ES2363685T3 - PROCEDURE OF PRODUCTION OF TITANIUM PRODUCTS. - Google Patents

Abstract

A process for the industrial purification of a titanium supply stream, of purity P1, by forming a double salt precipitate of titanium, of purity P2, and a titanium solution with purity P3, in which P2> P1> P3, said procedure comprising the steps of: i. forming, from said supply, a medium comprising water, titanium ion, a cation selected from the group consisting of ammonium, alkali metal cations, protons and a combination thereof, and an anion selected from the group consisting in OH, SO4 and H2SO4, halides and a combination thereof, formed medium which is further characterized by the presence of (a) a double salt precipitate comprising titanium ion, at least one of said cations and at least one of said anions; and (b) a titanium solution; and wherein the concentration of said anion in said titanium solution is greater than 15% and the ratio between the concentrations of said cation and said anion in said titanium solution is greater than 0.2 and less than 1.6; ii. separating at least a portion of said precipitate from said solution and, optionally iii. processing said precipitate to produce titanium oxide, a titanium product other than titanium oxide or metallic titanium.

Description

The present invention relates to a process for the production of titanium products. More particularly, the present invention relates to a process for the production of titanium products from a titanium solution of a low quality stream.

Industrial titanium production normally includes a chlorination or sulfonation phase, in which high quality titanium ores are used. In the chlorination process, HCl / Cl2 is used to extract the titanium from the minerals and the titanium chloride is distilled; in this way, a highly purified titanium is produced. However, the main disadvantage of this process is the high cost of the distillation and purification of titanium chloride.

Titanium dioxide is widely used as a white pigment with a market of approximately 7 million dollars a year.

Titanium oxide, which is a white pigment, is usually produced from high quality titanium minerals. The product has to meet strict levels of impurity content, particle size and particle size distribution. The particle size of the titanium oxide particles varies from several nanometers to several hundred nanometers. The cost of the raw material for the production of these products is high.

The process described in the present disclosure enables the production of titanium oxide from a stream of low quality titanium, using a purification phase in which a double titanium salt is produced.

Metallic titanium is produced from high quality titanium minerals. The product has to meet strict levels of impurity content. The cost of the raw material for the production of this product is high. Low quality titanium ores, or low quality solution streams obtained from industrial processes, are not used for the production of these products.

The procedures described in the present disclosure suggest the production of titanium products from a stream of low quality titanium, using a purification phase in which a double titanium salt is produced.

A double salt is defined as a crystal consisting of two different cations and / or anions. Normally, it is characterized by a significantly lower solubility, compared to the simple salts of its components.

Goroshchenko, Ya. G (Double titanium and ammonium sulfates) Doklady Akademii Nauk SSSR (1956), 109 532-4 have studied the precipitation of a double salt of Ti (iv) from pure solutions, and found that a salification effect is observed at high concentrations of ammonium sulfate or H2SO4, and the solubility of the double salt is reduced.

BR 20012509, authorized by SILVA HELIO JOSE in 2003, separates titanium oxide from the other polyvalent cations present in limenite, or other minerals containing titanium. In this proposed procedure, Fe and Al are separated from the titanium salt before precipitation of Fe (III) in the form of a double ammonium salt. The addition of ammonium sulfate to a solution obtained by leaching limenite with sulfuric acid, induced the precipitation of binary salts (NH4) Fe (SO4) 212H2O, (NH4) 2TiO (SO4) 2H2O, and (NH4) 2Fe (SO4) 26H2O together .

Double salts can be produced from a large number of polyvalent cations. Both titanium, Fe (III) and Fe (II) produce double salts; and these double salts normally precipitate together.

Said patent and articles teach that double salts of polyvalent cations precipitate easily, but tend to co-precipitate to form a low purity product. Precipitation of the salt at low temperatures can decrease the solubility of the double salts, thereby increasing the precipitation performance of the double titanium salt, although the purity of the product is expected to decrease. The result is that there is no industrial procedure for the purification of titanium salts using double salt technology.

In accordance with the present invention, it was surprisingly discovered that a double titanium salt can be precipitated in a solution containing a high proportion of polyvalent cation and, especially, Fe (II) and Fe (III), at a high yield and high selectivity , to produce a product with a high proportion of titanium to polyvalent cations.

Surprisingly, it was discovered that with the mother water in which the concentration of anions is greater than 20%, and in which the proportion of monovalent cation to anion is between 0.2 and 1.4, the crystallization yield is very high. high, while the purity of double salt is very high. It was also surprisingly discovered that the double salt produced could be washed with very little loss of titanium, to provide a product of sufficient quality for the production of metallic titanium, raw material for metallic titanium or other high purity metal products and of titanium oxides and titanium salts. This high purity is obtained despite the fact that both Fe (III) and Fe (II) are present in large quantities in the solution, and are capable of forming similar double salts. At a higher proportion of monovalent cation to anion, the double iron salt co-precipitates with the double titanium salt, thereby reducing the purity of the product.

