CN111606342B - Titanium ore recycling process - Google Patents
Titanium ore recycling process Download PDFInfo
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- CN111606342B CN111606342B CN202010655635.0A CN202010655635A CN111606342B CN 111606342 B CN111606342 B CN 111606342B CN 202010655635 A CN202010655635 A CN 202010655635A CN 111606342 B CN111606342 B CN 111606342B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/68—Aluminium compounds containing sulfur
- C01F7/74—Sulfates
- C01F7/76—Double salts, i.e. compounds containing, besides aluminium and sulfate ions, only other cations, e.g. alums
- C01F7/762—Ammonium or alkali metal aluminium sulfates
- C01F7/765—Ammonium aluminium sulfates
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/88—Concentration of sulfuric acid
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/14—Sulfates
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1204—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent
- C22B34/1213—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent by wet processes, e.g. using leaching methods or flotation techniques
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
- C22B34/1259—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching treatment or purification of titanium containing solutions or liquors or slurries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a titanium ore recycling process, which comprises the following steps: (1) carrying out two-stage leaching on the raw ore by sulfuric acid to obtain a first-stage leaching solution and a second-stage leaching residue; (2) adding ammonium sulfate into the first-stage leachate to enable the aluminum sulfate in the first-stage leachate to react with the ammonium sulfate to generate aluminum ammonium sulfate, and crystallizing to separate out the aluminum ammonium sulfate in the solution; (3) extracting and hydrolyzing tail liquid after the aluminum ammonium sulfate is crystallized to prepare titanium dioxide; (4) heating, concentrating and filtering the extracted waste acid to respectively obtain a sulfuric acid concentrated solution with a certain concentration and a ferric sulfate crystal with a certain yield, and returning the sulfuric acid concentrated solution to the first stage for leaching. The invention can realize the comprehensive recycling of main elements of titanium, iron, silicon and aluminum in the ore, the recycling rate of each element can reach more than 77 percent, and the invention points out the direction for realizing clean production and utilization of the ore without tail and wastewater discharge and improving the economic value of the ore.
Description
Technical Field
The invention belongs to the technical field of titanium ore recycling, and particularly relates to a titanium ore recycling process.
Background
TiO-containing Yaan Yanxi channel titanium ore2 6.19％、TFe 18.88％、Al2O3 21.39％、SiO231.90 percent, A/S is 0.67, and the main valuable component is TiO2。
The phase analysis result of the raw ore titanic compound shows that titanium is mainly present in rutile phase and anatase phase, and then titanite phase and silicate phase, and titanomagnetite phase and ilmenite phase are very little.
The natural types of the ores are heterochromatic bauxite ores and red mudstone ores. According to the mineral components, the mineral components are classified into kaolin type anatase ore and limonite type anatase ore. The deposit cause is lake phase sedimentary type ore. The ore structure is mainly a soil structure; the structure mainly comprises a muddy structure, a micro-scale structure, a microcrystalline structure, an altered silt structure and the like.
The mineral composition and main element occurrence state results of the ore show that the main minerals in the ore are anatase, hematite, quartz, kaolinite, rectorite, a small amount of bentonite, occasional chlorite, potash feldspar, mica and the like. Titanium in the ore is mainly present in anatase, and the particle size of the anatase is 4-20 mu m; the aluminum is mainly distributed in the kaolinite and the rectorite, and the particles of the aluminum are fine and are distributed in a fine dispersion state and a cryptocrystalline aggregate; the hematite and limonite are in a fine dispersion state, the granularity of the hematite and limonite is about 0.002mm, and the hematite and the limonite are locally distributed as a lump aggregate; the quartz is fine microcrystal and is a fine granular monomer or an irregular aggregate, the granularity of the monomer is about 0.002-0.008 mm, the monomer is not uniformly distributed, and the monomer is mostly filled in the pores of the ore. The mineral properties show that the ore is complex and difficult to beneficiate, and the conventional physical beneficiation method is difficult to effectively separate and recover anatase, so that the invention provides a chemical beneficiation method.
Disclosure of Invention
The invention provides a titanium ore recycling process, which aims to overcome the defects of the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a titanium ore recycling process comprises the following steps:
s1: two-stage leaching is carried out on raw ore by sulfuric acid to obtain a first-stage leaching solution and second-stage leaching slag (silicon dioxide);
s2: adding ammonium sulfate into the first-stage leachate to enable the aluminum sulfate in the first-stage leachate to react with the ammonium sulfate to generate aluminum ammonium sulfate, and crystallizing to separate out the aluminum ammonium sulfate in the solution;
s3: extracting and hydrolyzing tail liquid after the aluminum ammonium sulfate is crystallized to prepare titanium dioxide;
s4: heating, concentrating and filtering the extracted waste acid to respectively obtain a sulfuric acid concentrated solution with a certain concentration and a ferric sulfate crystal with a certain yield.
As a further description of the above technical solution: the process further comprises:
s5: the sulfuric acid concentrated solution is recycled through sulfuric acid two-stage leaching.
As a further description of the above technical solution: the step S1 includes the following sub-steps:
s11: grinding raw ore to fine particles;
s12: adding the ground raw ore and a sulfuric acid solution into a leacher, heating to boil, and performing first-stage leaching to obtain first-stage ore pulp;
s13: filtering the first-stage ore pulp to obtain first-stage leaching slag and first-stage leaching liquid;
s14: adding the first-stage leaching residue and a sulfuric acid solution into a leacher, heating to boil, and performing second-stage leaching to obtain second-stage ore pulp;
s15: and filtering the second-stage ore pulp to obtain second-stage leaching slag and second-stage leaching liquid.
As a further description of the above technical solution: the concentration of the sulfuric acid solution in the step S12 is 40-80% (volume concentration).
As a further description of the above technical solution: the leaching time in the step S12 is 60-150 min.
As a further description of the above technical solution: the solid ratio of the leaching solution in the step S12 is 4-6.
As a further description of the above technical solution: the leaching temperature in the step S12 is 140 °.
