CN102372306A - Method for recycling concentrated slag of wasted acid from titanium white production - Google Patents
Method for recycling concentrated slag of wasted acid from titanium white production Download PDFInfo
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- CN102372306A CN102372306A CN2011102293287A CN201110229328A CN102372306A CN 102372306 A CN102372306 A CN 102372306A CN 2011102293287 A CN2011102293287 A CN 2011102293287A CN 201110229328 A CN201110229328 A CN 201110229328A CN 102372306 A CN102372306 A CN 102372306A
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- iron
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide (Fe2O3)
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/14—Sulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses a method for recycling concentrated slag of wasted acid from titanium white production, mainly comprising the following steps of: pulping the concentrated slag of the wasted acid; adding superfluous iron powder or iron sheets into the pulped concentrated slag as much as possible on the premise of allowable cost; reacting at the temperature of 50-90 DEG C for 1-3h; converting sulfuric acid in the concentrated slag into iron sulfate, and converting ferric iron possibly existing in the concentrated slag into ferrous iron to form the iron sulfate, thus, not only are remnant sulfuric acid and ferric iron in the concentrated slag removed, but also the content of the iron sulfate in the concentrated slag is greatly increased, the proportion of iron is also greatly increased, i.e., the concentrated slag of the wasted acid is produced into the sulfuric acid with a high added value and iron trioxide cinder with high quality through pretreatment, the waste is turned into the wealth, the environment is protected, and resources are saved. The concentrated slag of the wasted acid from titanium white production can be completely produced into the sulfuric acid through the pretreatment through titanium white production and supporting devices by using a sulfuric acid method, so that the equipment investment is reduced, and the aims of circular economy as well as energy conservation and emission reduction are achieved.
Description
Technical field
The present invention relates to a kind of white titanium pigment and sulfuric acid industry disposal of waste gas, water and industrial residue method, specifically, relate to the method that a kind of pre-treatment titanium white spent acid condensed slag prepares sulfuric acid and higher-grade red oxide of iron slag.
Background technology
The production of white titanium pigment generally is divided into sulfuric acid process and chlorination.Because raw material and technology limitation, the titanium white production enterprise overwhelming majority adopts sulfuric acid process at present.
In the sulfuric acid method titanium pigment production process, the metatitanic acid slip after the filtration hydrolysis, the filtrating of containing a large amount of impurity that obtains is called sulfur waste acid, contains the dilute sulphuric acid of 20-30% in the sulfur waste acid.For the processing of spent acid, sulfuric acid method titanium pigment producer is general to adopt and concentrates or the complex acid mode is carried densely, to improve sulfuric acid concentration and to reduce impurity in the acid, is convenient to the recovering waste acid utilization.At present, most of factory brings up to 50～55% with acid-spending strength, to separate out most of impurity, removes the throw out of separating out through solid-liquid separation then.The sulfuric acid that reclaims can further utilize, and for example publication number is the patent of CN101214931, has introduced the quality and the purposes of a kind of titanium dioxide hydrolysis spent acid concentration technology and concentrated vitriol.The throw out that the recovery vitriol oil is separated out is commonly called as condensed slag, and the staple of condensed slag is the vitriol of various metals, and its typical component (in the oxide mass ratio) is: free H
2SO
410-30%, TiO
21.0-2.5%, Al
2O
30.15-0.35%, Fe
2O
320-28.6%, MgO 1.7-3.0%, H
2O 15-25%.Contain some useful components in the condensed slag; Like ferrous sulfate, but, recycle relatively difficulty owing to contain a large amount of impurity and sulfuric acid in the condensed slag; General at present employing alkaline matter will wherein be put with laggard windrow; Because treatment capacity is bigger, can take huge slag place, and environment is caused certain influence.At present the contriver except at application number be utilize in 200910312742.7 the patent condensed slag produce a water feed ferrous, also in further other Application Areass of developing condensed slag.
The main raw material of sulfuric acid method titanium pigment production is ilmenite concentrate and sulfuric acid, so the general all supporting sulfuric acid plant of titanium powder plant.To prepare raw material be to adopt one or more of Sulfur, sulfurous iron ore and pyrite etc. to vitriolic in the industry; It is burnt or roasting in air; To obtain sulfur dioxide flue gas. again it is passed through treating plant such as purifications such as tornado dust collector, electrostatic precipitator; After obtaining purified sulfurous gas, be sulphur trioxide with the sulfurous gas catalyzed oxidation again, double conversion and double absorption obtains the vitriol oil.Application number is that 03119051.0 one Chinese patent application has been reported a kind of low-grade sulphur and the baking mixed preparation vitriolic of sulfurous iron ore method of relating to; And application number is 200910042741.5 one Chinese patent application in order to improve slag roasting grade after the roasting, has also adopted sulphur, sulfurous iron ore, pyrrhotite, sulfur-containing magnetite roasting to prepare the vitriolic method.
