Treatment method of chlorination process titanium dioxide solid waste residues

Abstract

The invention provides a treatment method of chlorination process titanium dioxide solid waste residues, and belongs to the technical field of resources and environments. According to the method, the chlorination process titanium dioxide solid waste residues are dissolved and extracted step by step, high-value metal in the solid waste residues is recycled respectively, residual substances are evaporated and crystallized to obtain mixed salt, and zero emission and full resource utilization of the solid waste residues are achieved.

Description

Technical Field

[0001] The invention belongs to the technical field of resources and environment, and particularly relates to a method for treating solid waste residue of titanium dioxide produced by a chloride process. Background Art

[0002] The chloride process is the mainstream titanium dioxide production process, offering the advantages of high-quality titanium dioxide and minimal waste. However, every ton of titanium dioxide produced still generates over 300 kg of solid waste. This solid waste primarily contains unreacted titanium-rich slag, petroleum coke, ferrous chloride, aluminum chloride, calcium chloride, magnesium chloride, and other high-value metals such as scandium, zirconium, niobium, vanadium, and chromium. Disposal of this solid waste is technically challenging and costly. Currently, it is typically neutralized and then landfilled, resulting in significant costs and environmental risks for businesses, hindering the industry's green development.

[0003] Therefore, how to treat the solid waste residue of titanium dioxide produced by the chloride process to recover the valuable components therein is of great significance for reducing overall costs, reducing pollution, improving economic benefits and promoting green and low-carbon development of the industry. Summary of the Invention

[0004] The object of the present invention is to provide a method for treating solid waste residue of titanium dioxide produced by the chloride process, wherein the method provided by the present invention can recover valuable components in the solid waste residue of titanium dioxide produced by the chloride process.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions: The present invention provides a method for treating solid waste residue of titanium dioxide produced by a chloride process, comprising the following steps: (1) mixing solid waste residue of titanium dioxide produced by the chloride process with water and an additive, heating the mixture and performing a first solid-liquid separation to obtain a solid containing titanium dioxide and petroleum coke and a first solution; (2) cooling the first solution obtained in step (1) and performing a second solid-liquid separation to obtain ferrous chloride and a second solution; (3) mixing the second solution obtained in step (2) with a scandium extractant to perform a first extraction to obtain a first raffinate and a first oil phase, and mixing the first oil phase with a first alkaline solution to perform a first back extraction to obtain scandium hydroxide; (4) mixing the first raffinate obtained in step (3) with a zirconium-niobium extractant to perform a second extraction to obtain a second raffinate and a second oil phase, and mixing the second oil phase with a second alkali solution to perform a second back extraction to obtain a mixture of zirconium hydroxide and niobium hydroxide; (5) mixing the second raffinate obtained in step (4) with a titanium extractant to perform a third extraction to obtain a third raffinate and a third oil phase, and mixing the third oil phase with a third alkali solution to perform a third back extraction to obtain amorphous titanium dioxide; (6) mixing the third raffinate obtained in step (5) with an iron extractant and an iron auxiliary agent to perform a fourth extraction to obtain a fourth raffinate and a fourth oil phase, and mixing the fourth oil phase with a fourth alkali solution to perform a fourth back extraction to obtain ferric hydroxide; (7) mixing the fourth raffinate obtained in step (6) with a vanadium extractant to perform a fifth extraction to obtain a fifth raffinate and a fifth oil phase, and mixing the fifth oil phase with a fifth alkali solution to perform a fifth back extraction to obtain vanadate; (8) mixing the fifth raffinate obtained in step (7) with a manganese extractant to perform a sixth extraction to obtain a sixth raffinate and a sixth oil phase, and mixing the sixth oil phase with an acid solution to perform a sixth back extraction to obtain a manganese compound; (9) The sixth raffinate obtained in step (8) is mixed with an oxidant and activated carbon, and a third solid-liquid separation is performed to obtain a third solution, and the third solution is evaporated and crystallized to obtain a mixed salt.

[0006] Preferably, the auxiliary agent in step (1) includes one or more of sodium hypochlorite aqueous solution, hydrogen peroxide, sulfur dioxide, hydrochloric acid, iron powder and aluminum powder.

[0007] Preferably, the scandium extractant in step (3) comprises, by mass percentage, 5-10% P204, 4-6% TBP, 5-15% P507 and the remainder solvent.

[0008] Preferably, the zirconium-niobium extractant in step (4) comprises, by mass percentage, 19-21% P204, 4-6% TBP, 5-15% P507 and the remainder solvent.

[0009] Preferably, the titanium extractant in step (5) comprises, by mass percentage, 19-21% P204, 4-6% TBP, 4-6% LK-N21 and the remainder solvent.

[0010] Preferably, the iron extractant in step (6) comprises, by mass percentage, 1-15% of one or more of N235, P204, P507, MIBK and C902, 4-6% of TBP and the remainder of solvent.

[0011] Preferably, the iron additive in step (6) includes one or more of sodium hypochlorite, hydrogen peroxide, magnesium oxide and ozone.

[0012] Preferably, the vanadium extractant in step (7) comprises, by mass percentage, 10-15% N235 or P204, 4-6% TBP and the remainder solvent.

[0013] Preferably, the manganese extractant in step (8) comprises 38-42% P204 and the remainder solvent, calculated by mass percentage.

[0014] Preferably, the oxidant in step (9) comprises sodium hypochlorite.