As a further description of the above technical solution: the step S13 specifically includes: and cooling the first-stage ore pulp to 90 ℃, and filtering to obtain first-stage leaching residue.
As a further description of the above technical solution: the concentration of the sulfuric acid solution in the step S14 is 85 to 95% (volume concentration).
As a further description of the above technical solution: the leaching time in the step S14 is 90-150 min.
As a further description of the above technical solution: the solid ratio of the leaching solution in the step S14 is 3-4.
As a further description of the above technical solution: the leaching temperature in the step S14 is 250 °.
As a further description of the above technical solution: the step S15 specifically includes: and cooling the second-stage ore pulp to 90 ℃, and filtering to obtain second-stage leaching residues.
As a further description of the above technical solution: the step S1 further includes:
s16: and adding the second-stage leachate into the leacher in the step S12, heating to boil, and performing first-stage leaching.
As a further description of the above technical solution: the grinding equipment adopted in the step S11 is an XMB-70 three-roller four-cylinder rod grinder; the leachers in the steps S12 and S14 are mechanical agitation leachers; the steps S12 and S14 are heated to boiling by an electric furnace; filtering in the steps S13 and S15 by adopting a DZ-5C vacuum filter; and drying the first-stage leaching residue and the second-stage leaching residue obtained in the steps S13 and S15 respectively by adopting an HG101-3 electrothermal blowing drying box.
As a further description of the above technical solution: the conditions of step S2 are: the molar ratio of ammonium to aluminum is 1:2, the reaction temperature of ammonium and aluminum is 80 ℃, the reaction time of ammonium and aluminum is 30min, the vacuum degree is 2400Pa, the crystallization time is 40min, and the crystallization end point temperature is 30 ℃.
As a further description of the above technical solution: the step 3 comprises the following steps:
s31: carrying out three-stage countercurrent extraction on the tail liquid to obtain a loaded organic phase;
s32: carrying out back extraction on the loaded organic phase, and filtering to obtain coarse titanium slag;
s33: sequentially carrying out sodium removal, acidolysis, iron removal and concentration treatment on the coarse titanium slag;
s34: and (3) sequentially carrying out hydrolysis, washing, bleaching, salt treatment, roasting and crushing on the concentrated titanium solution to obtain the titanium dioxide.
As a further description of the above technical solution: the step S31 includes the following sub-steps:
s311: sequentially carrying out primary extraction, secondary extraction and tertiary extraction on tail liquid after the aluminum ammonium sulfate is crystallized to obtain raffinate;
s312: and sequentially carrying out three-stage extraction, two-stage extraction and one-stage extraction on the new organic phase to obtain a loaded organic phase.
As a further description of the above technical solution: the extracting agent adopted in the step S31 is an extracting agent KG-1, and the solvents adopted in the step S31 are sec-octanol and sulfonated kerosene respectively.
As a further description of the above technical solution: the step S32 includes the following sub-steps:
s321: carrying out back extraction on the loaded organic phase by using a back extractant to obtain an organic phase and titanium hydroxide precipitate;
s322: and filtering the hydroxide precipitate of the titanium to obtain crude titanium slag.
As a further description of the above technical solution: the step S32 further includes the following sub-steps:
s323: supplementing a back-extraction agent to the filtered filtrate for circular back-extraction;
s324: the organic phase is regenerated by hydrochloric acid pickling and then returns to the extraction operation;
s325: and concentrating and crystallizing the waste liquid regenerated by acid washing to obtain a sodium chloride by-product.
As a further description of the above technical solution: the stripping agent is sodium hydroxide solution.
As a further description of the above technical solution: the step S33 includes the following sub-steps:
s331: dissolving the coarse titanium slag in concentrated hydrochloric acid for sodium removal;
s332: dissolving the crude titanium slag after sodium removal in concentrated sulfuric acid for acidolysis;
s333: adding iron powder into the acidolysis solution, reducing to prepare a black titanium solution, and carrying out vacuum freezing crystallization on the reduced titanium solution to carry out iron removal treatment;
s334: heating the titanium liquid after iron removal for vacuum concentration.
As a further description of the above technical solution: in the step S331, the ratio of the mass of the coarse titanium slag to the volume of the concentrated hydrochloric acid is 5: 1.
As a further description of the above technical solution: in the step S332, the ratio of the mass of the coarse titanium slag to the volume of the concentrated sulfuric acid is 6: 1.
As a further description of the above technical solution: the step S34 includes the following sub-steps:
s341: hydrolyzing the concentrated titanium solution;
s342: adding acidified water into the hydrolyzed titanium solution for washing;
s343: adding the washed titanium liquid into aluminum powder for bleaching;
s344: adding the bleached titanium liquid into acidified water for secondary washing;
s345: adding potassium phosphate or phosphoric acid into the titanium liquid after secondary washing for salt treatment;
s346: roasting and crushing the titanium liquid after salt treatment to obtain the titanium dioxide.
The invention has the following beneficial effects:
the process comprises the steps of chemical ore dressing (sulfuric acid leaching) obtained by a titanium ore laboratory test, aluminum ammonium sulfate production by leaching liquid aluminum removal, titanium separation and extraction for preparing titanium dioxide, and waste acid concentration, wherein the obtained solid product comprises leaching slag (silicon dioxide), aluminum ammonium sulfate, ferric sulfate, crude titanium slag and sodium chloride, and the liquid is sulfuric acid concentrated solution.
1. Leaching residues: the high-silicon slag can be used as a concrete reinforcing agent and a raw material for producing water glass and the like, and is a commodity mineral product.
2. Aluminum ammonium sulfate: is a commodity mineral product and can be used as a raw material for preparing alumina.
3. Iron sulfate: is a commodity mineral product, can be used as a water purifying agent, and can also be sold in a sulfuric acid plant as a pyrite acid making ingredient.
4. Coarse titanium slag: is a commercial mineral product and is a raw material for producing sulfated titanium dioxide.
5. Sodium chloride: the byproducts can be regenerated into HCl and NaOH through electrolysis and then returned to the process for use.