Above-mentioned two patents prepare sulfurous iron ore that the vitriolic raw material all is various grades, sulphur etc., and various ores all need cost.From the composition analysis of white titanium pigment spent acid condensed slag, also mainly be that the staple of two kinds of elements of iron and sulphur and ore is similar; Can consider like this to use condensed slag in the vitriolic preparation and go, on the one hand can utilization of waste material, also can obtain high value-added product; But need overcome the influence of other impurity such as spent acid and moisture in the condensed slag; For example the acid content in the condensed slag is high more, and the amount that is decomposed into sulphur trioxide during roasting is just many more, and the sulphur trioxide that form this moment not only can not utilize; Also need wash and remove, otherwise the meeting etching apparatus; And the content of water is high more, and bonded acid is many more with it, and water vapour is high more, has also increased the load of subsequent handling dry decontamination, so the content of acid and water is low more good more.
Summary of the invention
Goal of the invention of the present invention is: the problem to above-mentioned existence provides a kind of white titanium pigment spent acid condensed slag recoverying and utilizing method.
The technical scheme that the present invention adopts is such: a kind of white titanium pigment spent acid condensed slag recoverying and utilizing method comprises following process step:
(1) condensed slag pre-treatment:
White titanium pigment spent acid condensed slag and iron vitriol are converted into mother liquor (staple is iron, sulfuric acid and water) that the ferrous sulfate monohydrate crystal produced to be mixed making beating and obtains slip; Control slip proportion is 1.2～1.4; Press 50～100% of free sulfuric acid quality and calculate the iron powder amount, and slowly add iron powder, under 50 ℃～90 ℃ temperature, react 1～3h; Regulate the mass content 4～10% of acid, weight of iron content 10～30% in the slip;
(2), crystallisation by cooling, separation:
Above-mentioned reacted slip is changed in the water cooler, slowly lower the temperature by the speed of 1～3 ℃/min, crystallisation by cooling 1～2h, the cooling outlet temperature is 10～25 ℃, sharp separation obtains iron vitriol and ferrous sulfate monohydrate mixture then;
(3), mixing match, roasting:
The iron vitriol and the ferrous sulfate monohydrate mixture of step (2) gained are mixed with at least a of sulphur, sulfurous iron ore; The iron after control mixes simultaneously in the material and the ratio of sulphur; Roasting then, maturing temperature is 600-900 ℃, the mass content of control oxygen is 4-8% during roasting;
(4), washing, purification:
The flue gas of gained is through washing during with step (3) roasting, and operations such as dedusting, demist obtain purified sulfurous gas and are used to prepare sulfuric acid.
As preferably: with the burning slag of gained after step (3) roasting through washing, separate, obtain high-grade red oxide of iron slag.The iron level of this high-grade red oxide of iron slag is suitable as steel mill's raw material greater than 65%.
As preferably: in the step (1) in the slip acid content be 6～8%, iron level is 15～25%.
As preferably: acid content 6～8% in step (2) gained iron vitriol and the ferrous sulfate monohydrate mixture, moisture content 4～10%, i.e. the content of control acid and water does not exceed standard, and helps follow-up roasting.
As preferably: in the step (3) control iron vitriol and ferrous sulfate monohydrate mixture and sulphur, sulfurous iron ore at least a to mix the ratio of iron, sulphur in the back material be 1:4～1:8.
As preferably: the roasting described in the step (3) is in fluidizing furnace, to carry out, and intensity of roasting is 10～14 tons/(m
2.h), operating gas velocity is 10-15m/s during roasting, and the residence time is 8-15s.The intensity of roasting (promptly per hour, the tonnage of every square meter area roasted ore) of at present general fluidizing furnace is 17～20 tons/(m
2.h), present patent application reduces intensity of roasting through increasing the roasting area.
The contriver of this patent at first carries out pre-treatment to condensed slag on the basis of 200910312742.7 patented claim, on technology and equipment, improves innovation again, has obtained better effect.
