- 239000000243 solution Substances 0.000 description 26
- 238000005374 membrane filtration Methods 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 229940088990 ammonium stearate Drugs 0.000 description 12
- JPNZKPRONVOMLL-UHFFFAOYSA-N azane;octadecanoic acid Chemical compound [NH4+].CCCCCCCCCCCCCCCCCC([O-])=O JPNZKPRONVOMLL-UHFFFAOYSA-N 0.000 description 12
- 229960005196 titanium dioxide Drugs 0.000 description 12
- 235000010215 titanium dioxide Nutrition 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 10
- 102220043159 rs587780996 Human genes 0.000 description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 9
- 239000000908 ammonium hydroxide Substances 0.000 description 9
- 229910005451 FeTiO3 Inorganic materials 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910001425 magnesium ion Inorganic materials 0.000 description 4
- 229910052758 niobium Inorganic materials 0.000 description 4
- 239000011435 rock Substances 0.000 description 4
- 229910052715 tantalum Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- WESWKIRSMKBCAJ-UHFFFAOYSA-N [F].[Fe] Chemical class [F].[Fe] WESWKIRSMKBCAJ-UHFFFAOYSA-N 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- -1 oxo ammonium titanium fluoride Chemical compound 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- IXQWNVPHFNLUGD-UHFFFAOYSA-N iron titanium Chemical compound [Ti].[Fe] IXQWNVPHFNLUGD-UHFFFAOYSA-N 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- 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
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Composite Materials (AREA)
- Environmental & Geological Engineering (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention provides a kind of methods for preparing titanium dioxide and iron oxide using fluoride purification ferrotianium material, comprising: by ferrotianium material and fluorine ammonium compounds solution Hybrid Heating, obtains mixture, the fluorine ammonium compounds is ammonium fluoride or ammonium acid fluoride；A pH value for adjusting the mixture, obtains the first precipitating；The secondary pH value of surplus materials will be adjusted after first precipitation and separation, obtain the second precipitating；By the first precipitating pyrohydrolysis, Fe is obtained2O3；By the second precipitating calcining, TiO is obtained2.Method provided by the invention can be completely separated titanium elements and ferro element in ferrotianium material, obtain the TiO of high-quality respectively2、Fe2O3Pigment product.Method provided by the invention is particularly suitable for the purification processing of the high contents of calcium and magnesium ferrotianium resource of Panxi Diqu (and ingredient is approximate with its), obtain the material of low calcium and magnesium impurity content, that is rich-titanium material, for subsequent sulfuric acid process, chloridising production titanium dioxide or titanium.
Description
Technical field
The present invention relates to ferrotianium technical fields more particularly to a kind of utilization fluoride purification ferrotianium material to prepare titanium dioxide
With the method for iron oxide.
Background technique
Ilmenite is iron and titanyl compound mineral, trigonal system, hardness 5~6,4.4~5g/cm of density3, ingredient is
FeTiO3, theory composition are as follows: FeO 47.36%, TiO252.64%, it is the main ore for extracting titanium and titanium dioxide.China
Ilmenite is resourceful, and the reserves whole world ranked fifth, and Panxi Diqu is the maximum ilmenite resources base in China.Originate in Ultrabasic
Ilmenite in rock, basic rock, content of MgO is higher, is substantially free of Nb, Ta；Ilmenite in alkaline rock, MnO content is higher, and
Containing Nb, Ta；The ilmenite in acidic rock is originated in, FeO, MnO content are high, and Nb, Ta content are also relatively high.
The ilmenite in 90% or more the whole world only utilizes titanium elements for producing titanium dioxide, and in ilmenite
Ferro element do not carry out reasonable utilization, be the production lower product containing ferro element of added value, some or even conduct mostly
Waste (ferrous sulfate) is accumulated, and more serious environmental issue is produced.The prior art only payes attention to Titanium in Ilmenite element
Utilization and ignore the utilization of ferro element, and the product quality containing titanium elements obtained is not high.
Summary of the invention
In view of this, the purpose of the present invention is to provide it is a kind of using fluoride purification ferrotianium material prepare titanium dioxide and
The method of iron oxide, method provided by the invention can extract iron and titanium elements in ferrotianium material simultaneously.
