CN114752772A - Method for preparing fluidized chlorination furnace charge by upgrading titanium slag - Google Patents

Method for preparing fluidized chlorination furnace charge by upgrading titanium slag Download PDF

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CN114752772A
CN114752772A CN202210258700.5A CN202210258700A CN114752772A CN 114752772 A CN114752772 A CN 114752772A CN 202210258700 A CN202210258700 A CN 202210258700A CN 114752772 A CN114752772 A CN 114752772A
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titanium
slag
titanium slag
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陈凤
王帅
杨凌志
郭宇峰
景建发
王超
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Central South University
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Abstract

The invention discloses a method for preparing a boiling chlorination furnace charge by upgrading titanium slag, which comprises the following steps: s1, carrying out oxidizing roasting reaction on titanium slag; s2, crushing the oxidation roasting product to obtain oxidation roasting titanium slag with preset fineness; s3, carrying out sulfuric acid hydrolysis reaction on the titanium slag obtained by oxidizing roasting, carrying out solid-liquid separation on slurry obtained after acid hydrolysis to obtain acidolysis solution and acidolysis slag, wherein the acidolysis solution can be returned to an acid washing process for repeated use, and can be used for sulfuric acid process titanium white production when the titanium content exceeds 120 g/L; s4, carrying out hydrochloric acid leaching reaction on the acidolysis residue obtained in the step S3, and carrying out solid-liquid separation on the leached slurry to obtain leaching residue and leaching liquid; s5, calcining the leaching slag obtained in the step S4 to obtain the boiling chlorination furnace burden. The invention can effectively improve the titanium slag TiO2The grade is reduced, the content of impurity elements in the titanium slag is reduced, and the titanium slag becomes a raw material for a chlorination process; and sulfuric acidThe acidolysis solution can be used as a sulfate process titanium dioxide raw material to realize effective recovery of titanium; the hydrochloric acid leaching solution can be recycled after impurity removal and concentration.

Description

Method for preparing fluidized chlorination furnace charge by upgrading titanium slag
Technical Field
The invention belongs to the technical field of titanium resource utilization, and relates to a method for preparing a fluidized chlorination furnace charge by upgrading titanium slag, in particular to a method for preparing a fluidized chlorination furnace charge by deeply removing impurities from the titanium slag.
Background
At present, the main products in the titanium industry comprise titanium dioxide and titanium alloy, the production method of the titanium dioxide comprises a sulfuric acid method and a chlorination method, the main raw material of the titanium alloy, namely sponge titanium, is mainly produced by the chlorination method-Kluer method, the titanium dioxide in the sulfuric acid method belongs to a medium-low-end titanium product, and the titanium dioxide in the chlorination method and the sponge titanium belong to a high-end titanium product. More than 85 percent of titanium raw materials in China are used for producing medium and low-end titanium dioxide by a sulfuric acid method, and a large amount of waste acid and green vitriol are generated in the production process of the sulfuric acid method, so that serious environmental pollution is caused. The chlorination process mainly comprises a boiling chlorination process and a molten salt chlorination process, wherein the boiling chlorination process requires TiO in the raw materials2>90％，(CaO+MgO)<1.5 percent, and generally adopts high-quality titanium-rich materials as boiling chlorination raw materials; although the content of impurities in the raw materials is not specifically required by the molten salt chlorination method, the amount of chlorination waste residues is large and the amount of waste molten salt is increased due to the fact that the content of impurities in the raw materials is too high, and TiO is generally adopted2The titanium-rich material with the content of more than 85 percent is used as a raw material.
More than 90% of titanium resources in China exist in Panxi area in Sichuan in the form of vanadium titano-magnetite, wherein the content of calcium and magnesium impurities is high, two titanium-containing products of vanadium titano-magnetite concentrate and ilmenite can be obtained after grinding and sorting, the vanadium titano-magnetite concentrate can only recover iron and vanadium in the vanadium titano-magnetite concentrate by a blast furnace method at present, and the titanium existing in blast furnace titanium slag is difficult to extract and utilize. The ilmenite is smelted by an electric furnace to obtain molten iron and titanium slag, and TiO in the titanium slag 2The content is about 72 percent, and the titanium white powder contains a large amount of calcium and magnesium impurities, and is mainly used as a titanium white powder raw material by a sulfuric acid method at present, so that the utilization level of titanium resources in China is low. The main mineral in the titanium slag comprises the black titanium stone and a small amount of silicate, part of iron, magnesium and aluminum impurities in the titanium slag are distributed in the black titanium stone, calcium, silicon and the rest of the magnesium, iron and aluminum impurities are distributed in the silicate, and impurity elements are complex in occurrence state, difficult to remove and not easy to removeCan be directly used as raw material of chlorination process.
