CN104140082B - A kind of recoverying and utilizing method of titanium white waste acid - Google Patents
A kind of recoverying and utilizing method of titanium white waste acid Download PDFInfo
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Abstract
The invention provides the recovery method of a kind of titanium white waste acid.Using twice complex acid mode, a complex acid, controlling the mass percent of sulfuric acid in nitration mixture is 45% 50%, then lowers the temperature, crystallization, curing, and separation of solid and liquid obtains a complex acid filtrate and condensed slag；Secondary complex acid: controlling the mass percent of sulfuric acid in nitration mixture is 60% 65%, then lowers the temperature, crystallization, curing, sedimentation separation obtains gelled acid clear liquid and thick oar, and thick slurry is back to a complex acid workshop section.The method is used to obtain the gelled acid of relatively low impurity content and the condensed slag of low acid content.Complex acid mode sulfuric acid yield reaches 99.5%, it is to avoid a difficult problem for condensed slag quality extreme difference in conventional method.Technological process is simple, and production cost and operating cost are extremely low, improve the yield of spent acid, improve the quality of condensed slag greatly, promote recycling of condensed slag.
Description
Technical field
The present invention relates to the recovery method of a kind of titanium white waste acid, be exactly the recovery side of a kind of titanium dioxide waste acid by sulfuric acid process
Method.
Background technology
Titanium dioxide is a kind of important Inorganic Chemicals, nontoxic, be harmless to the health, and is most important Chinese white,
Account for the 80% of whole Chinese white usage amount.Titanium dioxide is considered as a kind of Chinese white that performance is best in the world at present, extensively
It is applied to the industry such as coating, plastics, papermaking, is to be only second to synthesize ammonia and the third-largest inorganic chemical product of phosphoric acid.
Iron white powder industrial process mainly has chloridising and sulfuric acid process.Sulfuric acid process is ripe, adaptation to titanium material
Property is strong, production cost is low, technology maturation, and it both can produce anatase titanium dioxide product, can produce again rutile-type product, is existing titanium white
A kind of method commonly used in the powder mode of production.But sulfuric acid process often produces 1t titanium dioxide, need to consume more than 4t's
Sulfuric acid, produces the spent acid that 6 ~ 8t concentration is 20% ~ 25% simultaneously.Except containing main component H in spent acid2SO4Outward, possibly together with necessarily
FeSO4、TiO2、 A12(SO4)3、MgSO4Deng material.If the most treated direct discharge of these spent acid, not only pollute environment, also
Cause the serious waste of resource.How to process these spent acid, reclaim the most valuable part economically, it has also become sulfuric acid
One important technology difficult problem of method Producing Titanium Dioxide, is also the significant problem of puzzlement environmental protection and titanium dioxide industry development.At present
The relatively method of environmental protection, is to be concentrated by titanium white waste acid, makes the impurity such as ferrous sulfate, crystallization from spent acid, thus significantly drops
Impurity content in low spent acid, it is achieved recycling or producing the products such as phosphate in titanium white device.
The concentration method of titanium white waste acid is more, such as combustion gas concentration method, calcination method, vacuum concentrate methool, neutralisation, film mistake
Filter method etc..Concentration method is to be concentrated by spent acid, improves the concentration of spent acid, reaches the purpose that can recycle.Current spent acid
Concentration technique majority is to utilize a kind of direct concentration method of thermal source, and thermal source includes natural gas, steam or coal-fired hot gas etc..
CN1330562C by flue gas and steam secondary concentration mode to waste acid concentration to sulfuric acid 55-60%.CN102079512B uses one
Level flash distillation two or three grades is concentrated in vacuo mode, is concentrated into sulfuric acid 82%." separation of ferrous sulfate and waste acidity recovery in titanium white waste acid " is adopted
Use normal pressure concentration technology, waste acid concentration to 55-60%, after separating ferrous sulfate, it is concentrated in vacuo to 80-85%, filter residue uses clear water
Sulfuric acid is reclaimed in making beating, and the filtrate after making beating returns concentration section.Use above method can effective waste acid recovery, there is technological process
Long, equipment requirement high, concentrator costliness, energy consumption, a difficult problem that operation and maintenance cost is high, can not avoid waste acid concentration process
The scale formation of ferrous sulfate.Its concentrated cost is far above the price of the industry concentrated sulfuric acid.
