CN103395832A - Method for producing pigment titanium dioxide by using titanium dioxide waste acid for carrying out low-concentration titaniferous solution hydrolysis - Google Patents
Method for producing pigment titanium dioxide by using titanium dioxide waste acid for carrying out low-concentration titaniferous solution hydrolysis Download PDFInfo
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Abstract
The invention provides a method for producing pigment titanium dioxide by using titanium dioxide waste acid for carrying out low-concentration titaniferous solution hydrolysis. The method comprises the following steps of: settling and clarifying waste sulfuric acid of sulfate process titanium dioxide so as to obtain liquid supernatant; adding water to the liquid supernatant so as to obtain target liquid supernatant with the mass concentration of 8-23%; heating 10-25 parts of target liquid supernatant serving as a backing material by volume to 92 DEG C till boiling; adding 90-110 parts of low-concentration titaniferous solution by volume to the backing material, wherein the concentration of the titaniferous solution is 150-180g/l by TiO2, and the acidity coefficient F of the titaniferous solution is 1.70-1.95; uniformly stirring to form a hydrolysis system, and controlling the temperature of the hydrolysis system to 92-100 DEG C; heating the hydrolysis system to a first boiling point, and maintaining the hydrolysis system at boiling till hydrolysis reaction is ended, thus obtaining a hydrolyzing sizing agent; treating the hydrolyzing sizing agent so as to obtain the pigment titanium dioxide. The method has the advantages that the waste acid of the sulfate process titanium dioxide can be recycled, the treatment cost of the waste acid is reduced, a low-concentration titaniferous solution is used for hydrolysis, the concentration cost of the titaniferous solution is saved, and the working procedure is shortened.
Description
Technical field
The present invention relates to the Producing Titanium Dioxide technical field, specifically, relate to a kind of method that can utilize the spent acid of sulfate process titanium dioxide technique and be hydrolyzed production pigment titanium white with lower concentration titanium liquid.
Background technology
At present, the industrial production of pigment titanium white mainly adopts sulfuric acid process and chlorination process both at home and abroad,, at home still take sulfuric acid process as main, is divided into automatic growing crystal species thermal hydrolysis and plus seed thermal hydrolysis technique.One of fine or not key factor that determines pigment titanium white quality is exactly hydrolysising condition and hydrolysis operation, the crystal seed quality and quantity that in the automatic growing crystal species hydrolysis process, the hydrolysis initial stage forms plays decisive role to the metatitanic acid structure of follow-up hydrolysis gained, particle diameter and distribution etc., and then affects the pigment performance of product.
Yet in the production of sulfate process titanium dioxide, automatic growing crystal species is all with TiO at present
2The titanium liquid of concentration about 230g/l is as hydrolysis material, and mostly plus seed is with TiO
2The titanium liquid of concentration 190～210g/l is as hydrolysis material, these titanium liquid are by after ilmenite concentrate and titanium slag acidolysis, through leaching, purification, concentrated gained, enriching section expends a large amount of steam, production cost is increased, the input of concentrating unit and supporting piping system and maintenance also need to expend a large amount of costs, and the concentrated cost of the corresponding single ton of titanium white of enriching section is about 250 yuan of left and right.In addition, the production of steam will expend a large amount of coal or other fuel, and discharge also will be to environment.
In addition, for present domestic sulfate process titanium dioxide manufacturing enterprise, a ubiquitous problem is exactly that environmental protection pressure is large, and especially spent acid is processed, and 1 ton of titanium white of average every production can produce the spent acid that 5～7 tons of h 2 so 4 concentrations are 20% left and right.
At present, domestic and international processing to titanium pigment waste acid mainly contains following four kinds of methods:
Diffusive dialysis method, namely utilize the diffusion dialysis device to separate spent acid, produces dialyzate and penetrating fluid, contains the ferrous sulfate of 15% left and right and the sulfuric acid of 5% left and right in dialyzate, contains the sulfuric acid of 10% left and right and the ferrous sulfate of 5% left and right in penetrating fluid.Mainly there is the deficiency that all contains sulfuric acid and ferrous sulfate in dialyzate and penetrating fluid in the method, and the penetrating fluid availability is lower.
The concentration recycle method, namely utilize water vapour to carry out heating evaporation to spent acid, removes the moisture in spent acid, carries out condensing crystal after cooling, and after solid-liquid separation, concentrated solution returns to former technique reuse.Mainly there is energy consumption in the method greatly and the high deficiency of processing cost, and the concentration cost of titanium white waste acid is about 1000 yuan/tons of titanium white waste acids.