Therefore, a method for preparing the boiling chlorination furnace charge by deeply removing impurities from the titanium slag needs to be developed, and the utilization level of titanium resources in Panxi area of China is improved.
Disclosure of Invention
Aiming at the problems of high impurity content, complex occurrence state and difficult use as raw materials of a chlorination method in the titanium slag smelted by an ilmenite electric furnace, the invention aims to provide a method for preparing a boiling chlorination furnace charge by upgrading the titanium slag, and the method has the advantages of reasonable process flow design, simple operation and no environmental pollution.
The invention provides the following technical scheme: a method for preparing a boiling chlorination furnace charge by upgrading titanium slag comprises the following steps:
s1, carrying out oxidizing roasting reaction on titanium slag to obtain an oxidizing roasting product;
s2, crushing the oxidation roasting product obtained in the step S1 to obtain oxidation roasting titanium slag with predetermined fineness;
S3, carrying out sulfuric acid hydrolysis reaction on the oxidized and roasted titanium slag obtained in the step S2, carrying out solid-liquid separation on the slurry subjected to acid hydrolysis to obtain acid hydrolysis liquid and acid hydrolysis slag, wherein the acid hydrolysis liquid can be returned to the acid washing process for repeated use until the titanium content exceeds 120g/L, and is used for sulfuric acid process titanium dioxide production, and the acid hydrolysis slag is subjected to deep impurity removal;
s4, carrying out hydrochloric acid leaching reaction on the acidolysis residue obtained in the step S3, and carrying out solid-liquid separation on the leached slurry to obtain leaching residue and leaching solution;
s5, calcining the leaching slag obtained in the step S4 to obtain the boiling chlorination furnace burden.
In the oxidizing roasting reaction, part of the black titanium stone in the titanium slag is converted into stable rutile, the particle size of the rutile is aggregated and grown, and the phases in the titanium slag mainly comprise rutile, black titanium stone and silicate after oxidizing roasting.
In the sulfuric acid acidolysis reaction, rutile in the titanium slag obtained by oxidizing roasting is stable and cannot be subjected to acidolysis, the non-converted black titanium stone in the oxidizing roasting process is subjected to acidolysis, impurities of titanium, iron, magnesium and aluminum enter the acidolysis solution, part of silicate is also subjected to acidolysis, elements such as calcium, silicon and the like enter the acidolysis solution, and the rest of calcium exists in the acidolysis slag in the form of calcium sulfate and silicon metasilicate.
In the hydrochloric acid leaching reaction, the residual silicate is also decomposed, wherein elements such as calcium, silicon and the like enter acidolysis solution, calcium element enters leaching solution after calcium sulfate is decomposed, and the leaching solution is subjected to impurity removal and concentration and then is recycled.
Preferably, in step S1, TiO in the titanium slag2The content is more than 70 percent.
In the preferable scheme, in the step S1, the oxidation temperature is 1000-1600 ℃, and the oxidation time is 10-180 min.
Preferably, in step S2, the mixture is crushed until the particle size is less than 0.5mm and is more than 80%.
Preferably, in step S3, concentrated sulfuric acid is added to the finely ground titanium oxide-calcined slag for acidolysis, followed by aging and acid washing in this order, and the slurry after acidolysis is subjected to solid-liquid separation to obtain an acidolysis solution and acidolysis slag.
Further, in step S3, the concentration of the concentrated sulfuric acid is 90-98.3 wt%, and the acid-to-slag ratio is 0.5: 1-3: 1.
Further, in step S3, the curing temperature is 150-330 ℃ and the curing time is 10-180 min.
Further, in step S3, after curing, sulfuric acid pickling is performed, wherein the concentration of dilute sulfuric acid for pickling is 5-50 wt%, the solid-to-solid ratio of pickling liquid is 0-20: 1, the pickling temperature is 20-100 ℃, and the pickling time is 10-180 min.
In the preferable scheme, in the step S4, the concentration of the hydrochloric acid is 5-30 wt%, the solid-to-solid ratio of the acid leaching solution is 0-20: 1, the acid leaching temperature is 20-200 ℃, and the acid leaching time is 0.5-8 h.
Preferably, in step S4, hydrochloric acid is recovered from the leachate.
Preferably, in step S5, the calcination temperature is 200 to 1000 ℃, and the calcination time is 10 to 180 min.