At FeSO
4～H
2SO
4～H
2In the O ternary system, when temperature one timing, the solubleness of ferrous sulfate reduces with the increase of sulfuric acid concentration; When sulfuric acid concentration one timing, the rising of its solubility with temperature increases very fast; H in solution
2SO
4Concentration one timing, FeSO
4The rising of solubility with temperature a peak is arranged, the pairing temperature of this peak is again with FeSO in the solution
4The minimizing of content and reducing, the concrete reason contriver gets across in patented claim 200910312742.7 the insides.
According to above-mentioned mechanism, the present invention is with the making beating of spent acid condensed slag, under the prerequisite that cost allows; Add excessive iron powder or iron sheet in the condensed slag after making beating as far as possible; Under 50 ℃～90 ℃ temperature, react 1～3h, the sulfuric acid conversion in the condensed slag is become ferrous sulfate, and convert the ferric iron that possibly exist in the condensed slag to ferrous iron; Form ferrous sulfate; Thereby not only remove sulfuric acid remaining in the condensed slag, ferric iron, and make that the content of ferrous sulfate greatly increases in the condensed slag, the ratio of iron also greatly increases.Above-mentioned reacted slip is slowly lowered the temperature by the speed of 1～3 ℃/min; Crystallisation by cooling; To impel particle diameter in the spent acid condensed slag is that the ferrous sulfate monohydrate of 2～20 μ m partly changes into the iron vitriol that particle diameter is 200～500 μ m; Spinning obtains spent acid and the lower condensed slag of moisture then, has guaranteed that subsequent handling reduces the generation of sulphur trioxide.
One or more mixing with seven water of gained of last step and ferrous sulfate monohydrate mixture and sulphur, sulfurous iron ore; The quality proportioning of iron and sulphur is 1:4～1:8 after guaranteeing to mix; The ratio of sulphur is higher; Guarantee on the one hand to improve enough heats, also guaranteed the SO of gained flue gas the inside for the decomposition of ferrous sulfate and water
2Content high, help follow-up relieving haperacidity operation.React characteristics more slowly to the roasting that has added condensed slag, grope through a large amount of tests, the contriver innovates improvement to fluidizing furnace, has reduced the intensity of roasting of fluidizing furnace, and the intensity of roasting of general fluidizing furnace is 17-20 ton/(m
2.h), the intensity of roasting of this fluidizing furnace is 10～14 tons/(m
2.h), the improved fluidizing furnace of present patent application mainly is through increasing the roasting area, can adopting modes such as increase boiling furnace charge bed surface amasss to increase the roasting area; And the minimizing intensity of roasting, thereby reduced gas speed, the reaction times that has increased material; The acid of condensed slag the inside is fully decomposed, help the grade of follow-up purification and raising slag, reduced intensity of roasting; Gas speed is the 30%-50% of traditional gas speed, has increased to mix the reaction time of ore deposit in the stove the inside, and finding out best maturing temperature is 600-900 ℃; The content of control oxygen is at 4-8%; The product that makes roasting has suppressed the generation of sulphur trioxide as far as possible for sulfurous gas, has reduced the acid content in the washes.Pre-treatment adds iron powder reducing and follow-up suitable iron sulphur ratio in front, has guaranteed that the burning slag obtains high-grade red oxide of iron slag through washing, separation, and iron level is fit to steel mill's raw material greater than 65%.
Compared with prior art, technique effect of the present invention: the present invention produces the sulfuric acid of high added value and red oxide of iron burning slag of high grade with the spent acid condensed slag through pre-treatment, turns waste into wealth, and has protected environment, has practiced thrift resource.Sulfuric acid is produced in the pre-treatment of titanium white waste acid condensed slag, can utilize the production and the corollary apparatus of sulfuric acid method titanium pigment fully, reduction facility investment, the target of realization recycling economy, energy-saving and emission-reduction.
Embodiment
Do detailed explanation in the face of the present invention down.
In order to make the object of the invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with embodiment.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
Embodiment 1
Present embodiment comprises following process step:
(1) condensed slag pre-treatment:
In the glass reinforced plastic reaction kettle, add 8m
3The mother liquor (weight of iron content 7.23%, sour mass content 2.45%) that ferrous sulfate monohydrate is produced under the whipped state, adds 12 tons of titanium white waste acid condensed slags (Fe mass content 18.2%, H again
2SO
4Mass content 14.3%), condensed slag is mixed making beating with mother liquor, control slip proportion is 1.3, is warming up to 70 ℃, opens blower fan, slowly adds the 750kg iron powder then, 1 hour iron powder joining day, after the iron powder reaction finishes, adds 4 m again
3Wet method ferrous sulfate monohydrate mother liquor, and keep this temperature.This moment, slip weight of iron content 15.89%, sour mass content 4.56%.