The lime neutralisation, namely adopt Wingdale to neutralize to spent acid, and then precipitation is carried out mud-water separation.Mainly there is the deficiency that will produce a large amount of solid waste in the method, and solid waste is mainly the residue of calcium sulfate and Wingdale.The cost that the Wingdale neutralisation is processed titanium white waste acid is also higher, is about 800 yuan/tons of titanium white waste acids.
Also have a kind of method to utilize exactly spent acid and alkaline ore deposits such as cupric oxide, zinc oxide to neutralize, thus the treatment process of valuable element in the leaching ore deposit.The method at first be subject to alkaline mineral resources difficult selection or with long-distance transport; Next is subject to scope of the enterprise,, if want to obtain metal or other material of high added value, needs the investment of great number.
Because titanium liquid in production process of titanium pigment is concentrated and the spent acid processing cost is too high, improved the running cost of Producing Titanium Dioxide enterprise, this area is at present in the urgent need to reducing technology and the method for Producing Titanium Dioxide cost.
Publication number is that the patent documentation of CN102627319A discloses a kind of method that adopts the lower concentration titanium hydrolysis to produce the pigment titanium white, and it adopts water and TiO
2Count the titanium liquid reaction that total titanium concentration is 220～240g/l and generate on the basis of crystal seed, stand and add again 170～189g/l lower concentration titanium liquid to be hydrolyzed.The method does not fully utilize titanium white waste acid, and the titanium concentration of its control is higher than the present invention.
Summary of the invention
The object of the invention is to solve at least one in the deficiency that above-mentioned prior art exists.
For example, one of purpose of the present invention is to utilize the spent acid of sulfate process titanium dioxide technique and uses lower concentration titanium liquid (for example, with TiO
2Count 150～180g/l) and be hydrolyzed the method for producing the pigment titanium white.
A kind of method of utilizing titanium white waste acid to carry out lower concentration titanium hydrolysis production pigment titanium white is provided according to an aspect of the present invention.Said method comprising the steps of: the Waste Sulfuric Acid that production produces to sulfate process titanium dioxide carries out the sedimentation clarifying treatment, obtains supernatant liquor; Add water in described supernatant liquor, to obtain the target supernatant liquor of mass concentration as 8～23%; With by volume 10～25 parts described target supernatant liquor as bed material be heated to 92 ℃ to the boiling; Add the lower concentration titanium liquid of 90～110 parts by volume in bed material, stir, form hydrolyzation system, and the temperature of controlled hydrolysis system is 92～100 ℃, wherein, the concentration of described lower concentration titanium liquid is with TiO
2Count 150～180g/l and its acidity quotient F value is 1.70～1.95; Heating hydrolysis system to the first boiling point, keep hydrolyzation system to be in slight boiling condition to hydrolysis reaction and finish, and obtains being hydrolyzed slurry; After described hydrolysis slurry is carried out pickling, bleaching, washing, salt processing, calcining, pulverizing, obtain the anatase pigment titanium white, after perhaps described hydrolysis slurry being carried out pickling, bleaching, washing, salt processing, calcining, pulverizing and aftertreatment, obtain the rutile pigment titanium white.
A kind of method of utilizing titanium white waste acid to carry out lower concentration titanium hydrolysis production pigment titanium white is provided according to an aspect of the present invention.Said method comprising the steps of: the Waste Sulfuric Acid that production produces to sulfate process titanium dioxide carries out the sedimentation clarifying treatment, obtains supernatant liquor; Add water in described supernatant liquor, to obtain the target supernatant liquor of mass concentration as 8～23%; With by volume 10～25 parts described target supernatant liquor as bed material be heated to 92 ℃ to the boiling; Add the lower concentration titanium liquid of 90～110 parts by volume in bed material, stir, form hydrolyzation system, and the temperature of controlled hydrolysis system is 92～100 ℃, wherein, the concentration of described lower concentration titanium liquid is with TiO
2Count 150～180g/l and its acidity quotient F value is 1.70～1.95; Heating hydrolysis system to the first boiling point, keep hydrolyzation system to be in slight boiling condition, and after hydrolyzation system reached change ash point, stopped heating and stirring, to carry out slaking; The heating hydrolysis system is to second boiling point, keeps hydrolyzation system to be in slight boiling condition, and 20～120min that hydrolyzation system reaches after second boiling point adds the water of no more than 5 parts by volume in hydrolyzation system, treats that hydrolysis reaction finishes, and obtains being hydrolyzed slurry; After described hydrolysis slurry is carried out pickling, bleaching, washing, salt processing, calcining, pulverizing, obtain the anatase pigment titanium white, after perhaps described hydrolysis slurry being carried out pickling, bleaching, washing, salt processing, calcining, pulverizing and aftertreatment, obtain the rutile pigment titanium white.
