CN102191387B - Method for purifying titanium solution - Google Patents
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Abstract
The invention belongs to the technical field of the production of titanium dioxide. The invention specifically relates to a method which is utilized for purifying a titanium solution, which is treated through acidolysis, dissolution and filtration, in titanium dioxide production by sulfuric acid method. Through the method, wastwater discharge and waste acid discharge are reduced greatly. The method comprises the following steps: A, ferrous ions in a titanium solution is oxidized into ferric irons; B, hydrochloric acid or hydrogen chloride gas is fed into the titanium solution to promote complexation of the ferric irons; C, complexed ferric iron produced by the step B is extracted to enter an organic phase; and D, the organic phase is separated from the titanium solution and thus purified titanium solution is obtained. Through the method for purifying titanium solution, wastwater discharge and waste acid discharge are reduced greatly and the product quality of titanium dioxide is improved.
Description
Technical field
The invention belongs to the titanium white production field, be specifically related in the sulfuric acid method titanium pigment production technique, with the method for purification of the titanium liquid that obtains after acidolysis, dissolving, filtration.
Background technology
Chlorination process and sulfuric acid process are to produce two technical process of titanium dioxide in the world today.The production capacity ratio of whole world Titanium Dioxide Produced by Chloride Procedure and sulfuric acid method titanium pigment is approximately 56: 44.Titanium Dioxide Produced by Chloride Procedure production mainly concentrates on the European and American areas, and the sulfuric acid method titanium pigment production technique mainly concentrates on the Asian-Pacific area.Sulfuric acid process is compared with chlorination process, has that technical process is long, level of automation is low, a poor product quality, the shortcoming such as " three wastes " discharge capacity is large and initial cost is relatively high.Wherein poor product quality and large two aspects of " three wastes " discharge capacity are particularly outstanding, and the major cause of the superseded sulfuric acid process of American-European countries is large because of this method " three wastes " discharge capacity just, and are unfriendly to environment.If the problem that " three wastes " discharge capacity is large can not solve as early as possible, Chinese existing Production By Sulfuric Acid Process technique also can face the situation that is eliminated in the near future.Ore type ilmenite can't effectively be used thereby will there be a big chunk in China.
Sulfuric acid process usually adopt reduction, cooling, ferrous sulfate crystallization and separate, the titanyl sulfate hydrolysis removes impurity with separating, wash and bleach the operation such as washing; This impurity removal process process is long and complicated, controls difficulty large, will discharge a large amount of acid waste water simultaneously.In rare spent acid that sulfuric acid process produces, sulfuric acid concentration is about 15-20%, but because it contains complicated component, as FeSO
4, MgSO
4, CaSO
4, TiOSO
4, MnSO
4, Al
2(SO
4)
3Deng, the recycling difficulty is very large, is difficult to the sulfuric acid recycle of regeneration ideal concentration.In a word, the improvement of spent acid and acid waste water is the 25-30% that the expense of a thorny difficult problem, the especially waste acid treatment of sulfuric acid method titanium pigment production accounts for the sulfuric acid method titanium pigment production cost always, and good solution is not yet arranged so far.At present, the useless acid-treated research of the hydrolysis of sulfuric acid method titanium pigment production both at home and abroad mainly concentrates on the waste acid treatment aspect, and the source that seldom spent acid, waste water is produced is studied.
Summary of the invention
Technical problem solved by the invention is for the titanium liquid for preparing in the sulfuric acid method titanium pigment production technique, and a kind of new method of purification is provided, and adopting said method can greatly reduce the discharging of spent acid, waste water.
Method for producing gtitanium dioxide with sulphuric acid, common technique key step is as follows: ilmenite or titanium slag acidolysis, dissolving, clarification, hydrolysis is filtered, rinsing, bleaching, filtration washing, salt is processed, calcining powder process.
Acidolysis in sulfuric acid process, the resulting solution filter of dissolving step are made titanium liquid, then use method of purification of the present invention titanium liquid is processed, the method comprises the steps:
A, the oxidation of divalent iron ion in titanium liquid is become ferric ion;
B, hydrochloric acid or hydrogen chloride gas are passed into titanium liquid complexing ferric ion;
C, the ferric ion after complexing is extracted to organic phase;
D, separate organic phase and titanium liquid, namely get the titanium liquid after purification.