(2), crystallisation by cooling, separation:
Fall the slip after the acid, change in the vacuum cooler, slowly lower the temperature, make slip be cooled to 20 ℃, 2 hours cooling times, obtain seven water and ferrous sulfate monohydrate mixture that crystal particle diameter is about 0.23 millimeter by the speed of 1 ℃/min; Select quick spinning, obtain 16.5 ton of seven water and ferrous sulfate monohydrate mixture (iron level 19.43%, water-content 6.9 %), the muddiness that contains metatitanic acid is filtrated 11.3 tons, and filtrating iron level 6.09% obtains metatitanic acid and clear liquor reuse or makes other purposes.
(3), mixing match, roasting:
With 16.5 tons of the iron vitriols of gained by iron: the proportioning of sulphur is that 1:4 adds 16.2 tons in sulphur, in improved fluidizing furnace by 10 tons/(m of intensity of roasting
2.h), roasting gas speed is the 15s roasting for 10m/s, the residence time, maturing temperature is 750 ℃, the content of control oxygen is 6%.
(4), washing, purification:
Through washing, operations such as dedusting, demist obtain purified sulfurous gas and remove to prepare sulfuric acid with the flue gas of (3) gained, obtain 50.5 tons of 98% the vitriol oils; The burning slag of (3) gained is obtained 6.4 tons of high-grade red oxide of iron slags through washing, separation, and iron level 65.4% send steel mill's raw material.
Embodiment 2
Present embodiment comprises following process step:
(1) condensed slag pre-treatment:
In the glass reinforced plastic reaction kettle, add 8m
3The mother liquor (weight of iron content 7.23%, sour mass content 2.45%) that ferrous sulfate monohydrate is produced under the whipped state, adds 12 tons of titanium white waste acid condensed slags (Fe mass content 18.2%, H again
2SO
4Mass content 14.3%), condensed slag is mixed making beating with mother liquor, control slip proportion is 1.3 to be warming up to 70 ℃, opens blower fan, slowly adds the 750kg iron powder then, 2 hours iron powder joining days, after the iron powder reaction finishes, adds 4 m again
3Wet method ferrous sulfate monohydrate mother liquor, and keep this temperature.This moment, slip weight of iron content 16.51%, sour mass content 3.15%.
Other step is with embodiment 1, obtains 51.7 tons of 98% the vitriol oils at last; The burning slag of (3) gained is obtained 6.6 tons of high-grade red oxide of iron slags through washing, separation, and iron level 66.0% send steel mill's raw material.
Embodiment 3
Present embodiment comprises following process step:
(1) condensed slag pre-treatment:
In the glass reinforced plastic reaction kettle, add 8m
3The mother liquor (weight of iron content 7.23%, sour mass content 2.45%) that ferrous sulfate monohydrate is produced under the whipped state, adds 12 tons of titanium white waste acid condensed slags (Fe mass content 18.2%, H again
2SO
4Mass content 14.3%), condensed slag is mixed making beating with mother liquor, control slip proportion is 1.3 to be warming up to 70 ℃, opens blower fan, slowly adds the 750kg iron powder then, 3 hours iron powder joining days, after the iron powder reaction finishes, adds 4 m again
3Wet method ferrous sulfate monohydrate mother liquor, and keep this temperature.This moment, slip weight of iron content 16.51%, sour mass content 3.15%.
Other step is with embodiment 1, obtains 52.8 tons of 98% the vitriol oils; The burning slag of (3) gained is obtained 6.7 tons of high-grade red oxide of iron slags through washing, separation, and iron level 66.2% send steel mill's raw material.
Embodiment 4
Present embodiment comprises following process step:
(1) condensed slag pre-treatment:
In the glass reinforced plastic reaction kettle, add 8m
3The mother liquor (iron level 7.23%, acid content 2.45%) that ferrous sulfate monohydrate is produced under the whipped state, adds 12 tons of titanium white waste acid condensed slags (Fe18.2%, H again
2SO
414.3%), condensed slag is mixed making beating with mother liquor, control slip proportion is 1.3, is warming up to 70 ℃, opens blower fan, slowly adds the 1000kg iron powder then, 3 hours iron powder joining days, after the iron powder reaction finishes, adds 4 m again
3Wet method ferrous sulfate monohydrate mother liquor, and keep this temperature.This moment, the slip iron level 19.01%, acid content 3.12%.
