CN112429780B - Method for recycling valuable elements through segmented extraction of titanium dioxide waste acid by using chlorination process - Google Patents
Method for recycling valuable elements through segmented extraction of titanium dioxide waste acid by using chlorination process Download PDFInfo
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Abstract
The invention discloses a method for recycling valuable elements by sectionally extracting titanium dioxide waste acid by a chlorination process, which comprises the following steps: s1, adding a first organic phase into titanium white waste acid of a chlorination process to obtain a first extraction residual liquid and an iron load; back-extracting the iron load to obtain ferric chloride solution; s2, adding a second organic phase into the first extraction residual liquid to obtain a second extraction residual liquid and scandium titanium zirconium niobium load; s3, scandium load back extraction is carried out to obtain scandium titanium zirconium niobium concentrate; s4, adjusting the ph value of the second raffinate to prepare liquid; s5, adding a third organic phase after preparing liquid to obtain vanadium-aluminum load and a third raffinate; s6, carrying out back extraction on the vanadium-aluminum load to obtain a vanadium-aluminum mixed solution; s7, preparing liquid by adjusting the ph value of the third extraction residual liquid; s8, adding a fourth organic phase into the manganese extraction feed liquid after preparing the liquid to obtain manganese load and a fourth extraction residual liquid; carrying out back extraction on manganese load to obtain a manganese-containing solution; s9, neutralizing and filtering the fourth extraction residual liquid, concentrating and crystallizing to obtain NaCl salt and water, and recycling.
Description
Technical Field
The invention relates to the field of metallurgy, in particular to a method for recycling valuable elements by sectionally extracting titanium dioxide waste acid by a chloride process.
Background
Titanium dioxide is an important chemical raw material and is widely applied to various important industrial fields affecting national economy. In the boiling chlorination process for producing titanium dioxide, 0.4-0.6 m of titanium dioxide is produced per ton of titanium dioxide 3 Waste hydrochloric acid solution. The waste hydrochloric acid solution is usually subjected to neutralization treatment by lime milk to generate a large amount of slag phase, and then the slag phase is discarded, so that not only is a large amount of resource waste caused, but also the environment is seriously polluted; the waste acid contains a large amount of iron, manganese, aluminum and a small amount of elements such as titanium, zirconium, niobium, scandium, vanadium and the like; the valuable elements have high value, and a method for comprehensively recovering the valuable elements in the waste acid is necessary to be researched, so that the emission of waste water and waste residues is reduced, and the environment is protected.
Disclosure of Invention
Aiming at the problems, the invention provides a method which is convenient to operate, adopts sectional extraction to the titanium white waste acid of the chlorination process, recovers valuable elements, and simultaneously solves the problems of waste water and waste residue discharge and recycling.
In order to achieve the above object, the technical scheme of the present invention is as follows: (before the following modifications are made)
A method for recycling valuable elements by sectionally extracting titanium white waste acid by using a chlorination process comprises the following steps:
s1, adding an oxidant into titanium white waste acid of a chlorination process, then adding a first organic phase to perform iron extraction operation, and separating phases to obtain a first extraction residual liquid and an iron load; performing back extraction iron operation on the iron load by using the first back extraction liquid to obtain ferric chloride solution;
s2, adding a second organic phase into the first raffinate to extract scandium, and obtaining a second raffinate and scandium load after phase separation;
s3, washing the scandium load by using a washing liquid, adding a second stripping liquid into the scandium load after washing to carry out stripping operation, and filtering to obtain scandium titanium zirconium niobium concentrate;
s4, adjusting the pH value of the second extraction residual liquid to prepare liquid, so as to obtain vanadium-aluminum extraction liquid;
s5, adding a third organic phase into the vanadium-aluminum extraction feed liquid to perform vanadium-aluminum extraction operation, and obtaining vanadium-aluminum load and a third extraction residual liquid after phase separation;
s6, adding a third stripping solution into the vanadium-aluminum load to carry out back extraction on the vanadium-aluminum, so as to obtain a vanadium-aluminum mixed solution; oxidizing, hydrolyzing and precipitating vanadium in the vanadium-aluminum mixed solution to obtain an aluminum-containing solution and a poly-vanadate precipitate;
s7, adjusting the pH value of the third extraction residual liquid to prepare a liquid, so as to obtain manganese extraction liquid;
s8, adding a fourth organic phase into the manganese extraction feed liquid to extract manganese, and obtaining manganese load and fourth extraction residual liquid after phase separation; adding a fourth strip liquor into the manganese load to carry out strip manganese operation to obtain a manganese sulfate solution;
s9, neutralizing and filtering the fourth extraction residual liquid to obtain a sodium chloride solution; concentrating and crystallizing the sodium chloride solution to obtain NaCl solid and water, and recycling the water.