Compared with prior art, method of the present invention can fully utilize titanium dioxide waste acid by sulfuric acid process, and can be directly with the lower concentration titanium liquid without concentration (for example, with TiO
2Meter concentration is the titanium liquid of 150～180g/l) be hydrolyzed for raw material, obtain the pigment titanium white, thereby recycled the spent acid of sulfate process titanium dioxide, reduced the spent acid processing cost, and adopt the lower concentration titanium hydrolysis, saved the concentrated cost of titanium liquid and short operation.
Description of drawings
Fig. 1 is the size-grade distribution detected result according to the hydrolysis slurry of example 1 of the present invention.
Fig. 2 is the size-grade distribution detected result according to the hydrolysis slurry of example 2 of the present invention.
Fig. 3 is the size-grade distribution detected result according to the hydrolysis slurry of example 3 of the present invention.
Embodiment
Hereinafter, describe the method for utilizing titanium white waste acid to carry out lower concentration titanium hydrolysis production pigment titanium white of the present invention in detail in connection with exemplary embodiment.
The method of utilizing titanium white waste acid to carry out lower concentration titanium hydrolysis production pigment titanium white according to an aspect of the present invention comprises the following steps: the Waste Sulfuric Acid that production produces to sulfate process titanium dioxide carries out the sedimentation clarifying treatment, obtains supernatant liquor; Add water in described supernatant liquor, to obtain the target supernatant liquor of mass concentration as 8～23%, (that is, contain 8～23% H by mass in supernatant liquor
2SO
4); With by volume 10～25 parts described target supernatant liquor as bed material be heated to 92 ℃ to the boiling; Add the lower concentration titanium liquid of 90～110 parts by volume in bed material, stir, form hydrolyzation system, and the temperature of controlled hydrolysis system is 92～100 ℃, wherein, the concentration of described lower concentration titanium liquid is with TiO
2Count 150～180g/l and its acidity quotient F value is 1.70～1.95; Heating hydrolysis system to the first boiling point, keep hydrolyzation system to be in slight boiling condition to hydrolysis reaction and finish, and obtains being hydrolyzed slurry; After described hydrolysis slurry is carried out pickling, bleaching, washing, salt processing, calcining, pulverizing, obtain the anatase pigment titanium white, after perhaps described hydrolysis slurry being carried out pickling, bleaching, washing, salt processing, calcining, pulverizing and aftertreatment, obtain the rutile pigment titanium white.
The method of utilizing titanium white waste acid to carry out lower concentration titanium hydrolysis production pigment titanium white according to a further aspect of the invention comprises the following steps: the Waste Sulfuric Acid that production produces to sulfate process titanium dioxide carries out the sedimentation clarifying treatment, obtains supernatant liquor; Add water in described supernatant liquor, to obtain the target supernatant liquor of mass concentration as 8～23%, (that is, contain 8～23% H by mass in supernatant liquor
2SO
4); With by volume 10～25 parts described target supernatant liquor as bed material be heated to 92 ℃ to the boiling; Add the lower concentration titanium liquid of 90～110 parts by volume in bed material, stir, form hydrolyzation system, and the temperature of controlled hydrolysis system is 92～100 ℃, wherein, the concentration of described lower concentration titanium liquid is with TiO
2Count 150～180g/l and its acidity quotient F value is 1.70～1.95; Heating hydrolysis system to the first boiling point, keep hydrolyzation system to be in slight boiling condition, and after hydrolyzation system reached change ash point, stopped heating and stirring, to carry out slaking; The heating hydrolysis system is to second boiling point, keeps hydrolyzation system to be in slight boiling condition, and 20～120min that hydrolyzation system reaches after second boiling point adds the water of no more than 5 parts by volume in hydrolyzation system, treats that hydrolysis reaction finishes, and obtains being hydrolyzed slurry; After described hydrolysis slurry is carried out pickling, bleaching, washing, salt processing, calcining, pulverizing, obtain the anatase pigment titanium white, after perhaps described hydrolysis slurry being carried out pickling, bleaching, washing, salt processing, calcining, pulverizing and aftertreatment, obtain the rutile pigment titanium white.
In one exemplary embodiment of the present invention, method of the present invention also comprises that on the basis of above-mentioned two kinds of methods insoluble titanium that the sedimentation clarification steps is obtained (namely, be not dissolved in the compound of the titanium of Waste Sulfuric Acid) return to one of sulfate process titanium dioxide production and wash operation (namely, for the metatitanic acid slurry after hydrolysis, adopt filter plant that it is filtered, metatitanic acid is filtered medium and holds back, the process of then with the water after processing, filter cake being washed).
