CN101384512B - A process for the production of titanium products - Google Patents
A process for the production of titanium products Download PDFInfo
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- CN101384512B CN101384512B CN200680044166.7A CN200680044166A CN101384512B CN 101384512 B CN101384512 B CN 101384512B CN 200680044166 A CN200680044166 A CN 200680044166A CN 101384512 B CN101384512 B CN 101384512B
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- double salt
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- 239000010936 titanium Substances 0.000 title claims abstract description 229
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 205
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 203
- 238000000034 method Methods 0.000 title claims abstract description 99
- 150000001768 cations Chemical class 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 14
- 239000002244 precipitate Substances 0.000 claims abstract description 14
- 238000000746 purification Methods 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 150000001450 anions Chemical class 0.000 claims abstract description 8
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims description 126
- 239000000243 solution Substances 0.000 claims description 117
- 150000002500 ions Chemical class 0.000 claims description 79
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 73
- 239000000047 product Substances 0.000 claims description 42
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 34
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 22
- 238000001556 precipitation Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 20
- 229910052742 iron Inorganic materials 0.000 claims description 19
- -1 alkali metal cation Chemical class 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 10
- 238000010790 dilution Methods 0.000 claims description 8
- 239000012895 dilution Substances 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000012452 mother liquor Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 235000014413 iron hydroxide Nutrition 0.000 claims description 3
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 150000004820 halides Chemical class 0.000 abstract description 4
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- 150000003608 titanium Chemical class 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 11
- 229910021529 ammonia Inorganic materials 0.000 description 10
- 238000002386 leaching Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 8
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 6
- 229910052728 basic metal Inorganic materials 0.000 description 6
- 150000003818 basic metals Chemical class 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 6
- 238000005660 chlorination reaction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000011435 rock Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 238000000975 co-precipitation Methods 0.000 description 5
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- XFVGXQSSXWIWIO-UHFFFAOYSA-N chloro hypochlorite;titanium Chemical compound [Ti].ClOCl XFVGXQSSXWIWIO-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000012463 white pigment Substances 0.000 description 2
- 229910019931 (NH4)2Fe(SO4)2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- VULAXXNFNMUCIP-UHFFFAOYSA-M [NH4+].[O-]S(=O)(=O)O[Ti] Chemical group [NH4+].[O-]S(=O)(=O)O[Ti] VULAXXNFNMUCIP-UHFFFAOYSA-M 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010010 raising Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for the Industrial purification of a titanium feed stream of purity P1 , by the formation of a titanium-double-salt precipitate of purity P2 and a titanium solution with purity P3, wherein P2>P1 >P3, the method comprising the steps of: i. forming, from the feed, a medium comprising water, titanium ion, a cation selected from the group consisting of ammonium, cations of alkali metals, protons and a combination thereof, and an anion selected from the group consisting of OH, SO4, HSO4, halides and a combination thereof, which formed medium is further characterized by the presence of (a) a double-salt precipitate comprising titanium ion, at least one of the cations and at least one of the anions; and (b) a titanium solution; ; and wherein the concentration of the anion in the titanium solution is higher than 15% and the ratio between the concentrations of the cation and the anion in the titanium solution is higher than 0.2 and lower than 1.6; and ii. separating at least a portion of the precipitate from the solution.
Description
Technical field
The present invention relates to the method preparing titanium products.More specifically, the present invention relates to the method being prepared titanium products by the low-grade stream solution of titanium.
Background of invention
The industry preparation of titanium generally includes chlorination or sulfonation stage, wherein uses high-grade titanium ore.In chloridized, use HCl/Cl
2from ore, extract titanium and titanium chloride is distilled, producing highly purified titanium thus.But the main drawback of the method is the high cost of titanium chloride distillation and purification.
Titanium dioxide is widely used as white pigment, and its market is annual about 700 ten thousand dollars.
Titanium oxide as white pigment is normally prepared by high-grade titanium ore.This product must meet strict standard: foreign matter content, particle size and particle size distribution.The particle size range of Titanium oxide particles is that a few nanometer is to hundreds of nanometer.Prepare the raw-material costly of these products.
Method described in the disclosure makes it possible to use purification phase to prepare titanium oxide from low-grade titanium stream, produces the double salt of titanium in this purification phase.
Titanium metal is prepared by high-grade titanium ore.Product must meet strict foreign matter content standard.Prepare the raw-material costly of this product.The low-grade titanium ore obtained by industrial treatment or low-grade solution stream are not used in the preparation of these products.
Method suggestion described in the disclosure uses purification phase to prepare titanium products from low-grade titanium stream, produces the double salt of titanium in this purification phase.
Double salt is defined as the crystal be made up of two kinds of different positively charged ions and/or negatively charged ion.Usually it is characterized in that there is significantly lower solvability, compared to the simple salt of its component.
Goroshchenko, Ya.G (sulfuric acid double salt of titanium and ammonium) Doklady AkademiiNauk SSSR (1956), 109532-4 have studied the precipitation of double salt from purified solution of Ti (iv), and finds at high ammonium sulfate or H
2sO
4salting-out effect and the reduction of double salt solvability is observed under concentration.
Titanium oxide is separated with other polyvalent cation be present in ilmenite or other titaniferous ore at the patent BR 20012509 of creation in 2003 by SILVA HELIO JOSE.In the method for this proposal, before Fe (III) is with the Multiple salts forms of ammonium precipitation, Fe with Al is separated by from titanium salt.Add ammonium sulfate to the solution using sulfuric acid leaching ilmenite to obtain, cause binary salt (NH
4) Fe (SO
4)
212H
2o, (NH
4)
2tiO (SO
4)
2h
2o and (NH
4)
2fe (SO
4)
26H
2the coprecipitation of O.
Double salt can be produced by many polyvalent cations.Titanium, Fe (III) and Fe (II) can produce double salt, and the usual coprecipitation of these double salt.