The present invention provides a kind of method for preparing titanium dioxide and iron oxide using fluoride purification ferrotianium material, packets
It includes:
By ferrotianium material and fluorine ammonium compounds solution Hybrid Heating, mixture is obtained, the fluorine ammonium compounds is ammonium fluoride
Or ammonium acid fluoride；
A pH value for adjusting the mixture, obtains the first precipitating；
The secondary pH value of surplus materials will be adjusted after first precipitation and separation, obtain the second precipitating；
By the first precipitating pyrohydrolysis, Fe is obtained2O3；
By the second precipitating calcining, TiO is obtained2。
In the present invention, the iron-titanium material is the mineral containing titanium elements and ferro element, preferably includes ilmenite, titanium essence
One or more of mine and high titanium slag.The present invention does not have special limitation to the ingredient of the ferrotianium material, using this field
The ferrotianium material component of the known mentioned kind of technical staff.In the present invention, the ingredient of the ferrotianium material preferably includes
FeTiO3、TiO2、FeO、Fe2O3One or more of.In the present invention, titanium and the total matter of ferrous components in the ferrotianium material
Measuring content is preferably 86~98%, and more preferably 87~98%, most preferably 90~95%.
In the present invention, the ingredient of the ilmenite is preferred are as follows:
FeTiO390~95wt%；
1~3wt% of CaO；
4~6wt% of MgO；
Surplus is impurity.
In the present invention, the FeTiO3Mass content be preferably 91~94%, more preferably 92~93%.In this hair
In bright, the mass content of the CaO is preferably 1.5~2.5%, and more preferably 2%.In the present invention, the quality of the MgO contains
Amount preferably 4.5~5.5%, more preferably 5%.In the present invention, the impurity is preferably one of Mn, Nb and Ta or several
Kind.
In the present invention, the ingredient of the ilmenite concentrate is preferred are as follows:
In the present invention, the TiO2Mass content be preferably 48~50%, more preferably 49%.In the present invention,
The mass content of the FeO is preferably 35~37%, and more preferably 36%.In the present invention, the Fe2O3Mass content it is excellent
It is selected as 6~8%, more preferably 7%.In the present invention, the mass content of the CaO is preferably 1.5~2.5%, more preferably
2%.In the present invention, the mass content of the MgO is preferably 5.2~5.8%, and more preferably 5.4~5.6%.In the present invention
In, the impurity is preferably one or more of Al and Si.
In the present invention, the ingredient of the high titanium slag is preferred are as follows:
In the present invention, the TiO2Mass content be preferably 84~88%, more preferably 85~86%.In the present invention
In, the mass content of the FeO is preferably 6~7%.In the present invention, the mass content of the CaO be preferably 1.2~
1.8%, more preferably 1.4~1.6%.In the present invention, the mass content of the MgO is preferably 5~7%, more preferably
6%.In the present invention, the impurity is preferably one or more of Al and Si.
In the present invention, the fluorine ammonium compounds solution is preferably fluorine ammonium compounds aqueous solution.In the present invention, in order to add
Speed fluorination, the fluorine ammonium compounds solution is preferably the saturated solution of fluorine ammonium compounds.In the present invention, the fluorine ammonium compounds
The mass concentration of solution is preferably 40~60%, and more preferably 45~55%, most preferably 50%.
In the present invention, the solid-to-liquid ratio of the ferrotianium material and fluorine ammonium compounds solution is preferably (0.5~2): 1, it is more excellent
It is selected as (1~1.5): 1, most preferably (1.2~1.3): 1.In the present invention, the solid-to-liquid ratio > 2, can be due to reaction mass mistake
The reduction of more and titanium salt solubility causes reaction incomplete；The solid-to-liquid ratio < 0.5 can make water consumption in reaction solution excessive,
Lead to the workload for increasing post-processing weak solution.
In the present invention, the mixing preferably carries out under stirring conditions.In the present invention, the revolving speed of the stirring is excellent
It is selected as 80~120 turns/min, more preferably 90~110 turns/min, most preferably 100 turns/min.
In the present invention, 50~100 DEG C of the temperature of the heating, more preferably 70~100 DEG C, most preferably 90~100
DEG C, above-mentioned heating temperature can make fluorination process fully reacting and accelerate to be fluorinated speed.In the present invention, the time of the heating is excellent
It is selected as 0.5~4h, more preferably 1~3h, most preferably 1~2h.