[0015] The present invention provides a method for treating solid waste residue of titanium dioxide produced by a chloride process, comprising the following steps: (1) mixing the solid waste residue of titanium dioxide produced by the chloride process with water and an auxiliary agent, heating the mixture, and performing a first solid-liquid separation to obtain a solid containing titanium dioxide and petroleum coke and a first solution; (2) sequentially cooling the first solution obtained in step (1) and performing a second solid-liquid separation to obtain ferrous chloride and a second solution; (3) mixing the second solution obtained in step (2) with a scandium extractant to perform a first extraction to obtain a first raffinate and a first oil phase, mixing the first oil phase with a first alkali solution to perform a first back extraction to obtain scandium hydroxide; (4) mixing the first raffinate obtained in step (3) with a zirconium-niobium extractant to perform a second extraction to obtain a second raffinate and a second oil phase, mixing the second oil phase with a second alkali solution to perform a second back extraction to obtain a mixture of zirconium hydroxide and niobium hydroxide; and (5) mixing the second raffinate obtained in step (4) with a titanium extractant to perform a third extraction to obtain a third raffinate and The third oil phase is mixed with the third alkali solution for the third back extraction to obtain amorphous titanium dioxide; (6) the third raffinate obtained in the step (5) is mixed with an iron extractant and an iron auxiliary agent for the fourth extraction to obtain a fourth raffinate and a fourth oil phase, the fourth oil phase is mixed with a fourth alkali solution for the fourth back extraction to obtain iron hydroxide; (7) the fourth raffinate obtained in the step (6) is mixed with a vanadium extractant for the fifth extraction to obtain a fifth raffinate and a fifth oil phase, the fifth oil phase is mixed with a fifth alkali solution for the fifth back extraction to obtain vanadate; (8) the fifth raffinate obtained in the step (7) is mixed with a manganese extractant for the sixth extraction to obtain a sixth raffinate and a sixth oil phase, the sixth oil phase is mixed with an acid solution for the sixth back extraction to obtain a manganese compound; (9) the sixth raffinate obtained in the step (8) is mixed with an oxidant and activated carbon for the third solid-liquid separation to obtain a third solution, the third solution is evaporated and crystallized to obtain a mixed salt. The present invention dissolves and extracts titanium dioxide solid waste residue produced by the chloride process in steps, recovers high-value metals in the solid waste residue, and evaporates and crystallizes the remaining substances to obtain mixed salt, thereby achieving zero discharge of solid waste residue and full resource utilization. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 The present invention provides a flow chart of a method for treating solid waste residue of titanium dioxide produced by the chloride process. DETAILED DESCRIPTION

[0017] The present invention provides a method for treating solid waste residue of titanium dioxide produced by a chloride process, comprising the following steps: (1) mixing solid waste residue of titanium dioxide produced by the chloride process with water and an additive, heating the mixture and performing a first solid-liquid separation to obtain a solid containing titanium dioxide and petroleum coke and a first solution; (2) cooling the first solution obtained in step (1) and performing a second solid-liquid separation to obtain ferrous chloride and a second solution; (3) mixing the second solution obtained in step (2) with a scandium extractant to perform a first extraction to obtain a first raffinate and a first oil phase, and mixing the first oil phase with a first alkaline solution to perform a first back extraction to obtain scandium hydroxide; (4) mixing the first raffinate obtained in step (3) with a zirconium-niobium extractant to perform a second extraction to obtain a second raffinate and a second oil phase, and mixing the second oil phase with a second alkali solution to perform a second back extraction to obtain a mixture of zirconium hydroxide and niobium hydroxide; (5) mixing the second raffinate obtained in step (4) with a titanium extractant to perform a third extraction to obtain a third raffinate and a third oil phase, and mixing the third oil phase with a third alkali solution to perform a third back extraction to obtain amorphous titanium dioxide; (6) mixing the third raffinate obtained in step (5) with an iron extractant and an iron auxiliary agent to perform a fourth extraction to obtain a fourth raffinate and a fourth oil phase, and mixing the fourth oil phase with a fourth alkali solution to perform a fourth back extraction to obtain ferric hydroxide; (7) mixing the fourth raffinate obtained in step (6) with a vanadium extractant to perform a fifth extraction to obtain a fifth raffinate and a fifth oil phase, and mixing the fifth oil phase with a fifth alkali solution to perform a fifth back extraction to obtain vanadate; (8) mixing the fifth raffinate obtained in step (7) with a manganese extractant to perform a sixth extraction to obtain a sixth raffinate and a sixth oil phase, and mixing the sixth oil phase with an acid solution to perform a sixth back extraction to obtain a manganese compound; (9) The sixth raffinate obtained in step (8) is mixed with an oxidant and activated carbon, and a third solid-liquid separation is performed to obtain a third solution, and the third solution is evaporated and crystallized to obtain a mixed salt.

[0018] The invention mixes titanium dioxide solid waste residue produced by the chloride process with water and an auxiliary agent, performs a first solid-liquid separation after heating, and obtains a solid containing titanium dioxide and petroleum coke and a first solution.

[0019] The present invention has no special limitation on the source of the solid waste residue of titanium dioxide produced by the chloride process, and any solid waste residue of titanium dioxide produced by the chloride process well known to those skilled in the art can be used.

[0020] In the present invention, the mass ratio of the solid waste residue from the chloride process to water is preferably 1000 kg: (3500-5000) L. In one embodiment, the mass ratio of the solid waste residue from the chloride process to water can be 1000 kg: 3500 L, 1000 kg: 4000 L, 1000 kg: 4500 L, or 1000 kg: 5000 L.

[0021] In the present invention, the auxiliary agent preferably includes one or more of sodium hypochlorite aqueous solution, hydrogen peroxide, sulfur dioxide, hydrochloric acid, iron powder, and aluminum powder, and more preferably one or more of sodium hypochlorite aqueous solution, hydrogen peroxide, and hydrochloric acid. In the present invention, the mass concentration of the sodium hypochlorite aqueous solution is preferably 8-12%, more preferably 10%; the mass concentration of the hydrogen peroxide is preferably 25-35%, more preferably 30%; and the concentration of the hydrochloric acid is preferably 2-8 mol / L, more preferably 4-6 mol / L.

[0022] As an embodiment, the auxiliary agent can specifically be a mixed solution of hydrochloric acid and hydrogen peroxide, a sodium hypochlorite aqueous solution or hydrochloric acid.

[0023] When the auxiliary agent is a mixed solution of hydrochloric acid and hydrogen peroxide, the mass ratio of the hydrogen peroxide to the volume ratio of hydrochloric acid is preferably 10 kg: (1000-2000) L, more preferably 10 kg: 1500 L; the mass ratio of the solid waste residue of titanium dioxide produced by the chloride process to the volume ratio of hydrochloric acid in the mixed solution of hydrochloric acid and hydrogen peroxide is preferably 1000 kg: (1000-2000) L, more preferably 1000 kg: 1500 L; the mass ratio of the solid waste residue of titanium dioxide produced by the chloride process to the hydrogen peroxide in the mixed solution of hydrochloric acid and hydrogen peroxide is preferably (90-110): 1, more preferably 100: 1.