Further, the oxidant in the step S1 is one of hydrogen peroxide, sodium chlorate, sodium hypochlorite and sodium chlorite;
when iron extraction operation is carried out, the O/A=1-5:1 of the first organic phase compared with the extraction of titanium white waste acid by a chlorination process after oxidation;
when the back extraction iron operation is carried out, the first back extraction liquid has O/A=1-10 compared with the back extraction of iron load: 1, a step of; the first stripping liquid is water with the temperature of 20-60 ℃ or hydrochloric acid with the concentration of 0.1-0.5 mol/l or sodium chloride solution with the concentration of 1-20%.
Further, in the scandium extraction operation in step S2, the ratio O/a=1 of the second organic phase to the first raffinate: 10 to 50 percent.
Further, in the washing operation in the step S3, the washing liquid is washed with O/a=1 to 10 compared with the scandium load: 1, a step of;
the washing liquid is prepared by mixing sulfuric acid with the concentration of 3-6 mol/l and hydrofluoric acid with the concentration of 40%, and the volume ratio of the sulfuric acid to the hydrofluoric acid is 1:0.005-0.2;
when the stripping operation is performed, the second stripping solution has O/a=1 compared with the stripping of scandium load after washing: 1-3; the second stripping liquid is 2.5-7 mol/l liquid alkali.
Further, in the step S4, when the second raffinate is subjected to the liquid preparation operation, the alkali used is one of sodium carbonate, sodium hydroxide, calcium carbonate and carbide mud, and the ph value in the liquid preparation is 2-3.
Further, in the step S5, when the vanadium-aluminum extraction operation is performed, the extraction ratio O/a=1 of the third organic phase to the vanadium-aluminum extraction liquid: 1-8.
Further, in the step S6, when the vanadium-aluminum stripping operation is performed, the O/a=1-7 of the third stripping solution compared with the stripping of the vanadium-aluminum load: 1, a step of; the third extraction liquid is sulfuric acid with the concentration of 1-5 mol/l.
Further, in the step S7, when the third raffinate is subjected to the liquid preparation operation, the alkali used is one of sodium carbonate, sodium hydroxide, calcium carbonate and carbide mud, and the ph value during the liquid preparation is 4-6.
Further, in the step S8, when the operation of extracting manganese is performed, the O/a=1:2-6 of the fourth organic phase to the extraction of the manganese extraction liquid; when the manganese back extraction operation is carried out, the O/A=1-6:1 of the fourth back extraction liquid compared with the back extraction of manganese load; the fourth stripping liquid is sulfuric acid with the concentration of 1.5-3 mol/l.
Further, the first organic phase is prepared by mixing one of N235 and N503, sec-octanol and solvent oil; the second organic phase, the third organic phase and the fourth organic phase are prepared by mixing solvent oil and one of TBP, sec-octanol and one of P204, P507 and P272.
Compared with the prior art, the invention has the advantages and positive effects that:
according to the method, the iron-loaded organic phase is obtained through extraction by using the first organic phase, the scandium-loaded organic phase is obtained through extraction by using the second organic phase, the vanadium-aluminum-loaded organic phase is obtained through extraction by using the third organic phase, the manganese-loaded organic phase is obtained through extraction by using the fourth organic phase, and then the various loaded organic phases are subjected to back extraction operation by using each back extraction liquid, so that the enrichment of various valuable elements is obtained, the recovery of the valuable elements in the titanium white waste acid of the chloride process is realized, the situation that the titanium white waste acid of the chloride process is directly discarded or neutralized to cause serious environmental pollution is avoided, meanwhile, the waste of various metal resources in the titanium white waste acid of the chloride process is effectively avoided, and the waste acid value is improved.
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In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is a block diagram of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, modifications, equivalents, improvements, etc., which are apparent to those skilled in the art without the benefit of this disclosure, are intended to be included within the scope of this invention.