In the present invention, the reagent for adjusting pH value (including adjusting a pH value and secondary pH value) is preferably ammonium hydroxide,
Other cations can not be introduced.
In the present invention, a pH value can precipitate Fe, and a pH value is preferably 6.5~7.5, and more preferably 6.8
~7.2, most preferably 7.In the present invention, first precipitating is preferably the blue precipitate of iron fluorine compounds, contains CaF2、
MgF2Impurity.
In the present invention, the method for first precipitation and separation is preferably filtered.In the present invention, the side of the filtering
Method is preferably squeeze and filter.In the present invention, the equipment of the filtering is preferably membrane filtration machine.
In the present invention, secondary pH value can precipitate Ti, and the secondary pH value is preferably 8.5~9.5, and more preferably 8.8
~9.2, most preferably 9.In the present invention, the second precipitating preferably white of ammonium titanium fluoride and oxo ammonium titanium fluoride is heavy
It forms sediment.
In the present invention, the pyrohydrolysis temperature is preferably 500~900 DEG C, and more preferably 600~800 DEG C, most preferably
It is 650~750 DEG C.
In the present invention, it is described by first precipitate pyrohydrolysis after it is also preferable to include:
By product removal of impurities, cleaning and the drying after pyrohydrolysis, Fe is obtained2O3。
In the present invention, the method for the removal of impurities is preferred are as follows: by the product and ammonium stearate (C after pyrohydrolysis18H39NO2)
Mixing, ammonium stearate absorption Ca, Mg ion float on upper layer (cannot adsorb Fe ion), form suspended matter, then remove suspended matter.
In the present invention, the method for removing suspended matter can be to topple over upper solution or fish for suspended matter, the upper layer with filter bag
Solution is the solution containing Ca and Mg suspended matter.In the present invention, the dosage of the ammonium stearate is preferably and produces after pyrohydrolysis
The 0.1~0.2% of amount of substance, more preferably 0.12~0.18%, most preferably 0.14~0.16%.
In the present invention, the cleaning method is preferred are as follows: the product after removal of impurities is delivered to membrane filtration machine, squeeze water
Point；Water is added into membrane filtration machine again to be squeezed again, has not only completed cleaning, but also filtered moisture.
In the present invention, the temperature of the drying is preferably 80~120 DEG C, and more preferably 90~110 DEG C, most preferably
100℃。
In the present invention, the calcination temperature is preferably 500~1000 DEG C, and more preferably 600~900 DEG C, most preferably
700~800 DEG C.
In the present invention, it is preferred to be calcined after second precipitation and separation is come out.In the present invention, the separation
Method preferably filters.In the present invention, the method for the filtering is preferably squeeze and filter.In the present invention, the filtering
Equipment is preferably membrane filtration machine.
In the present invention, by it is described second precipitating calcined before it is also preferable to include:
Second precipitating is cleaned and dried.
In the present invention, the cleaning method is preferred are as follows: the product after removal of impurities is delivered to membrane filtration machine, squeeze water
Point；Water is added into membrane filtration machine again to be squeezed again, has not only completed cleaning, but also filtered moisture.
In the present invention, the temperature of the drying is preferably 80~120 DEG C, and more preferably 90~110 DEG C, most preferably
100℃。
It in the present invention, is production tail water by the product obtained after second precipitation and separation, main component is fluorine ammonium
Polymer solution.In the present invention, it is preferred to which the production tail water is removed water, fluorine ammonium compounds concentrate is obtained.In the present invention
In, the method for the water removal is preferably evaporated under reduced pressure.In the present invention, the mass concentration of the fluorine ammonium compounds concentrate is preferred
It is 30~60%, more preferably 35~55%, most preferably 40~50%.The present invention can be real by recycling to production tail water
The reuse of existing fluorine ammonium compounds.