The present invention provides a highly efficient, low cost purification process, in which low quality titanium streams are consumed for the production of high quality titanium, raw materials for the production of high quality titanium dioxide, metallic titanium High quality and other titanium products, such as titanyl chloride, titanyl sulfate and other titanium salts.

Disclosure of the invention

With this state of the art in mind, a process for the industrial purification of a low quality titanium supply stream of purity P1 is now provided in accordance with the present invention by forming a double salt precipitate. of titanium, of purity P2, and a solution of titanium with purity P3, wherein P2> P1> P3, said process comprising the steps of:

i. forming, from said supply, a medium comprising water, titanium ion, a cation selected from the group that sews in ammonium, alkali metal cations, protons and a combination thereof, and an anion selected from the group consisting of in OH, SO4, HSO4, halides and a combination thereof, formed medium which is further characterized by the presence of (a) a double salt precipitate comprising titanium ion, at least one of said cations and at least one of said anions; and (b) a titanium solution; and wherein the concentration of said anion in said titanium solution is greater than 15% and the ratio between the concentrations of said cation to said anion, in said titanium solution, is greater than 0.2 and less than 1.6 ; Y

ii. separating at least a portion of said precipitate from said solution.

The term "double titanium salt", as used herein, refers to a crystal consisting of an anion and two different cations, in which one of said cations is titanium.

The term "cation," as used herein, refers to the monovalent cation present in the double salt.

The term "anion," as used herein, refers to the anion present in the double salt.

The term purity, or P, will be defined as the weight ratio between titanium and total polyvalent metals, in which purity occurs in several cases in terms of percentage, for example P1, as used herein. , refers to the purity of the titanium supply solution, and P2 refers to the purity of the double titanium salt, and P3 refers to the purity of the titanium solution (which is the mother water formed in the production of the double titanium salt).

The term metallic titanium, used herein, will be referred to herein as elemental titanium, such as a titanium sponge, or any other titanium metal product.

The term "titanium products", used herein, refers to various products containing titanium, such as titanium hydroxide, titanium oxyhydroxide, titanium chloride, titanium oxychloride, titanium sulfate, titanium oxy sulfate and other salts. organic or inorganic titanium.

According to an embodiment of the present invention, said titanium supply could be a low quality titanium current solution, which is formed by leaching titanium ores using an acid solution. According to another embodiment, said titanium supply comprises an acid selected from the group consisting of acid halides, sulfuric acid, nitric acid or any combination thereof.

According to another embodiment of the present invention, said supply solution comprises a residual stream of industrial processes and, in another embodiment, said titanium supply comprises a residual stream of a titanium production process.

The present invention therefore provides a highly efficient process for the purification of a titanium supply stream and, especially, of low quality titanium streams.

In accordance with another embodiment, the present invention further comprises the step of processing said precipitate to produce titanium oxide.

Among the products of titanium oxide are anatase, rutile and brookite.

According to another embodiment, the present invention further comprises the step of processing said precipitate to produce titanium products other than titanium oxide.

Among the products are Ti (OH) 4, TiOCl2, TiOCl2, TiCl4, TiOSO4, TiO (NO3) 2, other inorganic titanium salts and organic titanium salts.

In other preferred embodiments of the invention, a process is provided comprising the additional step of processing said precipitate to produce metallic titanium.

In preferred embodiments of the present invention, said titanium supply stream is an aqueous residual solution.

In preferred embodiments of the present invention, said titanium supply is formed by leaching titanium ores, using an acid solution.

In one embodiment, the purity of said supply of titanium P1 is in the range of about 10% to about 90%. Preferably P1 is less than 60%. In especially preferred embodiments, P1 is less than 50% and in another preferred embodiment P1 is less than 45%.

According to one embodiment, said titanium supply includes iron, with a Fe / Ti ratio of at least 0.25, and the double titanium salt precipitate contains a Fe / Ti ratio of less than 0.02.

In preferred embodiments of the present invention, P1 is less than 70% and P2 is greater than 95%.

In especially preferred embodiments of the present invention, said titanium supply stream comprises protons and at least one anion, selected from the group consisting of halides, sulfate, nitrate and a combination thereof.

In preferred embodiments of the present invention, said titanium supply stream comprises a residual stream of an industrial process.

In some preferred embodiments of the present invention, said titanium supply stream includes iron, and the molar ratio between iron and titanium in said low quality stream is in a range of between about 0.2: 1 and about 3: one.

In said preferred embodiments, preferably the molar ratio between titanium and iron in said double salt is greater than the ratio in said supply stream by a factor of at least 5.

In some preferred embodiments of the present invention, said cation in said double salt is ammonium.

In other preferred embodiments of the present invention, the cation in said double salt is selected from the group consisting of sodium and potassium.