Waste Sulfuric Acid gained supernatant liquor insoluble impurities content after sedimentation is less than 0.003g/l, sulfuric acid quality percentage composition is 8～23%,, a relatively high level, control initial hydrolysis reaction with this F value that guarantees to be hydrolyzed initial system, thereby control metatitanic acid granularity and size-grade distribution.
In one exemplary embodiment of the present invention, the concentration of described lower concentration titanium liquid is with TiO
2Meter can be 155～169g/l, and acidity quotient F value can be 1.75～1.90.
In one exemplary embodiment of the present invention, to the step that adds lower concentration titanium liquid in bed material, also comprise the lower concentration titanium liquid in bed material to be added is preheated to the step of 90～98 ℃.
In one exemplary embodiment of the present invention, add the step of lower concentration titanium liquid that the feed time of lower concentration titanium liquid is controlled to be 16～20min in bed material.
In an exemplary embodiment of above-mentioned method according to a further aspect of the invention, the curing time of maturation stage is not more than 40min.
In an exemplary embodiment of above-mentioned method according to a further aspect of the invention, add step 55～65min after hydrolyzation system reaches second boiling point of no more than 5 parts of water by volume to carry out in hydrolyzation system.
In one exemplary embodiment of the present invention, the reaction times of hydrolysis reaction can be 3.0～4.0h.
In addition, at present some titanium white enterprises select for the purpose of the discharging that reduces the waste ferrous sulfate to prepare titanium liquid technology with titanium slag or titanium slag, ilmenite mixing acid solution dispensing mode, can reach 150～180g/l without concentrated titanium concentration after the prepared purification of such technology.Therefore, method of the present invention can be connected with this class technology well.
In one exemplary embodiment of the present invention, the method for utilizing titanium white waste acid to carry out lower concentration titanium hydrolysis production pigment titanium white can realize by following steps:
(1) Waste Sulfuric Acid that sulfate process titanium dioxide production is produced is after the sedimentation clarification, and insoluble titanium returns to production line one car wash and reclaims, and in the supernatant liquor Waste Sulfuric Acid, the mass concentration of sulfuric acid adds de-salted water and is adjusted to 8～23%;
(2) with the Waste Sulfuric Acid after modified as bed material by volume proportioning get 10～25 be heated in advance 90 ℃～boiling, then add immediately 90～110 parts of lower concentration titanium liquid that have been preheated to 90～98 ℃, titanium liquid feed time is 16～20min, stirring and evenly mixing, and the maintenance system temperature is 94～100 ℃;
The concentration of wherein said lower concentration titanium liquid is with TiO
2Count 150～180g/l, acidity quotient F value is 1.70～1.95;
(3) system is warming up to boiling (the first boiling point), keeps little and boil for some time after judging the ash point, slaking is carried out in stopped heating and stirring, curing time 0～40min;
(4) after slaking finishes, again be heated to boiling (second boiling point), keep little boiling, add by volume 0～5 part of de-salted water when 60min (after preferred second boiling point add de-salted water) after second boiling point during 20～120min, after second boiling point, 3.0～4.0h finishes hydrolysis reaction, obtains being hydrolyzed the metatitanic acid slurry;
(5) said hydrolyzed metatitanic acid slurry namely obtains the anatase pigments titanium white after pickling, bleaching, washing, salt are processed, calcine, pulverized; Said hydrolyzed metatitanic acid slurry obtains rutile type first product (be and obtain the rutile pigment titanium white after aftertreatment (inorganic coating and organic surface treatment), vapour powder) through pickling, bleaching, washing, salt processing, calcining, pulverizing.Concerned process steps in this step operates and gets final product according to a conventional method.
When titanium liquid carried out the automatic growing crystal species hydrolysis, the quality and quantity that initially adds the formed crystal seed of titanium liquid in bed material was the key factor that determines the metatitanic acid quality, and finally had influence on the quality of pigment titanium white product.The present invention utilizes titanium white waste acid as bed material exactly, utilize certain density sulfuric acid in titanium white waste acid to control F value and the ionic strength of regulating crystal seed generation phase and hydrolysis stage system, thereby the speed that the controlled hydrolysis reaction is carried out, to produce the metatitanic acid that globule size is suitable and be evenly distributed, being conducive to follow-up filtration and washing operation, is the basis of producing the pigment titanium white.
in sum, the inventive method is the improvement of carrying out on existing sulfate process titanium dioxide titanium liquid automatic growing crystal species hydrolysis process, and fully utilized the spent acid that sulfate process titanium dioxide produces, use and directly as hydrolysis material, produce the pigment titanium white without concentrated low-concentration industrial titanium liquid, under the precondition of the pigment performance index that guarantees the pigment titanium white, not only reduced titanium concentration, saved the concentrated required energy consumption of titanium liquid, material consumption and running cost, and comprehensive recycling a part of titanium white waste acid, further reduced useless acid-treated cost, reduced the environmental protection pressure that sulfate process titanium dioxide is produced, have good economic benefit and social benefit.