[0024] When the auxiliary agent is a sodium hypochlorite aqueous solution, the mass ratio of the chloride process titanium dioxide solid waste residue to the sodium hypochlorite aqueous solution is preferably (90-110):1, more preferably 100:1.

[0025] When the auxiliary agent is hydrochloric acid, the volume ratio of the mass of the chloride titanium dioxide solid waste residue to the hydrochloric acid is preferably 1000 kg: (1000-2000) L, more preferably 1000 kg: 1500 L.

[0026] In the present invention, the auxiliary agent helps dissolve the metal elements in the solid waste residue of titanium dioxide produced by the chloride process. The present invention controls the type and amount of the auxiliary agent within the above range, which can be more conducive to the dissolution of the metal elements in the solid waste residue of titanium dioxide produced by the chloride process.

[0027] The present invention has no special limitation on the operation of mixing the solid waste residue of titanium dioxide from the chloride process with water and the additives. The components can be evenly mixed using a material mixing technical solution well known to those skilled in the art.

[0028] In the present invention, the heating temperature is preferably 70-90°C; the heating time is preferably 30-60 minutes. By controlling the heating temperature and time within the above ranges, the present invention can further improve the dissolution effect of metal elements in the chloride titanium dioxide solid waste.

[0029] The present invention has no special limitation on the operation of the first solid-liquid separation. The solid and liquid can be separated by using a solid-liquid separation technical solution well known to those skilled in the art.

[0030] After the first solid-liquid separation is completed, the present invention preferably dries the solid obtained by the first solid-liquid separation to obtain a solid containing titanium dioxide and petroleum coke.

[0031] The present invention has no special limitation on the drying operation, and any drying technical solution well known to those skilled in the art may be used.

[0032] In the present invention, the solid containing titanium dioxide and petroleum coke is preferably recycled into the raw material for preparing titanium dioxide by the chlorination process.

[0033] After obtaining the first solution, the present invention sequentially cools the first solution and performs a second solid-liquid separation to obtain ferrous chloride and a second solution.

[0034] In the present invention, the terminal temperature of the cooling is preferably 20-25°C.

[0035] The present invention has no special limitation on the cooling operation, and cooling to the terminal temperature can be performed using a cooling technical solution well known to those skilled in the art.

[0036] The present invention has no special limitation on the second solid-liquid separation operation, and the solid and liquid can be separated by using a solid-liquid separation technical solution well known to those skilled in the art.

[0037] In the present invention, the ferrous chloride is preferably used as a water purifier.

[0038] After obtaining the second solution, the present invention mixes the second solution with a scandium extractant to perform a first extraction to obtain a first raffinate and a first oil phase, and then mixes the first oil phase with a first alkaline solution to perform a first back extraction to obtain scandium hydroxide.

[0039] In the present invention, the scandium extractant preferably comprises, by mass percentage, 5-10% P204 (di(2-ethylhexyl) phosphate), 4-6% TBP (tributyl phosphate), 5-15% P507 (2-ethylhexyl mono-2-ethylhexyl phosphate), and the balance solvent.

[0040] In the present invention, the solvent preferably includes one or more of kerosene, isobutanol, white oil, n-butanol, n-octanol and solvent oil; the solvent oil preferably includes one or more of 120# solvent oil, 180# solvent oil, 200# solvent oil and 260# solvent oil.

[0041] As an embodiment, the scandium extraction agent may be specifically 10% P204, 5% TBP, 5% P507 and the balance 260# solvent oil, or may be specifically 10% P204, 5% TBP, 15% P507 and the balance 260# solvent oil, or may be specifically 5% P204, 5% TBP, 10% P507 and the balance 260# solvent oil.

[0042] In the present invention, the volume ratio of the scandium extractant to the second solution is preferably 1:(9-11), more preferably 1:10. The present invention does not specifically limit the remaining steps of the first extraction; extraction techniques familiar to those skilled in the art can be employed. By controlling the composition and dosage of the scandium extractant within the aforementioned ranges, the present invention ensures that scandium is fully incorporated into the oil phase.

[0043] After the first extraction is completed, the product of the first extraction is preferably separated to obtain a first raffinate and a first oil phase.

[0044] The present invention has no particular limitation on the liquid separation operation, and the oil phase and the raffinate can be separated by using a liquid separation technical solution well known to those skilled in the art.

[0045] In the present invention, the first alkali solution preferably includes a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution; the mass concentration of the first alkali solution is preferably 5-15%, more preferably 10%.

[0046] In the present invention, the volume ratio of the first oil phase to the first alkaline solution is preferably 1:(1-5). Controlling the volume ratio of the first oil phase to the first alkaline solution within this range allows for sufficient stripping of scandium. The present invention does not specifically limit the remaining steps of the first stripping process; stripping techniques familiar to those skilled in the art may be employed.

[0047] After the first stripping is completed, the present invention preferably performs solid-liquid separation on the product of the first stripping to obtain scandium hydroxide.

[0048] The present invention has no special limitation on the solid-liquid separation operation, and the solid and liquid can be separated using a solid-liquid separation technical solution well known to those skilled in the art.

[0049] After obtaining the first raffinate, the present invention mixes the first raffinate with a zirconium-niobium extractant for a second extraction to obtain a second raffinate and a second oil phase, and then mixes the second oil phase with a second alkali solution for a second back extraction to obtain a mixture of zirconium hydroxide and niobium hydroxide.

[0050] In the present invention, the zirconium-niobium extractant preferably comprises, by mass percentage, 19-21% P204, 4-6% TBP, 5-15% P507 and the balance solvent.

[0051] In the present invention, the solvent preferably includes one or more of kerosene, isobutanol, white oil, n-butanol, n-octanol and solvent oil; the solvent oil preferably includes one or more of 120# solvent oil, 180# solvent oil, 200# solvent oil and 260# solvent oil.

[0052] As an embodiment, the zirconium-niobium extractant may specifically be 20% P204, 5% TBP, 5% P507 and the balance 260# solvent oil, or may specifically be 20% P204, 5% TBP, 15% P507 and the balance 260# solvent oil.

[0053] In the present invention, the volume ratio of the zirconium-niobium extractant to the first raffinate is preferably 1:(9-11), more preferably 1:10. The present invention does not specifically limit the other operations of the second extraction; extraction techniques familiar to those skilled in the art can be employed. By controlling the composition and dosage of the zirconium-niobium extractant within the aforementioned ranges, the present invention ensures that the zirconium-niobium is fully incorporated into the oil phase.

