CN106882838A - Method for producing titanium dioxide by using waste acid self-circulation non-blast furnace titanium slag sulfuric acid method - Google Patents
Method for producing titanium dioxide by using waste acid self-circulation non-blast furnace titanium slag sulfuric acid method Download PDFInfo
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Abstract
The invention discloses a method for producing titanium white by a waste acid self-circulation non-blast furnace titanium slag sulfuric acid method, belonging to the technical field of titanium white production. The method takes vanadium-titanium magnetite non-blast furnace smelting titanium slag as a raw material, waste acid produced in the titanium dioxide production process is mixed with the non-blast furnace titanium slag to obtain pre-treated titanium slag containing low iron, aluminum and magnesium, the pre-treated titanium slag is subjected to acidolysis and curing by concentrated sulfuric acid, then the titanium dioxide is produced by the procedures of water immersion, concentration, hydrolysis, roasting and the like, and the waste acid after hydrolysis is returned for recycling. The process is mainly characterized in that titanium white waste acid is adopted to pretreat titanium slag, so that most of aluminum and magnesium impurities in the titanium slag are removed, the influence of the aluminum, magnesium and other impurities in the titanium slag on titanium white production is eliminated, the process purification flow of the ilmenite sulfuric acid process is simplified, and a foundation is laid for producing high-quality titanium white; meanwhile, the direct recycling of the titanium white hydrolysis waste acid is realized, and the environmental problem caused by high-concentration acidic wastewater in the titanium white industry is solved.
Description
Technical field
The invention belongs to titanium white production technical field, it is related to one kind to be followed certainly using non-blast furnace titaniferous slag production titanium white and titanium white waste acid
The method that ring is utilized, and in particular to the method for producing titanium white using titanium white waste acid and vanadium titano-magnetite or ferrotitanium concentrated ore direct reduction slag.
Background technology
China's titanium resource very abundant, reserves are occupied first of the world, wherein, the titanium resource reserves of Panxi Diqu account for the 90% of the whole nation with
On, mainly there are Panzhihua, Baima, Taihe county, the big mining area of red lattice four.But there is congenital deficiency in the type of China's titanium ore reserves,
Mostly altogether, associated minerals, do not have single ore deposit, and the vanadium titano-magnetite of Panxi Diqu is exactly world-renowned many metals (companion) rawore altogether.
Titanium in vanadium titano-magnetite only has 30-40% preservations in ilmenite, and remaining titanium preservation is difficult to sort in titanomagnetite,
Enter blast furnace process flow with titanomagnetite, form titanium-containing blast furnace slag, because the Ti content in titanium-containing blast furnace slag only has 15~25%,
And the acid consumpting substance content such as aluminum oxide, calcium oxide, magnesia is high, in addition to a part is for building materials, economically viable synthesis is there is no
Utilization plan.Titanium in current vanadium titano-magnetite is mainly by ore dressing recovery section concentrated ilmenite, is subsequently used for Producing Titanium Dioxide,
Because the titanium ratio existed in ilmenite form in vanadium titano-magnetite is less, and sorting is difficult, causes the existing titanium of vanadium titano-magnetite
Comprehensive recovery is less than 20%.
In order to improve the level of comprehensive utilization of vanadium titano-magnetite, China has carried out the tackling key problem of direct reduction of V-Ti magnetite smelting, has opened
Send out the coal-based direct reductions such as rotary hearth furnace, tunnel cave, rotary kiln, multitube shaft furnace, or the gas base directly reducing technology such as car-bottom furnace,
The material for being reduced directly discharge selects isolated reduced iron and new titanium slag through molten point of electric furnace or mill --- and non-blast furnace titaniferous slag, this is new
The titanium grade that titanium slag compares the titanium-contained slag of traditional blast furnace process output is significantly improved, titaniferous up to 50% or so so that for titanium slag is comprehensive
Close recovery Pd, improve the comprehensive utilization ratio of vanadium titano-magnetite there is provided possible.