Describe exemplary embodiment of the present invention in detail below in conjunction with concrete example.
The correlation circumstance of table 1 lower concentration titanium liquid
| TiO 2g/l | The F value | Fe/TiO 2 | Ti 3+g/l | Stability | Solid content g/l |
| 150～180 | 1.7～1.95 | 0.20～0.40 | 1.0～5.0 | >=350 | <0.040 |
The correlation circumstance of table 2 bed material titanium white waste acid
| H 2SO 4% | TFe?g/l | Ca 2+g/l | Al 3+g/l | Mg 2+g./l | T?Ti?g/ |
| 8～23 | 6～35 | ＜0.30 | ＜1.5 | ＜6.0 | ＜2.50 |
In example 1 to 3, the correlation circumstance of Hydrolysis of Titanium liquid used is as shown in table 1.In example 1 to 3, the correlation circumstance of titanium white waste acid used is as shown in table 2.The lower concentration titanium liquid that the application uses and the correlation parameter of titanium white waste acid are controlled in the correlation parameter scope shown in table 1 and table 2 better, but are not limited to this scope.
Titanium liquid stability in table 1 claims again stability, is exactly in titanium white production, and titanium liquid, in the situation that condition changes, has generation to be hydrolyzed in early days and separates out the tendency of white colloidal particle, and the degree of strength of this tendency is called the stability of titanium liquid.The stability of titanium liquid be with every milliliter of titanium liquid with the distilled water diluting of 25 ℃ when just white casse occurring, the milliliter number of required distilled water represents.That is, the total milliliter of stability=water number/dense titanium liquid milliliter number.
Example 1
Titanium white waste acid after insoluble titanium is reclaimed in sedimentation, is adjusted to 21% with h 2 so 4 concentration, gets by volume 10 parts and joins in hydrolyzer as bed material, and be preheated to boiling under agitation condition.Then be preheated to 94 ℃ with 100 parts immediately, concentration is 178g/l, and the F value is that 1.74 lower concentration titanium liquid at the uniform velocity joins in hydrolyzer in 16min, and it is 98 ℃ that reinforced process is kept the hydrolyzation system temperature.Reinforced hydrolyzation system is warming up to the first boiling point (approximately 105 ℃) after complete, heat-up time 7min, 1.0 ℃/min of temperature rise rate; Maintenance system slight boiling condition, be stopped heating and stirring after judgement system ash point, slaking 35min.Open once again after slaking is complete to stir and to start and heat, system is warming up to second boiling point (approximately 106 ℃), heat-up time 11min, temperature rise rate is 1.0 ℃/min; Maintenance system slight boiling condition, 30min at the uniform velocity adds 5 parts of de-salted waters that have been preheated to 90 ℃ to system after second boiling point, impels further carrying out of hydrolysis reaction; After second boiling point, the 3.5h hydrolysis finishes.
The sampling of gained hydrolysis slurry is carried out size-grade distribution and is detected, and remainingly is divided into two parts, and a copy of it is processed, calcining, namely obtained the anatase pigments titanium white after pulverizing through pickling, bleaching, washing, salt; Portion obtains the rutile type first product after pickling, bleaching, washing, salt are processed, calcine, pulverized in addition.
The size-grade distribution of the hydrolysis slurry that this example obtains (that is, metatitanic acid) as shown in Figure 1.As shown in Figure 1, the D of metatitanic acid
50(being expressed as d(0.5 in Fig. 1)) be 2.008 μ m, span is 1.277, shows that the metatitanic acid size-grade distribution is better.Through the pigment performance test, the anatase titanium dioxide reducing power (Tcs) that this example obtains is standard specimen for 1320(R706), whiteness relative value 99.2(PTA120 is standard specimen); Rutile type first product (R706 is standard specimen) reducing power (Tcs) is 1705, and brightness Jasn value is 94.1, whiteness relative value 99.05.