Described patent and article instruction, the double salt of polyvalent cation is easy to precipitate but often co-precipitation forms the product of low-purity.Salt precipitation under low temperature may reduce the solvability of double salt, therefore increase the precipitation yield of titanium double salt, but expectation can reduce the purity of product.Result there is not the commercial run using double salt technology purification titanium salt.
According to the present invention, unexpected find that titanium double salt can precipitate with high yield and highly selective the solution of from the polyvalent cation containing height ratio and particularly Fe (II) and Fe (III), produce high titanium: the product of polyvalent cation ratio.
Unexpected find, use anion concentration higher than 20% and the ratio of monovalent cation and the negatively charged ion mother liquor that is 0.2-1.4, the while that crystallization yield being very high, the purity of double salt is very high.Also unexpected discovery, can wash the double salt produced under titanium loses low-down situation, there is provided the product of enough grades, this product can be used for preparing titanium metal, the starting material of titanium metal and other high purity metal product, and for the preparation of titanium oxide and titanium salt.Although Fe (III) and Fe (II) exists in solution in a large number and can form similar double salt, but still obtains this high purity.Monovalent cation higher: under the ratio of negatively charged ion, the double salt of iron and the complex salt deposition of titanium, thus the purity reducing product.
The invention provides the method for purification of very effective, low expense, wherein use low-grade titanium stream such as, to prepare high-grade titanium, starting material, higher-grade titanium metal and other titanium products for the preparation of higher-grade titanium dioxide, chlorination oxygen titanium, titanyl sulfate and other titanium salt.
Summary of the invention
Consider prior art, according to the invention provides the industrial purification method that purity is the low-grade titanium incoming flow of P1, to form purity be the titanium double salt precipitation thing of P2 and purity is the titanium solution of P3, wherein P2 > P1 > P3, described method comprises the steps:
I. formed from described charging and comprise water, titanium ion, the positively charged ion being selected from ammonium, alkali metal cation, proton (proton) and combining, and be selected from OH, SO
4, HSO
4, halogenide and combination thereof the medium of negatively charged ion, the medium of described formation is further characterized in that existence: (a) comprises the double salt precipitation thing of negatively charged ion described in positively charged ion described in titanium ion, at least one and at least one; (b) titanium solution; And the concentration of wherein said negatively charged ion in described titanium solution is higher than 15%, and described in described titanium solution positively charged ion and the ratio of the concentration of described negatively charged ion higher than 0.2 and lower than 1.6; With
Ii. from described solution, described throw out is at least partially separated.
The term titanium double salt used in this specification sheets refers to that one of wherein said positively charged ion is titanium by the crystal of negatively charged ion cation composition different from two kinds.
The term positively charged ion used in this specification sheets refers to the monovalent cation be present in double salt.
The term negatively charged ion used in this specification sheets refers to the negatively charged ion be present in double salt.
Term purity or P will be defined as the weight ratio of titanium and whole polyvalent metal, wherein this purity represents with per-cent in some situations, the P1 such as, used in this specification sheets refers to the purity of titanium feedstock solution, and P2 refers to the purity of titanium double salt and P3 refers to the purity of titanium solution (this titanium solution is the mother liquor formed in the preparation of titanium double salt).
The term titanium metal used in this specification sheets refers to simple substance titanium in the disclosure, such as the metal product of titanium sponge or other titanium any.
The term titanium products used in this specification sheets refers to the various products comprising titanium, the organic salt of such as titanium hydroxide, hydroxyl oxidize titanium, titanium chloride, titanium oxychloride, titanium sulfate, titanyl sulfate and other titanium or inorganic salt.
According to one embodiment of the invention, described titanium charging can be the low-grade stream solution by using acid solution to leach the titanium that titanium ore is formed.According to another embodiment, described titanium charging comprises the acid being selected from acid halide, sulfuric acid, nitric acid or their any combination.
According to another embodiment of the invention, described feedstock solution comprises the waste streams from industrial treatment, and in another embodiment, described titanium charging comprises the waste streams from titanium preparation process.
Therefore, the invention provides for purifying titanium incoming flow and particularly from the very effective method of the titanium incoming flow of low-grade titanium stream.
According to another embodiment, the present invention also comprises the described throw out of process to produce the step of titanium oxide.
Described titanium oxides product is anatase octahedrite, rutile and brookite.
According to another embodiment, the present invention also comprises the described throw out of process to produce the step of the titanium products beyond titanium oxide.
Described product is Ti (OH)
4, TiOCl
2, TiOCl
2, TiCl
4, TiOSO
4, TiO (NO
3)
2, other Ti-inorganic salt and titanium organic salt.
In other preferred embodiment of the present invention, provide the method comprising following step in addition: process described throw out to produce titanium metal.
In a preferred embodiment of the invention, described titanium incoming flow is water base lean solution.
In a preferred embodiment of the invention, described titanium charging is formed by using acid solution to leach titanium ore.
In one embodiment, the scope of the purity P1 of described titanium charging is about 10% to about 90%.P1 is preferably lower than 60%.P1 is lower than 50% in particularly preferred embodiments, and in another preferred embodiment of the present P1 lower than 45%.
According to an embodiment, described titanium charging comprises the iron that Fe/Ti ratio is at least 0.25, and the Fe/Ti ratio that described titanium double salt precipitation thing comprises is less than 0.02.
In a preferred embodiment of the invention, P1 is less than 70% and P2 is greater than 95%.
In particularly preferred embodiment of the present invention, described titanium incoming flow comprises proton and is selected from least one negatively charged ion of halogenide, sulfate radical, nitrate radical and combination thereof.
In a preferred embodiment of the invention, described titanium incoming flow comprises the waste streams from industrial treatment.