The method provided in an embodiment of the present invention that titanium dioxide and iron oxide are prepared using fluoride purification ferrotianium material
Process flow chart is as shown in Figure 1, comprising:
Ferrotianium material and fluorine ammonium compounds aqueous solution are mixed, heating, obtain mixed liquor；
The pH value of the mixed liquor is adjusted with ammonium hydroxide, (step is heavy for the blue precipitate of generation iron fluorine compounds (fluorine ammonium molysite)
Form sediment), wherein containing a small amount of CaF2、MgF2Impurity filters out blue precipitate；
By blue precipitate pyrohydrolysis, the Fe containing a small amount of CaO and MgO is obtained2O3；It cleaned again, clean (cleaning+mistake
Filter), drying, obtain Fe2O3；
The pH value of the solution obtained after adjusting filtering with ammonium hydroxide, obtains ammonium titanium fluoride and oxo ammonium titanium fluoride white precipitate
(two steps precipitating), filters out white precipitate；
White precipitate is cleaned into (cleaning+filtering), drying, calcining, obtains TiO2。
Method provided by the invention can inside ferrotianium material Ti and Fe simultaneously decompose purification, produce two kinds of productions
Product: TiO2And Fe2O3, accomplished the full utilization of ilmenite.Moreover, method provided by the invention can be Fe2O3Ca, Mg it is miscellaneous
Matter is removed clean.(>=99.99%), fine size (TiO with high purity can be prepared in method provided by the invention2< 500nm,
Fe2O3< 100nm) product.Method provided by the invention is easily operated, can effective control for product quality, and it is at low cost.This
The method that invention provides can be completely separated titanium elements and ferro element in ferrotianium material, obtain the TiO of high-quality respectively2(titanium
It is white), Fe2O3(iron oxide red) pigment product.Method provided by the invention is particularly suitable for the height of Panxi Diqu (and ingredient is approximate with its)
The purification of calcium and magnesium ferrotianium resource is handled, and obtains the material of low calcium and magnesium impurity content, i.e. rich-titanium material, is used for subsequent sulfuric acid
Method, chloridising production titanium dioxide or titanium production.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the process flow for the method that purification ilmenite provided in an embodiment of the present invention prepares titanium dioxide and iron oxide
Figure；
Fig. 2 is Fe prepared by the embodiment of the present invention 22O3XRD diffraction pattern；
Fig. 3 is TiO prepared by the embodiment of the present invention 22XRD diffraction pattern；
Fig. 4 is Fe prepared by the embodiment of the present invention 12O3SEM diffraction pattern；
Fig. 5 is TiO prepared by the embodiment of the present invention 12SEM diffraction pattern；
Fig. 6 is Fe prepared by the embodiment of the present invention 22O3SEM diffraction pattern；
Fig. 7 is TiO prepared by the embodiment of the present invention 22SEM diffraction pattern.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
The ingredient of ilmenite are as follows: FeTiO390wt%；CaO 1wt%；MgO 4wt%, surplus are impurity.
By mass concentration be 40% ammonium fluoride aqueous solution and ilmenite according to solid-to-liquid ratio 0.5:1 80 turns/min condition
Under mixed after heated 0.5 hour at 50 DEG C, obtain mixture；
It uses ammonium hydroxide to adjust the pH value of the mixture as 6.5, obtains the first precipitating；
First precipitating is separated using membrane filtration machine squeeze and filter, the pH of surplus solution is adjusted using ammonium hydroxide
Value is 8.5, obtains the second precipitating, and second precipitating is carried out squeeze and filter using membrane filtration machine and is separated.
Be deposited in pyrohydrolysis at 500 DEG C for first, by after pyrohydrolysis product and ammonium stearate mix clean,
Ammonium stearate absorption Ca, Mg ion floats on upper layer and forms suspended matter, topples over upper solution and removes oil removal, upper solution be containing
The solution of Ca and Mg suspended matter, the dosage of ammonium stearate are 0.1% of product quality after pyrohydrolysis；Product after removal of impurities is defeated
It send to membrane filtration machine, squeezes moisture；Water is added into membrane filtration machine again to be squeezed again, complete to clean and filters moisture；
Product after cleaning is dried at 80 DEG C, obtains Fe2O3；
Second precipitating is delivered to membrane filtration machine, squeezes moisture；Water is added into membrane filtration machine again to be squeezed again,
It completes to clean and filters moisture；Product after cleaning is dried at 80 DEG C；
Product after drying is calcined at 500 DEG C, obtains TiO2。
Fe in the method recycling ilmenite that the embodiment of the present invention 1 provides2O3And TiO2Yield be Fe2O3Yield be
99.7%, TiO2Yield be 99.8%.