In some preferred embodiments of the present invention, the anion in said double salt is selected from the group consisting of OH, SO4, HSO4 and halides.

In preferred embodiments of the present invention said precipitate is selected from the group consisting of double titanium salts and basic double titanium salts.

Preferably, said precipitate contains at least 80% of the titanium originally present in said low quality stream solution.

In preferred embodiments of the present invention, the P2 / P3 ratio is greater than 2.

In a more preferred embodiment of the present invention, the precipitate contains more than 85% of the titanium present in the titanium supply, and the proportion between the polyvalent impurities, ie (1-P3) / (1-P2), is higher from 10.

In an especially preferred embodiment of the present invention, the P2 / P3 ratio is greater than 10.

In preferred embodiments of the present invention, the temperature of said formed medium is in the range between 0-80 ° C.

In especially preferred embodiments of the present invention, the temperature at which said contact is made is in the range of 10-50 ° C.

In a more preferred embodiment of the present invention, the temperature at which said contact is made is in the range of 20-40 ° C.

In preferred embodiments of the present invention, said titanium solution is modified to form products selected from the group consisting of metallic iron, iron oxide and other polyvalent cation products present in said titanium delivery solution, wherein one of The modification phases is crystallization.

In said preferred embodiments, said iron-containing product is preferably selected from the group of double iron salt, iron oxide and iron hydroxide.

In said preferred embodiments, the anion of said double iron salt is preferably selected from the group consisting of monovalent anions, divalent anions, halide anions, sulfate and bisulfate anions and a combination thereof.

In said preferred embodiments, the second cation of said double iron salt is preferably selected from the group consisting of ammonium, sodium and potassium.

In said preferred embodiments, said polyvalent cation compound is preferably selected from the group consisting of neutral double salts, basic double salts, metal oxides and a metal hydroxide of said polyvalent cation.

In some preferred embodiments of the present invention, said process further includes a washing phase of the precipitate with a solution, to form a purified washed precipitate with a purity P4, and a washing solution with a purity P5, in which P4> P2 > P5.

According to a preferred embodiment, said wash solution comprises the same anion and cation present in the double titanium salt, wherein the cation is selected from the group consisting of ammonium, alkali metals and a combination thereof, and the anion is selected from the group consisting of SO4, HSO4 and halides and a combination thereof, and in which the concentration of said anion is greater than 15% and the ratio between the concentrations of said cation to said anion in said Titanium solution is greater than 0.2 and less than 1.6.

In said preferred embodiments, said washing is preferably with a solution comprising protons, ammonium and sulfate ions.

In said preferred embodiment, the purity of the washed precipitate is greater than 99%.

In other preferred embodiments of the present invention, said process further comprises the step of recrystallizing said precipitate, optionally prewash, to form a precipitate with a purity of P6 and a mother water with a purity P7, wherein P6> P2> P7.

In said preferred embodiment, the purity of the recrystallized precipitate is greater than 99% and, more preferably, greater than 99.9%.

Preferably, said crystallization is induced by an action selected from the group consisting of adding a monovalent cation salt, adding a monovalent cation base, increasing temperature, dilution and a combination thereof.

Preferably, said recrystallization uses a solution comprising at least one cation and at least one anion selected from the groups thereof mentioned hereinbefore.

In some preferred embodiments of the present invention, for the production of a titanium oxide from said titanium double salt solution by precipitation of titanium oxide, the process comprises the steps of:

to.

dissolution of a double titanium salt in aqueous solution; Y

b.

induction of a change in the conditions for precipitating titanium oxide from said solution, wherein said change is selected from the group consisting of dilution, temperature rise, pH increase and a combination thereof.

In said preferred embodiment, preferably the proportion by weight between the amount of titanium in said titanium oxide and that in said double titanium salt is greater than 0.8.

In said preferred embodiments, said temperature rise refers to increasing the temperature above 80 ° C.

Preferably, the purity of said double titanium salt (P2) is greater than 80%.

In especially preferred embodiments of the present invention, the purity of said double titanium salt (P2) is greater than 85%.

In a more preferred embodiment of the present invention, the purity of said double titanium salt (P2) is greater than 95%.

In other preferred embodiments of the present invention, the process of processing said precipitate includes a production phase of titanium oxide, said process comprising the steps of:

to.

dissolve a double salt of titanium in aqueous solution; Y

b.

inducing a change of conditions, to form the precipitation of titanium hydroxide from said solution, wherein said change is selected from the group consisting of dilution, temperature rise, increase in pH and a combination thereof.

C.

transform titanic acid into titanium oxide.

In said preferred embodiment, preferably said titanium oxide contains at least 70% of the titanium that was present in said titanium supply.

Preferably, the titanium oxide is in the form of nano-particles in the average range of 5-100 nanometers.