Although direct reduction of V-Ti magnetite can obtain titaniferous non-blast furnace titaniferous slag higher, the chemical composition and main mine of the slag
Thing is constituted, and compared with the existing titaniferous materials such as ilmenite, traditional acid-dissolved titanium slag or electro-titanium slag, titanium-containing blast furnace slag, is had
Significant difference, its physicochemical property is also dramatically different.The Ti content of non-blast furnace titaniferous slag is near or above concentrated ilmenite grade, though remote height
In titanium-containing blast furnace slag, but far below traditional acid-dissolved titanium slag.Impurity content aspect, the iron content of non-blast furnace titaniferous slag is significantly
Less than ilmenite concentrate, the content close to acid-dissolved titanium slag, but vanadium, chromium, aluminium, magnesium is several times of concentrated ilmenite and acid-dissolved titanium slag
Even more than more than ten times.
Research, report for non-blast furnace titaniferous slag recycling is less.CN102627321B discloses a kind of using ferrotianium oxygen
The method that the titanium slag that compound direct-reduction is obtained prepares titanium dioxide, is first leached, the leached mud for obtaining with hydrochloric acid solution to titanium slag
The steps such as acidolysis, curing, leaching, hydrolysis production titanium white is carried out with sulfuric acid again, although in can removing titanium slag using salt Ore Leaching
Most of aluminium, magnesium addition, but hydrochloric acid leaching process titanium slag, the impurity such as substantial amounts of titanium and aluminium, magnesium will be caused together with dissolution and damage
Lose, additionally, hydrochloric acid medium is strong to the corrosivity of equipment, liquid needs to regenerate hydrochloric acid through processes such as spray roastings after salt Ore Leaching, into
This height.CN101898791B discloses a kind of method that utilization new technological process titanium slag prepares rutile titanium white powder, by vanadium titano-magnetite
The titanium-contained slag that direct-reduction is obtained is cured with concentrated sulfuric acid direct acidolysis, then through leaching, settling and be filtrated to get titanium liquid, then toward titanium
Aluminium removal is added to remove the operation production titanium white such as part aluminium, then oxidized, concentration, hydrolysis in liquid, due to the aluminium removal for using
It is potassium sulfate or ammonium sulfate, high cost, and substantial amounts of ammonia nitrogen waste water can be produced, pollute environment.
Research and industrial practice situation with reference to concentrated ilmenite and titania Slag, should be non-at this stage using Titanium White Production By Sulfuric Acid Process
The preferred scheme of blast furnace titaniferous slag recycling.But on the one hand in non-blast furnace titaniferous slag containing it is a large amount of easily with the impurity of sulfuric acid reaction (such as
MgO、Al2O3And CaO), if directly using concentrated sulfuric acid acidolysis, not only consume a large amount of concentrated sulfuric acids, and due to these impurity first with
There is intense reaction in sulfuric acid, release big calorimetric, cause " solidifying " in advance for reactant, hamper titanium oxide with sulfuric acid reaction
Main reaction is completed, and causes acidolysis rate low.Another aspect Titanium White Production By Sulfuric Acid Process technique produces substantial amounts of spent acid, often produces 1t titaniums
8~10t of spent acid is discharged in vain, the ferrous sulfate containing 15%~25% sulfuric acid and 10%~15% in spent acid, while also containing
Al2(SO4)3、MgSO4Deng inorganic salts and TiO2, the spent acid of current titanium white factory is except a part of concentrated to sulfuric acid concentration 60% or so
For outside, remaining major part to rely on neutralisation treatment with concentrated sulfuric acid complex acid, waste acid concentration high cost, neutralization are costly, largely
Gypsum tailings is neutralized to be difficult to dispose.In sum, although direct reduction of V-Ti magnetite can obtain titaniferous amount near or above ferrotianium
The non-blast furnace titaniferous slag of concentrate grade, but due to the impure height of titanium slag, particularly aluminium, magnesium, vanadium etc., influence Production By Sulfuric Acid Process process
Continuous and steady operation and titanium white quality, lack the economic treatment or recycle utilization of titanium white waste acid, while scandium, gallium, vanadium etc.
Association rare element fails preferable synthetical recovery.