In certain preferred embodiments of the present invention, described titanium incoming flow comprises iron, and the molar ratio range of iron and titanium is about 0.2: 1 to about 3: 1 in described low-grade stream.
In described preferred embodiment, in described double salt, the molar ratio of titanium and iron is preferably at least 5 times of the described ratio in described incoming flow.
In certain preferred embodiments of the present invention, the described positively charged ion in described double salt is ammonium.
In other preferred embodiment of the present invention, the described positively charged ion in described double salt is selected from sodium and potassium.
In certain preferred embodiments of the present invention, the described negatively charged ion in described double salt is selected from OH, SO
4, HSO
4and halogenide.
In a preferred embodiment of the invention, described throw out is selected from the alkali formula double salt of titanium double salt and titanium.
Described throw out preferably comprises the titanium be present at first in described low-grade stream solution of at least 80%.
In a preferred embodiment of the invention, ratio P2/P3 is greater than 2.
In preferred embodiment of the present invention, this throw out comprises the titanium be present in titanium charging being greater than 85%, and ratio i.e. (1-P3)/(1-P2) between multivalence impurity is greater than 10.
In particularly preferred embodiment of the present invention, ratio P2/P3 is greater than 10.
In a preferred embodiment of the invention, the temperature of the medium of described formation is 0-80 DEG C.
In particularly preferred embodiment of the present invention, the temperature of carrying out described contact is 10-50 DEG C.
In most preferred embodiment of the present invention, the temperature of carrying out described contact is 20-40 DEG C.
In a preferred embodiment of the invention, adjust to form the product being selected from following group to described titanium solution: ferrous metal, ferriferous oxide and be present in the product of other polyvalent cation in described titanium feedstock solution, wherein one of adjusting stage is crystallization.
In described preferred embodiment, described iron-containing product is chosen from Fe double salt, ferriferous oxide and iron hydroxide preferably.
In described preferred embodiment, the negatively charged ion of described iron double salt is selected from univalent anion, dianion, halide anions, sulfate radical and anion hydrogen sulphate and their combination.
In described preferred embodiment, the second positively charged ion of described iron double salt is selected from ammonium, sodium and potassium.
In described preferred embodiment, the compound of described polyvalent cation is preferably selected from the neutral double salts of described polyvalent cation, alkali formula double salt, metal oxide and metal hydroxides.
In certain preferred embodiments of the present invention, described method also comprises with the solution washing sedimentary stage to form purifying washing precipitate that purity is P4 and purity is the washing soln of P5, wherein P4 > P2 > P5.
According to preferred embodiment, described washing soln comprises and the identical negatively charged ion existed in titanium double salt and positively charged ion, and wherein this positively charged ion is selected from ammonium, basic metal and combination thereof, and this negatively charged ion is selected from SO
4, HSO
4, halogenide and combination thereof, and the concentration of wherein said negatively charged ion is higher than 15%, and the ratio of the described positively charged ion in described titanium solution and the concentration of described negatively charged ion is higher than 0.2 and lower than 1.6.
In described preferred embodiment, described washing preferably uses the solution comprising proton, ammonium and sulfate ion.
In described preferred embodiment, the sedimentary purity of described washing is higher than 99%.
In other preferred embodiment of the present invention, described method also comprises makes (optional pre-wash) described throw out recrystallize to form throw out that purity is P6 and purity is the mother liquor of P7, wherein P6 > P2 > P7.
In described preferred embodiment, the sedimentary purity of this recrystallize is higher than 99% and more preferably higher than 99.9%.
Preferably, described crystallization causes by being selected from following effect: add the salt of monovalent cation, add the alkali of monovalent cation, improve temperature, dilution and combination thereof.
Described recrystallize preferably uses the solution comprising and be selected from least one positively charged ion in mentioned above group and at least one negatively charged ion.
In certain preferred embodiments of the present invention, in order to the precipitation by titanium oxide produces titanium oxide from described titanium complex salt solution, described method comprises the steps:
A. titanium double salt is dissolved in aqueous; With
B. cause condition to change to go out titanium oxide from described solution precipitation, wherein said change is selected from dilution, intensification, improves pH and combination thereof.
In described preferred embodiment, the weight ratio between the titanium amount in the titanium amount in described titanium oxide and described titanium double salt is preferably greater than 0.8.
In described preferred embodiment, described intensification refers to temperature to bring up to and is greater than 80 DEG C.
The purity (P2) of described titanium double salt is preferably greater than 80%.
In particularly preferred embodiment of the present invention, the purity (P2) of described titanium double salt is greater than 85%.
In the most preferred embodiment of the present invention, the purity (P2) of described titanium double salt is greater than 95%.
In other preferred embodiment of the present invention, the described sedimentary process of described process comprises the generation stage of titanium oxide, and described method comprises the steps:
A. titanium double salt is dissolved in aqueous; With
B. cause condition to change to form titanium hydroxide precipitation from described solution, wherein said change is selected from dilution, intensification, improves pH and combination thereof;
C. metatitanic acid is transformed into titanium oxide.
In described preferred embodiment, described titanium oxide preferably comprises the titanium be present in described titanium charging of at least 70%.
Preferably, the form of described titanium oxide is nano particle, and average range is 5-100 nanometer.
In a preferred embodiment of the invention, the form of described titanium oxide is nano particle, and average range is 100-300 nanometer.
According to the preferred embodiments of the invention, described titanium charging also comprises Fe except other polyvalent cation.
In some preferred embodiments, the residual concentration of the ammonium sulfate in described titanium solution is greater than 20%, and remaining NH
4/ SO
4ratio ranges is 0.2: 1 to 3.1: 1, and preferred scope is 0.2: 1 to 1.4: 1, and most preferred scope is 0.2: 1 to 0.7: 1.