In a preferred embodiment of the present invention, the titanium oxide is in the form of nanoparticles in the average range of 100-300 nanometers.

According to a preferred embodiment of the present invention, the titanium supply is composed of, among other things, polyvalent cations and also Fe.

According to some preferred embodiments, the residual concentration of ammonium sulfate is above 20%, and the proportion of residual NH4 / SO4 in the titanium solution is in the range of 0.2: 1 to 3.1: 1 and, more preferably, in the range of 0.2: 1 to 1.4: 1 and even more preferably in the range of 0.2: 1 to 0.7: 1.

Preferably, the precipitate formed is selected from the group consisting of double titanium salts and basic double titanium salts. Especially preferred are embodiments in which said precipitate contains at least 80% of the titanium that was present in said titanium supply, more preferably at least 85%.

In a preferred embodiment, the titanium supply contains a Fe / Ti ratio of at least 0.25 and the double titanium salt precipitate contains a Fe / Ti ratio of less than 0.04 and, more preferably, less than 0 , 02.

In a preferred embodiment, P1 is less than 70% and P2 is greater than 95%.

Both Ti (iv), Fe (II) and Fe (III) form double salts, and tend to co-precipitate together. Only at the end of the concentration of the second salt, present in the double salt, in which the cation is ammonia or alkali, and the anion is a double salt anion.

In a titanium solution, which is greater than 10%, and at a second proportion of anion cation between 0.1 and 1.6, the double titanium salt precipitates at high purity. At proportions outside that range, Fe (III) and, especially, Fe (II), co-precipitate with the double salt of Ti. This specific condition enables precipitation of the double titanium salt at a high yield. The precipitation yield increases with the increase in the concentration of the second residual salt and the purity is the highest in the narrow range of cation / anion ratio between 0.2 and 0.8.

Preferably, the purity of said precipitate, P2, is greater than 80%. In especially preferred embodiments, the purity is greater than 90% and, more preferably, it is of a P2 purity, greater than 95%.

According to a preferred embodiment, the medium comprises sulfate ions, in which the molar ratio between the cation (ammonia or alkali metals) to SO4 = is greater than 0.2 and less than 1.4 and, according to another embodiment preferred, greater than 0.4 and less than 0.8.

In a further preferred embodiment, the double titanium salt is ammonium and titanium sulfate, and said third solution used to wash the precipitate comprises protons, ammonia and sulfate at a ratio of ammonia to SO4 of between 0.2 to 1.4. According to another preferred embodiment, the solution also contains titanium.

Preferably, said solution for dissolving said precipitate comprises a cation that is selected from the group consisting of ammonium and alkali metals and a combination thereof, and an anion selected from the group consisting of OH, SO4, HSO4, halides and halides of acid and a combination thereof.

According to another preferred embodiment, said solution comprises water.

In a preferred embodiment, the final cation anion ratio in the wash solution is between 0.2 and 1.4.

The precipitate can be dissolved in water or any other solution, and the salt containing the anion and the cation present in the double salt is added to create a final salt concentration greater than 10% and, more preferably, greater than 20% and , even more preferably, greater than 30% and anion cation ratios between 0.2 and 1.4.

In especially preferred embodiments of the present invention, processing said precipitate includes a production phase of titanium chloride, comprising the steps of:

i. dissolution of a double titanium salt and a Cl salt in a solvent or minimum amount of water; Y

ii. distillation of TiCl4 from said solution.

In another additional preferred embodiment, the double titanium salt is contacted with a base at a lower temperature than to precipitate the titanic acid. The precipitate is washed and dissolved in acid.

In a preferred embodiment, the acid is HCl and the product is titanyl chloride. In another preferred embodiment, the acid is H2SO4 and the product is titanyl sulfate and in another preferred embodiment the acid is an organic acid or any inorganic acid.

In another further preferred embodiment, said titanium chloride contains at least 70% of the titanium that was present in said titanium delivery solution, and more preferably at least 85%.

Furthermore, according to a first preferred embodiment, said titanium chloride or titanyl chloride are additionally used for the production of metallic titanium.

According to another preferred embodiment, the metallic titanium is produced from any titanium salt that is produced and, more preferably, directly from the titanium double salt solution, by reduction using the Kroll method, with Na or Mg as reducing agents, or any other conventional reduction procedure.

According to a preferred embodiment, the product is elemental titanium, such as titanium sponge or titanium ingots, or any other elemental titanium product.

According to a preferred embodiment, said titanium solution is modified by crystallization to form products selected from the group consisting of metallic iron, iron oxide and products of other polyvalent cations present in said titanium supply.

According to another preferred embodiment, said iron-containing product is selected from the group consisting of a double iron salt, iron oxide and iron hydroxide.

According to a preferred embodiment, the anion comprising said double iron salt is selected from the group consisting of monovalent anions, divalent anions, halide anions, sulfate and bisulfate anions and a combination thereof.