The principle of the technical scheme of the invention is as follows:
the oxidizing roasting process of the invention aims to convert the low-valence titanium oxide and the iron oxide in the black titanium ore into a rutile phase and high-valence iron oxide and promote the rutile phase to grow, and the main phases in the oxidizing roasting slag are rutile, black titanium ore and a small amount of silicate. The reaction of the titanium slag in the oxidizing roasting process:
2Ti3O5(s)+O2(g)＝6TiO2(s) (1)
4FeTi2O5(s)+O2(g)＝2Fe2TiO5(s)+6TiO2(s) (2)
the sulfuric acid acidolysis process aims at acidolysis of the biotite and partial silicate in the titanium oxide slag to convert the biotite and partial silicate into soluble ions containing titanium, magnesium and aluminum, wherein the rutile phase in the titanium oxide slag is stable and does not have acidolysis reaction, thereby achieving the purpose of removing magnesium, iron and aluminum and partial calcium and silicon impurities. The titanium oxide slag sulfuric acid acidolysis process has the following chemical reactions:
Fe2TiO5(s)+4H2SO4(l)＝2Fe3+ (aq)+TiO2+ (aq)+4SO4 2- (aq)+4H2O(aq) (3)
Al2TiO5(s)+4H2SO4(l)＝2Al3+ (aq)+TiO2+ (aq)+4SO4 2- (aq)+4H2O(aq) (4)
MgTi2O5(s)+3H2SO4(l)＝Mg2+ (aq)+2TiO2+ (aq)+3SO4 2- (aq)+3H2O(aq) (5)
CaSiO3(s)+H2SO4(l)＝CaSO4(s)+H2SiO3(s) (6)
the hydrochloric acid leaching process aims to further decompose silicate which is not subjected to acidolysis and calcium sulfate generated in the sulfuric acid acidolysis process, so that calcium impurity elements contained in the silicate are converted into soluble calcium chloride, and the aim of deeply removing calcium and silicon impurities is fulfilled. Acid leaching reaction of acid hydrolysis residues with hydrochloric acid:
CaSiO3(s)+2HCl(aq)＝CaCl2(aq)+H2SiO3(aq) (7)
CaSO4(s)+2HCl(aq)＝CaCl2(aq)+H2SO4(aq) (8)
The invention has the beneficial technical effects that:
the invention can effectively improve the titanium slag TiO2The grade, the content of impurity elements in the titanium slag, particularly calcium and magnesium impurities, is reduced, the aim of removing calcium, magnesium, iron, aluminum and silicon from the titanium slag and upgrading the titanium slag into a fluidized bed chlorination furnace charge is achieved, and the titanium slag becomes a chlorination process raw material; the sulfuric acid acidolysis solution can be used as a sulfuric acid method titanium dioxide raw material to realize effective recovery of titanium; the hydrochloric acid leaching solution can be recycled after impurity removal and concentration. The process has reasonable design, simple operation and no environmental pollution.
Drawings
FIG. 1 is a process flow diagram of example 1 of the present invention.
Detailed Description
The following examples further illustrate embodiments of the present invention, but the embodiments of the present invention are not limited to the following examples.
In the examples of the present invention, unless otherwise specified, the means employed are those conventional in the art, and the reagents employed are commercially available in a conventional manner.
The technical solution of the present invention is explained in detail by the following embodiments and the accompanying drawings.
Example 1
With titanium-containing slag (72.52% TiO)2、9.35％TFe、5.39％SiO2、2.75％Al2O31.38 percent of CaO and 8.25 percent of MgO) as raw materials, and the temperature of the oxidizing roasting process is 1450 ℃, and the oxidizing time is 120 min. The oxidized and roasted product was crushed to a particle size of-0.5 mm in 84.25%. The sulfuric acid concentration in the acidolysis process of the sulfuric acid is 92 percent, the acid residue ratio is 1.7:1, the curing temperature is 250 ℃, the curing time is 120min, and the curing is performed after Carrying out sulfuric acid pickling, wherein the concentration of sulfuric acid for pickling is 20%, the solid-to-solid ratio of pickling solution is 5:1, the pickling temperature is 60 ℃, and the pickling time is 120 min. Acid leaching the filtered acid leaching residue after acid washing with hydrochloric acid, wherein the concentration of the hydrochloric acid is 15%, the solid-to-solid ratio of acid leaching solution is 8:1, the acid leaching temperature is 120 ℃, and the acid leaching time is 4 hours. The calcining temperature of the leached residue obtained by solid-liquid separation after hydrochloric acid leaching is 900 ℃ and the calcining time is 30min in the calcining process.