(2), crystallisation by cooling, separation:
Fall the slip after the acid, change in the vacuum cooler, slowly lower the temperature, make slip be cooled to 20 ℃, 2 hours cooling times, obtain seven water and ferrous sulfate monohydrate mixture that crystal particle diameter is about 0.34 millimeter by the speed of 1 ℃/min.Select quick spinning.Obtain 16.8 tons of iron vitriols and ferrous sulfate monohydrate (iron level 21.2%, water-content 5.1 %), the muddiness that contains metatitanic acid is filtrated 11.6 tons, and filtrating iron level 6.31% obtains metatitanic acid and clear liquor reuse or makes other purposes.
(3), mixing match, roasting:
With 16.8 tons in seven water of gained and ferrous sulfate monohydrate mixture by iron: the proportioning of sulphur is that 1:6 adds 24.2 tons of sulphur tons; In improved fluidizing furnace, press 10/(m2.h) roastings of intensity of roasting ton; Roasting gas speed is 10m/s; The residence time is 15s, and maturing temperature is 750 ℃, and the content of control oxygen is 6%.
(4), washing, purification:
Through washing, operations such as dedusting, demist obtain purified sulfurous gas and remove to prepare sulfuric acid with the flue gas of (3) gained, obtain 75.8 tons in 98% sulfuric acid; The burning slag of (3) gained is obtained 7.5 tons of high-grade red oxide of iron slags through washing, separation, and iron level send steel mill's raw material greater than 66.8%.
Embodiment 5
Present embodiment step (1) (2) is with embodiment 4
(3), mixing match, roasting:
With 16.8 tons of the iron vitriols of gained by iron: the proportioning of sulphur is the sulfurous iron ore that 1:6 adds 20.1 tons of sulphur tons and 8.2; In improved fluidizing furnace, press 10/(m2.h) roastings of intensity of roasting ton; Roasting gas speed is 10m/s; The residence time is 15s, and maturing temperature is 800 ℃, and the content of control oxygen is 8%.
(4), washing, purification:
With the flue gas process washing of (3) gained, operations such as dedusting, demist obtain purified sulfurous gas and remove to prepare sulfuric acid, obtain 74.5 tons in 98% sulfuric acid; The burning slag of (3) gained is obtained 12.1 tons of high-grade red oxide of iron slags through washing, separation, and iron level 67.5% send steel mill's raw material.
Embodiment 6
Present embodiment comprises following process step:
(1) (2) step is with embodiment 4.
With 16.8 tons in seven water of gained and ferrous sulfate monohydrate mixture by iron: the proportioning of sulphur is that 1:6 adds 24.2 tons of sulphur tons; In improved fluidizing furnace, press 14/(m2.h) roastings of intensity of roasting ton; Roasting gas speed is 14m/s; The residence time is 11s, and maturing temperature is 750 ℃, and the content of control oxygen is 6%.
(4), washing, purification:
Through washing, operations such as dedusting, demist obtain purified sulfurous gas and remove to prepare sulfuric acid with the flue gas of (3) gained, obtain 75.3 tons in 98% sulfuric acid; The burning slag of (3) gained is obtained 7.4 tons of high-grade red oxide of iron slags through washing, separation, and iron level send steel mill's raw material greater than 66.5%.
Comparative Examples 1
This Comparative Examples 1 directly the condensed slag of not handling directly and sulphur mix burning, comprise following process step:
(1), mixing match, roasting:
With 12 tons of condensed slags by iron: the proportioning of sulphur is that 1:4 adds 15.8 tons of sulphur tons, and by 10 tons/(m2.h) roasting of intensity of roasting, maturing temperature is 750 ℃ in improved fluidizing furnace, and the content of control oxygen is 6%.
(2), washing, purification:
Through washing, operations such as dedusting, demist obtain purified sulfurous gas and remove to prepare sulfuric acid with the flue gas of (1) gained, obtain 50.2 tons of 98% the vitriol oils; The burning slag of (1) gained is obtained 5.6 tons of high-grade red oxide of iron slags through washing, separation, and iron level 60.1% send steel mill's raw material.