Use complex acid technique to titanium white waste acid concentrate, in titanium white waste acid, i.e. add the sulfuric acid of high concentration, by improving sulphur
Acid concentration promotes the sulphate crystal in spent acid to separate out, and purifies the spent acid after concentrate and uses for titanium dioxide acidolysis or phosphorus ore extraction etc.
Sulfuric acid apparatus.CN102515114A directly improves the sulfuric acid concentration to 64% by complex acid, and the sulfuric acid after being purified is used further to
Phosphorous chemical industry.CN101973530A uses complex acid mode to directly obtain the sulfuric acid of 58-69%.CN101774557A, uses twice complex acid
Mode, complex acid concentration 80-90%, secondary complex acid concentration 65-70%.Complex acid technique reclaims titanium white waste acid, technological process is simple,
Investment and producing cost are extremely low, are the most suitable a kind of waste acidity recovery modes, but use above complex acid method gained condensed slag
Free sulfuric acid content higher.
Titanium white waste acid concentrates, and improves with sulfuric acid concentration, separates out the solid formation based on ferrous sulfate, is commonly called as concentrating
Slag.The free sulfuric acid content of condensed slag is higher, and its processing mode is generally used for sulfate system, mixes and fires standby sulfuric acid.Condensed slag
Free sulfuric acid content height can cause condensed slag adhere to agglomerating, mix burning mixing uneven, affect the stability contorting of acid-making process.Dense
The free acid content of contracting slag is high, deposits the period meeting moisture absorption, produces sour water in bottom, also can have a strong impact on and mix burning process and produce ring
Border.In addition condensed slag free acid content height, mixes burning procedure decomposition caloric receptivity big, causes mixing burning temperature decline and boiling bed is stably subject to
To extreme influence, thus cause the burning amount of mixing of condensed slag by bigger restriction.CN102372306A, condensed slag uses iron powder reducing
Preparing ferrous sulfate heptahydrate after reducing sulfuric acid, ferrous sulfate heptahydrate is then converted into ferrous sulfate monohydrate and fires acid for mixing.Though solving
Determine the impact on mixing burning of the free acid of condensed slag, but the difficult problem that it exists technological process length, production cost raises.
In sum, titanium white waste acid concentration is high, and the impurity content in acid is the lowest, it is simple to produce reuse or for phosphorous chemical industry etc.
Industry, but the sulfuric acid concentration of titanium white waste acid is high, and the free acid content of the condensed slag of generation is the highest, has a strong impact on the place of condensed slag
Reason.Under existing technique, titanium white waste acid reclaims and the quality of condensed slag becomes the difficult problem being difficult to coordinate.Low cost low energy consumption
Reclaim titanium white waste acid and condensed slag, become the difficult problem that sulfuric acid method titanium pigment enterprise faces, be also that the industry wishes to solve but always
Unsolved technical barrier.
Summary of the invention
For solving above-mentioned technical problem, it is provided that a kind of low cost reclaims the method for titanium white waste acid, it is possible to well by titanium white
Retrieval of sulfuric acid in spent acid, the free sulfuric acid of the impurity content in gelled acid and condensed slag is extremely low simultaneously.
The present invention is achieved by the following technical solutions:
The recovery method of a kind of titanium white waste acid, comprises the following steps:
A, spent acid pre-concentration and titanium reclaim: titanium white waste acid utilizes rotary kiln waste heat from tail gas pre-concentration to 25%-32%, then enters
Row recovery Pd operates, and obtains titanium white waste acid clear liquid；
B, a complex acid: titanium white waste acid clear liquid step A obtained, add concentrated sulfuric acid mixing, controls sulfuric acid in nitration mixture
Mass percent is 45%-50%, then lowers the temperature, crystallization, curing, and separation of solid and liquid obtains a complex acid filtrate and condensed slag；
C, secondary complex acid: complex acid filtrate step B obtained, add concentrated sulfuric acid mixing, controls sulfuric acid in nitration mixture
Mass percent is 60%-65%, then lowers the temperature, crystallization, curing, and sedimentation separation obtains gelled acid clear liquid and thick oar, and thick slurry returns
To a complex acid workshop section.