Example 2
Titanium white waste acid after insoluble titanium is reclaimed in sedimentation, is adjusted to 16% with h 2 so 4 concentration, gets by volume 15 parts and joins in hydrolyzer as bed material, and be preheated to 98 ℃ under agitation condition.Then be preheated to 97 ℃ with 100 parts immediately, concentration is 166g/l, and the F value is that 1.82 lower concentration titanium liquid at the uniform velocity joins in hydrolyzer in 18min, and it is 94 ℃ that reinforced process is kept the hydrolyzation system temperature.Reinforced hydrolyzation system is warming up to the first boiling point (approximately 104 ℃) after complete, heat-up time 10min, 1.0 ℃/min of temperature rise rate; Maintenance system slight boiling condition, be stopped heating and stirring after judgement system ash point, slaking 20min.Open once again after slaking is complete to stir and to start and heat, system is warming up to second boiling point (approximately 105 ℃), heat-up time 11min, temperature rise rate is 1.0 ℃/min; Maintenance system slight boiling condition, 60min at the uniform velocity adds 2 parts of de-salted waters that have been preheated to 90 ℃ to system after second boiling point, impels further carrying out of hydrolysis reaction; After second boiling point, the 3.0h hydrolysis finishes.
The sampling of gained hydrolysis slurry is carried out size-grade distribution and is detected, and remainingly is divided into two parts, and a copy of it is processed, calcining, namely obtained the anatase pigments titanium white after pulverizing through pickling, bleaching, washing, salt; Portion obtains the rutile type first product after pickling, bleaching, washing, salt are processed, calcine, pulverized in addition.
The size-grade distribution of the hydrolysis slurry that this example obtains (that is, metatitanic acid) as shown in Figure 2.As shown in Figure 2, the D of metatitanic acid
50(being expressed as d(0.5 in Fig. 2)) be 1.841 μ m, span is 1.189, shows that the metatitanic acid size-grade distribution is better.Through the pigment performance test, the anatase titanium dioxide reducing power (Tcs) that this example obtains is standard specimen for 1340(R706), whiteness relative value 99.4(PTA120 is standard specimen); Rutile type first product (R706 is standard specimen) reducing power (Tcs) is 1750, and brightness Jasn value is 94.3, whiteness relative value 99.35.
Example 3
Titanium white waste acid after insoluble titanium is reclaimed in sedimentation, is adjusted to 9% with h 2 so 4 concentration, gets by volume 23.5 parts and joins in hydrolyzer as bed material, and be preheated to 96 ℃ under agitation condition.Then be preheated to 90 ℃ with 100 parts immediately, concentration is 152g/l, and the F value is that 1.91 lower concentration titanium liquid at the uniform velocity joins in hydrolyzer in 20min, and it is 91 ℃ that reinforced process is kept the hydrolyzation system temperature.Reinforced hydrolyzation system is warming up to the first boiling point (approximately 104 ℃) after complete, heat-up time 13min, 1.0 ℃/min of temperature rise rate; Maintenance system slight boiling condition, after 4.0h, hydrolysis finishes.Hydrolytic process slaking 0min,, without second boiling point, do not add de-salted water and dilute.
The sampling of gained hydrolysis slurry is carried out size-grade distribution and is detected, and remainingly is divided into two parts, and a copy of it is processed, calcining, namely obtained the anatase pigments titanium white after pulverizing through pickling, bleaching, washing, salt; Portion obtains the rutile type first product after pickling, bleaching, washing, salt are processed, calcine, pulverized in addition.
The size-grade distribution of the hydrolysis slurry that this example obtains (that is, metatitanic acid) as shown in Figure 1.As shown in Figure 1, the D of metatitanic acid
50(being expressed as d(0.5 in Fig. 1)) be 2.125 μ m, span is 1.286, shows that the metatitanic acid size-grade distribution is better.Through the pigment performance test, the anatase titanium dioxide reducing power (Tcs) that this example obtains is standard specimen for 1325(R706), whiteness relative value 99.7(PTA120 is standard specimen); Rutile type first product (R706 is standard specimen) reducing power (Tcs) is 1720, and brightness Jasn value is 94.0, whiteness relative value 99.72.
Although the above has described the present invention with exemplary embodiment by reference to the accompanying drawings, those of ordinary skills should be clear,, in the situation that do not break away from the spirit and scope of claim, can carry out various modifications to above-described embodiment.