Preferably, the throw out of described formation is selected from the alkali formula double salt of titanium double salt and titanium.In particularly preferred embodiment, described throw out comprises the titanium be present in described titanium charging of at least 80%, and most preferably at least 85%.
In preferred embodiments, described titanium charging comprises the Fe/Ti ratio of at least 0.25, and described titanium double salt precipitation thing comprise be less than 0.04 and be more preferably less than 0.02 Fe/Ti ratio.
In preferred embodiments, P1 is less than 70% and P2 is greater than 95%.
Ti (iv), Fe (II) and Fe (III) all form double salt and often co-precipitation together.Only be present in double salt with the ultimate density of the second salt, its cationic is ammonia and basic metal and negatively charged ion is the negatively charged ion of double salt.
Higher than 10% and the ratio of the second positively charged ion and negatively charged ion is in the titanium solution of 0.1 to 1.6, titanium double salt precipitates with high purity.Under ratio outside this scope, Fe (III) and particularly Fe (II) and Ti complex salt deposition.This specified conditions make it possible to high yield precipitated titanium double salt.Along with the concentration of the second salt of remnants increases, precipitation yield increases, and purity is the highest in the narrow anionic/cationic ratio ranges of 0.2 to 0.8.
Preferably, described sedimentary purity P2 is greater than 80%.In particularly preferred embodiments, this purity is greater than 90%, and most preferably purity P2 is greater than 95%.
According to preferred embodiment, medium comprises sulfate ion, its cationic (ammonia or basic metal) and SO
4 -between mol ratio be greater than 0.1 and lower than 1.6.According to another preferred embodiment, described mol ratio is greater than 0.2 and lower than 1.4, and according to another preferred embodiment, is greater than 0.4 and lower than 0.8.
In another preferred embodiment of the present, described titanium double salt is titanium sulfate ammonium, and comprises proton, ammonia and sulfate radical for described 3rd solution of washing precipitate, and ammonia and SO
4ratio be 0.2 to 1.4.According to another preferred embodiment, this solution also comprises titanium.
Preferably, comprise for dissolving described sedimentary described solution the positively charged ion being selected from ammonium and basic metal and combination thereof, and be selected from OH, SO
4, HSO
4, halogenide and acid halide and combination thereof negatively charged ion.
According to another preferred embodiment, described solution comprises water.
In preferred embodiments, the final Anionic/Cationic ratio in washing soln is 0.2 to 1.4.
This throw out can be dissolved in water or other solution any, and add comprise be present in negatively charged ion in described double salt and cationic salt so as to produce higher than 10% and more preferably higher than 20% and most preferably higher than 30% final salt concn, and the ratio of positively charged ion and negatively charged ion is 0.2 to 1.4.
In particularly preferred embodiment of the present invention, process the generation stage that described throw out comprises titanium chloride, it comprises the steps:
I. in solvent or minimum water, titanium double salt and Cl salt is dissolved; With
Ii. from described solution, TiCl is distilled
4.
In another preferred embodiment, titanium double salt is contacted at the temperature lower than the temperature in order to precipitate metatitanic acid with alkali.Wash this throw out and be dissolved in acid.
In preferred embodiments, this acid is HCl and product is chlorination oxygen titanium.In a further preferred embodiment, this acid is H
2sO
4and product is titanyl sulfate, and this acid is organic acid or any mineral acid in another preferred embodiment of the present.
In another preferred embodiment, described titanium chloride comprises the titanium be present in described titanium feedstock solution of at least 70%, and more preferably at least 85%.
In addition, according to the first preferred embodiment, described titanium chloride or chlorination oxygen titanium are also for the preparation of titanium metal.
According to another preferred embodiment, by use Kroll technique using Na or Mg as reductive agent or or other conventional reduction method any reduce, by any titanium salt prepared and more preferably direct by titanium complex salt solution to prepare titanium metal.
According to preferred embodiment, this product is simple substance titanium, such as titanium sponge or titanium ingot or other simple substance titanium products any.
According to preferred embodiment, by crystallization, described titanium solution is adjusted to form the product being selected from following group: ferrous metal, ferriferous oxide and be present in the product of other polyvalent cation in described titanium charging.
According to preferred embodiment, described iron-containing product chosen from Fe double salt, ferriferous oxide and iron hydroxide.
According to preferred embodiment, the negatively charged ion forming described iron double salt is selected from univalent anion, dianion, halide anions, sulfate radical and anion hydrogen sulphate and their combination.
According to another preferred embodiment, the second positively charged ion of described iron double salt is selected from ammonium, sodium and potassium.
According to preferred embodiment, adjust described second solution by crystallisation stage to form the product of other polyvalent cation be present in described titanium charging, the product of other polyvalent cation described is selected from their cationic neutral double salts, alkali formula double salt, their cationic metal oxide or metal hydroxidess.
According to another preferred embodiment, described crystallisation stage causes by being selected from following step: add the salt of monovalent cation, add the alkali of monovalent cation, improve temperature, dilution and combination thereof.
In another aspect of the invention, provide the method being prepared titanium metal by reduction titanium double salt from titanium complex salt solution, described method comprises the steps:
I. titanium double salt is dissolved in the solution;
Ii. reductive condition is caused so that from the titanium described solution reduction double salt; With
Iii. this elemental metals is processed further.
According to preferred embodiment, the titanium total amount in described titanium metal or titanium chloride and the ratio between initial titanium amount are greater than 0.8, and more preferably greater than 0.95.
According to preferred embodiment, described method of reducing refers to be brought up to temperature higher than 80 DEG C.In particularly preferred embodiments, described intensification refers to temperature to bring up to and is greater than 200 DEG C, and most preferably brings up to temperature higher than 250 DEG C.