After titanium liquid is processed according to method of purification of the present invention, greatly reduce the discharging of spent acid in sulfuric acid process, waste water, and can improve the quality product of titanium dioxide.
For matching step C forms complex compound HFeCl
4, do not mix other impurity, in steps A, preferred chlorine, oxygen, ozone, hydrogen peroxide are used for the oxidation ferrous ion, or adopt electrolytic process to make ferrous ion change into ferric ion, and each oxidation style can select one or mix and use.
Because of the volumetric molar concentration of free ferric ion in the higher titanium liquid of volumetric molar concentration of chlorion in titanium liquid lower, titanium liquid after extraction is purer, carry out in order to impel complex reaction, form more complex compound, pass into hydrochloric acid or hydrogen chloride gas in step B, the volumetric molar concentration that makes chlorion in titanium liquid is 4 times of volumetric molar concentration of ferric ion at least.
For ferric ion is extracted to organic phase, extraction agent is one or more mixtures of acid organo phosphorous compounds, carboxylic acid, sulfonic acid hydroxyoxime, oxine, beta-diketon, neutral phosphate, phosphorus oxide, ketone, alcohols, ethers and amine.
In order to regulate extraction agent viscosity, to control the emulsion in extraction process, can also add suitable thinner, as adopting a kind of or any mixing in benzene, trichloromethane, toluene, kerosene, sulfonated kerosene, normal hexane etc. as thinner.When thinner was used, those skilled in the art can allocate according to practical situation, and the blending ratio of thinner and extraction agent (volume ratio) is (0-4.5): 1.
During extraction, the adding proportion of organic phase (O) and titanium liquid (A), (adding proportion that is organic phase and titanium liquid is 0.2-1.5 to the O/A volume ratio: 1) between 0.2 and 1.5.The O/A ratio is looked ferric iron concentration and extraction agent Fe in titanium liquid
3+Loading capacity and changing.As high in the ferric iron concentration in titanium liquid, select high O/A ratio.
Owing to also having a small amount of hydrochloric acid in the titanium liquid after purifying, for reclaiming hydrochloric acid, adopt circulating-heating and the mode of spray titanium liquid to resolve and reclaim hydrochloric acid in the inventive method; During heating, temperature should be lower than 110 ℃.。
Organic phase after step D separates renewable recycling after washing.Particularly, during washing, the volume ratio of organic phase and water is 1-2: 1, through stir with separate after, the iron more than 98% is transferred to water, organic phase can realize recycling.
Reduce the impurity in titanium liquid, help to reduce the generation of spent acid, waste residue, waste water, and can improve the quality product of titanium dioxide, so the preferred high hydrochloric acid leaching slag of raw material of the present invention's use.This high hydrochloric acid leaching slag is according to the disclosed content preparation of Chinese patent application 200910306494.5, the solid slag that is namely obtained through the hydrochloric acid leaching process leaching by ilmenite, and main chemical constitution is Al
2O
30.1-0.75%, CaO 0.1-1.15%, TFe 1.0-8%, MgO 0.1-1.8%, SiO
22-15%, TiO
265-97%, V
2O
5Less than 0.3%; Fe in slag is mainly FeO and Fe
2O
3
When preparing high hydrochloric acid leaching slag, hydrochloric acid leaching process used can directly leach method for hydrochloric acid, or is BCA hydrochloric acid leaching method, or is preoxidation-fluidization normal pressure lixiviation process, or is preoxidation-selecting smelting combination pressure leaching process.Simplicity for technique, preferred hydrochloric acid directly leaches method, processing step is as follows: A, mixed with titanium iron ore and hydrochloric acid, the volume (milliliter) of ilmenite quality (gram) and hydrochloric acid soln is than being 1: 2.5～5, concentration of hydrochloric acid is 18%～30%, be heated to 70 ℃～150 ℃ and carry out Leaching reaction, the reaction times is 1-8 hour; B, reacting liquid filtering, dry gained solid, this solid are acid soluble high hydrochloric acid leaching slag; When step B is dry, control temperature lower than 350 ℃.