Condensed slag can be mixed directly into sulfuric acid apparatus because sulfuric acid content is low and fires acid or prepare bodied ferric sulfate, and clear liquid is impurity
The spent acid that content is low can return directly to the workshop sections such as titanium dioxide acidolysis workshop section or phosphorus ore extraction.
The salts such as inventor is found by long-term experimental study, ferrous sulfate solubility in sulfuric acid solution and sulfuric acid
There is the relation of a kind of correspondence between concentration, along with the raising of sulfuric acid concentration, its solubility is gradually lowered, but sulfuric acid concentration is unsuitable
The highest, this is because sulfuric acid concentration is high, viscosity strengthens, and is unfavorable for separation of solid and liquid, and the condensed slag free sulfuric acid content of generation is higher,
Therefore the sulfuric acid concentration in general control titanium white waste acid is between 50 ~ 55%, with this understanding, the clearance of ferrous salt reach 80% with
On, ferrous content is down to 0.4 ~ 0.6%.The free sulfuric acid content of condensed slag raises with the rising of sulfuric acid concentration in spent acid.Concentrate
The free sulfuric acid content of slag raises, and will have a strong impact on subsequent processes and the yield of concentration process sulfuric acid of condensed slag.
When sulfuric acid concentration is higher, because containing a certain amount of titanyl sulfate in titanium white waste acid, it can cause sulfate at 50-80
DEG C time, exist and break out nucleation, sulfuric acid concentration is the highest, breaks out nucleation the most serious, and the crystallization causing condensed slag is tiny,
Free sulfuric acid content is higher, therefore need to control the suitable sulfuric acid concentration free sulfuric acid content with reduction condensed slag, so general bar
Under part, during waste acid concentration, sulfuric acid concentration is 50-55%.
Inventor is by under different titanium white waste acid concentration, and the morphological research of crystallization sulfate and analysis data obtain
Knowing, there is notable difference because of the difference of technological parameter in the crystallization of sulfate.Generate from nucleus and the control of crystal growing process
For, titanium white waste acid uses complex acid mode to be substantially better than direct condensing mode.Under suitable complex acid concentration, use complex acid mode
Reclaiming titanium white waste acid, early stage temperature is higher, separates out without sulfate, and in cooling procedure, the sulfate in titanium white waste acid reduces with temperature
Gradually separating out, raise with sulfuric acid concentration, the free sulfuric acid content of condensed slag raises.Titanium white waste acid directly concentrates the condensed slag of generation
For the aggregation of tiny vitriol, in cellular, surface pore is the most, and free sulfuric acid content is high.Titanium white waste acid is direct
Using complex acid mode (complex acid) to produce condensed slag is column or the aggregation of granular vitriol, and surface pore is more,
Free sulfuric acid content is higher, along with the raising of complex acid concentration, the column of formation or the aggregate particle size of granular vitriol become
Little, specific surface area becomes big, and the sulfuric acid amount of absorption increases, and causes the free sulfuric acid content of condensed slag to raise, and filters and separates difficulty.Adopt
The condensed slag produced with the secondary complex acid of the present invention is column or drop sulfur hydrochlorate crystalline aggregate, and surface pore is less, compares table
Area diminishes relatively, and the sulfuric acid amount of absorption is less, thus the free sulfuric acid content of condensed slag is relatively low.Using secondary complex acid, acid is dense
When degree is less than 45%, the concentration quantity of slag of generation is less, and the iron content in spent acid is higher, and the quantity of slag causing secondary complex acid to be formed is more,
Thick slurry amount to a complex acid increases, i.e. system internal circulating load increases, and has a strong impact on production efficiency.Use secondary complex acid side further
Formula, the concentration of raising complex acid, to 65-70%, adds sulfuric acid, i.e. has turbid phenomenon to occur, the crystal aggregates of the condensed slag of formation
Diminishing, filtration difficulty, free sulfuric acid content raises.The spent acid of the 65-70% arrived is improved concentration to 85-90%, formation white
The sulfuric acid solution of muddy shape, cannot settle at all, and long-term system circulates, and is easily caused line clogging.