Claims (9)
1. a method of utilizing titanium white waste acid to carry out lower concentration titanium hydrolysis production pigment titanium white, is characterized in that, said method comprising the steps of:
The Waste Sulfuric Acid that production produces to sulfate process titanium dioxide carries out the sedimentation clarifying treatment, obtains supernatant liquor;
Add water in described supernatant liquor, to obtain the target supernatant liquor of mass concentration as 8～23%;
With by volume 10～25 parts described target supernatant liquor as bed material be heated to 92 ℃ to the boiling;
Add the lower concentration titanium liquid of 90～110 parts by volume in bed material, stir, form hydrolyzation system, and the temperature of controlled hydrolysis system is 92～100 ℃, wherein, the concentration of described lower concentration titanium liquid is with TiO
2Count 150～180g/l and its acidity quotient F value is 1.70～1.95;
Heating hydrolysis system to the first boiling point, keep hydrolyzation system to be in slight boiling condition to hydrolysis reaction and finish, and obtains being hydrolyzed slurry;
After described hydrolysis slurry is carried out pickling, bleaching, washing, salt processing, calcining, pulverizing, obtain the anatase pigment titanium white, after perhaps described hydrolysis slurry being carried out pickling, bleaching, washing, salt processing, calcining, pulverizing and aftertreatment, obtain the rutile pigment titanium white.
2. a method of utilizing titanium white waste acid to carry out lower concentration titanium hydrolysis production pigment titanium white, is characterized in that, said method comprising the steps of:
The Waste Sulfuric Acid that production produces to sulfate process titanium dioxide carries out the sedimentation clarifying treatment, obtains supernatant liquor;
Add water in described supernatant liquor, to obtain the target supernatant liquor of mass concentration as 8～23%;
With by volume 10～25 parts described target supernatant liquor as bed material be heated to 92 ℃ to the boiling;
Add the lower concentration titanium liquid of 90～110 parts by volume in bed material, stir, form hydrolyzation system, and the temperature of controlled hydrolysis system is 92～100 ℃, wherein, the concentration of described lower concentration titanium liquid is with TiO
2Count 150～180g/l and its acidity quotient F value is 1.70～1.95;
Heating hydrolysis system to the first boiling point, keep hydrolyzation system to be in slight boiling condition, and after hydrolyzation system reached change ash point, stopped heating and stirring, to carry out slaking;
The heating hydrolysis system is to second boiling point, keeps hydrolyzation system to be in slight boiling condition, and 20～120min that hydrolyzation system reaches after second boiling point adds the water of no more than 5 parts by volume in hydrolyzation system, treats that hydrolysis reaction finishes, and obtains being hydrolyzed slurry;
After described hydrolysis slurry is carried out pickling, bleaching, washing, salt processing, calcining, pulverizing, obtain the anatase pigment titanium white, after perhaps described hydrolysis slurry being carried out pickling, bleaching, washing, salt processing, calcining, pulverizing and aftertreatment, obtain the rutile pigment titanium white.
3. the method for utilizing titanium white waste acid to carry out lower concentration titanium hydrolysis production pigment titanium white according to claim 1 and 2, is characterized in that, described method also comprises that the insoluble titanium that described sedimentation clarification steps is obtained returns to one of sulfate process titanium dioxide production and washes operation.
4. the method for utilizing titanium white waste acid to carry out lower concentration titanium hydrolysis production pigment titanium white according to claim 1 and 2, is characterized in that, the concentration of described lower concentration titanium liquid is with TiO
2Count 155～169g/l, acidity quotient F value is 1.75～1.90.
5. according to claim 1 and 2ly utilize titanium white waste acid to carry out the lower concentration titanium hydrolysis to produce the method for pigment titanium white, it is characterized in that, described step to adding lower concentration titanium liquid in bed material also comprises the lower concentration titanium liquid in bed material to be added is preheated to the step of 90～98 ℃.
6. according to claim 1 and 2ly utilize titanium white waste acid to carry out the lower concentration titanium hydrolysis to produce the method for pigment titanium white, it is characterized in that, describedly add the step of lower concentration titanium liquid that the feed time of lower concentration titanium liquid is controlled to be 16～20min in bed material.
7. the method for utilizing titanium white waste acid to carry out lower concentration titanium hydrolysis production pigment titanium white according to claim 2, is characterized in that, the curing time of described maturation stage is not more than 40min.
8. according to claim 2ly utilize titanium white waste acid to carry out the lower concentration titanium hydrolysis to produce the method for pigment titanium white, it is characterized in that, describedly add step 55～65min after hydrolyzation system reaches second boiling point of no more than 5 parts of water by volume to carry out in hydrolyzation system.