As follows take high hydrochloric acid leaching slag as the step of the using sulfated method of raw material:
A, mix sulfuric acid and high hydrochloric acid leaching slag, after being heated to 130-200 ℃, controlling heating and allow react and carry out and keep its temperature of reaction; Wherein acid sludge is 1.4～1.9: 1 than by weight;
Obtain thick solid mixt after B, reaction;
C, this mixture is placed in 140-220 ℃ of slaking 1-4 hour, cooling, add warm water, amount of water is 2～3 times of sulfuric acid volume; Adding water is for titanyl sulfate and titanium sulfate are dissolved in the water;
Wherein, slaking is namely that acid hydrolysate-thick solid mixt is further carried out acidolysis reaction;
D, be stirred to solid mixt dissolving, filter to get titanium liquid, this titanium liquid is the mixture of titanyl sulfate and titanium sulfate.
For the production technique that adopts hydrochloric acid leaching process leaching ilmenite, in order to improve leaching ilmenite speed, can use the disclosed leaching liquid of Chinese patent application 200910311886.0, the compound system that is namely formed by solubility chlorination salt and hydrochloric acid, in leaching liquid, the concentration of solubility chlorination salt is that 0.5mol/L is to saturation concentration; Solubility chlorination salt can adopt at least a in sodium-chlor, Repone K, lithium chloride, ammonia chloride, calcium chloride, magnesium chloride, iron protochloride, Manganous chloride tetrahydrate, aluminum chloride, iron trichloride.Use the hydrochloric acid leaching process of this leaching liquid, the acidleach condition is temperature 80-150 ℃; The acidleach condition is pressure 0-4kg/cm
2The ratio 2.5-4L/kg of leaching liquid and ilmenite concentrate in step of acid dipping.
The beneficial effect of method of purification of the present invention:
1, spent acid is realized recycle.After titanium hydrolysis after purification, in spent acid, impurity is low, need not removal of impurities and processes, and just this spent acid directly can be condensed into utilization again after ideal concentration, thereby realizes the recycle of sulfuric acid.
2, the washing times after the titanium hydrolysis after the purification reduces.It is only to wash away spent acid that washing purpose after hydrolysis is become by in the past removal of impurities, can greatly reduce washing progression, thereby can reduce generation and the discharging of acid waste water, and CER can reach 80%.
3, the titanium dioxide quality product is high.Use method of purification of the present invention, titanium liquid is after organic extraction, and the total amount of contained staining impurity Fe, Mn, Cr, Ni is about 20ppm, and quality product and the chlorination process of titanium dioxide are suitable.
4, the extraction agent of using in method of purification and hydrochloric acid can recycles.Titanium liquid after extracting and separating contains a small amount of hydrochloric acid, and under condition of negative pressure, hydrochloric acid is resolved and reclaimed to circulating-heating with spray titanium liquid; Titanium liquid Heating temperature should be lower than its hydrolysis temperature, and one should be lower than 110 ℃.The extraction agent that is loaded with the chloride complex of iron circulate after washing regeneration and re-uses: extraction agent washing regeneration can be (1-2) by the volume ratio of extraction agent and water: 1 mixes, through stirring with separate after, the iron more than 98% is transferred to water.
Description of drawings
The classical process flow sheet of Fig. 1 sulfuric acid process.
The classical process flow sheet of Fig. 2 sulfuric acid process.
Fig. 3 process flow sheet of the present invention.
Embodiment
Below by specific description of embodiments of the present invention the explanation but do not limit the present invention.
Method of purification of the present invention is that acidolysis in sulfuric acid process, the resulting solution filter of dissolving step are made titanium liquid, then uses method of purification of the present invention titanium liquid is processed.Method of purification comprises the steps:
A, the oxidation of divalent iron ion in titanium liquid is become ferric ion;
B, hydrochloric acid or hydrogen chloride gas are passed into titanium liquid complexing ferric ion;
C, the ferric ion after complexing is extracted to organic phase;
D, separate organic phase and titanium liquid, namely get the titanium liquid after purification.