[0054] After the second extraction is completed, the product of the second extraction is preferably separated to obtain a second raffinate and a second oil phase.

[0055] The present invention has no particular limitation on the liquid separation operation, and the oil phase and the raffinate can be separated by using a liquid separation technical solution well known to those skilled in the art.

[0056] In the present invention, the second alkali solution preferably includes a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution; the mass concentration of the second alkali solution is preferably 5-15%, more preferably 10%.

[0057] In the present invention, the volume ratio of the second oil phase to the second alkali solution is preferably 1:(1-5). Controlling the volume ratio of the second oil phase to the second alkali solution within this range allows for sufficient stripping of zirconium and niobium. The present invention does not specifically limit the remaining steps of the second stripping process; stripping techniques familiar to those skilled in the art may be employed.

[0058] After the second stripping is completed, the present invention preferably performs solid-liquid separation on the product of the second stripping to obtain a mixture of zirconium hydroxide and niobium hydroxide.

[0059] The present invention has no special limitation on the solid-liquid separation operation, and the solid and liquid can be separated using a solid-liquid separation technical solution well known to those skilled in the art.

[0060] After obtaining the second raffinate, the present invention mixes the second raffinate with a titanium extractant to perform a third extraction to obtain a third raffinate and a third oil phase, and mixes the third oil phase with a third alkali solution to perform a third back extraction to obtain amorphous titanium dioxide.

[0061] In the present invention, the titanium extractant comprises, by mass percentage, 19-21% P204, 4-6% TBP, 4-6% LK-N21 (mixed long-chain (C7-C9) carboxylic acid extractant) and the balance solvent.

[0062] In the present invention, the solvent preferably includes one or more of kerosene, isobutanol, white oil, n-butanol, n-octanol and solvent oil; the solvent oil preferably includes one or more of 120# solvent oil, 180# solvent oil, 200# solvent oil and 260# solvent oil.

[0063] As an embodiment, the titanium extractant may specifically be 20% P204, 5% TBP, 5% LK-N21 and the remainder 260# solvent oil.

[0064] In the present invention, the volume ratio of the titanium extractant to the second raffinate is preferably 1:(9-11), more preferably 1:10. The present invention does not specifically limit the other operations of the third extraction; extraction techniques familiar to those skilled in the art can be employed. By controlling the composition and dosage of the titanium extractant within the aforementioned ranges, the present invention ensures that the titanium is fully incorporated into the oil phase.

[0065] After the third extraction is completed, the present invention preferably separates the product of the third extraction to obtain a third raffinate and a third oil phase.

[0066] The present invention has no particular limitation on the liquid separation operation, and the oil phase and the raffinate can be separated by using a liquid separation technical solution well known to those skilled in the art.

[0067] In the present invention, the third alkali solution preferably includes a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution; the mass concentration of the third alkali solution is preferably 5-15%, more preferably 10%.

[0068] In the present invention, the volume ratio of the third oil phase to the third alkali solution is preferably 1:(1-5). Controlling the volume ratio of the third oil phase to the third alkali solution within this range allows for sufficient stripping of titanium. The present invention does not specifically limit the remaining steps of the third stripping process; stripping techniques familiar to those skilled in the art may be employed.

[0069] After the third stripping is completed, the present invention preferably performs solid-liquid separation on the product of the third stripping to obtain amorphous titanium dioxide.

[0070] The present invention has no special limitation on the solid-liquid separation operation, and the solid and liquid can be separated using a solid-liquid separation technical solution well known to those skilled in the art.

[0071] After obtaining the third raffinate, the present invention mixes the third raffinate with an iron extractant and an iron auxiliary agent to perform a fourth extraction to obtain a fourth raffinate and a fourth oil phase, and mixes the fourth oil phase with a fourth alkali solution to perform a fourth back extraction to obtain ferric hydroxide.

[0072] In the present invention, the iron extractant includes, by mass percentage, one or more of N235 (trialkylamine (C8-C10)), P204, P507, MIBK (methyl isobutyl ketone) and C902 (bifunctional modified phosphonate extractant), 4-6% TBP and the balance solvent.

[0073] In the present invention, the solvent preferably includes one or more of kerosene, isobutanol, white oil, n-butanol, n-octanol and solvent oil; the solvent oil preferably includes one or more of 120# solvent oil, 180# solvent oil, 200# solvent oil and 260# solvent oil.

[0074] As an embodiment, the iron extractant may be specifically 10% N235, 5% TBP and the balance 260# solvent oil, or may be specifically 10% P204, 5% TBP and the balance 260# solvent oil, or may be specifically 10% P507, 5% TBP and the balance 260# solvent oil, or may be specifically 10% MIBK, 1% C902, 5% TBP and the balance 260# solvent oil.

[0075] In the present invention, the volume ratio of the iron extractant to the third raffinate is preferably 1:(9-11), more preferably 1: 10. By controlling the composition and amount of the iron extractant within the above range, the iron can be fully incorporated into the oil phase.

[0076] In the present invention, the iron additive preferably includes one or more of sodium hypochlorite, hydrogen peroxide, magnesium oxide and ozone, more preferably hydrogen peroxide; the mass concentration of the hydrogen peroxide is preferably 15-25%, more preferably 20%.

[0077] In the present invention, the mass ratio of the third raffinate to the iron auxiliary agent is preferably (3000-5000):20. The present invention adds the iron auxiliary agent and controls its dosage to enable sufficient extraction of iron.

[0078] The present invention has no special limitation on other operations of the fourth extraction, and any extraction technical solution well known to those skilled in the art may be used.

[0079] After the fourth extraction is completed, the present invention preferably separates the product of the fourth extraction to obtain a fourth raffinate and a fourth oil phase.

[0080] The present invention has no particular limitation on the liquid separation operation, and the oil phase and the raffinate can be separated by using a liquid separation technical solution well known to those skilled in the art.

[0081] In the present invention, the fourth alkali solution preferably includes a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution; the mass concentration of the fourth alkali solution is preferably 5-15%, more preferably 10%.