Example 1, as shown in fig. 1, the present example discloses a method for extracting and recovering valuable elements from titanium white waste acid by a chloride process in a sectional manner, which comprises the following steps:
s1, adding hydrogen peroxide into titanium dioxide waste acid by a chlorination method, performing iron oxide operation, oxidizing an end point potential of 710mv, performing iron extraction operation by using 50% N235+10% sec-octanol+40% solvent oil, wherein the ratio of O/A=3:1 in extraction, and obtaining a first extraction residual liquid and an iron load after phase separation; the iron loaded organic was subjected to a stripping iron operation using 50 degrees water, and the stripping phase was compared to O/a=6:1 to give an iron chloride solution.
S2, adding 20% of P204+5% of TBP+75% of solvent oil into the first extraction residual liquid to perform scandium, titanium, zirconium and niobium extraction operation, wherein the extraction ratio O/A=1:10, and phase separation is performed to obtain a second extraction residual liquid and scandium, titanium, zirconium and niobium loaded organic phases;
s3, washing the scandium titanium zirconium niobium load by using a washing solution, wherein the washing solution is 6mol/l sulfuric acid+40% hydrofluoric acid, and the volume ratio of the sulfuric acid to the hydrofluoric acid is 1:0.05; the washing phase ratio was O/a=2:1; adding 2mol/l sodium hydroxide solution into scandium-titanium-zirconium-niobium loaded organic phase to carry out back extraction operation, wherein the back extraction ratio O/A=1:2; the back extraction temperature is 60 ℃, and scandium-titanium-zirconium-niobium enrichment is obtained after filtration;
s4, adding sodium hydroxide into the second extraction residual liquid, and adjusting the PH to 2.7 to obtain vanadium-aluminum extraction feed liquid;
s5, adding 20% P507+10% sec-octyl alcohol+70% solvent oil into the vanadium-aluminum extraction liquid, performing vanadium-aluminum extraction operation, wherein the extraction ratio O/A=1:2, and separating phases to obtain a vanadium-aluminum loaded organic phase and a third extraction residual liquid;
s6, adding 2mol/l sulfuric acid into the vanadium-aluminum loaded organic phase to carry out back extraction on vanadium-aluminum, wherein the back extraction ratio O/A=3:1, and obtaining a vanadium-aluminum mixed solution; the vanadium-aluminum mixed solution is subjected to sodium chlorate vanadium oxide and hydrolysis vanadium precipitation operation to obtain an aluminum-containing solution and a poly-vanadate precipitate;
s7, adding sodium carbonate into the third extraction residual liquid, and adjusting the PH to 5.2 to obtain manganese extraction feed liquid;
s8, adding 15% of P204+5% of TBP+80% of solvent oil into the manganese extraction feed liquid to extract manganese, wherein the extraction ratio O/A=1:2, and phase separation to obtain a manganese loaded organic phase and a fourth extraction residual liquid; adding 3mol/l sulfuric acid into the manganese loaded organic phase to carry out manganese back extraction operation, and obtaining manganese sulfate solution by back extraction compared with O/A=2:1;
s9, neutralizing the fourth extraction residual liquid with sodium hydroxide until the PH is 9, concentrating and crystallizing the filtrate to obtain NaCl salt and water; and (5) recycling the salt and the water.