Method of purification of the present invention is to adopt the method for organic solvent extraction to substitute the removal of impurities operation that has now in the sulfuric acid method titanium pigment production technique, and a kind of method of organic solvent extraction deironing is provided.Because iron in titanium liquid mainly exists with three valence states, exist with ferrous form but still have on a small quantity,, need at first oxidation of ferrous iron to ferric iron except de-iron for complexing.Method for oxidation can be adopted one or more mixing of following method and use:
(1) with chlorine oxidation: 2Fe
2++ Cl
2→ 2Fe
3++ 2Cl
-
(2) with dioxygen oxidation: 2Fe
2++ 1/2O
2+ H
2O → 2Fe
3++ 2OH
-
(3) with ozone oxidation: 2Fe
2++ O
3+ H
2O → 2Fe
3++ 2OH
-+ O
2
(4) with hydrogen peroxide oxidation: 2Fe
2++ H
2O
2→ 2Fe
3++ 2OH
-
(5) with electrolytic process oxidation: Fe
2+→ Fe
3++ e.
Ferrous ion in titanium liquid, add stoichiometric or excessive oxygenant to carry out oxidation in titanium liquid relatively, oxidation at an easy rate 98% or more ferrous ion.
In step B with HCl as Fe
3+Complexing agent adds hydrochloric acid or hydrogen chloride gas in the titanium liquid after the oxidation, makes Fe
3+With Cl
-Following complex reaction: Fe occurs
3++ 4HCl → HFeCl
4+ 3H
+
Reduce the impurity in titanium liquid, help to reduce the generation of spent acid, waste residue, waste water, therefore the raw material (according to the contents preparation of Chinese patent application 200910306494.5 and 2009103118860 records) of the leached mud sulfuric acid method titanium pigment production technique that obtains of preferably salt Ore Leaching of the present invention, titanium liquid (TiOSO
4Solution) according to the content preparation of Chinese patent application 200910306494.5 records, the titanium liquid foreign matter content that obtains thus is low.Typical titanium liquid component is as shown in table 1.It contains manganese, calcium, magnesium plasma hardly, and aluminum ion is also very low, and iron mainly exists with three valence states.
The typical titanium fluid component of table 1
The preparation of embodiment 1 high hydrochloric acid leaching slag
Prepare high hydrochloric acid leaching slag according to the disclosed hydrochloric acid direct leaching of Chinese patent application 200910306494.5, processing parameter is as follows:
A, mixed with titanium iron ore and hydrochloric acid, the volume (milliliter) of ilmenite quality (gram) and hydrochloric acid soln is than being 1: 2.5～5, and concentration of hydrochloric acid is 18%～30%, is heated to 70 ℃～150 ℃ and carries out Leaching reaction, and the reaction times is 1-8 hour;
B, reacting liquid filtering, dry gained solid, this solid are acid soluble high hydrochloric acid leaching slag; When step B is dry, control temperature lower than 350 ℃, 4-8 hour time of drying.
Proportioning raw materials and reaction conditions detailed in the present embodiment are as follows:
1, measure the hydrochloric acid of 45 liter 20%, be poured in 50 liters of glass lining retort.
2, take 15 kilograms of ilmenite concentrates, pour in retort, sealing, and start agitator.
3, be heated to rapidly 120 ℃ of left and right.
4, after 5 hours, stopped heating naturally cools to 80 ℃.
5, the material in 3 liters of retort is filtered rapidly.Filtration is to be connected with vacuum pump by the Bu Shi flask to form.
6, clean filter cake three times with 3 liters of deionization moisture.Drying is 6 hours under 110 ℃, namely makes high hydrochloric acid leaching slag.
The chemical composition of this batch of high hydrochloric acid leaching slag is analyzed, and the results are shown in Table 2.