Fe is detected using XRD2O3And TiO2Purity, testing result is Fe2O3Purity be 99.99%, TiO2Purity
It is 99.99%.
Detection Fe is detected using SEM2O3And TiO2Granularity, testing result is Fe2O3Granularity be D50=90nm (as scheme
Shown in 4), TiO2Granularity be D50=450nm (as shown in Figure 5).
Embodiment 2
The ingredient of ilmenite are as follows: FeTiO392wt%；CaO 2wt%；MgO 4wt%, surplus are impurity.
By mass concentration be 50% ammonium fluoride aqueous solution and ilmenite according to solid-to-liquid ratio 1:1 100 turns/min condition
Under mixed after heated 1.5 hours at 75 DEG C, obtain mixture；
It uses ammonium hydroxide to adjust the pH value of the mixture as 7, obtains the first precipitating；
First precipitating is separated using membrane filtration machine squeeze and filter, the pH of surplus solution is adjusted using ammonium hydroxide
Value is 9, obtains the second precipitating and is separated using membrane filtration machine progress squeeze and filter.
Be deposited in pyrohydrolysis at 700 DEG C for first, by after pyrohydrolysis product and ammonium stearate mix clean,
Ammonium stearate absorption Ca, Mg ion floats on upper layer and forms suspended matter, topples over upper solution and removes oil removal, upper solution be containing
The solution of Ca and Mg suspended matter, the dosage of ammonium stearate are 0.15% of product quality after pyrohydrolysis；By the product after removal of impurities
It is delivered to membrane filtration machine, squeezes moisture；Water is added into membrane filtration machine again to be squeezed again, complete to clean and crosses drainage
Point；Product after cleaning is dried at 100 DEG C, obtains Fe2O3；
Second precipitating is delivered to membrane filtration machine, squeezes moisture；Water is added into membrane filtration machine again to be squeezed again,
It completes to clean and filters moisture；Product after cleaning is dried at 100 DEG C；Product after drying is forged at 750 DEG C
It burns, obtains TiO2。
Fe in the method recycling ilmenite that the embodiment of the present invention 2 provides2O3And TiO2Yield be Fe2O3Yield be
99.9%, TiO2Yield be 99.9%.
Fe is detected according to the method for embodiment 12O3And TiO2Purity, testing result is Fe2O3Purity be 100% (such as
Shown in Fig. 2), TiO2Purity be 100% (as shown in Figure 3).
Fe is detected according to the method for embodiment 12O3And TiO2Granularity, testing result is Fe2O3Granularity be D50=
80nm (as shown in Figure 6), TiO2Granularity be D50=400nm (as shown in Figure 7).
Embodiment 3
The ingredient of ilmenite are as follows: FeTiO394wt%；CaO 3wt%；MgO 2wt%, surplus are impurity.
By mass concentration be 60% ammonium fluoride aqueous solution and ilmenite according to solid-to-liquid ratio 2:1 120 turns/min condition
Under mixed after heated 4 hours at 100 DEG C, obtain mixture；
It uses ammonium hydroxide to adjust the pH value of the mixture as 7.5, obtains the first precipitating；
First precipitating is separated using membrane filtration machine squeeze and filter, the pH of surplus solution is adjusted using ammonium hydroxide
Value is 9.5, obtains the second precipitating and is separated using membrane filtration machine progress squeeze and filter.
Be deposited in pyrohydrolysis at 900 DEG C for first, by after pyrohydrolysis product and ammonium stearate mix clean,
Ammonium stearate absorption Ca, Mg ion floats on upper layer and forms suspended matter, topples over upper solution and removes oil removal, upper solution be containing
The solution of Ca and Mg suspended matter, the dosage of ammonium stearate are 0.2% of product quality after pyrohydrolysis；Product after removal of impurities is defeated
It send to membrane filtration machine, squeezes moisture；Water is added into membrane filtration machine again to be squeezed again, complete to clean and filters moisture；
Product after cleaning is dried at 120 DEG C, obtains Fe2O3；
Second precipitating is delivered to membrane filtration machine, squeezes moisture；Water is added into membrane filtration machine again to be squeezed again,
It completes to clean and filters moisture；Product after cleaning is dried at 120 DEG C；Product after drying is forged at 1000 DEG C
It burns, obtains TiO2。
Fe in the method recycling ilmenite that the embodiment of the present invention 3 provides2O3And TiO2Yield be Fe2O3Yield be
99.8%, TiO2Yield be 99.8%.