9. the method for utilizing titanium white waste acid to carry out lower concentration titanium hydrolysis production pigment titanium white according to claim 1 and 2, is characterized in that, the reaction times of described hydrolysis reaction is 3.0～4.0h.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103910381A (en) * | 2014-04-21 | 2014-07-09 | 济南裕兴化工有限责任公司 | Titanium dioxide solution production method capable of reducing acid consumption |
| CN105502481A (en) * | 2014-09-26 | 2016-04-20 | 河南佰利联化学股份有限公司 | Preparation method for anatase titanium dioxide |
| CN107500347A (en) * | 2017-09-05 | 2017-12-22 | 河北麦森钛白粉有限公司 | A kind of method for controlling decorating base paper titanium dioxide particle diameter |
| CN109205663A (en) * | 2018-10-19 | 2019-01-15 | 攀枝花学院 | Automatic growing crystal species and preparation method thereof are hydrolyzed in Producing Titanium Dioxide |
| CN113213529A (en) * | 2021-05-26 | 2021-08-06 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for producing titanium dioxide by sulfuric acid process and recycling metatitanic acid in titanium dioxide waste acid |
| CN114149025A (en) * | 2021-12-30 | 2022-03-08 | 龙佰集团股份有限公司 | Comprehensive utilization method of sulfate process titanium dioxide wastewater |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1396119A (en) * | 2002-07-01 | 2003-02-12 | 四川大学 | Process for comprehensive utilization of waste acid containing titanium oxide |
| CN101284680A (en) * | 2008-05-05 | 2008-10-15 | 攀钢集团攀枝花钢铁研究院有限公司 | Hydrolyzing method for preparing titanium white |
| CN101607737A (en) * | 2009-07-30 | 2009-12-23 | 攀钢集团攀枝花钢铁研究院有限公司 | Produce the method for titanium dioxide |
| CN101700907A (en) * | 2009-11-13 | 2010-05-05 | 攀钢集团研究院有限公司 | Hydrolysis method for preparing rutile type titanium dioxide |
| CN102627319A (en) * | 2012-04-24 | 2012-08-08 | 攀枝花学院 | Method for producing titanium white pigment by hydrolyzing low-concentration titanium liquid |
-
2013
- 2013-07-24 CN CN201310312347.5A patent/CN103395832B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1396119A (en) * | 2002-07-01 | 2003-02-12 | 四川大学 | Process for comprehensive utilization of waste acid containing titanium oxide |
| CN101284680A (en) * | 2008-05-05 | 2008-10-15 | 攀钢集团攀枝花钢铁研究院有限公司 | Hydrolyzing method for preparing titanium white |
| CN101607737A (en) * | 2009-07-30 | 2009-12-23 | 攀钢集团攀枝花钢铁研究院有限公司 | Produce the method for titanium dioxide |
| CN101700907A (en) * | 2009-11-13 | 2010-05-05 | 攀钢集团研究院有限公司 | Hydrolysis method for preparing rutile type titanium dioxide |
| CN102627319A (en) * | 2012-04-24 | 2012-08-08 | 攀枝花学院 | Method for producing titanium white pigment by hydrolyzing low-concentration titanium liquid |
Non-Patent Citations (1)
| Title |
|---|
| 范兵等: ""硫酸法钛白废酸的处理"", 《河南化工》, vol. 30, no. 34, 30 April 2013 (2013-04-30), pages 12 - 15 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103910381A (en) * | 2014-04-21 | 2014-07-09 | 济南裕兴化工有限责任公司 | Titanium dioxide solution production method capable of reducing acid consumption |
| CN103910381B (en) * | 2014-04-21 | 2016-03-09 | 济南裕兴化工有限责任公司 | A kind of titanium liquid production method reducing acid consumption |
| CN105502481A (en) * | 2014-09-26 | 2016-04-20 | 河南佰利联化学股份有限公司 | Preparation method for anatase titanium dioxide |
| CN107500347A (en) * | 2017-09-05 | 2017-12-22 | 河北麦森钛白粉有限公司 | A kind of method for controlling decorating base paper titanium dioxide particle diameter |
| CN109205663A (en) * | 2018-10-19 | 2019-01-15 | 攀枝花学院 | Automatic growing crystal species and preparation method thereof are hydrolyzed in Producing Titanium Dioxide |
| CN109205663B (en) * | 2018-10-19 | 2020-09-29 | 攀枝花学院 | Hydrolytic authigenic crystal seed in titanium white production and preparation method thereof |
| CN113213529A (en) * | 2021-05-26 | 2021-08-06 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for producing titanium dioxide by sulfuric acid process and recycling metatitanic acid in titanium dioxide waste acid |
| CN113213529B (en) * | 2021-05-26 | 2022-08-02 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for producing titanium dioxide by sulfuric acid process and recycling metatitanic acid in titanium dioxide waste acid |
| CN114149025A (en) * | 2021-12-30 | 2022-03-08 | 龙佰集团股份有限公司 | Comprehensive utilization method of sulfate process titanium dioxide wastewater |
| CN114149025B (en) * | 2021-12-30 | 2023-10-13 | 龙佰集团股份有限公司 | Comprehensive utilization method of sulfuric acid process titanium dioxide wastewater |
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