Although the present invention will be described so that aspect of the present invention is more fully understood and evaluates for some preferred embodiment in combining embodiment below with reference to the accompanying drawings, but be not intended the present invention to be limited to these specific embodiments.On the contrary, be intended that comprise may be included in claims limit the scope of the invention in all substitute, change and equivalence.Therefore, the following example comprising preferred embodiment will for illustration of enforcement of the present invention, be to be understood that shown details is only citing and object illustrates the preferred embodiments of the invention, and be in order to provide it is believed that be layoutprocedure of the present invention and principle and concept aspect the most effectively and be easy to understand and describe.
Accompanying drawing illustrates:
Fig. 1-3 shows the schema of embodiment of the present invention.
Fig. 1 shows the schema of one of preferred method according to embodiments of the present invention.In the stage 1, use acid solution to leach titanium ore to form the titanium feedstock solution of titanium salt, wherein said acid is selected from acid halide, sulfuric acid, nitric acid or their any combination.In order to for simplicity, the acid in this figure is selected to be sulfuric acid.Two kinds of streams leave leaching stage: comprise the waste streams of non-dissolved solids and be defined as the stream of titanium charging, this titanium incoming flow enters the stage 2---precipitate phase.
As the substituting of method wherein forming titanium charging in leaching stage, in another preferred embodiment of the present invention, in the stage 2 by the waste streams from titanium preparation process or be incorporated into precipitate phase from the waste streams of iron preparation process.
In the stage 2 (precipitate phase), by titanium charging and the reagent mix be selected from the group that is made up of negatively charged ion and monovalent cation are formed described medium, the positively charged ion of wherein said salt is selected from ammonium and basic metal and their combination, and the negatively charged ion of described salt is selected from OH, SO
4, HSO
4, halogenide and combination thereof, to form the titanium double salt of precipitation and the mother liquor of preferably titanium solution here.
In order to for simplicity, Fig. 1 illustrates to the stage 2 and adds containing (NH
4)
2sO
4solution.
In preferred embodiments, in the temperature range of 0-80 DEG C, carry out this stage, and in another preferred embodiment, in the temperature range of 10-50 DEG C, carry out this stage, and in yet another preferred embodiment, in the temperature range of 20-40 DEG C.
Two kinds of streams leave precipitate phase: the titanium double salt of the formation be settled out, and titanium solution.Ammonia in mother liquor and SO
4 -mol ratio be greater than 0.1.It is greater than 0.2 in another preferred embodiment of the present, and in another preferred embodiment of the present, it is greater than 0.4 and is less than 0.8.
In the figure, the second positively charged ion in described titanium double salt is ammonium, and in another preferred embodiment of the present, it is selected from sodium, potassium or any basic metal.
This stage is very effective.In preferred embodiments, described titanium double salt comprise at least 80% and more preferably at least 85% the titanium be present in described titanium charging.
In addition, the feature in this stage is to be formed very pure titanium double salt, wherein the purity (P2) of this titanium double salt is greater than 80%, be preferably greater than 85%, more preferably greater than 90%, and 95% is greater than in the most preferred embodiment, wherein ratio P2/P3 is greater than 2, is most preferably greater than 10 more preferably greater than 5.
Two kinds of streams leave precipitate phase: the titanium double salt of the formation be settled out, and enter the solution in stage 5.
Using the titanium double salt formed at least partially of precipitation in the stage 2 and described solution separating and the stage 3 entered as the washing stage.In this stage, with the 3rd this double salt of solution washing to form purifying throw out that titanium purity is the titanium salt of P4 and titanium purity is the washings of P5, wherein P4 > P2 > P5.
Described 3rd solution comprises identical positively charged ion used and negatively charged ion in precipitate phase (stage 2).In preferred embodiments, as shown in the figure, this solution comprises NH
4hSO
4and H
2sO
4, wherein in preferred embodiment more specifically, the SO in described solution
4/ HSO
4mol ratio is less than 2.
It is the recirculation flow leaving the stage 4 that Fig. 1 shows described 3rd solution.In addition this figure show described washing soln leave the washing stage and its part interpolation NH
4after OH, recirculation is back to the stage 2, and its another part is at interpolation H
2sO
4rear recirculation is back to leaching stage (stage 1).
Then titanium double salt precipitation thing enters dissolving and redeposition stage (stage 4) to form the second washing soln that titanium salt throw out that titanium purity is the purifying of P6 and titanium purity are P7, wherein P6 > P2 > P7.
In preferred embodiments, the solution in this stage comprises identical positively charged ion used in the stage 2 and negatively charged ion.According to another embodiment, described solution comprises NH
4hSO
4and H
2sO
4, and it is recycled the stage of being back to 3.According to another embodiment and as shown in Figure 1, described solution is water.
In preferred embodiments, the described recrystallize stage is caused by being selected from dilution, heating, raising pH or its step combined.The titanium products leaving the recrystallize stage comprises the titanium be present in the solution of described low-grade source of at least 70%, and more preferably at least 85%.In a further preferred embodiment, this titanium products is titanium chloride or the chlorination oxygen titanium that purity is enough to produce titanium metal.
In preferred embodiments, described second solution leaving the stage 2 is adjusted to form chosen from Fe metal, ferriferous oxide and to be present in the product of other polyvalent cation in the low-grade source of titanium charging.
Fig. 2 shows the schema of one of preferred method according to embodiments of the present invention.This figure and Fig. 1 is very similar, but difference is the washing stage (stage 3) of titanium double salt, the figure shows the dissolving for the final purification of titanium double salt and recrystallize step.
Fig. 3 shows for the schema from one of the titanium complex salt solution preferred process of the present invention preparing titanium metal, comprises the steps: to dissolve titanium double salt in the solution and cause condition so that from described solution distillation titanium chloride.
According to the preferred embodiment of the method, the negatively charged ion of titanium double salt is muriate, and in statu quo or at interpolation water or/and distill titanium chloride after solvent from described salt.