The content of the invention
It is an object of the invention to provide a kind of method of the non-blast furnace titaniferous slag Production By Sulfuric Acid Process titanium white of spent acid self-loopa, for vanadium titanium magnetic
Titanium white waste acid is difficult to economic recovery profit during during iron ore exploitation is utilized, the titanium resource for existing is made a low multiple use, sulfate process titanium dioxide is industrial
With the synthetical recoveries such as, Producing Titanium Dioxide process vanadium gallium scandium it is difficult the problems such as, with the non-blast furnace titaniferous slag of vanadium titano-magnetite as raw material, using titanium
The spent acid of white production process is pre-processed to non-blast furnace titaniferous slag, obtains, containing the relatively low pretreatment titanium slag of aluminium, magnesium, pre-processing titanium slag
Cured with concentrated sulfuric acid acidolysis again, then produce titanium white through operations such as water logging, concentration, hydrolysis, roastings.Located in advance using titanium white waste acid
Reason, had both been stripped of most of aluminium, magnesium addition in titanium slag, the influence of the impurity to Producing Titanium Dioxide such as aluminium, magnesium, letter in elimination titanium slag
Ilmenite sulfuric acid process purification process is changed, for production high quality titanium white is laid a good foundation；Simultaneously using in spent acid titanium slag general
Vanadium, scandium, gallium etc. leach, obtain residual acid concentration it is relatively low containing vanadium, scandium, gallium leachate, be beneficial to synthetical recovery vanadium, scandium,
Gallium；Additionally, can realize that the direct circulation of titanium white waste acid is utilized, the environment that the high content acid wastewater of solution titanium dioxide industry brings is asked
Topic.
The purpose of the present invention is achieved through the following technical solutions.A kind of non-blast furnace titaniferous slag Production By Sulfuric Acid Process titanium of spent acid self-loopa
White method, with non-blast furnace titaniferous slag as raw material, it is characterised in that comprise the following steps：
(1) non-blast furnace titaniferous slag pretreatment：It is and a certain amount of after by ilmenite or the gained titanium slag fine grinding of vanadium titano-magnetite non-blast furnace process
Titanium dioxide hydrolysis spent acid mix pretreatment, then filter, obtain pre-process titanium slag and solution after pretreatment；
(2) pretreatment titanium slag acidolysis curing：The pretreatment titanium slag that step (1) is obtained, is added by sour ore deposit mass ratio 1.3~2
The concentrated sulfuric acid is well mixed, and after acidolysis, curing, obtains solid mixt；
(3) pulp is leached：The solid mixt that step (2) is obtained is carried out into pulp leaching with suitable quantity of water, then separation of solid and liquid
Obtain leached mud and titanium liquid；
(4) conventional sulfuric acid method production titanium white：Titanium liquid that step (3) is obtained is concentrated, hydrolysis, filtering, washing, calcining
Deng known sulfate process titanium dioxide production technology production titanium white, iron is removed without freezing and crystallizing, titanium hydrolysis raffinate is titanium dioxide hydrolysis spent acid,
Titanium dioxide hydrolysis spent acid return to step (1) is recycled；
(5) synthetical recovery aluminium, vanadium, scandium and gallium：The solution after pretreatment that step (1) is obtained be used for synthetical recovery aluminium therein,
Vanadium, scandium and gallium, the tail washings return to step (3) after synthetical recovery is used as pulp leaching water.
Further, described non-blast furnace titaniferous slag is, with vanadium titano-magnetite, concentrated ilmenite or the mixture of the two as raw material, to use
Reducing agent in the reduction furnace of non-blast furnace reduzate obtained by direct-reduction through titanium slag obtained from slag sluicing system, it is preferable that with vanadium
Titanomagnetite is raw material.Wherein described reducing agent is the mixture of one or more in coal, Jiao, coal gas, natural gas, described
Reduction furnace is one kind of rotary hearth furnace, continuous tunnel furnace, tube furnace, rotary kiln, shaft furnace, car-bottom furnace or microwave ore deposit stove.
Further, the slag sluicing system of described vanadium titano-magnetite or ferrotitanium concentrated ore direct reduction gained reduzate, being will be direct
Reduzate obtained by reduction isolates metallic iron and obtains non-blast furnace titaniferous slag using electric furnace high-temperature is molten, or by gained reduzate
Metallic iron is isolated through broken, ore dressing physical separation mode and obtain non-blast furnace titaniferous slag；Preferably, gained reduzate is used
Electric furnace high-temperature is molten to isolate metallic iron, and slag obtains non-blast furnace titaniferous slag through water quenching.
Further, titanium slag fine grinding in step (1), is the ratio that titanium slag is finely ground to 74 μm (200 mesh sieves) particle below
>=90%；Preferably, titanium slag is finely ground to ratio >=90% of 45 μm (325 mesh sieves) particle below.
In the present invention unless otherwise indicated beyond, ratio, concentration and percentage are on the basis of quality.