Example 2, as shown in fig. 1, the present embodiment discloses a method for extracting and recovering valuable elements from titanium white waste acid by a chloride process in a sectional manner, which comprises the following steps:
s1, adding sodium hypochlorite into titanium white waste acid of a chlorination process, performing iron oxide operation, oxidizing an end point potential of 800mv, performing iron extraction operation by using 40% N235+12% sec-octanol+48% solvent oil, wherein the ratio of the extraction to O/A=2:1, and separating phases to obtain a first extraction residual liquid and an iron load organic phase; carrying out back extraction on the iron load by using 60-DEG C water, wherein the back extraction ratio O/A=4:1, so as to obtain ferric chloride solution;
s2, adding 20% P272+5% TBP+75% solvent oil into the first extraction residual liquid to extract scandium, titanium, zirconium and niobium, wherein the extraction ratio O/A=1:40, and phase separation is carried out to obtain a second extraction residual liquid and scandium, titanium, zirconium and niobium loaded organic phase;
s3, washing the scandium titanium zirconium niobium load by using a washing solution, wherein the washing solution is 3.5mol/l sulfuric acid+40% hydrofluoric acid, and the volume ratio of the sulfuric acid to the hydrofluoric acid is 1:0.1; the washing phase ratio was O/a=1:1; adding 5mol/l sodium hydroxide solution into scandium-titanium-zirconium-niobium loaded organic phase to carry out back extraction operation, wherein the back extraction ratio O/A=1:1; the back extraction temperature is 70 ℃, and scandium-titanium-zirconium-niobium enrichment is obtained after filtration;
s4, adding sodium carbonate into the second extraction residual liquid to adjust the PH to 3, so as to obtain vanadium-aluminum extraction feed liquid;
s5, adding 30% of p204+10% of TBP+60% of solvent oil into the vanadium-aluminum extraction liquid, performing vanadium-aluminum extraction operation, wherein the extraction ratio O/A=1:1, and separating phases to obtain a vanadium-aluminum loaded organic phase and a third extraction residual liquid;
s6, adding 1.5mol/l sulfuric acid into the vanadium-aluminum loaded organic phase to carry out back extraction on vanadium-aluminum, wherein the back extraction ratio O/A=6:1 is compared to obtain a vanadium-aluminum mixed solution; the vanadium-aluminum mixed solution is subjected to sodium chlorite vanadium oxide and hydrolysis vanadium precipitation operation to obtain an aluminum-containing solution and a poly-vanadate precipitate;
s7, adding liquid alkali into the third extraction residual liquid to adjust the PH to 5.6, so as to obtain manganese extraction feed liquid;
s8, adding 20% P507+10% TBP+70% solvent oil into the manganese extraction feed liquid to extract manganese, wherein the extraction ratio O/A=1:3, and phase separation to obtain a manganese loaded organic phase and a fourth extraction residual liquid; adding 2mol/l sulfuric acid into the manganese loaded organic phase to carry out back extraction of manganese, wherein the back extraction ratio O/A=6:1, and obtaining manganese sulfate solution;
s9, neutralizing the fourth extraction residual liquid with liquid alkali until the pH value is 8, concentrating and crystallizing the filtrate to obtain NaCl salt and water;
according to the method, the iron-loaded organic phase is obtained through extraction by using the first organic phase, the scandium-titanium-zirconium-niobium-loaded organic phase is obtained through extraction by using the second organic phase, the vanadium-aluminum-loaded organic phase is obtained through extraction by using the third organic phase, the manganese-loaded organic phase is obtained through extraction by using the fourth organic phase, and then the various loaded organic phases are subjected to stripping operation by using each stripping liquid to obtain the concentrate of various valuable elements, so that the recovery of the valuable elements in the titanium white waste acid of the chloride process is realized, the condition that the titanium white waste acid of the chloride process is discarded to cause serious environmental pollution is avoided, meanwhile, the waste of various metal resources in the titanium white waste acid of the chloride process is effectively avoided, and the waste acid value is improved.
Claims (7)
1. A method for recycling valuable elements by sectionally extracting titanium dioxide waste acid by using a chlorination process is characterized by comprising the following steps of: the method comprises the following steps:
s1, adding an oxidant into titanium white waste acid of a chlorination process, then adding a first organic phase to perform iron extraction operation, and separating phases to obtain a first extraction residual liquid and an iron-loaded organic phase; performing back extraction on the iron-loaded organic phase by using the first back extraction solution to obtain an iron chloride solution; when iron extraction operation is carried out, the O/A=1-5:1 of the first organic phase compared with the extraction of titanium white waste acid by a chlorination process after oxidation;
s2, adding a second organic phase into the first extraction residual liquid to extract scandium, and obtaining a second extraction residual liquid and scandium-loaded organic phase after phase separation; in scandium extraction operation, the second organic phase has a ratio O/a=1 of the first raffinate: 10 to 50 percent;
s3, washing the scandium-loaded organic phase by using a washing liquid, adding a second stripping liquid into the scandium-loaded organic phase for stripping operation after washing, and filtering to obtain scandium-titanium-zirconium-niobium concentrate;
