CN102191387A - 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, the filtration.
Background technology
Chlorination process and sulfuric acid process are two main technique flow processs of producing titanium dioxide in the world today.The production capacity ratio of whole world chloride process titanium dioxide powder and sulfuric acid method titanium pigment is approximately 56: 44.The production of chloride process titanium dioxide powder 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 big relative more high shortcoming with initial cost of " three wastes " discharge capacity.Wherein poor product quality and big two aspects of " three wastes " discharge capacity are particularly outstanding, and the major cause of the superseded sulfuric acid process of American-European countries is big because of this method " three wastes " discharge capacity just, and are unfriendly to environment.If the problem that " three wastes " discharge capacity is big can not solve as early as possible, Chinese existing Production By Sulfuric Acid Process technology 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 adopt reduction, cooling, ferrous sulfate crystallization usually and separate, the titanyl sulfate hydrolysis removes impurity with separating, wash and bleach operations such as washing; This impurity removal process process is long, and the control difficulty is big and complicated, will discharge a large amount of acid waste water simultaneously.Sulfuric acid concentration is about 15-20% in rare spent acid that sulfuric acid process produces, but because of 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 big, 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 arranged so far as yet.At present, the research of sulfuric acid method titanium pigment production hydrolysis spent acid processing both at home and abroad mainly concentrates on the waste acid treatment aspect, and seldom the source that spent acid, waste water are produced is studied.
Summary of the invention
Technical problem solved by the invention is at 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 significantly reduce the discharging of spent acid, waste water.
Method for producing gtitanium dioxide with sulphuric acid, common technology key step is as follows: ilmenite or titanium slag acidolysis, dissolving, clarification, hydrolysis is filtered, rinsing, bleaching, filtration washing, salt is handled, calcining powder process.
Acidolysis in the sulfuric acid process, the resulting solution of dissolving step are filtered and makes titanium liquid, use method of purification of the present invention then titanium liquid is handled, this method comprises the steps:
A, the oxidation of divalent iron ion in the titanium liquid is become ferric ion;
B, hydrochloric acid or hydrogen chloride gas are fed titanium liquid complexing ferric ion;
C, the ferric ion after the complexing is extracted to organic phase;
D, separation organic phase and titanium liquid promptly get the titanium liquid after purifying.
After titanium liquid handled according to method of purification of the present invention, significantly reduce the discharging of spent acid in the sulfuric acid process, waste water, and can improve the quality product of titanium dioxide.
For matching step C forms complex compound HFeCl
4, not mixing other impurity, preferred chlorine, oxygen, ozone, hydrogen peroxide are used for the oxidation ferrous ion in the steps A, 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 high more titanium liquid of volumetric molar concentration of chlorion in the titanium liquid low more, titanium liquid after the extraction is pure more, carry out in order to impel complex reaction, form more complex compound, feed hydrochloric acid or hydrogen chloride gas among the step B, the volumetric molar concentration that makes chlorion in the 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, the emulsion of control in the extraction process, can also add the suitable dilution agent, as adopting a kind of or any mixing in benzene, trichloromethane, toluene, kerosene, sulfonated kerosene, the 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 the titanium liquid
3+Loading capacity and changing.As the ferric iron concentration height in the titanium liquid, then select high O/A ratio for use.
Owing to also have small amount of hydrochloric acid in the titanium liquid after purifying,, adopt the circulation heating and the mode of spray titanium liquid to resolve and reclaim hydrochloric acid in the inventive method for reclaiming hydrochloric acid; During heating, temperature should be lower than 110 ℃.。
Organic phase renewable recycling after washing after step D separates.Particularly, the volume ratio of organic phase and water is 1-2 during washing: 1, through stir with separate after, the iron more than 98% is transferred to water, organic phase can realize recycling.