[0082] In the present invention, the volume ratio of the fourth oil phase to the fourth alkali solution is preferably 1:(1-5). Controlling the volume ratio of the fourth oil phase to the fourth alkali solution within this range allows for sufficient stripping of the iron. The present invention does not specifically limit the remaining steps of the fourth stripping process; stripping techniques familiar to those skilled in the art may be employed.

[0083] After the fourth stripping is completed, the present invention preferably performs solid-liquid separation on the product of the fourth stripping to obtain ferric hydroxide.

[0084] The present invention has no special limitation on the solid-liquid separation operation, and the solid and liquid can be separated using a solid-liquid separation technical solution well known to those skilled in the art.

[0085] After obtaining the fourth raffinate, the present invention mixes the fourth raffinate with a vanadium extractant to perform a fifth extraction to obtain a fifth raffinate and a fifth oil phase, and then mixes the fifth oil phase with a fifth alkali solution to perform a fifth back extraction to obtain vanadate.

[0086] In the present invention, the vanadium extractant preferably comprises, by mass percentage, 10-15% N235 or P204, 4-6% TBP and the balance solvent.

[0087] In the present invention, the solvent preferably includes one or more of kerosene, isobutanol, white oil, n-butanol, n-octanol and solvent oil; the solvent oil preferably includes one or more of 120# solvent oil, 180# solvent oil, 200# solvent oil and 260# solvent oil.

[0088] As an embodiment, the vanadium extractant may be specifically 10% N235, 5% TBP and the balance 260# solvent oil, or may be specifically 10% P204, 5% TBP and the balance 260# solvent oil.

[0089] In the present invention, the volume ratio of the vanadium extractant to the fourth raffinate is preferably 1:(9-11), more preferably 1:10. By controlling the composition and dosage of the vanadium extractant within the aforementioned range, the present invention ensures that the vanadium is fully incorporated into the oil phase. The present invention does not specifically limit the remaining steps of the fifth extraction; extraction techniques familiar to those skilled in the art may be employed.

[0090] After the fifth extraction is completed, the present invention preferably separates the product of the fifth extraction to obtain a fifth raffinate and a fifth oil phase.

[0091] The present invention has no particular limitation on the liquid separation operation, and the oil phase and the raffinate can be separated by using a liquid separation technical solution well known to those skilled in the art.

[0092] In the present invention, the fifth alkali solution preferably includes a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution; the mass concentration of the fifth alkali solution is preferably 5-15%, more preferably 10%.

[0093] In the present invention, the volume ratio of the fifth oil phase to the fifth alkali solution is preferably 1:(1-5). Controlling the volume ratio of the fifth oil phase to the fifth alkali solution within this range allows for sufficient stripping of vanadium. The present invention does not specifically limit the remaining steps of the fifth stripping process; stripping techniques familiar to those skilled in the art may be employed.

[0094] After the fifth stripping is completed, the present invention preferably separates the product of the fifth stripping to obtain a stripping solution, and evaporates and crystallizes the stripping solution to obtain vanadate.

[0095] The present invention has no special limitation on the operation of the evaporative crystallization, and vanadate can be obtained by using the evaporative crystallization technical solution well known to those skilled in the art.

[0096] After obtaining the fifth raffinate, the present invention mixes the fifth raffinate with a manganese extractant to perform a sixth extraction to obtain a sixth raffinate and a sixth oil phase, and then mixes the sixth oil phase with an acid solution to perform a sixth back extraction to obtain a manganese compound.

[0097] In the present invention, the manganese extractant preferably comprises 38-42% P204 and the remainder solvent, calculated by mass percentage.

[0098] In the present invention, the solvent preferably includes one or more of kerosene, isobutanol, white oil, n-butanol, n-octanol and solvent oil; the solvent oil preferably includes one or more of 120# solvent oil, 180# solvent oil, 200# solvent oil and 260# solvent oil.

[0099] As an embodiment, the manganese extractant may specifically be 40% P204 and the balance 260# solvent oil.

[0100] In the present invention, the volume ratio of the manganese extractant to the fifth raffinate is preferably 1:(9-11), more preferably 1:10. By controlling the composition and dosage of the manganese extractant within the above range, the present invention ensures that manganese is fully incorporated into the oil phase. The present invention does not specifically limit the remaining steps of the sixth extraction; extraction techniques familiar to those skilled in the art may be employed.

[0101] After the sixth extraction is completed, the present invention preferably separates the product of the sixth extraction to obtain a sixth raffinate and a sixth oil phase.

[0102] The present invention has no particular limitation on the liquid separation operation, and the oil phase and the raffinate can be separated by using a liquid separation technical solution well known to those skilled in the art.

[0103] In the present invention, the acid solution preferably includes one or more of hydrochloric acid, sulfuric acid, acetic acid, nitric acid and phosphoric acid; and the concentration of the acid solution is preferably 4-12 mol / L.

[0104] In the present invention, the volume ratio of the sixth oil phase to the acid solution is preferably 1:(1-5). Controlling the volume ratio of the sixth oil phase to the acid solution within this range allows for sufficient stripping of manganese. The present invention does not specifically limit the remaining steps of the sixth stripping process; stripping techniques familiar to those skilled in the art may be employed.

[0105] When the acid solution is sulfuric acid, after the sixth stripping is completed, the present invention preferably separates the product of the sixth stripping to obtain a stripping solution, and evaporates and crystallizes the stripping solution to obtain a manganese compound.

[0106] The present invention has no particular limitation on the operation of the evaporation crystallization, and the manganese compound can be obtained by using the evaporation crystallization technical solution well known to those skilled in the art.

[0107] After obtaining the sixth raffinate, the present invention mixes the sixth raffinate with an oxidant and activated carbon, performs a third solid-liquid separation to obtain a third solution, and evaporates and crystallizes the third solution to obtain a mixed salt.

[0108] In the present invention, the oxidant preferably includes sodium hypochlorite.

[0109] In the present invention, the mass ratio of the sixth raffinate to the oxidant is preferably (330-410):1.

[0110] In the present invention, the mass ratio of the sixth raffinate to the activated carbon is preferably (3300-4100):5.

[0111] The present invention has no special limitation on the operation of the third solid-liquid separation, and the technical solution of solid-liquid separation well known to those skilled in the art can be adopted.

[0112] The present invention has no special limitation on the operation of the evaporation crystallization, and the technical solution of evaporation crystallization well known to those skilled in the art can be adopted.