Further, pretreatment is stirred after titanium slag finely ground in step (1) mixes with a certain amount of titanium white waste acid, pretreatment
Solid-to-liquid ratio (mass volume ratio) is 1:10~1:2kg/L, it is preferable that solid-to-liquid ratio is 1:5~1:3kg/L；80 DEG C~160 DEG C of extraction temperature,
2~8h of extraction time；Described titanium white waste acid is the raffinate after titanium hydrolysis separate out titanium, and the h 2 so 4 concentration in spent acid is
15%~25%, it is preferable that hydrolysis separates out the raffinate after titanium through being concentrated by evaporation to h 2 so 4 concentration 25%~35% for leaching.
Further, in step (2), the pretreatment titanium slag that step (1) is filtrated to get is added by sour ore deposit mass ratio 1.3~2
Enter the concentrated sulfuric acid to be well mixed, the moisture content 0%~20% of the pretreatment titanium slag, concentrated sulfuric acid mass concentration >=92%；If pre-processing titanium
Slag moisture content>20%, then need to be used after drying；Preferably, the moisture content 0%~5% of titanium slag is pre-processed, the quality of the concentrated sulfuric acid is dense
Degree >=98%, initial h 2 so 4 concentration >=80% in pretreatment titanium slag and concentrated sulfuric acid compound.
Further, described in step (2) acidolysis, curing, acidolysis temperature are 130 DEG C~200 DEG C, and curing temperature is 170 DEG C
~250 DEG C, the curing time is 1h~4h.
Further, synthetical recovery aluminium, vanadium, scandium and gallium in the solution after pretreatment described in step (5), are handed over using extraction or ion
Change absorption method and reclaim scandium, gallium, vanadium, aluminium is reclaimed using ammonia-alum or potassium alum method；Preferably, using di-(2-ethylhexyl)phosphoric acid
(trade name DEPHA or P 204) extracting scandium, is then reclaimed aluminium in ammonia-alum form with ammoniacal liquor or ammonium sulfate precipitation, adjustment
Solution ph reclaims vanadium to 0.5-2 with D301 resin adsorptions, then with the extraction and recovery galliums of P 204.
Further, the tail washings after step (5) synthetical recovery is soaked with return to step (3) after lime neutralization precipitation magnesium as pulp
Go out to use water.
Further, TiO in described non-blast furnace titaniferous slag2Weight/mass percentage composition 40~60%, CaO, MgO, Al2O3Quality
Percentage composition is respectively 3~10%, 5~15%, 5~15%.
The method of the non-blast furnace titaniferous slag Production By Sulfuric Acid Process titanium white of a kind of spent acid self-loopa provided by the present invention, by titanium slag and titanium white
Spent acid mixing pretreatment, can be by titanium slag 50~80% Al2O3Dissolving is removed, while the remaining sulfuric acid concentration in spent acid is reduced
To 30~100g/L.
The method of the non-blast furnace titaniferous slag Production By Sulfuric Acid Process titanium white of a kind of spent acid self-loopa provided by the present invention, using Producing Titanium Dioxide mistake
The spent acid that journey is produced mixes pretreatment with non-blast furnace titaniferous slag, and the most of aluminium and magnesium in titanium slag are leached into solution, reduces titanium slag
Middle aluminium, content of magnesium, had both solved the problem that recycles of titanium white waste acid, also solved because using non-blast furnace titaniferous slag Production By Sulfuric Acid Process titanium
The influence Producing Titanium Dioxide such as acidolysis material " solidifies " in advance when white, magnalium is separated out in advance, acidolysis fluid viscosity is big in titanium liquid and quality are asked
Topic.
A kind of advantage of the method for the non-blast furnace titaniferous slag Production By Sulfuric Acid Process titanium white of spent acid self-loopa provided by the present invention is：
(1) titanium white waste acid is mixed into pretreatment with non-blast furnace titaniferous slag, has both solved the treatment of titanium white waste acid and recycled problem,
Eliminate non-blast furnace titaniferous slag again influences titanium white continuously to produce because aluminum and magnesium content is high, while the remaining titanium in recyclable spent acid, improves
The rate of recovery of titanium；
(2) pre-processed by titanium slag, eliminate influence of the harmful elements such as vanadium to titanium white product quality, be production high-quality titanium
Lay a good foundation in vain；
(3) titanium white waste acid is realized with titanium, scandium, vanadium, gallium, the synthetical recovery of aluminium in titanium slag.