Reduce the impurity in the 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 titanium salt acidleach of raw material that the present invention uses is slagged tap.It is according to Chinese patent application 200910306494.5 disclosed content preparations that this high titanium salt acidleach is slagged tap, and promptly leaches the solid slag that obtains by ilmenite through the salt acid leaching process, 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 the slag is mainly FeO and Fe
2O
3
Prepare high titanium salt acidleach when slagging tap, used salt acid leaching process 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 technology, 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 leach reaction, the reaction times is 1-8 hour; B, reacting liquid filtering, dry gained solid, this solid are acid soluble high titanium salt acidleach and slag tap; When step B was dry, controlled temperature was lower than 350 ℃.
Slagging tap with high titanium salt acidleach is that the step of the using sulfated method of raw material is as follows:
A, mix sulfuric acid and slag tap with high titanium salt acidleach, be heated to 130-200 ℃ after, the control heating allows react to be carried out and keeps its temperature of reaction; Wherein acid sludge is 1.4～1.9: 1 than by weight;
Obtain thick solid mixt after B, the reaction;
C, this mixture was placed 140-220 ℃ of slaking 1-4 hour, cooling adds warm water, and 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 promptly is that acid hydrolysate-thick solid mixt is further carried out acidolysis reaction;
D, be stirred to solid mixt dissolving, filter titanium liquid, this titanium liquid is the mixture of titanyl sulfate and titanium sulfate.
At the production technique that adopts salt acid leaching process leaching ilmenite, in order to improve the ilmenite leaching velocity, can use Chinese patent application 200910311886.0 disclosed leaching liquids, the i.e. compound system of forming by solubility chlorination salt and hydrochloric acid, the concentration of solubility chlorination salt is that 0.5mol/L is to saturation concentration in the leaching liquid; 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, the iron trichloride.Use the salt 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 the step of acid dipping.
The beneficial effect of method of purification of the present invention:
1, spent acid is realized recycle.Behind the titanium hydrolysis after the purification, impurity is low in the spent acid, need not removal of impurities and handles, utilize once more after just this spent acid directly can being condensed into ideal concentration, thus the recycle of realization vitriolic.
2, the washing times behind the titanium hydrolysis after the purification reduces.It only is flush away spent acid that washing purpose after the hydrolysis is become by in the past removal of impurities, can significantly reduce washing progression, thereby can reduce the generation and the discharging of acid waste water, and CER can reach 80%.
3, titanium dioxide quality product height.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 the quality product and the chlorination process of titanium dioxide are suitable.
4, extraction agent of using in the method for purification and hydrochloric acid can recycles.Titanium liquid after extracting and separating contains a spot of hydrochloric acid, and under condition of negative pressure, hydrochloric acid is resolved and reclaimed to the circulation 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 through washing regeneration back 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 the sulfuric acid process, the resulting solution of dissolving step are filtered and makes titanium liquid, uses method of purification of the present invention then titanium liquid is handled.Method of purification comprises the steps:
A, the oxidation of divalent iron ion in the titanium liquid is become ferric ion;
B, hydrochloric acid or hydrogen chloride gas are fed titanium liquid complexing ferric ion;
C, the ferric ion after the complexing is extracted to organic phase;
D, separation organic phase and titanium liquid promptly get the titanium liquid after purifying.
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 mainly exists with three valence states in the titanium liquid, exist with ferrous form but still have on a small quantity, for complexing removes de-iron, need at first oxidation of divalent to be become ferric iron.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 the titanium liquid adds stoichiometric or excessive oxygenant and carry out oxidation in titanium liquid relatively, oxidation at an easy rate 98% or more ferrous ion.
Among the step B with HCl as Fe
3+Complexing agent adds hydrochloric acid or hydrogen chloride gas in the titanium liquid after oxidation, make Fe
3+With Cl
-Following complex reaction: Fe takes place
3++ 4HCl → HFeCl
4+ 3H
+
Reduce the impurity in the 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 preferably salt acidleach of the present invention leached mud sulfuric acid method titanium pigment production technique that goes out to obtain, 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 that embodiment 1 high titanium salt acidleach is slagged tap
Prepare high titanium salt acidleach according to Chinese patent application 200910306494.5 disclosed hydrochloric acid direct leachings and slag tap, 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 leaches reaction, and the reaction times is 1-8 hour;
B, reacting liquid filtering, dry gained solid, this solid are acid soluble high titanium salt acidleach and slag tap; When step B was dry, controlled temperature was lower than 350 ℃, 4-8 hour time of drying.