6. Sulfuric acid concentrated solution: tests show that the liquid can be returned to a section of leaching operation to be used as acid for leaching. Through flow balance calculation, the process has no discharged waste liquid.
Therefore, the invention can comprehensively utilize the main elements of titanium, iron, silicon and aluminum in the ore, achieve zero tail and zero waste water discharge and meet the development and utilization requirements of green mines.
Drawings
FIG. 1 is a flow chart of a titanium ore recycling process provided by the present invention;
FIG. 2 is a schematic flow chart of step 1;
FIG. 3 is a partial flow chart of step 3;
fig. 4 is a partial flowchart of step 3.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in fig. 1, a titanium ore recycling process includes the following steps:
(1) the raw ore is leached in two stages by sulfuric acid to obtain a first-stage leaching liquid and a second-stage leaching slag (silicon dioxide), and the leaching slag can be used as a concrete reinforcing agent and a raw material for producing water glass and the like.
(2) The ammonium sulfate is added into the first-stage leachate to enable the aluminum sulfate in the first-stage leachate to react with the ammonium sulfate to generate ammonium aluminum sulfate, and the ammonium aluminum sulfate in the first-stage leachate is crystallized to separate out the ammonium aluminum sulfate in the solution. The crystallization of the aluminum ammonium sulfate adopts the current advanced vacuum crystallization process, and the project carries out the condition test research of the system on the main factors affecting the crystallization of the aluminum ammonium sulfate, such as feed liquid concentration, ammonium-aluminum molar ratio, ammonium-aluminum reaction temperature, ammonium-aluminum reaction time and the like.
(3) Extracting and hydrolyzing the tail liquid after the aluminum ammonium sulfate is crystallized to prepare the titanium dioxide.
(4) The extracted waste acid is heated, concentrated and filtered to respectively obtain a sulfuric acid concentrated solution with a certain concentration and a ferric sulfate crystal with a certain yield, and the ferric sulfate can be used as a pyrite acid-making ingredient to be sold in a sulfuric acid plant, so that iron in the ore is comprehensively utilized.
(5) The sulfuric acid concentrated solution is recycled through sulfuric acid two-stage leaching.
Example 1
As shown in fig. 2, the step (1) includes the following sub-steps:
(11) the raw ore is ground to fine particles.
(12) Adding the ground raw ore and a sulfuric acid solution into a leacher, heating to boil, and carrying out first-stage leaching to obtain first-stage ore pulp.
(13) And filtering the first-stage ore pulp to obtain first-stage leaching slag and first-stage leaching liquid.
(14) And adding the first-stage leaching residue and the sulfuric acid solution into a leacher, heating to boil, and performing second-stage leaching to obtain second-stage ore pulp.
(15) And filtering the second-stage ore pulp to obtain second-stage leaching slag and second-stage leaching liquid.
(16) And (3) adding the second-stage leachate into the leacher in the step (12), heating to boil, and performing first-stage leaching to realize recycling.
In this embodiment, the step (11) is specifically: 100g of-2 mm raw ore is ground to-0.075 mm raw ore, and the-0.075 mm raw ore accounts for 85% of the total raw ore. At this time, the leaching residue contains TiO2、Al2O3TFe 13.92%, 6.93%, 1.46%, TiO respectively2、Al2O3And the leaching rates of TFe are respectively 6.54%, 86.53% and 96.79%, so that the aim of mainly leaching aluminum and iron is fulfilled. In this embodiment, the concentration of the sulfuric acid solution in the step (12) is 40-80% (volume concentration), and preferably, the sulfuric acid solution in the step (12)The concentration of the sulfuric acid solution was 50%. The yield of the leaching residue is 41.20 percent at the time, and the yield of the leaching residue is TiO2、Al2O3The TFe extraction rates were 6.09%, 84.89% and 96.90%, respectively.
In this embodiment, the leaching time in the step (12) is 60-150min, and preferably, the leaching time is 120 min. In this case TiO2、Al2O3The TFe extraction rates were 8.49%, 93.82% and 97.44%, respectively.
In the present embodiment, the ratio of the leaching solution to the solid in the step (12) is 4:1-6:1, and preferably, the ratio of the leaching solution to the solid is 5. At this time, the leaching residue contains TiO2 14.11％，TiO2、Al2O3TFe leaching rates were 7.95%, 93.06% and 96.89%, respectively.
In this example, the leaching temperature in the step (12) was 140 °.
After determining all the parameters through the tests, a first-stage leaching comprehensive test is carried out, wherein 1000g of the raw material is fed, the fineness of the raw material is-0.075 mm and accounts for 85%, the sulfuric acid concentration is 50%, the liquid-solid ratio is 5, the leaching time is 120min, and the leaching temperature is 140 ℃. The yield of the leaching residue is 40.12 percent, and the contents of the leaching residue are respectively as follows: TiO 22 14.13％、SiO2 76.36％、Al2O3 3.75％、TFe 1.40％、Na29.85 percent of O; the leaching rates of the slag meter are respectively as follows: TiO 22 8.42％、SiO2 3.96％、Al2O392.97%, TFe 97.03%; the leaching solution and the washing solution are mixed and then respectively contain: TiO 22 1.04g/L、SiO2 2.01g/L、Al2O345.02g/L, TFe 33.43.43 g/L, and the total volume of the solution is 5.75L. The first stage leaching mainly takes iron and aluminum in leached ore as main materials, the leaching rate of titanium is less than 9%, silicon is not leached in a sulfuric acid leaching environment, the yield of leaching slag is only 40.12%, the produced leaching slag has low aluminum and iron contents, and favorable conditions are created for the next step of leaching titanium.
In this embodiment, the step (13) is specifically: and cooling the first-stage ore pulp to 90 ℃, and filtering to obtain first-stage leaching residue.
In this example, the sulfuric acid solution in the step (14)The concentration is 85-95% (volume concentration), and preferably, the concentration of the sulfuric acid solution is 95%. The total leaching rate of iron is 99.71 percent, the total leaching rate of titanium is 91.45 percent, the total leaching rate of aluminum is 98.80 percent, the slag contains 0.18 percent of TFe and TiO2 1.73％、Al2O3Good index of 0.84%.