Fe is detected according to the method for embodiment 12O3And TiO2Purity, testing result is Fe2O3Purity be 99.99%,
TiO2Purity be 99.99%.
Fe is detected according to the method for embodiment 12O3And TiO2Granularity, testing result is Fe2O3Granularity be D50=
85nm, TiO2Granularity be.D50=450nm.
Embodiment 4
Fe is obtained according to the method for embodiment 22O3And TiO2, the difference from example 2 is that by the ferrotianium in embodiment 2
Mine replaces with ilmenite concentrate, the ingredient of ilmenite concentrate are as follows: TiO247wt%；FeO 36wt%；Fe2O37wt%；CaO 2wt%；MgO
6wt%, surplus are impurity.
Fe in the method recycling ilmenite concentrate that the embodiment of the present invention 4 provides2O3And TiO2Yield be Fe2O3Yield be
99.9%, TiO2Yield be 99.9%.
Fe is detected according to the method for embodiment 12O3And TiO2Purity, testing result is Fe2O3Purity be 99.99%,
TiO2Purity be 99.99%.
Fe is detected according to the method for embodiment 12O3And TiO2Granularity, testing result is Fe2O3Granularity be D50=
70nm, TiO2Granularity be D50=400nm.
Embodiment 5
Fe is obtained according to the method for embodiment 22O3And TiO2, the difference from example 2 is that by the ferrotianium in embodiment 2
Mine replaces with high titanium slag, the ingredient of high titanium slag are as follows: TiO285wt%；FeO 6wt%；CaO 1.5wt%；MgO 6.5wt%,
Surplus is impurity.
Fe in the method recycling high titanium slag that the embodiment of the present invention 5 provides2O3And TiO2Yield be Fe2O3Yield be
99.9%, TiO2Yield be 99.9%.
Fe is detected according to the method for embodiment 12O3And TiO2Purity, testing result is Fe2O3Purity be 99.99%,
TiO2Purity be 99.99%.
Fe is detected according to the method for embodiment 12O3And TiO2Granularity, testing result is Fe2O3Granularity be D50=
80nm, TiO2Granularity be D50=350nm.
As seen from the above embodiment, the present invention provides it is a kind of using fluoride purification ferrotianium material prepare titanium dioxide and
The method of iron oxide, comprising: by ferrotianium material and fluorine ammonium compounds solution Hybrid Heating, obtain mixture, the fluorine ammonium chemical combination
Object is ammonium fluoride or ammonium acid fluoride；A pH value for adjusting the mixture, obtains the first precipitating；By first precipitation and separation
The secondary pH value for adjusting surplus materials afterwards, obtains the second precipitating；By the first precipitating pyrohydrolysis, Fe is obtained2O3；It will be described
Second precipitating calcining, obtains TiO2.Method provided by the invention can be completely separated titanium elements and ferro element in ferrotianium material,
The TiO of high-quality is obtained respectively2(titanium white), Fe2O3(iron oxide red) pigment product.Method provided by the invention is particularly suitable for Pan Xi
The purification processing of the high contents of calcium and magnesium ferrotianium resource of regional (and ingredient is approximate with its), obtains the material of low calcium and magnesium impurity content,
That is rich-titanium material, for subsequent sulfuric acid process, chloridising production titanium dioxide or titanium.
Claims (10)
1. a kind of method for preparing titanium dioxide and iron oxide using fluoride purification ferrotianium material, comprising:
By ilmenite and fluorine ammonium compounds solution Hybrid Heating, mixture is obtained, the fluorine ammonium compounds is ammonium fluoride or fluorination
Hydrogen ammonium；
A pH value for adjusting the mixture, obtains the first precipitating；
The secondary pH value of surplus materials will be adjusted after first precipitation and separation, obtain the second precipitating；
By the first precipitating pyrohydrolysis, Fe is obtained2O3；
By the second precipitating calcining, TiO is obtained2。
2. the method according to claim 1, wherein the ferrotianium material includes ilmenite, ilmenite concentrate and high titanium
One or more of slag.