Brief description of the drawings
Fig. 1 is a kind of principle process of the method for the non-blast furnace titaniferous slag Production By Sulfuric Acid Process titanium white of spent acid self-loopa provided by the present invention
Figure.
Specific embodiment
The present invention is made below in conjunction with accompanying drawing being further illustrated.
By vanadium titano-magnetite non-blast furnace process gained titanium slag it is finely ground after, at 80 DEG C after mixing with a certain amount of titanium dioxide hydrolysis spent acid
Pretreatment is stirred at a temperature of~160 DEG C, is then filtered, obtain pre-processing titanium slag and solution after pretreatment, Al in titanium slag2O3It is molten
Solution rate is 50~80%, 30~100g/L of remaining sulfuric acid concentration in solution after pretreatment；By the pretreatment titanium slag of gained, by sour mineral amount
Add the industrial sulphuric acid of concentration more than 92% to be well mixed than 1.3~2, after acidolysis, curing, obtain solid mixt, then
Leached with aquation, be filtrated to get titanium liquid, titanium liquid is concentrated, hydrolyzes, filter, washing, calcine production titanium white, and titanium hydrolysis are residual
Liquid is titanium white waste acid, and titanium white waste acid returns to pretreatment process；Solution after pretreatment is used for synthetical recovery aluminium, vanadium, scandium and gallium.
The method of the present invention is further described with nonlimiting examples below, with help to understand present disclosure and
Its advantage, and not as limiting the scope of the present invention, protection scope of the present invention is determined by claims.
Titanium slag composition in embodiment：
| Composition | Fe | CaO | MgO | ||
| Content % | 50.08 | 2.34 | 5.33 | 10.06 | 12.15 |
Embodiment 1
The titanium slag of accounting 90% below 74 μm of grain diameter is ground into drying first, by solid-to-liquid ratio 1:5kg/L, titanium white waste acid concentration
25%, pretreatment 5h is stirred at 90 DEG C.The pretreatment slag that ore pulp press filtration after leaching is obtained adds the acidolysis for filling the concentrated sulfuric acid
Acidolysis reaction is carried out in groove, slag moisture content 15% is pre-processed, the sour ore deposit ratio of acidolysis process is 1.8, and sulfuric acid concentration is 98%, acid
Solution temperature is 180 DEG C.Cured after acidolysis reaction terminates slurry curing, curing temperature is 200 DEG C, curing soaking time is
2h.Be proportionally added into for water after terminating being leached in the acidolysis groove after curing by curing, is finally filtrated to get titanium liquid.After titanium liquid is concentrated
It is hydrolyzed, the filter cake for obtaining obtains titanium white product after bleaching, salt treatment, calcining, post processing, can reach YST299-2010
Synthetic rutile trade mark standard.
Embodiment 2
The titanium slag of accounting 90% below 45 μm of grain diameter is ground into drying first, by solid-to-liquid ratio 1:5kg/L, titanium white waste acid concentration
20%, pretreatment 6h is stirred at 95 DEG C.The pretreatment slag that will be obtained after ore pulp press filtration after leaching adds the acid for filling the concentrated sulfuric acid
Acidolysis reaction is carried out in solution groove, slag moisture content 10% is pre-processed, the sour ore deposit ratio of acidolysis process is 1.7, and sulfuric acid concentration is 98%,
Acidolysis temperature is 190 DEG C.Cured after acidolysis reaction terminates slurry curing, curing temperature is 220 DEG C, cures soaking time
It is 3h.Be proportionally added into for water after terminating being leached in the acidolysis groove after curing by curing, is finally filtrated to get titanium liquid.Titanium liquid is concentrated
After be hydrolyzed, the filter cake for obtaining obtains titanium white product after bleaching, salt treatment, calcining, post processing, can reach YST299-2010
Synthetic rutile trade mark standard.