The main chemical constitution (wt.%) of table 2 Flos Bombacis Malabarici ilmenite concentrate and high hydrochloric acid leaching slag
| Al 2O 3 | CaO | FeO | Fe 2O 3 | MgO | SiO 2 | TiO 2 | V 2O 5 | |
| Raw ore (ilmenite concentrate) | 1.37 | 1.08 | 33.51 | 10.84 | 3.12 | 5.05 | 42.78 | 0.15 |
| High hydrochloric acid leaching slag | 0.75 | 1.15 | 3.31 | 3.33 | 1.29 | 9.87 | 72.00 | 0.10 |
The preparation of embodiment 2 titanium liquid
The standby titanium liquid of using sulfated legal system, can carry out according to the disclosed method of Chinese patent application 200910306494.5 take high hydrochloric acid leaching slag as raw material.Particularly, the processing parameter in the present embodiment is as follows:
With containing 72%TiO
2High hydrochloric acid leaching slag (press embodiment 1 method preparation) 20Kg, add the vitriol oil of 19.4 liter 98%, the weight ratio of high hydrochloric acid leaching slag and 100% vitriol oil is 1: 1.75.Begin heating after stirring.Be heated under agitation condition 175 ℃ of left and right allow the reaction spontaneous carrying out.Continue 5 minutes afterreaction things of stir about and form thick solid mixt, mixture is placed in 180 ℃ of slakings and kept temperature 4 hours.Be cooled to room temperature.Add 30 liters of 60 ℃ of 20% dilute sulphuric acids, till being stirred to the whole dispersions of resultant of reaction.Then be diluted to 70 liters, keep 70-85 ℃ of system temperature, stir leaching to dissolving fully, then use ceramic funnel suction filtration, the filtrate of filtration is titanium liquid, and it the results are shown in table 3 its compositional analysis.
Compositional analysis is learned in the liquefaction of table 3 titanium
The purification of embodiment 3 titanium liquid
Press embodiment 2 preparation titanium liquid, get 2 liters of titanium liquid, its chemical constitution is as shown in table 3.At first, pass into titanium liquid with the chlorine of 1.5 equivalents (with respect to ferrous ion), make oxidation of divalent iron ion become ferric ion.After chlorine oxidation, the chemical constitution of titanium liquid is as shown in table 4.
The chemical constitution of titanium liquid after table 4 oxidation
In titanium liquid after oxidation, add 360 milliliter of 11 mole hydrochloride with the complexing ferric ion.After adding hydrochloric acid, the chemical constitution of titanium liquid is as shown in table 5.
Table 5 adds the chemical constitution of titanium liquid after hydrochloric acid
Add titanium liquid after hydrochloric acid fully to mix with 1 liter of methyl iso-butyl ketone (MIBK) with 2.36 liters and contact, ferric ion optionally is extracted into organic phase and removes.With after organic phase is separated, obtain titanium liquid after 2.36 liters of extractions through liquid phase, its chemical constitution is as shown in table 6.
The chemical constitution of titanium liquid after table 6 extraction
Titanium liquid after 2.36 liters of extractions under 80 ℃ of constant temperatures, is got pure titanium liquid after negative pressure spray demineralizing acid is concentrated, and its chemical constitution is as shown in table 7.
The chemical constitution of titanium liquid after table 7 deacidification
With 1 liter of methyl iso-butyl ketone (MIBK) organic phase that is loaded with ferric ion, strip with 1 premium on currency.The aqueous solution that obtains contains the iron of 12.4g/L and the chlorine of 34g/L.
The purification of embodiment 4 titanium liquid
Press embodiment 2 preparation titanium liquid, get 2 liters of titanium liquid, its chemical constitution is as shown in table 2.At first, pass into titanium liquid with the chlorine of 1.5 equivalents (with respect to ferrous ion), make oxidation of divalent iron ion become ferric ion.After chlorine oxidation, the chemical constitution of titanium liquid is as shown in table 8.
The chemical constitution of titanium liquid after table 8 oxidation
In titanium liquid after oxidation, pass into pure hydrochloric acid gas with the complexing ferric ion.After passing into hydrochloric acid gas, the chemical constitution of titanium liquid is as shown in table 9.
Table 9 adds the chemical constitution of titanium liquid after hydrochloric acid
Pass into after hydrochloric acid gas titanium liquid with 2 liters and fully mix with 1 liter of methyl iso-butyl ketone (MIBK) and contact, ferric ion optionally is extracted into organic phase and removes.With after organic phase is separated, obtain titanium liquid after 2 liters of extractions through liquid phase, its chemical constitution is as shown in table 10.
The chemical constitution of titanium liquid after table 10 extraction
Titanium liquid after 2 liters of extractions under 80 ℃ of constant temperatures, is got pure titanium liquid after negative pressure spray demineralizing acid is concentrated, and its chemical constitution is as shown in table 11.