Proportioning raw materials and reaction conditions detailed in the present embodiment are as follows:
1, measures 45 liter 20% hydrochloric acid, be poured in 50 liters of glass lining retort.
2, take by weighing 15 kilograms of ilmenite concentrates, pour in the retort, sealing, and start agitator.
3, be heated to rapidly about 120 ℃.
4, after 5 hours, stop heating, naturally cool to 80 ℃.
5, the material in 3 liters of retort is filtered rapidly.Filtration is to link to each other 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 ℃, promptly makes high titanium salt acidleach and slags tap.
The chemical ingredients that this batch high titanium salt acidleach is slagged tap is analyzed, and the results are shown in Table 2.
The main chemical constitution (wt.%) that table 2 Flos Bombacis Malabarici ilmenite concentrate and high titanium salt acidleach are slagged tap
| 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 titanium salt acidleach is slagged tap | 0.75 | 1.15 | 3.31 | 3.33 | 1.29 | 9.87 | 72.00 | 0.10 |
The preparation of embodiment 2 titanium liquid
Slagging tap with high titanium salt acidleach is that the using sulfated legal system of raw material is equipped with titanium liquid, can carry out according to Chinese patent application 200910306494.5 disclosed methods.Particularly, the processing parameter in the present embodiment is as follows:
With containing 72%TiO
2High titanium salt acidleach (the press embodiment 1 method preparation) 20Kg that slags tap, add 19.4 liter 98% the vitriol oil, the weight ratio that high titanium salt acidleach is slagged tap with 100% vitriol oil is 1: 1.75.Begin heating after stirring.Under agitation condition, be heated to allow about 175 ℃ and react spontaneous carrying out.Continue 5 minutes afterreaction things of stir about and form thick solid mixt, mixture is placed 180 ℃ of slakings and kept temperature 4 hours.Be cooled to room temperature.Add 30 liters of 60 ℃ of 20% dilute sulphuric acids, be stirred to till the whole dispersions of resultant of reaction.Be diluted to 70 liters then, keep 70-85 ℃ of system temperature, stir leaching to dissolving fully, use ceramic funnel suction filtration then, filtering filtrate 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, the chlorine feeding titanium liquid with 1.5 equivalents (with respect to ferrous ion) makes oxidation of divalent iron ion become ferric ion.Behind 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 the 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.
The chemical constitution of titanium liquid behind the table 5 adding hydrochloric acid
Titanium liquid behind 2.36 liters of adding hydrochloric acid is contacted with 1 liter of methyl iso-butyl ketone (MIBK) thorough mixing, and 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 table 6 extraction back titanium liquid
Titanium liquid after 2.36 liters of extractions under 80 ℃ of constant temperatures, is got pure titanium liquid after negative pressure spray demineralizing acid concentrates, and its chemical constitution is as shown in table 7.
The chemical constitution of table 7 deacidification back titanium liquid
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, the chlorine feeding titanium liquid with 1.5 equivalents (with respect to ferrous ion) makes oxidation of divalent iron ion become ferric ion.Behind 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 the titanium liquid after oxidation, feed pure hydrochloric acid gas with the complexing ferric ion.After feeding hydrochloric acid gas, the chemical constitution of titanium liquid is as shown in table 9.
The chemical constitution of titanium liquid behind the table 9 adding hydrochloric acid
Titanium liquid behind 2 liters of feeding hydrochloric acid gases is contacted with 1 liter of methyl iso-butyl ketone (MIBK) thorough mixing, and 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 table 10 extraction back titanium liquid
Titanium liquid after 2 liters of extractions under 80 ℃ of constant temperatures, is got pure titanium liquid after negative pressure spray demineralizing acid concentrates, and its chemical constitution is as shown in table 11.