Embodiment 3
The titanium slag of accounting 90% below 45 μm of grain diameter is ground into drying first, by solid-to-liquid ratio 1:5kg/L, titanium white waste acid concentration
16%, pretreatment 8h is stirred at 85 DEG C.The pretreatment slag that will be obtained after ore pulp press filtration after leaching adds the acid for filling the concentrated sulfuric acid
Acidolysis reaction is carried out in solution groove, slag moisture content 18% is pre-processed, the sour ore deposit ratio of acidolysis process is 1.9, and sulfuric acid concentration is 98%,
Acidolysis temperature is 200 DEG C.Cured after acidolysis reaction terminates slurry curing, curing temperature is 200 DEG C, cures soaking time
It is 3h.Be proportionally added into for water after terminating being leached in the acidolysis groove after curing by curing, is finally filtrated to get titanium liquid.Titanium liquid is concentrated
After be hydrolyzed, the filter cake for obtaining obtains titanium white product after bleaching, salt treatment, calcining, post processing, can reach YST299-2010
Synthetic rutile trade mark standard.
Embodiment 4
The titanium slag of accounting 90% below 45 μm of grain diameter is ground into drying first, by solid-to-liquid ratio 1:3kg/L, titanium white waste acid is concentrated into
Concentration 35%, stirs pretreatment 3h at 100 DEG C.The pretreatment slag that will be obtained after ore pulp press filtration after leaching is added and fills dense sulphur
Acidolysis reaction is carried out in the acidolysis groove of acid, slag moisture content 18% is pre-processed, the sour ore deposit ratio of acidolysis process is 1.9, and sulfuric acid concentration is
98%, acidolysis temperature is 200 DEG C.Cured after acidolysis reaction terminates slurry curing, curing temperature is 200 DEG C, and curing is protected
The warm time is 3h.Be proportionally added into for water after terminating being leached in the acidolysis groove after curing by curing, is finally filtrated to get titanium liquid.Titanium liquid
It is hydrolyzed after concentrated, the filter cake for obtaining obtains titanium white product after bleaching, salt treatment, calcining, post processing, can reach
YST299-2010 synthetic rutile trade mark standards.
Claims (10)
1. the method for the non-blast furnace titaniferous slag Production By Sulfuric Acid Process titanium white of a kind of spent acid self-loopa, with non-blast furnace titaniferous slag as raw material, it is characterised in that including with
Lower step：
(1) non-blast furnace titaniferous slag pretreatment：After by ilmenite or the non-blast furnace process gained titanium slag fine grinding of vanadium titano-magnetite, with a certain amount of titanium dioxide hydrolysis
Spent acid mixes pretreatment, then filters, and obtains pre-processing titanium slag and solution after pretreatment；
(2) pretreatment titanium slag acidolysis curing：The pretreatment titanium slag that step (1) is obtained, adds concentrated sulfuric acid mixing equal by sour ore deposit mass ratio 1.3~2
It is even, after acidolysis, curing, obtain solid mixt；
(3) pulp is leached：The solid mixt that step (2) is obtained is carried out into pulp leaching with suitable quantity of water, then separation of solid and liquid obtain leached mud and
Titanium liquid；
(4) conventional sulfuric acid method production titanium white：The known sulfuric acid such as titanium liquid that step (3) is obtained is concentrated, hydrolysis, filtering, washing, calcining
Method Producing Titanium Dioxide technique productions titanium white, iron is removed without freezing and crystallizing, and titanium hydrolysis raffinate is titanium dioxide hydrolysis spent acid, by titanium dioxide hydrolysis spent acid return to step
(1) recycle；
(5) synthetical recovery aluminium, vanadium, scandium and gallium：The solution after pretreatment that step (1) is obtained is used for synthetical recovery aluminium therein, vanadium, scandium and gallium,
Tail washings return to step (3) after synthetical recovery is used as pulp leaching water.
2. method according to claim 1, it is characterised in that described non-blast furnace titaniferous slag be with vanadium titano-magnetite, concentrated ilmenite or the two
Mixture is raw material, using reducing agent in the reduction furnace of non-blast furnace reduzate obtained by direct-reduction through titanium slag obtained from slag sluicing system；Wherein institute
It is the mixture of one or more in coal, Jiao, coal gas, natural gas to state reducing agent, and the reduction furnace is rotary hearth furnace, continuous tunnel furnace, tube furnace, returns
One kind of rotary kiln, shaft furnace, car-bottom furnace or microwave ore deposit stove.