In this embodiment, the leaching time in the step (14) is 90-150min, and preferably, the leaching time is 120 min. The total leaching rate of iron is 99.72 percent, the total leaching rate of titanium is 91.16 percent, the total leaching rate of aluminum is 98.86 percent, and the slag contains 0.17 percent of TFe and TiO2 1.79％、Al2O3Good index of 0.80%.
In the embodiment, the ratio of the leaching solution to the solid in the step (14) is 3:1-4:1, and preferably, the ratio of the leaching solution to the solid is 3. The total leaching rate of iron is 99.69 percent, the total leaching rate of titanium is 91.45 percent, the total leaching rate of aluminum is 98.84 percent, the TFe content in the slag is 0.19 percent, and the TiO content in the slag is 98.19 percent2 1.73％、Al2O3Good index of 0.81%.
In this example, the leaching temperature in the step (14) was 250 °.
In this embodiment, the step (15) is specifically: and cooling the second-stage ore pulp to 90 ℃, and filtering to obtain second-stage leaching residues.
After determining each parameter through the test, carrying out a second-stage leaching comprehensive test
The optimal conditions for the second stage leaching are as follows: feeding 1000g of the raw materials, wherein the sulfuric acid concentration is 95%, the solid ratio of the leaching solution is 3, heating to boil and leaching, and the leaching time is 120 min. The operation yield of the leaching slag is 76.25 percent, and the leaching slag respectively comprises the following components in percentage by weight: TiO 22 1.71％、Al2O30.81% and TFe 0.19 g/L; the total leaching rates are respectively: TiO 22 91.55％、Al2O398.84%, TFe 99.69%; the content of the mixed leaching solution and the washing solution is respectively as follows: TiO 22 23.13g/L、Al2O36.94g/L, TFe 2.24.24 g/L, and the total volume of the solution is 2.04L.
In this example, the step (16) adds the second stage leachate to the extractor in the step (12) and heats the second stage leachate to boiling for the first stage leaching.
After the raw ore is leached by two stages, most of the titanium-iron-aluminum components are dissolved out, and particularly, the leaching rate of the titanium which is difficult to dissolve in acid is over 90 percent under the condition of two stages of high acid. However, the acidity of the leachate obtained by the second-stage leaching is high, and the leachate contains iron, titanium and aluminum, so that the leachate is convenient to comprehensively utilize, the leachate obtained by the second-stage leaching is returned to the first-stage leaching for leaching, whether the consumption of the neo-acid obtained by the first-stage leaching can be reduced is examined, and the similar leaching index is achieved.
In this embodiment, the step (16) specifically includes: the test was run at 1000g feed and the other test conditions were as before. The yield of the first-stage leaching residue of the recycled acid is 40.25 percent, and the contents of the leaching residues are respectively as follows: TiO 22 14.21％、Al2O33.72%, TFe 1.37%; the leaching rates of the slag meter are respectively as follows: TiO 22 7.60％、Al2O393.00% and TFe 97.08%. The yield of the first-stage leaching residue of the new acid is 40.12 percent, and the contents of the leaching residues are respectively as follows: TiO 22 14.13％、Al2O33.75%, TFe 1.40%; the leaching rates of the slag meter are respectively as follows: TiO 22 8.42％、Al2O392.97%, TFe 97.03%; the contents of the recycled acid first-stage leaching solution and the washing solution after mixing are respectively as follows: h2SO4 398.72g/L、TiO2 7.15g/L、TFe 27.73g/L、Al2O339.89g/L, and the total volume of the solution is 7.40L. After the first stage leaching operation adopts second-stage acid for recycling leaching, the leaching indexes of iron, aluminum and titanium are equivalent to the leaching result of the new acid, so that the second-stage leaching solution can be returned to the first stage for use. The leachate is a stock solution for comprehensively recovering sulfuric acid, aluminum, titanium and iron in the next step.
In the embodiment, the grinding equipment adopted in the step (1) is an XMB-70 three-roller four-cylinder rod mill; the leacher in the steps (2) and (4) is a mechanical stirring leacher; heating the steps (2) and (4) to boiling by using an electric furnace; filtering in the steps (3) and (5) by adopting a DZ-5C vacuum filter; and (4) drying the first-stage leached residues and the second-stage leached residues obtained in the steps (3) and (5) by adopting an HG101-3 electrothermal blowing drying box.
The invention provides a research result of a Yaan Yanxi channel titanium ore leaching process
Through two-stage leaching experimental research, the Yaan Yanxi ditch titanium ore recycling process is determined to be a two-stage countercurrent sulfuric acid leaching process. The process flow is shown in figure 2, and the raw ore content is respectively as follows: TiO 22 6.19％、Al2O321.39% and TFe 18.88%. The technical parameters of the leaching process are as follows: raw ore with the feeding fineness of-0.075 mm accounts for more than 85% of the total raw ore, the sulfuric acid concentration is 50%, the liquid-solid ratio is 5:1, the leaching temperature is 140 ℃, and the leaching time is 120 min; the conditions of the second stage leaching are as follows: the concentration of sulfuric acid is 95%, the liquid-solid ratio is 3:1, the leaching temperature is 250 ℃, and the leaching time is 120 min. The contents of the first-stage leaching residues are respectively as follows: TiO 22 14.21％、Al2O33.72%, TFe 1.37%; the corresponding leaching rates are respectively as follows: TiO 22 7.60％、Al2O393.00%, TFe 97.08%; the total leaching rates are respectively: TiO 22 91.42％、Al2O398.79% and TFe 99.70%. The content of the mixed leaching solution and the washing solution is respectively as follows: h2SO4 398.72g/L、TiO2 7.15g/L、TFe 27.73g/L、Al2O339.89g/L, and the total volume of the solution is 7.40L. The content of main elements in the final leaching residue is shown in a table 1-1, and the measurement result of part of physical property parameters of the micro powder after the final leaching residue is ground is shown in a table 1-2.