According to another preferred embodiment of the method, the negatively charged ion of titanium double salt is sulfate radical, and produces titanium chloride or chlorination oxygen titanium by adding chloride salt or HCl and water and/or solvent.
According to another preferred embodiment of the method, produce simple substance titanium by Kroll technique reduction titanium double salt.
Stage 1 represents the dissolving in aqueous of titanium double salt.In order to for simplicity, indicating this stream in this figure is water.
Preferred embodiment describes
Comparative example 1
By obtaining the solution of different amount with sulfuric acid leaching ilmenite, by the ammonia of difference amount and (NH
4)
2sO
4add flask.At 25 DEG C, rock this flask continue 20 minutes or 1.5 hours.Form throw out.The composition of leach liquor ilmenite solution lists in table 1, and the composition of throw out and titanium solution is listed in table 2 and table 3.
Table 1
| Ti(SO 4) 2 | Fe 2(SO 4) 3 | FeSO 4 |
| Wt％ | Wt％ | Wt％ |
| 11.0 | 2.0 | 8.17 |
The result of table 2 RT after lower 1.5 hours
| Sequence number | (NH 4) 2SO 4 Wt％ | (NH 4) 2SO 4Final Wt% | Ti(SO 4) 2Wt% in solution | Fe +3 2(SO 4) 3Wt% in solution | Fe +2SO 4Wt% in solution | Fe +2Moles/mole in/Ti crystal |
| 1 | 24 | 9.59 | 1.3 | 2.5 | 2.76 | 0.88 |
| 2 | 21 | 6.01 | 2.2 | 2.3 | 4.80 | 0.60 |
| 3 | 17 | 4.73 | 3.7 | 2.6 | 7.92 | 0.05 |
The result of table 3 after 20 minutes
| Sequence number | (NH 4) 2SO 4 Wt％ | (NH 4) 2SO 4Final Wt% | Ti(SO 4) 2Wt% in solution | Fe +3 2(SO 4) 3Wt% in solution | Fe +2SO 4Wt% in solution | Fe +2/ Ti moles/mole |
| 4 | 20 | 4.73 | 1.9 | 2.3 | 3.37 | 0.83 |
| 5 | 24 | 8.34 | 1.0 | 2.7 | 2.11 | 0.96 |
| 6 | 28 | 13.14 | 0.8 | 2.4 | 0.98 | 1.1 |
This embodiment instructs our Fe positively charged ion and titanium positively charged ion with Multiple salts forms co-precipitation, has low remaining titanium and Fe concentration or low remaining ammonium sulfate concentrations, forms impure double salt.
Embodiment 2
By obtaining the solution of different amount with sulfuric acid leaching ilmenite, by ammonia and (NH
4)
2sO
4add flask.At 25 DEG C, rock this flask continue 1.5 hours.Form throw out.The composition of throw out and solution is as shown in table 4.
The result of table 4 RT after lower 1.5 hours
| Sequence number | (NH 4) 2SO 4 Wt％ | (NH 4) 2SO 4Final Wt% | Ti(SO 4) 2Wt% in solution | Fe +3 2(SO 4) 3Wt% in solution | Fe +2SO 4Wt% in solution | Fe +2Moles/mole in/Ti crystal |
| 3 | 17 | 4.73 | 3.7 | 2.6 | 7.92 | 0.05 |
This embodiment instructs us even to precipitate from residual Fe concentration far above also obtaining highly purified titanium salt the solution of Ti.
Embodiment 3
By obtaining the solution of different amount with sulfuric acid leaching ilmenite, by ammonia and (NH
4)
2sO
4add flask.At 25 DEG C, rock this flask continue 1.5 hours.Form throw out.The composition of throw out and solution is as shown in table 5.
Table 5
This embodiment instructs the purity of ratio on double salt between we residual ammonia and residual sulfur acid group to have remarkably influenced.
Embodiment 4
By obtaining the solution of different amount with sulfuric acid leaching ilmenite, and by (NH
4)
2sO
4add flask.At 30 DEG C, rock this flask continue 20 minutes.Form throw out.The composition of initial soln is as shown in table 6, and result is shown in Table 7.
Table 6 starting condition
Table 7 result
| (NH 4) 2SO 4(interpolation) Wt% in solution | Ti(SO 4) 2Wt% in solution | Fe 2(SO 4) 3Wt% in solution | FeSO 4Wt% in solution | Fe +2Moles/mole in/Ti crystal |
| 13 | 6.7 | 6.2 | 6.01 | 0.00 |
| 10 | 5.1 | 6.0 | 5.62 | 0.02 |
This embodiment instructs us, at suitable remaining NH
4/ SO
4under ratio, throw out contains Fe hardly, even if Fe/Ti ratio is in the solution very high.
Embodiment 5.1
By obtaining the solution of different amount with sulfuric acid leaching ilmenite, by ammonia and (NH
4)
2sO
4add flask.At 25 DEG C, rock this flask continue 1.5 hours.Form throw out.The composition of throw out and solution is as shown in table 8.
Table 8
Embodiment 5.2
The crystal that will obtain in No. 2 bottles (vial) and 20%NH
4hSO
4solution adds in bottle.At 30 DEG C, rock this bottle continue 20 minutes.The composition of solid is as shown in table 9.
Table 9
Embodiment 5.3
Obtain in embodiment 5.2 2.0 grams of double salt are dissolved in 10 grams of water.This solution is heated to 169 DEG C.Form throw out.In residual solution, the concentration of Ti is about 0.05%.
Embodiment 6
Obtain in embodiment 5.1 2.0 grams of double salt are dissolved in 2 grams of water.The NaOH solution slowly adding 0.2M is 4.2 to pH.Form throw out.Throw out be separated and wash, finding that it is metatitanic acid.
4N HCl solution is added to form titanium oxychloride solution in solution.