According to another preferred embodiment, the second cation of said double iron salt is selected from the group consisting of ammonium, sodium and potassium.

According to a preferred embodiment, said second solution is modified by a crystallization phase to form products of other polyvalent cations present in said titanium supply, selected from the group consisting of neutral double salts of its cation, basic double salts, oxides metallic or metal hydroxides of its cation.

According to another preferred embodiment, said crystallization phase is induced by a stage selected from the group consisting of addition of monovalent cation salt, addition of a monovalent cation base, temperature increase, dilution and a combination thereof.

In yet another aspect of the present invention, there is now provided a process for the production of metallic titanium from a solution of double titanium salt, by reduction of the double salt of titanium, comprising the steps of:

i. dissolution of a double salt of titanium in solution;

ii. induction of reduction conditions, to reduce the titanium in the double salt of said solution; Y

iii. additional processing of elemental metal.

According to a preferred embodiment, the ratio between the amount of total titanium in said metallic titanium, or titanium chloride, is greater than 0.8 of the initial amount and, more preferably, greater than 0.95.

According to a preferred embodiment, said reduction procedures refer to increasing the temperature above 80 ° C. In especially preferred embodiments, said temperature rise refers to increasing the temperature above 200 ° C and, more preferably, increasing the temperature above 250 ° C.

Although the invention will now be described in connection with certain preferred embodiments in the following examples and with reference to the attached figures, so that aspects thereof are better understood and appreciated, it is not intended to limit the invention to these particular embodiments. On the contrary, it is intended to cover all alternatives, modifications and equivalents that may be included within the scope of the invention as defined by the appended claims. Thus, the following examples, which include preferred embodiments, will serve to illustrate the practice of the present invention, it being understood that the particular situations shown are by way of example and only for purposes of illustrative analysis of the preferred embodiments of the present invention, and are presented to provide what is believed to be the most useful and most easily understood description of the formulation procedures, as well as the principles and conceptual aspects of the invention.

In the drawings:

Figures 1-3 present flow charts of embodiments of the present invention.

Figure 1 presents a flow chart of one of the preferred methods according to the embodiments of the present invention. In Phase 1, titanium ores are leached using an acid solution to form a titanium salt titanium supply solution, in which the acid is selected from the group consisting of acid halides, sulfuric acid, acid nitric or any combination thereof. For simplification, the acid in the present figure was chosen to be sulfuric acid. Two streams from the leachate phase come out: a residual stream, which contains undissolved solids, and a stream defined as the titanium supply, which enters Phase 2 - the precipitation phase.

As an alternative to the process in which the titanium supply is formed in the leaching phase, in another preferred embodiment of the present invention, a residual stream of a titanium production process, or residual streams of an iron production process, it is introduced in Phase 2 to the precipitation phase.

In Phase 2 (the precipitation phase), said medium is formed by mixing the titanium supply with a reagent selected from the group consisting of an anion and a monovalent cation, in which the salt cation is chosen from the group consisting of ammonium, alkali metals and a combination thereof, and the salt anion is selected from the group consisting of OH, SO4, HSO4, halide and a combination thereof, to form a double titanium salt that precipitates and a mother liquor here called titanium solution.

For simplification, Figure 1 demonstrates the addition of a solution containing (NH4) 2SO4 to Phase2.

In a preferred embodiment, this phase is performed in a temperature range of 0-80 ° C, in another preferred embodiment, this phase is performed in a temperature range of 10-50 ° C and, in another additional preferred embodiment, in the range of 20 -40 ° C.

Two streams leave the precipitation phase: the double salt of titanium formed, which precipitates, and the titanium solution. The molar ratio between ammonia and SO4 in the mother liquor, in a preferred embodiment, is greater than 0.2 and less than 1.4 and, in another preferred embodiment, is greater than 0.4 and less than 0, 8.

In the present figure, the second cation in said double titanium salt is ammonium, while in another more preferred embodiment it is selected from the group consisting of sodium, potassium or any alkali metal.

This phase is very effective. In a preferred embodiment, said double titanium salt comprises at least 80% of the titanium that was present in said titanium supply, more preferably at least 85%.

In addition, this phase is characterized by the formation of a double salt of very pure titanium in its interior, its purity (P2) being greater than 80%, preferably greater than 85%, more preferably greater than 90% and, in the embodiment more preferred, it is greater than 95%, in which the P2 / P3 ratio is greater than 2, more preferably greater than 5 and even more preferably greater than 10.

Two streams leave the precipitation phase: the double titanium salt formed, which precipitates, and a solution that enters Phase 5.

At least a portion of the double titanium salt formed, which precipitates in Phase 2, is separated from said solution and enters Phase 3 for a washing phase. In this phase, the double salt is washed with a third solution to form a purified precipitate of titanium salt, with a titanium purity of P4 and a wash solution with a purity of P5, in which P4> P2> P5.