Example 1 TiO is finally obtained289 percent of boiling chlorination furnace burden, 0.35 percent of CaO and 0.55 percent of MgO, and the total removal rate of impurities of magnesium, iron, calcium and silicon can reach 91.33 percent, 89.67 percent, 81.96 percent and 42.77 percent. The specific process flow is shown in figure 1.
Example 2
With titanium-containing slag (74.46% TiO)2、8.84％TFe、9.69％SiO2、0.72％Al2O31.94 percent of CaO and 6.61 percent of MgO) as raw materials, and the temperature of the oxidizing and roasting process is 1500 ℃, and the oxidizing time is 120 min. The oxidized and roasted product was crushed to a particle size of-0.5 mm in 82.13%. The sulfuric acid concentration in the sulfuric acid acidolysis process is 92%, the acid residue ratio is 2:1, the curing temperature is 250 ℃, the curing time is 120min, sulfuric acid pickling is carried out after curing, the sulfuric acid concentration for pickling is 30%, the pickling liquid-solid ratio is 10:1, the pickling temperature is 60 ℃, and the pickling time is 120 min. Acid leaching the filtered acid leaching residue after acid washing with hydrochloric acid, wherein the concentration of the hydrochloric acid is 15%, the solid-to-solid ratio of acid leaching solution is 10:1, the acid leaching temperature is 120 ℃, and the acid leaching time is 4 hours. The calcining temperature of the leached residue obtained by solid-liquid separation after hydrochloric acid leaching is 900 ℃ and the calcining time is 30min in the calcining process.
Example 2 TiO was finally obtained291.3 percent of the raw materials, 0.15 percent of CaO and 0.32 percent of MgO, and the total removal rate of impurities of magnesium, iron, calcium and silicon can reach 93.45 percent, 91.21 percent, 86.46 percent and 46.74 percent.
Example 3
With titanium-containing slag (72.43% TiO)2、8.84％TFe、7.39％SiO2、2.55％Al2O30.86 percent of CaO and 3.12 percent of MgO) as raw materials, and the temperature of the oxidizing and roasting process is 1500 ℃, and the oxidizing time is 120 min. Crushing the oxidized and roasted product to a particle size of-0.5 mm81.68 percent. In the acidolysis process of sulfuric acid, the sulfuric acid concentration is 94%, the acid residue ratio is 2:1, the curing temperature is 300 ℃, the curing time is 120min, sulfuric acid pickling is carried out after curing, the sulfuric acid concentration for pickling is 20%, the pickling liquid solid ratio is 5:1, the pickling temperature is 60 ℃, and the pickling time is 120 min. Acid leaching the filtered acid leaching residue after acid washing by using hydrochloric acid, wherein the concentration of the hydrochloric acid is 10 percent, the solid-to-solid ratio of acid leaching liquid is 10:1, the acid leaching temperature is 120 ℃, and the acid leaching time is 4 hours. The calcining temperature of the leached residue obtained by solid-liquid separation after hydrochloric acid leaching is 900 ℃ and the calcining time is 30min in the calcining process.
Example 3 TiO is finally obtained294.13 percent of boiling chloridized furnace burden, 0.12 percent of CaO and 0.23 percent of MgO, and the total removal rate of impurities of magnesium, iron, calcium and silicon can reach 94.12 percent, 90.13 percent, 87.86 percent and 43.14 percent.
Comparative example 1
With titanium-containing slag (72.52% TiO)2、9.35％TFe、5.39％SiO2、2.75％Al2O31.38 percent of CaO and 8.25 percent of MgO) as raw materials, and the temperature of the oxidizing roasting process is 1450 ℃, and the oxidizing time is 120 min. The oxidized roasted product was crushed to a particle size of-0.5 mm 84.25%. In the acidolysis process of the sulfuric acid, the sulfuric acid concentration is 92%, the acid residue ratio is 1.7:1, the curing temperature is 250 ℃, the curing time is 120min, sulfuric acid pickling is carried out after curing, the sulfuric acid concentration for pickling is 30%, the pickling liquid solid ratio is 5:1, the pickling temperature is 60 ℃, and the pickling time is 120 min. The calcining temperature of the leaching residue obtained by solid-liquid separation in the calcining process is 900 ℃, and the calcining time is 30 min. Final calcined slag TiO271.05%, CaO 3.44%, MgO 0.90%.