Comparative Examples 2
This Comparative Examples 2 is directly used acid production with sulphur, comprises following process step:
(1), mixing match, roasting:
With 15.8 tons of sulphur tons, by 10 tons/(m2.h) intensity of roasting roasting, maturing temperature is 750 ℃ in improved fluidizing furnace, and the content of control oxygen is 6%.
(2), washing, purification:
Through washing, operations such as dedusting, demist obtain purified sulfurous gas and remove to prepare sulfuric acid with the flue gas of (1) gained, obtain 47.8 tons of 98% the vitriol oils.
The flue gas composition of the foregoing description and Comparative Examples is seen table 1
The different embodiment flue gas composition of table 1 mass content
The sulfuric acid quality of the different embodiment preparations of table 2 and the iron level of tailings
The embodiment interpretation of result:
(1) finds out with all embodiment from Comparative Examples 1,2, adopt present patent application to recycle the method for condensed slag, can improve vitriolic output, obtain high-grade red oxide of iron slag;
(2) comparative example 1-3 result finds, the reaction times that adds iron powder is the parameter of a key, and for improving the slip weight of iron, reducing sour mass content has significant effects.
(3) comparative example 1-3 and embodiment 4 results find, the amount that the condensed slag pre-treatment adds iron powder increases, and can improve the grade of red oxide of iron slag, mixture iron and sulphur than constant situation under, can increase vitriolic output.
(4) comparative example 4 finds with embodiment 5 results, and a kind of of sulphur and sulfurous iron ore or two kinds are mixed in roasting can adopt present method, mixes sulphur and can improve vitriolic output, mixes the grade that sulfurous iron ore can improve the red oxide of iron slag.
Comparative example 4 and embodiment 6 results find that the strength ratio during roasting is lower, and roasting gas speed is low, and the residence time is long, helps improving the grade of vitriolic output and red oxide of iron slag.
Claims (6)
1. white titanium pigment spent acid condensed slag recoverying and utilizing method is characterized in that comprising following process step:
(1) condensed slag pre-treatment:
White titanium pigment spent acid condensed slag and iron vitriol are converted into mother liquor that the ferrous sulfate monohydrate crystal produced to be mixed making beating and obtains slip; Control slip proportion is 1.2～1.4; Press 50～100% of free sulfuric acid quality and calculate the iron powder amount, and slowly add iron powder, under 50 ℃～90 ℃ temperature, react 1～3h; Regulate the mass content 4～10% of acid, weight of iron content 10～30% in the slip;
(2), crystallisation by cooling, separation:
Above-mentioned reacted slip is changed in the water cooler, slowly lower the temperature by the speed of 1～3 ℃/min, crystallisation by cooling 1～2h, the cooling outlet temperature is 10～25 ℃, sharp separation obtains iron vitriol and ferrous sulfate monohydrate mixture then;
(3), mixing match, roasting:
The iron vitriol and the ferrous sulfate monohydrate mixture of step (2) gained are mixed with at least a of sulphur, sulfurous iron ore; The iron after control mixes simultaneously in the material and the ratio of sulphur; Roasting then, maturing temperature is 600-900 ℃, the mass content of control oxygen is 4-8% during roasting;
(4), washing, purification:
The flue gas of gained is through washing during with step (3) roasting, and operations such as dedusting, demist obtain purified sulfurous gas and are used to prepare sulfuric acid.
2. white titanium pigment spent acid condensed slag recoverying and utilizing method according to claim 1 is characterized in that: the washing of burning slag process, separation with gained after step (3) roasting obtain high-grade red oxide of iron slag.
3. white titanium pigment spent acid condensed slag recoverying and utilizing method according to claim 1 is characterized in that: acid content is 6～8% in the middle slip of step (1), and iron level is 15～25%.
4. white titanium pigment spent acid condensed slag recoverying and utilizing method according to claim 1 is characterized in that acid content 6～8% in step (2) gained iron vitriol and the ferrous sulfate monohydrate mixture, moisture content 4～10%.
5. white titanium pigment spent acid condensed slag recoverying and utilizing method according to claim 1 is characterized in that step (3) middle control iron vitriol and ferrous sulfate monohydrate mixture are 1:4～1:8 with at least a ratio of mixing iron, sulphur in the material of back of sulphur, sulfurous iron ore.