The chemical constitution of titanium liquid after table 11 deacidification
With 1 liter of methyl iso-butyl ketone (MIBK) organic phase that is loaded with ferric ion, strip with 1 premium on currency.The aqueous solution that obtains contains the iron of 12.6g/L and the chlorine of 35g/L.
The purification of embodiment 5 titanium liquid
Press embodiment 2 preparation titanium liquid, get 2 liters of titanium liquid, its chemical constitution is as shown in table 2.At first, open ozonizer and pass into ozone in titanium liquid, make oxidation of divalent iron ion become ferric ion, get at regular intervals titanium liquid and analyze Fe
2+, the Fe that do not measure to be checked
2+After close ozonizer, show Fe
2+Oneself is all become Fe by ozone oxidation
3+After ozone oxidation, the chemical constitution of titanium liquid is as shown in table 12.
The chemical constitution of titanium liquid after table 12 oxidation
In titanium liquid after oxidation, pass into pure hydrochloric acid gas with the complexing ferric ion.After passing into hydrochloric acid, the chemical constitution of titanium liquid is as shown in table 13.
Table 13 adds the chemical constitution of titanium liquid after hydrochloric acid
Pass into after hydrochloric acid gas titanium liquid with 2 liters and fully mix with 1 liter of methyl iso-butyl ketone (MIBK) and contact, ferric ion optionally is extracted into organic phase and removes.With after organic phase is separated, obtain titanium liquid after 2 liters of extractions through liquid phase, its chemical constitution is as shown in table 14.
The chemical constitution of titanium liquid after table 14 extraction
Titanium liquid after 2 liters of extractions under 80 ℃ of constant temperatures, is got pure titanium liquid after negative pressure spray demineralizing acid is concentrated, and its chemical constitution is as shown in Table 15.
The chemical constitution of titanium liquid after table 15 deacidification
With 1 liter of methyl iso-butyl ketone (MIBK) organic phase that is loaded with ferric ion, strip with 1 premium on currency.The aqueous solution that obtains contains the iron of 12.1g/L and the chlorine of 32g/L.
The purification of embodiment 6 titanium liquid
Press embodiment 2 preparation titanium liquid, get 2 liters of titanium liquid, its chemical constitution is as shown in table 2.At first, open ozonizer and pass into ozone in titanium liquid, make oxidation of divalent iron ion become ferric ion, get at regular intervals titanium liquid and analyze Fe
2+, the Fe that do not measure to be checked
2+After close ozonizer, show Fe
2+Oneself is all become Fe by ozone oxidation
3+After ozone oxidation, the chemical constitution of titanium liquid is shown in table 16.
The chemical constitution of titanium liquid after table 16 oxidation
In titanium liquid after oxidation, add 360 milliliter of 11 mole hydrochloride with the complexing ferric ion.After adding hydrochloric acid, the chemical constitution of titanium liquid is shown in table 17.
Table 17 adds the chemical constitution of titanium liquid after hydrochloric acid
Add titanium liquid after hydrochloric acid fully to mix with 1 liter of tributyl phosphate with 2.36 liters and contact, ferric ion optionally is extracted into organic phase and removes.With after organic phase is separated, obtain titanium liquid after 2.36 liters of extractions through liquid phase, its chemical constitution is shown in table 18.
The chemical constitution of titanium liquid after table 18 extraction
Titanium liquid after 2.36 liters of extractions under 80 ℃ of constant temperatures, is got pure titanium liquid after negative pressure spray demineralizing acid is concentrated, and its chemical constitution is shown in table 19.
The chemical constitution of titanium liquid after table 19 deacidification
With 1 liter of tributyl phosphate organic phase that is loaded with ferric ion, strip with 1 premium on currency.The aqueous solution that obtains contains the iron of 12.5g/L and the chlorine of 36g/L.
The purification of embodiment 7 titanium liquid
Press embodiment 2 preparation titanium liquid, get 2 liters of titanium liquid.At first, open ozonizer and pass into ozone in titanium liquid, make oxidation of divalent iron ion become ferric ion, get at regular intervals titanium liquid and analyze Fe
2+, the Fe that do not measure to be checked
2+After close ozonizer, show Fe
2+Oneself is all become Fe by ozone oxidation
3+After ozone oxidation, the chemical constitution of titanium liquid is shown in table 19.