The third solution comprises the same cation and anion used in the precipitation phase (Phase 2). In a preferred embodiment, and as indicated in the present Figure, this solution contains NH4HSO4 and H2SO4, in which in a specific preferred embodiment the SO4 / HSO4 molar ratio is less than 2.

Figure 1 shows that said third solution is a recycle stream that exits Phase 4. In addition, this figure shows that said wash solution exits the wash phase and a part thereof is recycled back to Phase 2. , with the addition of NH4OH and another part of its recycling back to the leaching phase, Phase 1, with the addition of H2SO4.

The double titanium salt precipitate is then introduced into the dissolution and re-precipitation phases (Phase 4) to form the purified titanium salt precipitate, with a P6 titanium purity and a second wash solution, with a purity of titanium P7, in which P6> P2> P7.

5

10

fifteen

twenty

25

30

35

In a preferred embodiment, the solution in this phase comprises the same cation and anion used in Phase 2. According to another embodiment, said solution comprises NH4HSO4 and H2SO4, which is recycled back to Phase 3. According to another embodiment. , and as described in Figure 1, said solution is water.

In a preferred embodiment, the recrystallization phase is induced by a stage selected from the group consisting of dilution, heating, pH increase or a combination thereof. The titanium product leaving the recrystallization phase contains at least 70% of the titanium that was present in said low quality source solution, more preferably at least 85%. In another preferred embodiment, the titanium product is titanium chloride or titanyl chloride, of sufficient purity to produce metallic titanium.

In a preferred embodiment, said second solution exiting Phase 2 is modified to form products selected from the group consisting of metallic iron, iron oxide and other polyvalent cation products presented at the source of low titanium supply quality.

Figure 2 presents a flow chart of one of the preferred methods according to the embodiments of the present invention. This figure is very similar to Figure 1, however, instead of the washing phase of the double titanium salt (Phase 3) this figure presents Dissolution and Re-Crystallization stages for the final purification of the double titanium salt .

Figure 3 presents a flow chart of one of the preferred methods according to the present invention, for a process of producing a titanium metal from the titanium double salt solution, which comprises the dissolution steps of a double salt of titanium in solution, and induce the conditions to distill titanium chloride from said solution.

According to a preferred embodiment of the process; The anion of the double titanium salt is chloride and the titanium chloride is distilled out of the salt, as is, or after the addition of water and / or solvent.

According to another preferred embodiment of the process, the anion of the double titanium salt is sulfate and the titanium chloride or titanyl chloride are produced by the addition of chloride or HCl salt and water and / or solvent.

According to another preferred embodiment of the process, the double titanium salt is reduced by the Kroll process to produce elemental titanium.

Phase 1 presents dissolution of a double titanium salt in an aqueous solution. For simplicity, it was indicated that this current in this figure was water.

Description of preferred embodiments

EXAMPLE 1 (Reference)

Various amounts of the solution obtained by leaching limenite with sulfuric acid, various amounts of ammonia and (NH4) SO4 in flasks were added. The flasks were stirred at 25 ° C for 20 minutes or 1.5 hours. A precipitate formed. The composition of the leached limenite solution is presented in Table 1 and that of the precipitate and the titanium solution in Tables 2 and 3.

Table 1

Ti (SO4) 2

Fe2 (SO4) 3 FeSO4

% p

% p

% p

11.0

2.0 8.17

Table 2 Results after 1.5 hours at RT Table 3 Results after 20 minutes

No.

(NH4) 2SO4% p (NH4) 2SO4% p Final Ti (SO4) 2% p in solution Fe + 3 2 (SO4) 3% p in solution Fe + 2SO4% p in solution Fe + 2 / Ti in mol / mol crystals

one

24 9.59 1.3 2.5 2.76 0.88

2

twenty-one 6.01 2.2 2.3 4.80 0.60

No.

(NH4) 2SO4% p (NH4) 2SO4% p Final Ti (SO4) 2% p in solution Fe + 3 2 (SO4) 3% p in solution Fe + 2SO4% p in solution Fe + 2 / Ti in mol / mol crystals

4

twenty 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

The example teaches us that Fe cations and titanium cations co-precipitate in the form of double salts at low residual titanium and Fe concentrations, or low residual ammonium sulfate concentrations to form an impure double salt.

EXAMPLE 2

Various amounts of solutions obtained by leaching limenite with sulfuric acid, ammonia and (NH4) 2SO4 in flasks were added. The flasks were stirred at 25 ° C for 1.5 hours. A precipitate formed. The composition of the precipitate and the solution are presented in Table 4.

10 Table 4 Results after 1.5 hours at RT

No.