s4, performing alkali neutralization operation on the second extraction residual liquid, and adjusting the PH value to be 2-3 to obtain vanadium-aluminum extraction liquid;
s5, adding a third organic phase into the vanadium-aluminum extraction feed liquid, performing vanadium-aluminum extraction operation, and separating phases to obtain a vanadium-aluminum loaded organic phase and a third extraction residual liquid; when vanadium-aluminum extraction is carried out, the extraction ratio O/a=1 of the third organic phase to the vanadium-aluminum extraction liquid: 1-8;
s6, adding a third stripping solution into the vanadium-aluminum loaded organic phase, and carrying out stripping vanadium-aluminum operation to obtain a vanadium-aluminum mixed solution; the vanadium-aluminum mixed solution is subjected to oxidation, hydrolysis and vanadium precipitation operation to obtain an aluminum-containing solution and a poly-vanadate precipitate;
s7, carrying out alkali neutralization operation on the third extraction residual liquid, and regulating the PH value to be 4-6 to obtain manganese extraction feed liquid;
s8, adding a fourth organic phase into the manganese extraction feed liquid, extracting manganese, and separating phases to obtain a manganese loaded organic phase and a fourth extraction residual liquid; adding a fourth strip liquor into the manganese load, and carrying out strip manganese operation to obtain a manganese sulfate solution; when the operation of extracting manganese is carried out, the extraction ratio O/A of the fourth organic phase to the manganese extraction feed liquid is 1:2-6;
s9, neutralizing the fourth extraction residual liquid alkali, regulating the PH value, and filtering to obtain sodium chloride solution; concentrating and crystallizing the sodium chloride solution to obtain salt and water, and recycling the water and the salt;
the first organic phase is prepared by mixing one of N235 and N503, sec-octanol and TBP and solvent oil; the second organic phase, the third organic phase and the fourth organic phase are prepared by mixing one of P204, P507 and P272, one of TBP and sec-octyl alcohol and solvent oil;
the first organic phase has a composition of 50% N235+10% sec-octanol+40% mineral spirits or 40% N235+12% sec-octanol+48% mineral spirits; the composition of the second organic phase was 20% p204+5% tbp+75% mineral spirits or 20% p272+5% tbp+75% mineral spirits; the composition of the third organic phase was 20% p507+10% sec-octanol +70% mineral spirits or 30% p204+10% tbp +60% mineral spirits; the fourth organic phase had a composition of 20% P507+10% TBP+70% mineral spirits or 15% P204+5% TBP+80% mineral spirits.
2. The method for recycling valuable elements by chloridizing titanium white waste acid sectional extraction according to claim 1, which is characterized in that: the oxidant in the step S1 is one of hydrogen peroxide, sodium chlorate, sodium hypochlorite and sodium chlorite; when the back extraction iron operation is carried out, the first back extraction liquid has O/A=1-10 compared with the back extraction of iron load: 1, a step of; the first stripping liquid is water with the temperature of 20-60 ℃.
3. The method for recycling valuable elements by chloridizing titanium white waste acid sectional extraction according to claim 2, which is characterized in that: in the washing operation in the step S3, the washing liquid is washed with O/a=1 to 10 as compared with the scandium load: 1, a step of;
the washing liquid is prepared by mixing sulfuric acid with the concentration of 3-6 mol/l and hydrofluoric acid with the concentration of 40%, and the volume ratio of the sulfuric acid to the hydrofluoric acid is 1:0.005-0.2;
during the stripping operation, the second stripping solution had O/a=1 compared to the stripping of the scandium loaded organic phase after washing: 1-3; the second stripping liquid is 2.5-7 mol/l liquid alkali.
4. The method for recycling valuable elements by chloridizing titanium white waste acid sectional extraction according to claim 3, which is characterized in that: in the step S4, when the second raffinate is subjected to the liquid preparation operation, the alkali used is one of sodium carbonate, sodium hydroxide, calcium carbonate and carbide mud.
5. The method for recycling valuable elements by chloridizing titanium white waste acid sectional extraction according to claim 4, which is characterized in that: when the vanadium-aluminum back extraction operation is performed in the step S6, compared with the back extraction of the vanadium-aluminum loaded organic phase, the third stripping solution has O/a=1-7: 1, a step of; the third extraction liquid is sulfuric acid with the concentration of 1-5 mol/l.
6. The method for recycling valuable elements by chloridizing titanium white waste acid sectional extraction according to claim 5, which is characterized in that: in the step S7, when the third raffinate is subjected to alkali neutralization, the alkali is one of sodium carbonate, sodium hydroxide, calcium carbonate and carbide sludge.
7. The method for recycling valuable elements by chloridizing titanium white waste acid sectional extraction according to claim 6, which is characterized in that: when the manganese back extraction operation is carried out, the O/A=1-6:1 of the fourth back extraction liquid compared with the back extraction of the manganese loaded organic phase; the fourth stripping liquid is sulfuric acid with the concentration of 1.5-3 mol/l.
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