Comparative example 2
With titanium-containing slag (72.52% TiO)2、9.35％TFe、5.39％SiO2、2.75％Al2O31.38 percent of CaO and 8.25 percent of MgO) as raw materials, and the temperature of the oxidizing roasting process is 1450 ℃, and the oxidizing time is 120 min. The oxidized and roasted product was crushed to a particle size of-0.5 mm in 84.25%. The concentration of hydrochloric acid is 36.5%, the solid-to-solid ratio of the acid leaching solution is 10:1, the acid leaching temperature is 120 ℃, and the acid leaching time is 4 hours. The calcining temperature of the leaching residue obtained by solid-liquid separation after hydrochloric acid leaching in the calcining process is 900 ℃, and the calcining time is 30min. Final calcined slag TiO281.59%, CaO 1.71%, and MgO 0.65%.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.

Claims (10)

1. The method for preparing the boiling chlorination furnace charge by upgrading the titanium slag is characterized by comprising the following steps:
s1, carrying out oxidation roasting reaction on titanium slag to obtain an oxidation roasting product;
s2, crushing the oxidation roasting product obtained in the step S1 to obtain oxidation roasting titanium slag with preset fineness;
s3, carrying out sulfuric acid hydrolysis reaction on the oxidized and roasted titanium slag obtained in the step S2, carrying out solid-liquid separation on the slurry subjected to acid hydrolysis to obtain acid hydrolysis liquid and acid hydrolysis slag, wherein the acid hydrolysis liquid can be returned to an acid washing process for repeated use until the titanium content exceeds 120g/L, and is used for sulfuric acid process titanium dioxide production, and the acid hydrolysis slag is subjected to deep impurity removal;
s4, carrying out hydrochloric acid leaching reaction on the acidolysis residue obtained in the step S3, and carrying out solid-liquid separation on the leached slurry to obtain leaching residue and leaching liquid;
s5, calcining the leaching slag obtained in the step S4 to obtain the boiling chlorination furnace burden.
2. The method for preparing boiling chlorination furnace charge through titanium slag upgrading according to claim 1, wherein in step S1, TiO in the titanium slag is used 2The content is more than 70 percent.
3. The method for preparing the boiling chlorination furnace burden through upgrading of the titanium slag as recited in claim 1, wherein in the step S1, the oxidation temperature is 1000-1600 ℃, and the oxidation time is 10-180 min.
4. The method for preparing the boiling chlorination furnace charge through titanium slag upgrading according to claim 1, wherein in step S2, crushing is carried out until the particle size is less than 0.5mm and accounts for more than 80%.
5. The method for preparing a boiling chlorination furnace charge by upgrading titanium slag as claimed in claim 1, wherein in step S3, concentrated sulfuric acid is added into the finely ground titanium slag after oxidizing roasting for acidolysis, then aging and acid washing are sequentially carried out, and the slurry after acidolysis is subjected to solid-liquid separation to obtain acidolysis solution and acidolysis slag.
6. The method for preparing the boiling chlorination furnace charge through titanium slag upgrading according to claim 5, wherein in the step S3, the concentration of concentrated sulfuric acid is 90-98.3 wt%, and the acid-slag ratio is 0.5: 1-3: 1.
7. The method for preparing the boiling chlorination furnace charge by upgrading titanium slag according to claim 5, wherein in the step S3, the curing temperature is 150-330 ℃, and the curing time is 10-180 min.
8. The method for preparing the fluidized chlorination furnace charge by upgrading titanium slag according to claim 5, wherein in step S3, sulfuric acid pickling is performed after curing, the concentration of dilute sulfuric acid for pickling is 5-50 wt%, the solid-to-solid ratio of pickling liquid is 0-20: 1, the pickling temperature is 20-100 ℃, and the pickling time is 10-180 min.
9. The method for preparing the boiling chlorination furnace burden through upgrading of the titanium slag according to claim 1, wherein in the step S4, the concentration of the hydrochloric acid is 5-30 wt%, the solid-to-solid ratio of the acid leaching solution is 0-20: 1, the acid leaching temperature is 20-200 ℃, and the acid leaching time is 0.5-8 h.
10. The method for preparing the boiling chlorination furnace burden through upgrading the titanium slag as recited in claim 1, wherein in the step S5, the calcination temperature is 200-1000 ℃, and the calcination time is 10-180 min.
CN202210258700.5A 2022-03-16 2022-03-16 Method for preparing fluidized chlorination furnace charge by upgrading titanium slag Pending CN114752772A (en)

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