(NH4) 2SO4% p (NH4) 2SO4% p Final Ti (SO4) 2% p in solution Fe + 3 2 (SO4) 3% p in solution Fe + 2SO4% p in solution Fe + 2 / Ti in mol / mol crystals

3

17 4.79 3.7 2.6 7.92 0.05

The example teaches us that the precipitation of the high purity titanium salt can be obtained even in a solution in which the concentration of residual Fe is much greater than that of Ti.

EXAMPLE 3

Various amounts of solutions obtained by leaching limenite with sulfuric acid, ammonia and (NH4) 2SO4 in flasks were added. The flasks were stirred at 25 ° C for 1.5 hours. A precipitate formed. The composition of the precipitate and the solution are presented in Table 5.

Table 5

Initial

Final

No.

Ti (SO4) 2% p in solution (NH4) 2SO4,% p (NH4) 2SO4% p Calculated Final Ti% p Fe2 (SO4) 3% p FeSO% p Fe + 2 / Ti in mol / mol crystals

7

20.5 2. 3 16 1.5 3.8 1.7 0.41

8

20.5 19 12 2.7 4.0 5.8 0.09

9

20.5 13 7.3 9.0 4.3 7.0 0.00

10

20.5 16 8.8 3.9 3.9 6.7 0.02

20 The example teaches us that the ratio between residual ammonia and residual sulfate has a dramatic effect on the purity of the double salt.

EXAMPLE 4

Various amounts of solutions obtained by leaching limenite with sulfuric acid and (NH4) 2SO4 in flasks were added. The flasks were stirred at 30 ° C for 20 minutes. A precipitate formed. The composition of the initial solution is presented in Table 6 and that of the results in Table 7.

Table 6 Initial conditions

Concentration in leaching solutions

No.

(NH4) 2SO4% p Ti (SO4) 2% p Fe2 (SO4) 3% p FeSO4% p

one

14.8 6.5 5.3 6.3

2

14.4 12.1 5.1 6.1

3

14.4 18.1 4.9 5.9

Table 7 Results

(NH4) 2SO4% p in solution (added)

Ti (SO4) 2% p in solution Fe2 (SO4) 3% p in solution FeSO4% p in solution Fe + 2 / Ti in mol / mol crystals

13

6.7 6.2 6.01 0.00

10

5.1 6.0 5.62 0.02

5 The example shows us that at the correct residual NH4 / SO4 ratio, the precipitate is practically free of Fe, even at a very high Fe / Ti ratio in solution.

EXAMPLE 5.1

Various amounts of solutions obtained by leaching limenite with sulfuric acid, ammonia and (NH4) 2SO4 in flasks were added. The flasks were stirred at 25 ° C for 1.5 hours. A precipitate formed. The composition of the precipitate and the solution are presented in Table 8.

Table 8

Initial

Final (calculated for the initial solution)

No.

Ti (SO4) 2% p in solution (NH4) 2SO4,% p (NH4) 2SO4% p Final Ti% p Fe2 (SO4) 3% p FeSO4% p Fe + 2 / Ti in the crystals, calculated, mol / mol

one

20.5 2. 3 16 1.5 3.8 1.7 0.41

2

20.5 22 13 2.5 4.0 5.4 0.19

EXAMPLE 5.2

The crystal obtained in Vial No. 2 and the 20% NH4HSO4 solution were added to a vial. The vial was stirred for 20 minutes at 30 ° C. The composition of the solid is presented in Table 9.

Table 9

Initial

Solid finish

No.

Ti (SO4) 2% p in solution NH4HSO4% p in solution Fe (II) / Ti% p Fe2 (SO4) 3% p FeSO4% p Fe + 2 / Ti in the crystals, calculated, mol / mol

one

20.5 twenty 0.41 ~ 0 0.01 0

2

20.5 twenty 0.19 ~ 0 0.03 0.02

EXAMPLE 5.3

2.0 g of the double salt obtained in Example 5.2 was dissolved in 10 g of water. The solution was heated to 169 ° C. A precipitate formed. The concentration of Ti in the remaining solution was approximately 0.05%.

EXAMPLE 6

2.0 g of the double salt obtained in Example 5.1 was dissolved in 2 g of water. A solution of 0.2 M NaOH was added slowly at a pH of 4.2. A precipitate formed. The precipitate was separated and washed, and found to be titanic acid.

A solution of 4 N HCl was added to the solution to form a solution of titanyl chloride.

EXAMPLE 7

2.0 g of double salt obtained in Example 5.2 was dissolved in 2 g of water. A solution of 0.2 M NaOH was added slowly at a pH of 4.2. A precipitate formed. The precipitate was separated and washed, and found to be titanic acid.

A solution of 4 N H2SO4 was added to the solution to form a solution of titanyl sulfate.

EXAMPLE 8

2.0 g of the double salt obtained in Example 5.2 was dissolved in 2 g of water. A solution of 0.2 M NaOH was added slowly at a pH of 4.2. A precipitate formed. The precipitate was separated and washed, and found to be titanic acid. The precipitate was washed with propanol.