3. the method according to claim 1, wherein the fluorine ammonium compounds solution is that fluorine ammonium compounds is water-soluble
Liquid；
The mass concentration of the fluorine ammonium compounds solution is 40~60%.
4. the method according to claim 1, wherein the solid-to-liquid ratio of the ferrotianium material and fluorine ammonium compounds solution
For (0.5~2): 1.
5. the method according to claim 1, wherein the temperature of the heating is 50~100 DEG C；
The time of the heating is 0.5~4h.
6. the method according to claim 1, wherein a pH value is 6.5~7.5；
The secondary pH value is 8.5~9.5.
7. the method according to claim 1, wherein the pyrohydrolysis temperature is 500~900 DEG C.
8. the method according to claim 1, wherein the calcination temperature is 500~1000 DEG C.
9. the method according to claim 1, wherein after the completion of the pyrohydrolysis further include:
By product removal of impurities, cleaning and the drying after pyrohydrolysis, Fe is obtained2O3。
10. the method according to claim 1, wherein before the calcining further include:
Second precipitating is cleaned and dried.
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| CN110422876A (en) * | 2019-09-11 | 2019-11-08 | 中南大学 | A kind of method that fluoride process titanium liquid prepares ammonium titanium fluoride |
| CN110468285A (en) * | 2019-09-11 | 2019-11-19 | 中南大学 | A kind of Ti-containing slag produces TiO2The method of powder |
| CN110484739A (en) * | 2019-09-11 | 2019-11-22 | 中南大学 | A method of removing iron, manganese, vanadium, chromium impurity from Ti-containing slag fluoride process leachate |
| CN110482601A (en) * | 2019-09-11 | 2019-11-22 | 中南大学 | It is a kind of to produce TiO with rutile ore2The method of powder |
| CN110484712A (en) * | 2019-09-11 | 2019-11-22 | 中南大学 | A kind of prereduction-electric furnace depth reduction-fluoride process comprehensive utilization of V-Ti magnetite technique |
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| CN110468285A (en) * | 2019-09-11 | 2019-11-19 | 中南大学 | A kind of Ti-containing slag produces TiO2The method of powder |
| CN110484739A (en) * | 2019-09-11 | 2019-11-22 | 中南大学 | A method of removing iron, manganese, vanadium, chromium impurity from Ti-containing slag fluoride process leachate |
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| CN110484712A (en) * | 2019-09-11 | 2019-11-22 | 中南大学 | A kind of prereduction-electric furnace depth reduction-fluoride process comprehensive utilization of V-Ti magnetite technique |
| CN110482597A (en) * | 2019-09-11 | 2019-11-22 | 中南大学 | A kind of preparation process of fluoride process titanium white |
| CN110498450A (en) * | 2019-09-11 | 2019-11-26 | 中南大学 | It is a kind of to produce TiO with ilmenite2The method of powder and iron oxide red |
| CN110498436A (en) * | 2019-09-11 | 2019-11-26 | 中南大学 | A method of titanium dioxide powder and calcirm-fluoride are produced with perovskite |
| CN110482601B (en) * | 2019-09-11 | 2020-10-09 | 中南大学 | Preparation of TiO from rutile ore2Method for producing powder |
| CN110498450B (en) * | 2019-09-11 | 2020-10-09 | 中南大学 | Preparation of TiO from ilmenite2Powder and method for producing iron oxide red |
| CN110484712B (en) * | 2019-09-11 | 2020-10-09 | 中南大学 | Process for comprehensively utilizing vanadium-titanium magnetite by prereduction-electric furnace deep reduction-fluorination method |
| CN110482597B (en) * | 2019-09-11 | 2020-10-09 | 中南大学 | Preparation process of titanium white by fluorination method |
| CN110484739B (en) * | 2019-09-11 | 2020-12-18 | 中南大学 | Method for removing iron, manganese, vanadium and chromium impurities from titanium-containing slag fluorination process leachate |
| CN117509715A (en) * | 2023-10-31 | 2024-02-06 | 衡阳市东氟新材料股份有限公司 | Continuous production process of potassium fluotitanate |
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