The chemical constitution of titanium liquid after table 20 oxidation
In titanium liquid after the oxidation, pass into pure hydrochloric acid gas with the complexing ferric ion.After passing into hydrochloric acid, the chemical constitution of titanium liquid is shown in table 21.
Table 21 adds the chemical constitution of titanium liquid after hydrochloric acid
It is to mix by the tributyl phosphate of three parts of unit volumes and the sulfonated kerosene of a unit volume that tributyl phosphate has the preparation of agent extraction solvent.
Pass into after hydrochloric acid gas titanium liquid with 2 liters and contain tributyl phosphate and have the agent extraction solvent fully to mix to contact with 1.5 liters, ferric ion optionally is extracted into organic phase and removes.With after organic phase is separated, obtain titanium liquid after 2 liters of extractions through liquid phase, its chemical constitution is shown in table 22.
The chemical constitution of titanium liquid after table 22 extraction
Titanium liquid after 2 liters of extractions under 80 ℃ of constant temperatures, is got pure titanium liquid after negative pressure spray demineralizing acid is concentrated, and its chemical constitution is shown in table 23.
The chemical constitution of titanium liquid after table 23 deacidification
With 1 liter of methyl iso-butyl ketone (MIBK) organic phase that is loaded with ferric ion, strip with 1 premium on currency.The aqueous solution that obtains contains the iron of 12.4g/L and the chlorine of 33g/L.
With the titanium hydrolysis in above-described embodiment, because impurity in spent acid is low, need not removal of impurities and process, just this spent acid directly can be condensed into utilization again after ideal concentration, realize recycle sulfuric acid; And the minimizing of the washing times after hydrolysis, realize reducing generation and the discharging of acid waste water, CER can reach 80%.And the titanium dioxide quality of making is high, and the titanium dioxide quality that makes with chlorination process is suitable.
Claims (12)
1. the method for purification of titanium liquid, it is characterized in that: it comprises the steps:
A, the oxidation of divalent iron ion in titanium liquid is become ferric ion;
B, hydrochloric acid or hydrogen chloride gas are added titanium liquid complexing ferric ion after oxidation in steps A;
C, the ferric ion after complexing in step B is extracted to organic phase;
Organic phase and titanium liquid that D, separating step C obtain namely get the titanium liquid after purification,
Wherein, the titanium liquid in described steps A is to prepare take high hydrochloric acid leaching slag as raw material to get, and described high hydrochloric acid leaching slag is the solid slag that is obtained through the hydrochloric acid leaching process leaching by ilmenite; And the method that wherein, prepares titanium liquid take high hydrochloric acid leaching slag as raw material as:
A ', mix sulfuric acid and high hydrochloric acid leaching slag, after being heated to 130-200 ℃, controlling heating and allow react and carry out and keep its temperature of reaction; Wherein acid sludge is 1.4～1.9:1 than by weight;
Obtain thick solid mixt after B ', reaction;
C ', this mixture is placed in 140-220 ℃ of slaking 1-4 hour, cooling, add warm water, amount of water is 2～3 times of sulfuric acid volume;
D ', be stirred to solid mixt dissolving, filter and namely get titanium liquid.
2. the method for purification of titanium liquid according to claim 1, it is characterized in that: be to adopt a kind of method or several method in chlorine oxidation, dioxygen oxidation, ozone oxidation, hydrogen peroxide oxidation or electrolytic oxidation to mix in steps A, oxidation of divalent iron ion is become ferric ion.
3. the method for purification of titanium liquid described according to claim l is characterized in that: pass into hydrochloric acid or hydrogen chloride gas in step B, the volumetric molar concentration that makes chlorion in titanium liquid is 4 times of volumetric molar concentration of ferric ion at least.
4. the method for purification of titanium liquid described according to claim l is characterized in that: the extraction agent that in step C, extraction is adopted is one or more mixtures of acid organo phosphorous compounds, carboxylic acid, sulfonic acid hydroxyoxime, oxine, beta-diketon, neutral phosphate, phosphorus oxide, ketone, alcohols, ethers and amine.