A concentrated solution of H2SO4 was added to the solution to form a solution of titanyl sulfate. Metallic Mg was added to the solution. The metallic titanium precipitated while the magnesium salt formed.

EXAMPLE 9

2.0 g of the double salt obtained in Example 5.2 was dissolved in 2 g of water. A solution of 0.2 M NaOH was added slowly at a pH of 4.2. A precipitate formed. The precipitate was separated and washed, and found to be titanic acid.

A solution of lauryl sulfonate was added to the solution to form an organic titanyl salt.

It will be apparent to those skilled in the art that the invention is not limited to the details of the preceding illustrative examples, and that the present invention can be carried out in other specific ways, without departing from the essential attributes thereof and, therefore, , it is desired that the present embodiments and examples be considered in all aspects as illustrative and not as restrictive, with reference to the appended claims, rather than the above description, and all changes included within the meaning and the equivalence range of the claims, therefore, are intended to be encompassed therein.

5

fifteen

25

35

Four. Five

Claims (15)

1. A process for the industrial purification of a titanium supply stream, of purity P1, by forming a double salt precipitate of titanium, of purity P2, and a titanium solution with purity P3, in which P2> P1> P3, said procedure comprising the steps of: i. forming, from said supply, a medium comprising water, titanium ion, a cation selected from the group consisting of ammonium, alkali metal cations, protons and a combination thereof, and an anion selected from the group consisting in OH, SO4 and H2SO4, halides and a combination thereof, formed medium which is further characterized by the presence of (a) a double salt precipitate comprising titanium ion, at least one of said cations and at least one of said anions; and (b) a titanium solution; and wherein the concentration of said anion in said titanium solution is greater than 15% and the ratio between the concentrations of said cation and said anion in said titanium solution is greater than 0.2 and less than 1.6; ii. separating at least a portion of said precipitate from said solution and, optionally iii. processing said precipitate to produce titanium oxide, a titanium product other than titanium oxide or metallic titanium.

2.

A process according to claim 1, wherein said titanium supply stream is selected from a group consisting of the product of leaching titanium ores with an acid solution; an aqueous residual solution; a solution comprising a byproduct stream of an industrial process; and a solution comprising protons and at least one anion selected from the group consisting of halides, sulfate, bisulfate, nitrate and a combination thereof.

3.

A method according to claim 1, wherein P1 is less than 50%.

Four.

A method according to claim 1, wherein P1 is less than 70%, P2 is greater than 95% or both.

5.

A process according to claim 1, wherein the titanium supply stream comprises iron with a Fe / Ti molar ratio of at least 0.25 and wherein said ratio in said double titanium salt precipitate is less than 0.02.

6.

A process according to claim 1, wherein said titanium supply stream comprises iron, and wherein the Fe / Ti molar ratio in said supply stream is in a range between about 0.2: 1 and about 3 : 1, or comprises at least 2% by weight of iron cations.

7.

A process according to claim 6, wherein said titanium supply stream comprises iron, and wherein the Fe / Ti molar ratio in said supply stream is in a range between about 0.2: 1 and about 3 : 1 and in which the Fe / Ti molar ratio in said double salt precipitate is less than the proportion in said supply stream by a factor of at least 5.

8.

A process according to claim 1, wherein said precipitate contains at least 80% of the titanium originally present in said supply stream.

9.

A method according to claim 1, wherein the P2 / P3 ratio is greater than 10.

10.

A process according to claim 1, wherein the temperature of said formed medium is in the range between 20-40 ° C.

eleven.

A method according to claim 1, further comprising at least one of:

to.

the step of washing said precipitate separately, to form the precipitate washed with a purity of P4, and a washing solution with a purity of P5, wherein P4> P2> P5; Y

b.

the step of recrystallizing said precipitate, optionally pre-washing, to form a precipitate with a purity of P6 and a mother water with a purity of P7, in which P6> P2> P7.

12.

A method according to claim 1, further comprising the steps of:

to.

dissolve a double salt of titanium in aqueous solution; Y

b.

induce the precipitation of titanium oxide from said solution, by an action selected from the group consisting of dilution, temperature rise, increase in pH and a combination thereof.

13.

A method according to claim 1, wherein said titanium oxide comprises nanoparticles, in an average size range of 5-100 nanometers, or nanoparticles in an average size range of 100300 nanometers.

13

14.

A process according to claim 1, wherein said titanium oxide contains at least 70% of the titanium that was present in said titanium supply stream solution.

fifteen.

A process according to claim 1, further comprising a step of processing said titanium solution to form a product selected from the group consisting of metallic iron, iron oxides, double iron salt, iron hydroxide other than the product of iron, products of other polyvalent cations present in said titanium delivery solution and combinations thereof, said crystallization process comprising.