TABLE 1-1 Yaan Yanxi channel titanium mine final leaching residue multielement analysis result
| Principal Components | TiO2 | Al2O3 | TFe | SiO2 |
| Content (%) | 1.73 | 0.84 | 0.18 | 87.50 |
| Principal Components | CaO | MgO | K2O | Loss on ignition |
| Content (%) | 0.02 | 0.012 | 0.094 | 10 |
TABLE 1-2 measurement results of some physical property parameters of the final leached slag micropowder of Yaan Yanxi channel titanium mine
According to the table 1-1, the main mineral of the Yaan Yanxi channel titanium ore final leaching slag is silicon dioxide. The table 1-2 shows that the micro powder of the leached residue after being ground is 7d active silicon dioxide with the activity index of 95 percent, and the residue powder can be used as a concrete reinforcing agent and a raw material for producing water glass and the like.
Example 2
In this embodiment: the conditions of the step (2) are as follows: the molar ratio of ammonium to aluminum is 1:2, the reaction temperature of ammonium and aluminum is 80 ℃, the reaction time of ammonium and aluminum is 30min, the vacuum degree is 2400Pa, the crystallization time is 40min, and the crystallization end point temperature is 30 ℃.
Aluminum ammonium sulfateThe main principle of the crystallization process is as follows: adding (NH) to the first-stage infusion4)2SO4Al in pickle liquor2(SO4)3And (NH)4)2SO4The reaction generates aluminum ammonium sulfate, and the aluminum ammonium sulfate is cooled and crystallized to be separated out as aluminum ammonium sulfate NH4Al(SO4)2·12H2And O. The ammonium aluminum sulfate has wide application, can be used as a buffering agent and a swelling agent of food-grade products, a coagulant for sewage purification, an aluminum tanning agent and a post-treatment agent of leather tanning in the leather industry, a dye-proofing agent in the dye industry, a dye-coating agent for sizing paper in the paper industry, a coloring agent of yellow glass in the glass industry, a medical fencing agent and a printing and dyeing mordant, and can also be used in the industrial fields of pigment, electroplating, starch and the like, and the high-purity ammonium aluminum sulfate is a raw material for preparing nano aluminum oxide powder. The crystallization of the aluminum ammonium sulfate adopts the current advanced vacuum crystallization process, and the process conditions are as follows: the molar ratio of ammonium to aluminum is 1:2, the reaction temperature of ammonium and aluminum is 80 ℃, the reaction time of ammonium and aluminum is 30min, the vacuum degree is 2400Pa, the crystallization time is 40min, and the crystallization end point temperature is 30 ℃. At the moment, the crystallization rate of the aluminum ammonium sulfate can reach 83.48 percent, the inclusion rate of iron in the aluminum ammonium sulfate is 18.79 percent, and the content of the obtained crude product of the aluminum ammonium sulfate is respectively as follows: al (Al)2O310.8% and TFe 1.32%. The leachate after crystallization contains H2SO4 405.56g/L、TFe 28.15g/L、TiO2 8.27g/L、Al2O38.10g/L, and the aluminum-iron separation effect is obvious.
Example 3
As shown in fig. 3 and 4: the step (3) comprises the following steps:
(31) carrying out three-stage countercurrent extraction on the tail liquid to obtain a loaded organic phase;
(32) carrying out back extraction on the loaded organic phase, and filtering to obtain coarse titanium slag;
(33) sequentially carrying out sodium removal, acidolysis, iron removal and concentration treatment on the coarse titanium slag;
(34) and (3) sequentially carrying out hydrolysis, washing, bleaching, salt treatment, roasting and crushing on the concentrated titanium solution to obtain the titanium dioxide.
As shown in fig. 3, in the present embodiment, step (31) includes the following sub-steps:
(311) sequentially carrying out primary extraction, secondary extraction and tertiary extraction on tail liquid after the aluminum ammonium sulfate is crystallized to obtain raffinate;
(312) and sequentially carrying out three-stage extraction, two-stage extraction and one-stage extraction on the new organic phase to obtain a loaded organic phase.
In this embodiment, the extractant used in step S31 is KG-1, and the solvents used in step S31 are sec-octanol and sulfonated kerosene, respectively.
Taking a certain amount of tail solution (undiluted tail solution), KG-1 extractant (20%), 1# solvent (5%) and 2# solvent (75%); o/a 1: 1; shaking for 5min, and performing three-stage countercurrent extraction. TFe 28.15g/L, TiO in extraction stock solution28.27 g/L; 26.15g/L, TiO g of TFe in raffinate20.82 g/L; the extraction rates of TFe 7.10% and TiO respectively2 90.08％。
As shown in fig. 2, in the present embodiment, the step (32) includes the following sub-steps:
(321) the loaded organic phase is back extracted by a back extractant (sodium hydroxide) to obtain an organic phase and a hydroxide precipitate of titanium;
(322) filtering the hydroxide precipitate of the titanium to obtain coarse titanium slag;
(323) supplementing a back-extraction agent to the filtered filtrate for circular back-extraction;
(324) the organic phase is regenerated by hydrochloric acid pickling and then returns to the extraction operation;
(325) and concentrating and crystallizing the pickling waste liquid to obtain a sodium chloride byproduct.
Organic phase stripping conditions: 3M/L stripping agent KG-2 (the main component is strong base); the back extraction phase ratio O/A is 3: 1; shaking time 5 min. At this time, the titanium back extraction rate can reach 99.09%, and the iron back extraction rate can reach 97.13%.
The regeneration of the organic phase can not only solve the pollution problem of the organic phase to the environment, but also greatly reduce the production cost in the extraction process. This test was conducted to investigate whether the regenerated organic phase had an effect on the extraction rate of titanium.
Test fixing conditions: organic phase hydrochloric acid solution; s1: extractant KG-1 (20%), 1#Solvent (5%), 2#Solvent 75%) (organic phase after stripping); o/a ═ 1: 1; shaking time 5 min.