Embodiment 7
Obtain in embodiment 5.2 2.0 grams of double salt are dissolved in 2 grams of water.The NaOH solution slowly adding 0.2M is 4.2 to pH.Form throw out.Throw out be separated and wash, finding that it is metatitanic acid.
4N H is added in solution
2sO
4solution is to form titanyl sulfate solution.
Embodiment 8
Obtain in embodiment 5.2 2.0 grams of double salt are dissolved in 2 grams of water.The NaOH solution slowly adding 0.2M is 4.2 to pH.Form throw out.Throw out be separated and wash, finding that it is metatitanic acid.Use propanol rinse throw out.
Dense H is added in solution
2sO
4solution is to form titanyl sulfate solution.Mg metal is added in solution.Magnesium salts is formed while titanium metal precipitation.
Embodiment 9
Obtain in embodiment 5.2 2.0 grams of double salt are dissolved in 2 grams of water.The NaOH solution slowly adding 0.2M is 4.2 to pH.Form throw out.Throw out be separated and wash, finding that it is metatitanic acid.
Sulfonic acid lauryl is added to form organic titanyl salt in solution.
It will be apparent to those skilled in that, the invention is not restricted to the details of aforesaid illustrative embodiment and can the present invention be implemented by other particular form and not depart from base attribute of the present invention, therefore wish with reference to appended claim but not aforesaid specification sheets, consider embodiment of the present invention and embodiment by way of example and not limitation in all respects.Therefore the invention is intended to comprise all changes in the connotation of claim Equivalent and scope.
Claims (49)
1. purity is the industrial purification method of the titanium incoming flow of P1, and the method is the titanium solution of P3 by form purity be the titanium double salt precipitation thing of P2 and purity, and wherein P2 > P1 > P3, described method comprises the steps:
I. formed from described charging and comprise water, titanium ion, be selected from the positively charged ion in the group be made up of ammonium, alkali metal cation, proton and combination thereof, and be selected from by OH, SO
4and HSO
4the medium of the negatively charged ion in the group formed, the medium of described formation is further characterized in that existence: (a) comprises the double salt precipitation thing of negatively charged ion described in positively charged ion described in titanium ion, at least one and at least one; (b) titanium solution; And wherein said negatively charged ion concentration is in the medium higher than 15%, and in the medium described positively charged ion and the ratio of the concentration of described negatively charged ion higher than 0.2 and lower than 1.6; With
Ii. from described solution, described throw out is at least partially separated.
2. method according to claim 1, also comprises the described throw out of process to produce the step of titanium oxide.
3. method according to claim 1, also comprises the described throw out of process to produce the step of the titanium products beyond titanium oxide.
4. method according to claim 1, also comprises the described throw out of process to produce the step of titanium metal.
5. method according to claim 1, wherein said titanium incoming flow is water base lean solution.
6. method according to claim 1, wherein said titanium incoming flow comprises the iron positively charged ion of at least 2 % by weight.
7. method according to claim 1, wherein said titanium charging is formed by using acid solution to leach titanium ore.
8. method according to claim 1, wherein the scope of P1 is 10% to 90%.
9. method according to claim 1, wherein P1 is lower than 60%.
10. method according to claim 1, wherein P1 is lower than 50%.
11. methods according to claim 1, wherein said titanium incoming flow comprises the iron that Fe/Ti mol ratio is at least 0.25, and the described Fe/Ti mol ratio in wherein said titanium double salt precipitation thing is less than 0.02.
12. methods according to claim 1, wherein P1 is less than 70% and P2 is greater than 95%.
13. methods according to claim 1, wherein said titanium incoming flow comprises proton and is selected from least one negatively charged ion of sulfate radical and bisulfate ion.
14. methods according to claim 1, wherein said titanium incoming flow comprises the byproduct stream from industrial treatment.
15. methods according to claim 1, wherein said titanium incoming flow comprises iron, and Fe/Ti molar ratio range is 0.2: 1 to 3: 1 in described incoming flow.
16. methods according to claim 15, the Fe/Ti molar ratio in wherein said double salt precipitation thing is at the most 1/5th of described ratio in described incoming flow.
17. methods according to claim 1, the described positively charged ion in wherein said double salt is ammonium.
18. methods according to claim 1, the described positively charged ion in wherein said double salt is selected from sodium and potassium.
19. methods according to claim 1, the described negatively charged ion in wherein said double salt is selected from OH, SO
4and HSO
4.
20. methods according to claim 1, wherein said throw out is selected from the alkali formula double salt of titanium double salt and titanium.
21. methods according to claim 1, wherein said throw out comprises the titanium be present at first in described incoming flow of at least 80%.
22. methods according to claim 1, wherein ratio P2/P3 is greater than 2.
23. methods according to claim 1, wherein ratio P2/P3 is greater than 10.
24. methods according to claim 1, the temperature of the medium of wherein said formation is 0-80 DEG C.
25. methods according to claim 1, the temperature of the medium of wherein said formation is 10-50 DEG C.
26. methods according to claim 1, the temperature of the medium of wherein said formation is 20-40 DEG C.
27. methods according to claim 1, the method also comprises and to process described titanium solution to form the step of the product being selected from following group: ferrous metal, ferriferous oxide, iron double salt, iron hydroxide, the product being present in other polyvalent cation in described titanium feedstock solution and their combination, described process comprises crystallization.
28. methods according to claim 1, described method also comprises the sedimentary step of the described separation of washing, to form washing precipitate that purity is P4 and purity is the washing soln of P5, wherein P4 > P2 > P5.
29. methods according to claim 28, wherein said washing uses the solution comprising at least one positively charged ion and at least one negatively charged ion, described positively charged ion and negatively charged ion are selected from described group in claim 1, and the concentration of wherein said negatively charged ion is higher than 15%, and the ratio of described positively charged ion in described titanium solution and the concentration of described negatively charged ion is higher than 0.2 and lower than 1.6.