3. method according to claim 2, it is characterised in that described vanadium titano-magnetite or ferrotitanium concentrated ore direct reduction gained reduzate
Slag sluicing system, is to melt the reduzate obtained by direct-reduction using electric furnace high-temperature to isolate metallic iron and obtain non-blast furnace titaniferous slag；Or by gained also
Thing is originated in isolate metallic iron and obtain non-blast furnace titaniferous slag through broken, ore dressing physical separation mode；It is preferred that described vanadium titano-magnetite or concentrated ilmenite are straight
Connect reduction gained reduzate and isolate metallic iron using electric furnace high-temperature is molten, slag obtains non-blast furnace titaniferous slag through water quenching.
4. method according to claim 1, it is characterised in that titanium slag fine grinding described in step (1), be by titanium slag be finely ground to 74 μm with
Under particle ratio >=90%, titanium slag is preferably finely ground to ratio >=90% of less than 45 μm of particle.
5. method according to claim 1, it is characterised in that after finely ground titanium slag mixes with a certain amount of titanium white waste acid in step (1)
Stirring pretreatment, the solid-to-liquid ratio of pretreatment is 1:10~1:2kg/L, solid-to-liquid ratio preferably 1:5~1:3kg/L, 80 DEG C~160 DEG C of extraction temperature, during leaching
Between 2~8h；H 2 so 4 concentration in described titanium white waste acid is 15%~25%, preferably by titanium white waste acid through being concentrated by evaporation to h 2 so 4 concentration
Pretreatment is used further to after 25%~35%.
6. method according to claim 1, it is characterised in that in step (2), the pretreatment titanium slag that step (1) is filtrated to get is pressed
Sour ore deposit mass ratio 1.3~2 adds the concentrated sulfuric acid to be well mixed, the moisture content 0%~20% of the pretreatment titanium slag, preferably 0%~5%；Concentrated sulfuric acid quality is dense
Degree >=92%, preferred mass concentration >=98%；Initial h 2 so 4 concentration >=80% in pretreatment titanium slag and concentrated sulfuric acid compound.
7. method according to claim 1, it is characterised in that acidolysis, curing described in step (2), acidolysis temperature is 130 DEG C~200 DEG C,
Curing temperature is 170 DEG C~250 DEG C, and the curing time is 1h~4h.
8. method according to claim 1, it is characterised in that solution after pretreatment synthetical recovery aluminium, vanadium, scandium and gallium described in step (5),
Scandium, gallium, vanadium are reclaimed using extraction or ion exchange adsorption, aluminium is reclaimed using ammonia-alum or potassium alum method；It is preferred that using two (2- ethylhexyls) phosphorus
Sour (trade name DEPHA or P 204) extracting scandium, is then reclaimed aluminium in ammonia-alum form with ammoniacal liquor or ammonium sulfate precipitation, adjusts solution ph
To 0.5~2, vanadium is reclaimed with D301 resin adsorptions, then with the extraction and recovery galliums of P 204.
9. method according to claim 1, it is characterised in that the tail washings after step (5) synthetical recovery is returned with after lime neutralization precipitation magnesium
Step (3) is used as pulp leaching water.
10. method according to claim 1, it is characterised in that TiO in non-blast furnace titaniferous slag2Weight/mass percentage composition be 40~60%, CaO,
MgO、Al2O3Weight/mass percentage composition be respectively 3~10%, 5~15%, 5~15%.
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| CN111646502A (en) * | 2020-06-10 | 2020-09-11 | 攀钢集团研究院有限公司 | Slag ore mixing continuous acidolysis leaching method and equipment |
| CN112320842A (en) * | 2020-11-13 | 2021-02-05 | 昆明理工大学 | Method for acidolysis of titanium slag |
| CN113430391A (en) * | 2021-07-16 | 2021-09-24 | 沈阳有色金属研究院有限公司 | Method for treating titanium dioxide acidolysis residue by low-temperature roasting-water leaching |
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| CN101638719A (en) * | 2009-09-08 | 2010-02-03 | 北京矿冶研究总院 | Method for producing synthetic rutile by wet process |
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| CN111646502A (en) * | 2020-06-10 | 2020-09-11 | 攀钢集团研究院有限公司 | Slag ore mixing continuous acidolysis leaching method and equipment |
| CN112320842A (en) * | 2020-11-13 | 2021-02-05 | 昆明理工大学 | Method for acidolysis of titanium slag |
| CN113430391A (en) * | 2021-07-16 | 2021-09-24 | 沈阳有色金属研究院有限公司 | Method for treating titanium dioxide acidolysis residue by low-temperature roasting-water leaching |
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| CN106882838B (en) | 2018-12-14 |
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