[0113] In the present invention, the mixed salt is preferably used as a grinding aid.

[0114] The present invention dissolves and extracts titanium dioxide solid waste residue produced by the chloride process in steps, recovers high-value metals in the solid waste residue, and evaporates and crystallizes the remaining substances to obtain mixed salt, thereby achieving zero discharge of solid waste residue and full resource utilization.

[0115] The schematic flow chart of the method for treating solid waste residue of titanium dioxide produced by the chloride process provided by the present invention is preferably as follows: Figure 1 As shown: titanium dioxide waste residue from the chloride process is mixed with water and an additive and then subjected to solid-liquid separation to obtain a solid containing titanium dioxide and petroleum coke and a first solution. The first solution is cooled and then subjected to solid-liquid separation to obtain ferrous chloride and a second solution. Subsequently, various metal compounds (a mixture of scandium hydroxide, zirconium hydroxide and niobium hydroxide, amorphous titanium dioxide, ferric hydroxide, vanadate, and manganese compound) are obtained through various extraction and stripping steps. Finally, the raffinate is mixed with an oxidant and activated carbon, and subjected to solid-liquid separation and evaporation crystallization to obtain a mixed salt.

[0116] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions of the present invention. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0117] Example 1 A method for treating solid waste residue of titanium dioxide produced by a chloride process is as follows: (1) taking 1000 kg of solid waste residue of titanium dioxide produced by a chloride process, adding 5000 L of water and 10 kg of a 10% sodium hypochlorite aqueous solution, heating to 90° C. for reaction for 30 minutes, and performing solid-liquid separation to obtain 480 kg of a solid containing titanium dioxide and petroleum coke and 4295 kg of a first solution; (2) Cooling the solution obtained in step (1) to 20° C. and performing solid-liquid separation to obtain 444 kg of ferrous chloride solid and 3851 kg of a second solution; (3) adding a scandium extractant (10 wt% P204 + 5 wt% TBP + 5 wt% P507 + 80 wt% 260# solvent oil, the volume ratio of the scandium extractant to the second solution is 1:10) to the second solution obtained in step (2), performing a first extraction to obtain a first raffinate (3850 kg) and a first oil phase, and performing a first back extraction on the first oil phase with a 10 wt% sodium hydroxide aqueous solution (the volume ratio of the first oil phase to the sodium hydroxide aqueous solution is 1:1) to obtain 0.42698 kg of solid scandium hydroxide; (4) adding a zirconium-niobium extractant (20 wt% P204 + 5 wt% TBP + 5 wt% P507 + 70 wt% 260# solvent oil, the volume ratio of the zirconium-niobium extractant to the first raffinate being 1:10) to the first raffinate obtained in step (3) and performing a second extraction to obtain a second raffinate (3828 kg) and a second oil phase, and performing a second back extraction on the second oil phase using a 10 wt% sodium hydroxide aqueous solution (the volume ratio of the second oil phase to the sodium hydroxide aqueous solution being 1:1) to obtain 11 kg of a solid zirconium hydroxide and niobium hydroxide mixture; (5) adding a titanium extractant (20 wt% P204 + 5 wt% TBP + 5 wt% LK-N21 + 70 wt% 260# solvent oil, the volume ratio of the titanium extractant to the second raffinate being 1:10) to the second raffinate obtained in step (4), performing a third extraction to obtain a third raffinate (3688 kg) and a third oil phase, and performing a third back extraction on the third oil phase using a 10 wt% sodium hydroxide aqueous solution (the volume ratio of the third oil phase to the sodium hydroxide aqueous solution being 1:1) to obtain 70 kg of solid amorphous titanium dioxide; (6) Adding an iron extractant (10 wt% N235 + 5 wt% TBP + 85 wt% 260# solvent, the volume ratio of the iron extractant to the third raffinate is 1:10) and 20 kg of 20 wt% hydrogen peroxide to the third raffinate obtained in step (5), performing a fourth extraction to obtain a fourth raffinate (3486 kg) and a fourth oil phase, and performing a fourth back extraction on the fourth oil phase using a 10 wt% sodium hydroxide aqueous solution (the volume ratio of the fourth oil phase to the sodium hydroxide aqueous solution is 1:1) to obtain 222 kg of solid iron hydroxide; (7) adding a vanadium extractant (10 wt% P204 + 5 wt% TBP + 85 wt% 260# solvent oil, the volume ratio of the vanadium extractant to the fourth raffinate being 1:10) to the fourth raffinate obtained in step (6), performing a fifth extraction to obtain a fifth raffinate (3466 kg) and a fifth oil phase, performing a fifth back extraction on the fifth oil phase using a 10 wt% sodium hydroxide aqueous solution (the volume ratio of the fifth oil phase to the sodium hydroxide aqueous solution being 1:1), and then separating the liquid to obtain a back extract, and performing evaporation and crystallization on the back extract to obtain 10 kg of solid sodium vanadate; (8) adding a manganese extractant (40 wt% P204 + 60% 260# solvent oil, the volume ratio of the manganese extractant to the fifth raffinate being 1:10) to the fifth raffinate obtained in step (7) to perform a sixth extraction to obtain a sixth raffinate (3356 kg) and a sixth oil phase, and subjecting the sixth oil phase to a sixth stripping with 4 mol / L sulfuric acid (the volume ratio of the sixth oil phase to sulfuric acid being 1:1) and then separating the liquid to obtain a stripping solution, and subjecting the stripping solution to evaporation and crystallization to obtain 110 kg of a manganese compound; (9) 10 kg of sodium hypochlorite and 5 kg of activated carbon were added to the sixth raffinate obtained in step (8), and the mixture was filtered. The liquid was evaporated and crystallized to obtain 503 kg of mixed salt.