5. the method for purification of titanium liquid according to claim 4 is characterized in that: adopt during extraction a kind of or any mixing in benzene, trichloromethane, toluene, kerosene, sulfonated kerosene, normal hexane etc. as thinner in step C.
6. the method for purification of titanium liquid according to claim 1 is characterized in that: during step C extraction, the adding proportion of organic phase and titanium liquid is 0.2-1.5:1.
7. the method for purification of titanium liquid according to claim 1, is characterized in that: under condition of negative pressure, with the titanium liquid after the purification of step D gained, resolve and reclaim hydrochloric acid with circulating-heating and the mode of spray titanium liquid.
8. the method for purification of titanium liquid according to claim 7 is characterized in that: reclaim hydrochloric acid when heating, temperature is lower than 110 ℃.
9. the method for purification of titanium liquid described according to claim l, is characterized in that: step D is separated the organic phase that obtains and recycle after washing.
10. the method for purification of titanium liquid according to claim 9, it is characterized in that: during washing, the volume ratio of organic phase and water is 1-2:1.
11. the method for purification of titanium liquid according to claim 1, it is characterized in that: described hydrochloric acid leaching process is that hydrochloric acid directly leaches method, or be BCA hydrochloric acid leaching method, or be preoxidation-fluidization normal pressure lixiviation process, or be preoxidation one selecting smelting combination pressure leaching process.
12. the method for purification of titanium liquid according to claim 11 is characterized in that: it is as follows that described hydrochloric acid directly leaches the processing step of method:
A, mixed with titanium iron ore and hydrochloric acid, the proportion relation 1:2.5 of ilmenite and hydrochloric acid soln～5 grams per milliliters, concentration of hydrochloric acid is 18%～30%, is heated to 70 ℃～150 ℃ and carries out Leaching reaction, the reaction times is 1-8 hour;
B, reacting liquid filtering, dry gained solid, this solid are acid soluble high hydrochloric acid leaching slag.
Priority Applications (1)
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| CN102951678B (en) * | 2011-08-19 | 2014-07-02 | 中国科学院过程工程研究所 | Method for separating zirconium from titanium solution |
| CN102627321B (en) * | 2012-04-01 | 2014-05-07 | 沙立林 | Method for preparing titanium pigment by using titanium residues obtained by directly reducing titanium-iron oxide |
| CN102616842A (en) * | 2012-04-01 | 2012-08-01 | 攀枝花新中钛科技有限公司 | Method for preparing titanium white |
| CN102660678A (en) * | 2012-05-17 | 2012-09-12 | 四川大学 | Method for selectively separating iron from hydrochloric acid solution containing ferrous chloride |
| AU2013354851A1 (en) * | 2012-12-04 | 2015-05-28 | Process Research Ortech Inc. | Process for the separation of iron in extraction of titanium in mixed chloride media |
| CN103723697B (en) * | 2013-12-27 | 2016-03-09 | 安徽六国化工股份有限公司 | Improve the method for quality of acid for diammonium phosphate |
| CN112429780B (en) * | 2020-12-14 | 2023-04-21 | 河南荣佳钪钒科技有限公司 | Method for recycling valuable elements through segmented extraction of titanium dioxide waste acid by using chlorination process |
| CN113582225A (en) * | 2021-08-09 | 2021-11-02 | 武汉工程大学 | High-purity artificial rutile and preparation method thereof |
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| US4230542A (en) * | 1978-10-13 | 1980-10-28 | Oronzio De Nora Impianti Elettrochimici S.P.A. | Electrolytic process for treating ilmenite leach solution |
| GB2055779B (en) * | 1980-08-11 | 1983-05-05 | Nl Industries Inc | Preparing titanium compounds |
| JP2968877B2 (en) * | 1991-11-08 | 1999-11-02 | 日鉄鉱業株式会社 | Method for recovering sulfuric acid from waste sulfuric acid containing metal sulfate |
| CN101367546B (en) * | 2008-09-27 | 2010-08-11 | 攀钢集团研究院有限公司 | Method for preparing titanium liquid and method for preparing titanium dioxide |
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