The chemical constitution of table 11 deacidification back titanium liquid
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 feed ozone in titanium liquid, make oxidation of divalent iron ion become ferric ion, get titanium liquid at regular intervals and analyze Fe
2+, to be detectedly do not go out Fe
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 the titanium liquid after oxidation, feed pure hydrochloric acid gas with the complexing ferric ion.After feeding hydrochloric acid, the chemical constitution of titanium liquid is as shown in table 13.
The chemical constitution of titanium liquid behind the table 13 adding hydrochloric acid
Titanium liquid behind 2 liters of feeding hydrochloric acid gases is contacted with 1 liter of methyl iso-butyl ketone (MIBK) thorough mixing, and 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 table 14 extraction back titanium liquid
Titanium liquid after 2 liters of extractions under 80 ℃ of constant temperatures, is got pure titanium liquid after negative pressure spray demineralizing acid concentrates, and its chemical constitution is as shown in Table 15.
The chemical constitution of table 15 deacidification back titanium liquid
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 feed ozone in titanium liquid, make oxidation of divalent iron ion become ferric ion, get titanium liquid at regular intervals and analyze Fe
2+, to be detectedly do not go out Fe
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 the 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.
The chemical constitution of titanium liquid behind the table 17 adding hydrochloric acid
Titanium liquid behind 2.36 liters of adding hydrochloric acid is contacted with 1 liter of tributyl phosphate thorough mixing, and 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 table 18 extraction back titanium liquid
Titanium liquid after 2.36 liters of extractions under 80 ℃ of constant temperatures, is got pure titanium liquid after negative pressure spray demineralizing acid concentrates, and its chemical constitution is shown in table 19.
The chemical constitution of table 19 deacidification back titanium liquid
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 feed ozone in titanium liquid, make oxidation of divalent iron ion become ferric ion, get titanium liquid at regular intervals and analyze Fe
2+, to be detectedly do not go out Fe
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 the titanium liquid after oxidation, feed pure hydrochloric acid gas with the complexing ferric ion.After feeding hydrochloric acid, the chemical constitution of titanium liquid is shown in table 21.
The chemical constitution of titanium liquid behind the table 21 adding 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.
Feed behind the hydrochloric acid gases titanium liquid with 2 liters and contain tributyl phosphate and have agent extraction solvent thorough mixing 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 table 22 extraction back titanium liquid
Titanium liquid after 2 liters of extractions under 80 ℃ of constant temperatures, is got pure titanium liquid after negative pressure spray demineralizing acid concentrates, and its chemical constitution is shown in table 23.
The chemical constitution of table 23 deacidification back titanium liquid
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 the foregoing description, because of impurity in the spent acid is low, need not removal of impurities and handle, utilize realization recycle sulfuric acid once more after just this spent acid directly can being condensed into ideal concentration; And the minimizing of the washing times after the hydrolysis, realize reducing the generation and the discharging of acid waste water, CER can reach 80%.And the titanium dioxide quality height of making, the titanium dioxide quality that makes with chlorination process is suitable.
Claims (14)
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 the titanium liquid is become ferric ion;
B, hydrochloric acid is added titanium liquid complexing ferric ion;
C, the ferric ion after the complexing is extracted to organic phase;
D, separation organic phase and titanium liquid promptly get the titanium liquid after purifying.
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 the electrolytic oxidation to mix in the steps A, oxidation of divalent iron ion is become ferric ion.
3. the method for purification of titanium liquid according to claim 1 is characterized in that: feed hydrochloric acid or hydrogen chloride gas among the step B, the volumetric molar concentration that makes chlorion in the titanium liquid is 4 times of volumetric molar concentration of ferric ion at least.
4. the method for purification of titanium liquid according to claim 1 is characterized in that: the extraction agent that extraction is adopted among the step C 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: a kind of or any mixing when extracting among the step C in employing benzene, trichloromethane, toluene, kerosene, sulfonated kerosene, the normal hexane etc. is as thinner.