[0118] Example 2 A method for treating solid waste residue of titanium dioxide produced by a chloride process is as follows: (1) taking 1000 kg of solid waste residue of titanium dioxide produced by a chloride process, adding 3500 L of water and 1500 L of 6 mol / L hydrochloric acid, heating to 70° C. and reacting for 60 min, and then performing solid-liquid separation to obtain 470 kg of solid containing titanium dioxide and petroleum coke and 4950 kg of a first solution; (2) Cooling the solution obtained in step (1) to 20° C. and performing solid-liquid separation to obtain 440 kg of ferrous chloride solid and 4810 kg of a second solution; (3) adding a scandium extractant (10 wt% P204 + 5 wt% TBP + 15 wt% P507 + 70 wt% 260# solvent oil, the volume ratio of the scandium extractant to the second solution is 1:10) to the second solution obtained in step (2), performing a first extraction to obtain a first raffinate (4809 kg) and a first oil phase, and performing a first back extraction on the first oil phase with a 10 wt% sodium hydroxide aqueous solution (the volume ratio of the first oil phase to the sodium hydroxide aqueous solution is 1:1) to obtain 0.43 kg of solid scandium hydroxide; (4) adding a zirconium-niobium extractant (20 wt% P204 + 5 wt% TBP + 5 wt% P507 + 70 wt% 260# solvent oil, the volume ratio of the zirconium-niobium extractant to the first raffinate being 1:10) to the first raffinate obtained in step (3) and performing a second extraction to obtain a second raffinate (4788 kg) and a second oil phase, and performing a second back extraction on the second oil phase using a 10 wt% sodium hydroxide aqueous solution (the volume ratio of the second oil phase to the sodium hydroxide aqueous solution being 1:1) to obtain 10.5 kg of a solid zirconium hydroxide and niobium hydroxide mixture; (5) adding a titanium extractant (20 wt% P204 + 5 wt% TBP + 5 wt% LK-N21 + 70 wt% 260# solvent oil, the volume ratio of the titanium extractant to the second raffinate is 1:10) to the second raffinate obtained in step (4), performing a third extraction to obtain a third raffinate (4648 kg) and a third oil phase, and performing a third back extraction on the third oil phase using a 10 wt% sodium hydroxide aqueous solution (the volume ratio of the third oil phase to the sodium hydroxide aqueous solution is 1:1) to obtain 70 kg of solid amorphous titanium dioxide; (6) Adding an iron extractant (10 wt% P204 + 5 wt% TBP + 85 wt% 260# solvent oil, the volume ratio of the iron extractant to the third raffinate is 1:10) and 20 kg of 20 wt% hydrogen peroxide to the third raffinate obtained in step (5), performing a fourth extraction to obtain a fourth raffinate (4208 kg) and a fourth oil phase, and performing a fourth back extraction on the fourth oil phase using a 10 wt% sodium hydroxide aqueous solution (the volume ratio of the fourth oil phase to the sodium hydroxide aqueous solution is 1:1) to obtain 220 kg of solid iron hydroxide; (7) adding a vanadium extractant (10 wt% N235 + 5 wt% TBP + 85 wt% 260# solvent oil, the volume ratio of the vanadium extractant to the fourth raffinate being 1:10) to the fourth raffinate obtained in step (6), performing a fifth extraction to obtain a fifth raffinate (4188 kg) and a fifth oil phase, performing a fifth back extraction on the fifth oil phase using a 10 wt% sodium hydroxide aqueous solution (the volume ratio of the fifth oil phase to the sodium hydroxide aqueous solution being 1:1), and then separating the liquid to obtain a back extract, and performing evaporation and crystallization on the back extract to obtain 10.2 kg of solid sodium vanadate; (8) adding a manganese extractant (40 wt% P204 + 60% 260# solvent oil, the volume ratio of the manganese extractant to the fifth raffinate being 1:10) to the fifth raffinate obtained in step (7) to perform a sixth extraction to obtain a sixth raffinate (4077 kg) and a sixth oil phase, and subjecting the sixth oil phase to a sixth stripping with 4 mol / L sulfuric acid (the volume ratio of the sixth oil phase to sulfuric acid being 1:1) and then separating the liquid to obtain a stripping solution, and subjecting the stripping solution to evaporation and crystallization to obtain 111 kg of a manganese compound; (9) 10 kg of sodium hypochlorite and 5 kg of activated carbon were added to the sixth raffinate obtained in step (8), and the mixture was filtered. The liquid was evaporated and crystallized to obtain 550 kg of mixed salt.

[0119] Example 3 A method for treating solid waste residue of titanium dioxide produced by a chloride process is as follows: (1) taking 1000 kg of solid waste residue of titanium dioxide produced by a chloride process, adding 3500 L of water, 1500 L of 6 mol / L hydrochloric acid, and 10 kg of 30 wt% hydrogen peroxide, heating to 70° C. and reacting for 60 min, and then performing solid-liquid separation to obtain 460 kg of solid containing titanium dioxide and petroleum coke and 4550 kg of a first solution; (2) Cooling the solution obtained in step (1) to 20° C. and performing solid-liquid separation to obtain 440 kg of ferrous chloride solid and 4110 kg of a second solution; (3) adding a scandium extractant (5 wt% P204 + 5 wt% TBP + 10 wt% P507 + 80 wt% 260# solvent oil, the volume ratio of the scandium extractant to the second solution is 1:10) to the second solution obtained in step (2), performing a first extraction to obtain a first raffinate (4100 kg) and a first oil phase, and performing a first back extraction on the first oil phase with a 10 wt% sodium hydroxide aqueous solution (the volume ratio of the first oil phase to the sodium hydroxide aqueous solution is 1:1) to obtain 0.395 kg of solid scandium hydroxide; (4) adding a zirconium-niobium extractant (20 wt% P204 + 5 wt% TBP + 5 wt% P507 + 70 wt% 260# solvent oil, the volume ratio of the zirconium-niobium extractant to the first raffinate being 1:10) to the first raffinate obtained in step (3) and performing a second extraction to obtain a second raffinate (4078 kg) and a second oil phase, and performing a second back extraction on the second oil phase using a 10 wt% sodium hydroxide aqueous solution (the volume ratio of the second oil phase to the sodium hydroxide aqueous solution being 1:1) to obtain 11 kg of a solid zirconium hydroxide and niobium hydroxide mixture; (5) adding a titanium extractant (20 wt% P204 + 5 wt% TBP + 5 wt% LK-N21 + 70 wt% 260# solvent oil, the volume ratio of the titanium extractant to the second raffinate being 1:10) to the second raffinate obtained in step (4), performing a third extraction to obtain a third raffinate (3938 kg) and a third oil phase, and performing a third back extraction on the third oil phase using a 10 wt% sodium hydroxide aqueous solution (the volume ratio of the third oil phase to the sodium hydroxide aqueous solution being 1:1) to obtain 71 kg of solid amorphous titanium dioxide; (6) Adding an iron extractant (10 wt% N235 + 5 wt% TBP + 85 wt% 260# solvent oil, the volume ratio of the iron extractant to the third raffinate is 1:10) and 20 kg of 20 wt% hydrogen peroxide to the third raffinate obtained in step (5), performing a fourth extraction to obtain a fourth raffinate (3717 kg) and a fourth oil phase, and performing a fourth back extraction on the fourth oil phase using a 10 wt% sodium hydroxide aqueous solution (the volume ratio of the fourth oil phase to the sodium hydroxide aqueous solution is 1:1) solution to obtain 221 kg of solid iron hydroxide; (7) adding a vanadium extractant (10 wt% N235 + 5 wt% TBP + 85 wt% 260# solvent oil, the volume ratio of the vanadium extractant to the fourth raffinate being 1:10) to the fourth raffinate obtained in step (6), performing a fifth extraction to obtain a fifth raffinate (3697 kg) and a fifth oil phase, performing a fifth back extraction on the fifth oil phase using a 10 wt% sodium hydroxide aqueous solution (the volume ratio of the fifth oil phase to the sodium hydroxide aqueous solution being 1:1), and then separating the liquid to obtain a back extract, and performing evaporation and crystallization on the back extract to obtain 10.2 kg of solid sodium vanadate; (8) adding a manganese extractant (40 wt% P204 + 60% 260# solvent oil, the volume ratio of the manganese extractant to the fifth raffinate being 1:10) to the fifth raffinate obtained in step (7) to perform a sixth extraction to obtain a sixth raffinate (3586 kg) and a sixth oil phase, and subjecting the sixth oil phase to a sixth stripping with 4 mol / L sulfuric acid (the volume ratio of the sixth oil phase to sulfuric acid being 1:1) and then separating the liquid to obtain a stripping solution, and subjecting the stripping solution to evaporation and crystallization to obtain 111 kg of a manganese compound; (9) 10 kg of sodium hypochlorite and 5 kg of activated carbon were added to the sixth raffinate obtained in step (8), and the mixture was filtered. The liquid was evaporated and crystallized to obtain 537.9 kg of mixed salt.