S2: extractant KG-1 (20%), 1#Solvent (5%), 2#Solvent (75%) (newly prepared organic phase); o/a ═ 1:1(S + W); shaking time 5 min. TiO in regenerated organic phase quenching residual liquid22.51g/L, the extraction rate is 69.52 percent; TiO in newly prepared organic phase quenching residual liquid22.50g/L, the extraction rate is 69.77 percent, the index difference is not large, and the regeneration of the organic phase is feasible.
Separating and extracting coarse titanium slag from titanium, and testing extraction process conditions: tail liquid (undiluted), extractant KG-1 (20%), solvent # 1 (5%), solvent # 2 (75%), and O/A ═ 1: 1.
Technological conditions of back extraction and organic phase regeneration
Primary stripping: stripping agent KG-2(3M/L), O/A ═ 3: 1.
First-stage acid washing organic phase regeneration: dilute hydrochloric acid (3M/L), O/a ═ 5: 1.
Technical indexes of a titanium separation and extraction process, tail liquid after crystallization of aluminum ammonium sulfate: h2SO4 405.56g/L、TiO2 8.27g/L、Al2O38.10g/L, TFe 28.15 g/L; raffinate after three-stage countercurrent extraction: h2SO4 456.35g/L、TiO2 0.82g/L、Al2O38.43g/L, TFe 26.15.15 g/L; loading an organic phase: TiO 225.72g/L, TFe 1.08.08 g/L; and (3) organic phase after back extraction: TiO 220.024g/L, TFe 0.052.052 g/L; crude titanium slag (strip slag): TiO 22 31.35％、Al2O3 1.52％、TFe 11.14％、Na2And O9.85 percent. The three-stage countercurrent extraction rate of titanium is 90.08%, the back extraction rate is more than 99%, and TiO in the coarse titanium slag2The content was 31.35%. The titanium coarse slag is a commodity mineral product which can be directly sold and is mainly used as a raw material for producing titanium dioxide by a sulfuric acid method.
As shown in fig. 4, in the present embodiment, the step (33) includes the following sub-steps:
(331) and dissolving the coarse titanium slag in concentrated hydrochloric acid for sodium removal treatment.
The coarse titanium slag obtained after back extraction still contains a large amount of titaniumNaOH has adverse effect on the subsequent preparation of titanium dioxide powder. Dissolving the coarse titanium slag in concentrated hydrochloric acid according to the ratio of 5:1 (slag mass/concentrated hydrochloric acid volume), stirring for 1h at normal temperature to neutralize and remove residual NaOH in the coarse titanium slag, and filtering after removing sodium from the slag. Before the sodium removal of the coarse titanium slag: TiO 22 31.35％、TFe 11.14％、Al2O3 1.52％、Na29.85 percent of O; after sodium removal: TiO 22 52.31％、TFe 18.56％、Al2O3 0.75％、Na2O2.40 percent; the removal rate is as follows: TiO 22 1.35％、TFe 1.50％、Al2O3 70.83％、Na2O85.60 percent. The titanium slag after the sodium removal treatment of concentrated hydrochloric acid removes a large amount of NaOH, wherein TiO in the titanium slag252.31% was enriched and the losses were smaller. The filtrate after sodium removal can be concentrated, crystallized and recovered. The conditions are as follows: the filtrate was concentrated to 2/5 of the original volume, the vacuum was-0.074 MPa, the end point temperature of crystallization was 5 ℃ and sodium chloride was recovered by crystallization.
(332) And dissolving the crude titanium slag after sodium removal in concentrated sulfuric acid for acidolysis.
The process and conditions are as follows: and dissolving the crude titanium slag after sodium removal into concentrated sulfuric acid, wherein the dissolving ratio is 6/1 (slag mass/concentrated sulfuric acid volume), and stirring for 30min at the temperature of 60 ℃ to completely dissolve the crude titanium slag. Titanium solution after dissolution: TiO 22 161.75g/L、TFe 57.38g/L、H2SO478.35 g/L. (333) Adding iron powder into the acidolysis solution, reducing to prepare a black titanium solution, and carrying out vacuum freezing crystallization on the reduced titanium solution to carry out iron removal treatment;
heating the acid liquor to 60 ℃, preserving heat, adding iron powder to reduce the acid liquor to prepare a black titanium liquid until Ti3+The content is 1-3 g/L qualified. And (3) after reduction, performing vacuum freezing crystallization on the titanium liquid to remove iron, wherein the final temperature is 10 ℃, and concentration hydrolysis can be performed after the iron-titanium ratio reaches 0.3-0.35.
(334) Heating the titanium liquid after iron removal for vacuum concentration.
Heating the titanium liquid to 60 ℃, and concentrating in vacuum at the vacuum degree of-0.074 MPa, wherein the volume is twice of that of the titanium liquid. The properties of the concentrated titanium solution are shown in tables 1-3.
TABLE 1-3 concentrated titanium liquids Properties
| Name (R) | TiO2(g/L) | TFe(g/L) | H2SO4(g/L) | Iron to titanium ratio | F value | Stability of |
| Index (I) | 230.75 | 70.36 | 176 | 0.3 | 2.24 | ≥500 |
The results in tables 1-3 show that the concentrated titanium liquid is qualified stock solution for preparing the sulfuric acid method titanium dioxide, and qualified sulfuric acid method titanium dioxide products can be obtained through conventional sulfuric acid method titanium dioxide production processes such as hydrolysis, washing, bleaching and the like. The subsequent test work is not continuously completed due to the shortage of raw materials in the test, but the direction is pointed for the utilization of the titanium in the ore, and a good technical basis is laid for the next expansion test.
Preferably, the ratio of the mass of the crude titanium slag to the volume of the concentrated hydrochloric acid in the step (331) is 5: 1; the ratio of the mass of the coarse titanium slag to the volume of the concentrated sulfuric acid in the step (332) is 6: 1.
As shown in fig. 4, in the present embodiment, the step (34) includes the following sub-steps:
(341) hydrolyzing the concentrated titanium solution;
(342) adding acidified water into the hydrolyzed titanium solution for washing;
(343) adding the washed titanium liquid into aluminum powder for bleaching;
(344) adding the bleached titanium liquid into acidified water for secondary washing;
(345) adding potassium phosphate or phosphoric acid into the titanium liquid after secondary washing for salt treatment;
(346) roasting and crushing the titanium liquid after salt treatment to obtain the titanium dioxide.