6. white titanium pigment spent acid condensed slag recoverying and utilizing method according to claim 1 is characterized in that the roasting described in the step (3) is in fluidizing furnace, to carry out, and intensity of roasting is 10～14 tons/(m
2.h), operating gas velocity is 10-15m/s during roasting, and the residence time is 8-15s.
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| CN2011102293287A CN102372306A (en) | 2011-08-11 | 2011-08-11 | Method for recycling concentrated slag of wasted acid from titanium white production |
| PCT/CN2012/078213 WO2013020431A1 (en) | 2011-08-11 | 2012-07-05 | Method for recycling concentrate residues of titanium dioxide waste acid |
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| CN2011102293287A CN102372306A (en) | 2011-08-11 | 2011-08-11 | Method for recycling concentrated slag of wasted acid from titanium white production |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102923674A (en) * | 2012-11-28 | 2013-02-13 | 四川龙蟒钛业股份有限公司 | Recycling method of ferrous-sulfate-containing by-product generated in titanium dioxide production process |
| WO2013020431A1 (en) * | 2011-08-11 | 2013-02-14 | 四川龙蟒钛业股份有限公司 | Method for recycling concentrate residues of titanium dioxide waste acid |
| CN103193278A (en) * | 2013-04-25 | 2013-07-10 | 白银富提拉化工科技有限公司 | Reductive calcining process of ferrous sulfate as byproduct of titanium dioxide |
| CN103224221A (en) * | 2013-04-14 | 2013-07-31 | 张彭成 | Method for separating sulfuric acid and ferrous sulfate by using ferrous sulfate monohydrate residue |
| CN103318849A (en) * | 2013-07-10 | 2013-09-25 | 四川大学 | Method for recycling sulfur-iron resources |
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| CN115028207A (en) * | 2022-06-24 | 2022-09-09 | 杭州安永环保科技有限公司 | Method for concentrating titanium dioxide waste acid by sulfuric acid process |
| CN116143179A (en) * | 2022-09-09 | 2023-05-23 | 河北圣雪大成制药有限责任公司 | Method for preparing ferrous sulfate for Fenton oxidation by using oxytetracycline hydrochloride waste acid |
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| CN110697792A (en) * | 2019-10-31 | 2020-01-17 | 襄阳龙蟒钛业有限公司 | Method for preparing yellow ferrous iron with controllable particle size by using waste acid from titanium dioxide production |
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| WO2013020431A1 (en) * | 2011-08-11 | 2013-02-14 | 四川龙蟒钛业股份有限公司 | Method for recycling concentrate residues of titanium dioxide waste acid |
| CN102923674A (en) * | 2012-11-28 | 2013-02-13 | 四川龙蟒钛业股份有限公司 | Recycling method of ferrous-sulfate-containing by-product generated in titanium dioxide production process |
| CN103224221A (en) * | 2013-04-14 | 2013-07-31 | 张彭成 | Method for separating sulfuric acid and ferrous sulfate by using ferrous sulfate monohydrate residue |
| CN103224221B (en) * | 2013-04-14 | 2016-08-24 | 张彭成 | A kind of method utilizing ferrous sulfate monohydrate slag separation sulfuric acid and ferrous sulfate |
| CN103193278A (en) * | 2013-04-25 | 2013-07-10 | 白银富提拉化工科技有限公司 | Reductive calcining process of ferrous sulfate as byproduct of titanium dioxide |
| CN103318849A (en) * | 2013-07-10 | 2013-09-25 | 四川大学 | Method for recycling sulfur-iron resources |
| CN104694747A (en) * | 2015-03-30 | 2015-06-10 | 攀枝花学院 | Rich-titanium material preparation method using titanium white waste acid to treat ilmenite concentrate |
| CN105329952A (en) * | 2015-11-07 | 2016-02-17 | 宜兴华谊着色科技有限公司 | Refining method of titanium dioxide by-product ferrous sulfate |
| CN106904658A (en) * | 2017-02-20 | 2017-06-30 | 四川龙蟒钛业股份有限公司 | A kind of method of acid content in reduction ferrous slag |
| CN115028207A (en) * | 2022-06-24 | 2022-09-09 | 杭州安永环保科技有限公司 | Method for concentrating titanium dioxide waste acid by sulfuric acid process |
| CN116143179A (en) * | 2022-09-09 | 2023-05-23 | 河北圣雪大成制药有限责任公司 | Method for preparing ferrous sulfate for Fenton oxidation by using oxytetracycline hydrochloride waste acid |
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