30. methods according to claim 28, wherein said washing uses the solution comprising proton, ammonium and sulfate ion.
31. methods according to claim 1, described method also comprises the step making the optional described throw out recrystallize through pre-wash, to form throw out that purity is P6 and purity is the mother liquor of P7, wherein P6 > P2 > P7.
32. according to the method for claim 31, and wherein said recrystallize uses the solution comprising at least one positively charged ion and at least one negatively charged ion, and described positively charged ion and negatively charged ion are selected from described group in claim 1.
33. methods according to claim 1, the method also comprises the steps:
A. titanium double salt is dissolved in aqueous; With
B. cause condition to change to form titanium oxide precipitation from described solution, wherein said change is selected from dilution, intensification, improves pH and combination thereof.
34. methods according to claim 2, wherein said titanium oxide comprises the titanium be present at first in described incoming flow of at least 70%.
35. methods according to claim 2, wherein said titanium oxide comprises the nano particle that medium size range is 5-100 nanometer.
36. methods according to claim 2, wherein said titanium oxide comprises the nano particle that medium size range is 100-300 nanometer.
37. methods according to claim 27, the negatively charged ion of wherein said iron double salt is selected from univalent anion and dianion.
38. according to the method for claim 37, and the negatively charged ion of wherein said iron double salt is selected from sulfate radical and anion hydrogen sulphate.
39. according to the method for claim 37, and wherein said iron double salt comprises the positively charged ion being selected from ammonium, sodium and potassium.
40. methods according to claim 27, the product of wherein said polyvalent cation is selected from neutral double salts, alkali formula double salt, oxide compound, oxyhydroxide and their combination.
41. according to the method for claim 31, and wherein said recrystallize causes by being selected from following effect: add the salt of monovalent cation, add the alkali of monovalent cation, improve temperature, dilution and combination thereof.
42. methods according to claim 2, for producing titanium oxide from described titanium complex salt solution, described method comprises the steps:
A. titanium double salt is dissolved in aqueous; With
B. by being selected from dilution, intensification, the effect that improves pH and combination thereof cause titanium oxide to precipitate from described solution.
43. according to the method for claim 42, and wherein said titanium oxide comprises the titanium be present at first in described double salt of at least 80%.
44. according to the method for claim 42, and wherein said intensification relates to be brought up to temperature higher than 80 DEG C.
45. methods according to claim 1, wherein P2 is greater than 80%.
46. methods according to claim 1, wherein P2 is greater than 85%.
47. methods according to claim 1, wherein P2 is greater than 95%.
48. methods according to claim 2, wherein said titanium oxide comprises the titanium be present in described titanium feed stream solution of at least 70%.
49. according to the method for claim 42, and wherein said intensification refers to be brought up to temperature in the scope of 120 DEG C to 250 DEG C.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IL17136305A IL171363A (en) | 2005-10-11 | 2005-10-11 | Process for the production of titanium products |
| IL171363 | 2005-10-11 | ||
| IL171364 | 2005-10-11 | ||
| IL17136405 | 2005-10-11 | ||
| IL178477 | 2006-10-05 | ||
| IL178477A IL178477A0 (en) | 2006-10-05 | 2006-10-05 | A process for the production of titanium products |
| PCT/IL2006/001185 WO2007043055A1 (en) | 2005-10-11 | 2006-10-15 | A process for the production of titanium products |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101384512A CN101384512A (en) | 2009-03-11 |
| CN101384512B true CN101384512B (en) | 2015-05-20 |
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ID=40463748
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200680044166.7A Expired - Fee Related CN101384512B (en) | 2005-10-11 | 2006-10-15 | A process for the production of titanium products |
Country Status (4)
| Country | Link |
|---|---|
| CN (1) | CN101384512B (en) |
| ES (1) | ES2363685T3 (en) |
| IL (1) | IL171363A (en) |
| ZA (1) | ZA200803180B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1357690A (en) * | 1918-12-06 | 1920-11-02 | Oscar T Coffelt | Process for the recovery of titanium from its ores |
| US2345980A (en) * | 1939-09-22 | 1944-04-04 | Du Pont | Production of titanium pigments |
| US4396387A (en) * | 1979-11-11 | 1983-08-02 | Motov David L | Method for preparing titanium tanning agent and use thereof in leather tanning process |
| IT1127261B (en) * | 1979-11-26 | 1986-05-21 | Uop Inc | Recovering iron and titanium values from ilmenite |
-
2005
- 2005-10-11 IL IL17136305A patent/IL171363A/en not_active IP Right Cessation
-
2006
- 2006-10-15 ES ES06809756T patent/ES2363685T3/en active Active
- 2006-10-15 CN CN200680044166.7A patent/CN101384512B/en not_active Expired - Fee Related
-
2008
- 2008-04-10 ZA ZA200803180A patent/ZA200803180B/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1357690A (en) * | 1918-12-06 | 1920-11-02 | Oscar T Coffelt | Process for the recovery of titanium from its ores |
| US2345980A (en) * | 1939-09-22 | 1944-04-04 | Du Pont | Production of titanium pigments |
| US4396387A (en) * | 1979-11-11 | 1983-08-02 | Motov David L | Method for preparing titanium tanning agent and use thereof in leather tanning process |
| IT1127261B (en) * | 1979-11-26 | 1986-05-21 | Uop Inc | Recovering iron and titanium values from ilmenite |
Non-Patent Citations (1)
| Title |
|---|
| 卢铁城 等.金红石生长用TiO2 纳米晶粉体制备及表征.《功能材料》.2001,第32卷(第6期),655-656,659. * |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2363685T3 (en) | 2011-08-11 |
| ZA200803180B (en) | 2009-07-29 |
| CN101384512A (en) | 2009-03-11 |
| IL171363A (en) | 2011-12-29 |
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