Example 4
As shown in figure 1, the titanium ore is leached by high-concentration sulfuric acid, and a more satisfactory titanium leaching effect is obtained. By adopting two-stage leaching, the leaching rate of titanium reaches 91.42 percent. Because of high leaching acidity, the acidity of tail liquid (waste acid for short) after crystallization to obtain ammonium aluminum sulfate and extraction of titanium is high, and alkali neutralization treatment is not suitable. The concentration treatment is adopted to concentrate the acid with a certain concentration to return to the ore leaching operation for use. Ferric sulfate is crystallized in the concentration process and can be used for preparing ores to pyrite for acid making, so that the project realizes tailless discharge and clean production.
The waste acid concentration test is to heat waste acid with a certain volume until ferric sulfate is crystallized and separated out, and then filter the waste acid to respectively obtain acid liquor with a certain concentration and ferric sulfate crystals with a certain yield. The concentration of sulfuric acid may be determined by the concentration time.
Concentrated to 50% (volume fraction) sulfuric acid solution, raffinate: TFe 26.15g/L, Al2O3 8.43g/L、TiO20.82g/L、H2SO4456.35 g/L; concentrating the solution: TFe 1.23g/L, Al2O3 12.64g/L、TiO2 0.84g/L、H2SO4716.50 g/L. The crystallization rate of ferric sulfate reaches 98.87%, the content of iron, aluminum and titanium in the concentrated solution is low, and the concentrated solution can be returned to the first-stage acid leaching for use. Spent acidThe TFe content of the concentrated and crystallized ferric sulfate crystals is 23.40 percent, and the ferric sulfate crystals can be sold to a sulfuric acid plant to be matched with pyrite for acid preparation, so that the iron-containing grade of a sulfuric acid residue (iron ore concentrate) product can be improved to a certain extent.
Example 5
The two-stage countercurrent leaching process is characterized in that the first stage leaching conditions are as follows: raw ore with the feeding fineness of-0.075 mm accounts for more than 85% of the total raw ore, the sulfuric acid concentration is 50%, the liquid-solid ratio is 5:1, the leaching temperature is 140 ℃, and the leaching time is 120 min; the conditions of the second stage leaching are as follows: the concentration of sulfuric acid is 95%, the liquid-solid ratio is 3:1, the leaching temperature is 250 ℃, and the leaching time is 120 min. The technological parameters of the aluminum ammonium sulfate preparation by aluminum removal and the crystallization conditions of the aluminum ammonium sulfate are as follows: the molar ratio of ammonium to aluminum is 1:2, the reaction temperature of ammonium and aluminum is 80 ℃, the reaction time of ammonium and aluminum is 30min, the vacuum degree is 2400Pa, the crystallization time is 40min, and the crystallization end point temperature is 30 ℃.
Technical parameters of the titanium separation and extraction process, and extraction process conditions: tail liquid (undiluted), extractant KG-1 (20%), solvent # 1 (5%), solvent # 2 (75%), and O/A ═ 1: 1; primary stripping conditions: stripping agent KG-2(3M/L), O/A is 3: 1; the regeneration conditions of the first-stage acid washing organic phase are as follows: dilute hydrochloric acid (3M/L), O/a ═ 5: 1; the sodium removal treatment condition of the coarse titanium slag is as follows: dissolving the coarse titanium slag in concentrated hydrochloric acid according to the proportion of 5:1 (slag mass/concentrated hydrochloric acid volume), and stirring for 1h at normal temperature to neutralize and remove residual NaOH in the coarse titanium slag.
Two-stage countercurrent leaching process technical indexes, leaching slag: TiO 22 1.73％、SiO2 87.50％、Al2O30.84 percent and TFe 0.18 percent, and the leaching rates of corresponding slag are respectively as follows: TiO 22 91.42％、SiO2 16.09％、Al2O398.79 percent of TFe 99.70 percent and the yield of the leached residue is 30.59 percent; the content of the mixed leaching solution and the washing solution is respectively as follows: h2SO4 398.72g/L、TiO2 7.15g/L、TFe 27.73g/L、Al2O339.89 g/L. Leachate after aluminum removal (aluminum ammonium sulfate crystallization tail solution): h2SO4405.56g/L、TFe 28.15g/L、TiO2 8.27g/L，Al2O38.10 g/L. The crystallization rate of the aluminum ammonium sulfate is 83.48 percent, and the obtained crude product of the aluminum ammonium sulfate contains Al2O310.80％，TFe 1.32％。
Tail liquid after crystallization of aluminum ammonium sulfate: h2SO4 405.56g/L、TiO2 8.27g/L、Al2O38.10g/L, TFe 28.15 g/L; raffinate after three-stage countercurrent extraction: h2SO4 456.35g/L、TiO2 0.82g/L、Al2O38.43g/L, TFe 26.15.15 g/L; loading an organic phase: TiO 225.72g/L, TFe 1.08.08 g/L; and (3) organic phase after back extraction: TiO 220.024g/L, TFe 0.052.052 g/L; crude titanium slag (strip slag): TiO 22 31.35％、Al2O3 1.52％、TFe 11.14％、Na29.85 percent of O; after sodium removal of the crude titanium slag: TiO 22 52.31％、TFe 18.56％、Al2O3 0.75％、Na2O2.40 percent; the removal rate is as follows: TiO 22 1.35％、TFe 1.50％、Al2O3 70.83％、Na2O85.60 percent. Aiming at 1kg of raw materials, 0.175kg of sodium-removed titanium slag, 0.3059kg of leaching slag (silicon slag), 1.634kg of aluminum ammonium sulfate and 0.629kg of ferric sulfate are obtained in an experiment, and the indexes of the recovery rate of each element calculated by the method are shown in tables 1-4.