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 the circulation 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 according to claim 1 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 is characterized in that: the volume ratio of organic phase and water is 1-2 during washing: 1.
11. the method for purification of titanium liquid according to claim 1 is characterized in that: the titanium liquid in the steps A is that to slag tap with high titanium salt acidleach be that feedstock production gets; Wherein, to slag tap be the solid slag that is obtained through salt acid leaching process leaching by ilmenite in high titanium salt acidleach.
12. the method for purification of titanium liquid according to claim 11, it is characterized in that: described salt 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-selecting smelting combination pressure leaching process.
13. the method for purification of titanium liquid according to claim 12 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 of ilmenite and hydrochloric acid soln 1: 2.5～5 grams per milliliters, concentration of hydrochloric acid is 18%～30%, is heated to 70 ℃～150 ℃ and leaches reaction, the reaction times is 1-8 hour;
B, reacting liquid filtering, dry gained solid, this solid are acid soluble high titanium salt acidleach and slag tap.
14. the method for purification of titanium liquid according to claim 11 is characterized in that: slagging tap with high titanium salt acidleach is that the method for feedstock production titanium liquid is:
A, mix sulfuric acid and slag tap with high titanium salt acidleach, be heated to 130-200 ℃ after, the control heating allows react to be carried out and keeps its temperature of reaction; Wherein acid sludge is 1.4～1.9: 1 than by weight;
Obtain thick solid mixt after B, the reaction;
C, this mixture was placed 140-220 ℃ of slaking 1-4 hour, cooling adds warm water, and amount of water is 2～3 times of sulfuric acid volume;
D, be stirred to solid mixt dissolving, filter and promptly get titanium liquid.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN102627321A (en) * | 2012-04-01 | 2012-08-08 | 沙立林 | Method for preparing titanium pigment by using titanium residues obtained by directly reducing titanium-iron oxide |
| CN102660678A (en) * | 2012-05-17 | 2012-09-12 | 四川大学 | Method for selectively separating iron from hydrochloric acid solution containing ferrous chloride |
| CN102951678A (en) * | 2011-08-19 | 2013-03-06 | 中国科学院过程工程研究所 | Method for separating zirconium from titanium solution |
| CN103723697A (en) * | 2013-12-27 | 2014-04-16 | 安徽六国化工股份有限公司 | Method for improving quality of acid for diammonium phosphate |
| WO2014085903A1 (en) * | 2012-12-04 | 2014-06-12 | Process Research Ortech Inc. | Process for the separation of iron in extraction of titanium in mixed chloride media |
| CN112429780A (en) * | 2020-12-14 | 2021-03-02 | 河南荣佳钪钒科技有限公司 | Method for recovering valuable elements by sectional extraction of titanium white waste acid by 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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| CN102951678A (en) * | 2011-08-19 | 2013-03-06 | 中国科学院过程工程研究所 | Method for separating zirconium from titanium solution |
| 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 |
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| CN102627321A (en) * | 2012-04-01 | 2012-08-08 | 沙立林 | Method for preparing titanium pigment by using titanium residues obtained by directly reducing titanium-iron oxide |
| 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 |
| CN102660678A (en) * | 2012-05-17 | 2012-09-12 | 四川大学 | Method for selectively separating iron from hydrochloric acid solution containing ferrous chloride |
| WO2014085903A1 (en) * | 2012-12-04 | 2014-06-12 | Process Research Ortech Inc. | Process for the separation of iron in extraction of titanium in mixed chloride media |
| US10041141B2 (en) | 2012-12-04 | 2018-08-07 | Process Research Ortech Inc. | Process for the separation of iron in extraction of titanium in mixed chloride media |
| CN103723697A (en) * | 2013-12-27 | 2014-04-16 | 安徽六国化工股份有限公司 | Method for improving quality of acid for diammonium phosphate |
| CN112429780A (en) * | 2020-12-14 | 2021-03-02 | 河南荣佳钪钒科技有限公司 | Method for recovering valuable elements by sectional extraction of titanium white waste acid by 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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