[0120] In summary, the treatment method of the present invention is used to treat solid waste residue of titanium dioxide produced by the chloride process, thereby achieving zero emission and full resource utilization of solid waste residue of titanium dioxide produced by the chloride process.

[0121] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A method for treating solid waste residue of titanium dioxide produced by chloride process, characterized in that: The following steps are involved: (1) mixing solid waste residue of titanium dioxide produced by the chloride process with water and an additive, heating the mixture and performing a first solid-liquid separation to obtain a solid containing titanium dioxide and petroleum coke and a first solution; (2) cooling the first solution obtained in step (1) and performing a second solid-liquid separation to obtain ferrous chloride and a second solution; (3) mixing the second solution obtained in step (2) with a scandium extractant to perform a first extraction to obtain a first raffinate and a first oil phase, and mixing the first oil phase with a first alkaline solution to perform a first back extraction to obtain scandium hydroxide; (4) mixing the first raffinate obtained in step (3) with a zirconium-niobium extractant to perform a second extraction to obtain a second raffinate and a second oil phase, and mixing the second oil phase with a second alkali solution to perform a second back extraction to obtain a mixture of zirconium hydroxide and niobium hydroxide; (5) mixing the second raffinate obtained in step (4) with a titanium extractant to perform a third extraction to obtain a third raffinate and a third oil phase, and mixing the third oil phase with a third alkali solution to perform a third back extraction to obtain amorphous titanium dioxide; (6) mixing the third raffinate obtained in step (5) with an iron extractant and an iron auxiliary agent to perform a fourth extraction to obtain a fourth raffinate and a fourth oil phase, and mixing the fourth oil phase with a fourth alkali solution to perform a fourth back extraction to obtain ferric hydroxide; (7) mixing the fourth raffinate obtained in step (6) with a vanadium extractant to perform a fifth extraction to obtain a fifth raffinate and a fifth oil phase, and mixing the fifth oil phase with a fifth alkali solution to perform a fifth back extraction to obtain vanadate; (8) mixing the fifth raffinate obtained in step (7) with a manganese extractant to perform a sixth extraction to obtain a sixth raffinate and a sixth oil phase, and mixing the sixth oil phase with an acid solution to perform a sixth back extraction to obtain a manganese compound; (9) The sixth raffinate obtained in step (8) is mixed with an oxidant and activated carbon, and a third solid-liquid separation is performed to obtain a third solution, and the third solution is evaporated and crystallized to obtain a mixed salt.

2. The processing method according to claim 1, characterized in that The auxiliary agent in step (1) includes one or more of sodium hypochlorite aqueous solution, hydrogen peroxide, sulfur dioxide, hydrochloric acid, iron powder and aluminum powder.

3. The processing method according to claim 1, characterized in that Calculated by mass percentage, the scandium extractant in step (3) includes 5-10% P204, 4-6% TBP, 5-15% P507 and the balance solvent.

4. The processing method according to claim 1, characterized in that Calculated by mass percentage, the zirconium-niobium extractant in step (4) includes 19-21% P204, 4-6% TBP, 5-15% P507 and the balance solvent.

5. The processing method according to claim 1, characterized in that Calculated by mass percentage, the titanium extractant in step (5) includes 19-21% P204, 4-6% TBP, 4-6% LK-N21 and the balance solvent.

6. The processing method according to claim 1, characterized in that Calculated by mass percentage, the iron extractant in step (6) includes 1-15% of one or more of N235, P204, P507, MIBK and C902, 4-6% of TBP and the balance of solvent.

7. The processing method according to claim 1, characterized in that The iron additive in step (6) includes one or more of sodium hypochlorite, hydrogen peroxide, magnesium oxide and ozone.

8. The processing method according to claim 1, characterized in that Calculated by mass percentage, the vanadium extractant in step (7) includes 10-15% N235 or P204, 4-6% TBP and the balance solvent.

9. The processing method according to claim 1, characterized in that: Calculated by mass percentage, the manganese extractant in step (8) includes 38-42% P204 and the remainder solvent.

10. The processing method according to claim 1, characterized in that: The oxidant in step (9) includes sodium hypochlorite.

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