TABLE 1-4 technical indexes of comprehensive recovery and utilization of Yaan Yanxi channel titanium ore
Laboratory test research results show that the Yaan Yanxi channel titanium ore can realize comprehensive recycling of main elements titanium, iron, silicon and aluminum in the ore by adopting the chemical ore dressing process, the recycling rate of each element can reach more than 77 percent, and the direction is pointed for realizing clean production and utilization without tail and wastewater discharge and improving the economic value of the ore.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.
Claims (4)
1. The titanium ore recycling process is characterized by comprising the following steps:
s1: carrying out two-stage leaching on the raw ore by sulfuric acid to obtain a first-stage leaching solution and a second-stage leaching residue;
s2: adding ammonium sulfate into the first-stage leachate to enable the aluminum sulfate in the first-stage leachate to react with the ammonium sulfate to generate aluminum ammonium sulfate, and crystallizing to separate out the aluminum ammonium sulfate in the solution;
s3: extracting and hydrolyzing tail liquid after the aluminum ammonium sulfate is crystallized to prepare titanium dioxide;
s31: carrying out three-stage countercurrent extraction on the tail liquid to obtain a loaded organic phase;
s32: carrying out back extraction on the loaded organic phase, and filtering to obtain coarse titanium slag;
s33: sequentially carrying out sodium removal, acidolysis, iron removal and concentration treatment on the coarse titanium slag;
s34: sequentially carrying out hydrolysis, washing, bleaching, salt treatment, roasting and crushing on the concentrated titanium solution to obtain titanium dioxide;
s311: sequentially carrying out primary extraction, secondary extraction and tertiary extraction on tail liquid after the aluminum ammonium sulfate is crystallized to obtain raffinate;
s312: sequentially carrying out three-stage extraction, two-stage extraction and one-stage extraction on the new organic phase to obtain a loaded organic phase;
s321: carrying out back extraction on the loaded organic phase by using a back extractant to obtain an organic phase and titanium hydroxide precipitate;
s322: filtering the hydroxide precipitate of the titanium to obtain coarse titanium slag;
s323: supplementing a back-extraction agent to the filtered filtrate for circular back-extraction;
s324: the organic phase is regenerated by hydrochloric acid pickling and then returns to the extraction operation;
s325: concentrating and crystallizing the pickling waste liquid to obtain a sodium chloride byproduct;
s331: dissolving the coarse titanium slag in concentrated hydrochloric acid for sodium removal;
s332: dissolving the crude titanium slag after sodium removal in concentrated sulfuric acid for acidolysis;
s333: adding iron powder into the acidolysis solution, reducing to prepare a black titanium solution, and carrying out vacuum freezing crystallization on the reduced titanium solution to carry out iron removal treatment;
s334: heating the titanium liquid after iron removal for vacuum concentration;
s341: hydrolyzing the concentrated titanium solution;
s342: adding acidified water into the hydrolyzed titanium solution for washing;
s343: adding the washed titanium liquid into aluminum powder for bleaching;
s344: adding the bleached titanium liquid into acidified water for secondary washing;
s345: adding potassium phosphate or phosphoric acid into the titanium liquid after secondary washing for salt treatment;
s346: roasting and crushing the titanium liquid after salt treatment to obtain titanium dioxide;
s4: heating, concentrating and filtering the extracted waste acid to respectively obtain a sulfuric acid concentrated solution and ferric sulfate crystals;
the two-stage countercurrent leaching process is characterized in that the first stage leaching conditions are as follows: raw ore with the feeding fineness of-0.075 mm accounts for more than 85% of the total raw ore, the sulfuric acid concentration is 50%, the liquid-solid ratio is 5:1, the leaching temperature is 140 ℃, and the leaching time is 120 min; the conditions of the second stage leaching are as follows: the concentration of sulfuric acid is 95%, the liquid-solid ratio is 3:1, the leaching temperature is 250 ℃, the leaching time is 120min, the technological parameters of the process for preparing aluminum ammonium sulfate by removing aluminum are as follows, and the crystallization conditions of the aluminum ammonium sulfate are as follows: the molar ratio of ammonium to aluminum is 1:2, the reaction temperature of ammonium and aluminum is 80 ℃, the reaction time of ammonium and aluminum is 30min, the vacuum degree is 2400Pa, the crystallization time is 40min, and the crystallization end point temperature is 30 ℃;
technical parameters of the titanium separation and extraction process, and extraction process conditions: taking a certain amount of undiluted tail liquid, adding 20% of extraction agent KG-1, 5% of solvent No. 1 and 75% of solvent No. 2, and controlling the ratio of O/A to 1: 1; primary stripping conditions: using 3M/L stripping agent KG-2, and controlling the ratio of O/A to 3: 1; the regeneration conditions of the first-stage acid washing organic phase are as follows: using 3M/L diluted hydrochloric acid, controlling the ratio of O/A to 5: 1; the sodium removal treatment condition of the coarse titanium slag is as follows: and dissolving the coarse titanium slag in concentrated hydrochloric acid according to the ratio of slag mass to concentrated hydrochloric acid volume of 5:1, and stirring for 1h at normal temperature to neutralize and remove residual NaOH in the coarse titanium slag.
2. The titanium ore recycling process according to claim 1, further comprising:
s5: the sulfuric acid concentrated solution is recycled through sulfuric acid two-stage leaching.
3. The titanium ore recycling process according to claim 1, wherein the step S1 comprises the following substeps:
s11: grinding raw ore to fine particles;
s12: adding the ground raw ore and a sulfuric acid solution into a leacher, heating to boil, and performing first-stage leaching to obtain first-stage ore pulp;
s13: filtering the first-stage ore pulp to obtain first-stage leaching slag and first-stage leaching liquid;
s14: adding the first-stage leaching residue and a sulfuric acid solution into a leacher, heating to boil, and performing second-stage leaching to obtain second-stage ore pulp;
s15: and filtering the second-stage ore pulp to obtain second-stage leaching slag and a second-stage leaching liquid.
4. The titanium ore recycling process according to claim 3, wherein the step S1 further comprises:
s16: and adding the second-stage leachate into the leacher in the step S12, heating to boil, and performing first-stage leaching.
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