Preferably, step C adds system content 5-10ppm flocculant.It is heavy that suitable flocculant there was added beneficially auxiliary
Fall separates, and reduces the sulfuric acid content in condensed slag.
Preferably, the cooldown rate in step B, C is 5-10 DEG C/h, and the curing time is 1-3h.Because ferrous sulfate is at knot
Brilliant process experience crystal seed is formed, crystal growth processes, and temperature and time is critically important to the growth of crystal, and applicant is by a large amount of
Experiment finds, when falling temperature gradient is at 5-10 DEG C/h, during the time 1-3h of curing, the crystallization effect of ferrous sulfate is preferable, it is easier to
Forming column crystallization or granular crystal condensate, in ferrous sulfate, sulfuric acid content is lower.
Preferably, the cooling final temperature in step B, C is 60-65 DEG C.By considering crystallization effect, the effect of filtration obtains
To filtration temperature.
Beneficial effects of the present invention: avoid titanium white waste acid concentrate during, sulfate mass crystallization separate out cause
Equipment and the fouling of pipeline and blockage problem, extend service life and the maintenance cycle of equipment, there is acid recovering rate high, dense
Contracting slag free sulfuric acid content is extremely low, processes the simple advantage of technique.The present invention, by secondary complex acid mode, has obtained low impurity
The gelled acid of content and the condensed slag of low free acid content, be the most excellent a kind of titanium white waste acid processing mode, which obviate equipment
Fouling, technique is simple, and production cost is extremely low, improves utilization rate and the yield of spent acid, improves the quality of condensed slag greatly,
Promote recycling of condensed slag.
Accompanying drawing explanation
Fig. 1 be in gelled acid iron content with acid concentration change curve.
Fig. 2 be in condensed slag acid content with acid concentration change curve.
Fig. 3 is present invention process process blocks schematic diagram.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.Following example are only used for this is clearly described
The technical scheme of invention, and can not limit the scope of the invention with this.
Embodiment 1
By the spent acid in production process of titanium pigment, its main component, it is calculated as in mass ratio: H2SO420.51%, FeSO4
9.13%, Al2(SO4)3 0.66% MgSO42.16%, TiO20.36%, calcine tail gas through countercurrent spray rotary kiln, utilize calcining
The waste heat concentrate of tail gas is to H2SO425%, then reclaimed after metatitanic acid by flocculating setting, obtain limpid spent acid；Spent acid is joined
In complex acid groove, being slow added into the concentrated sulfuric acid that sulfuric acid mass fraction is 98%, it is dense that the spent acid of every 5t 28% adds 1.33t
Sulfuric acid, the two mixes, and obtains nitration mixture.Then carrying out Slow cooling cooling, curing, the speed of cooling is 8 DEG C/h, terminal
Temperature 60 C, is cooled to outlet temperature post curing 1h, and whole nitration mixture are squeezed into filter press and carried out separation of solid and liquid, and isolated is once joined
Acidleach liquid, its sulfuric acid mass fraction is 48.14%, and iron content mass fraction is 1.04%, free sulfuric acid matter in the condensed slag obtained
Amount mark is 8.43%, and condensed slag is mixed for sand acid and fired standby sulfuric acid or bodied ferric sulfate production.One time complex acid filtrate the most quickly adds
Entering the concentrated sulfuric acid that sulfuric acid mass fraction is 98%, a complex acid filtrate of every 5t 48% adds the 1.5t concentrated sulfuric acid, lowers the temperature and cures
Condition is with a complex acid, and curing terminates, and adding system content is the flocculant of 5ppm, after sedimentation separation 30min, i.e. obtains secondary
Complex acid clear liquid, its sulfuric acid mass fraction is 61.09%, and iron content mass fraction is 0.19%, and this acid is for titanium dioxide acidolysis or phosphorus
The acid workshop section such as chemical industry extraction.Thick slurry is back to a complex acid workshop section and continues complex acid.The rate of recovery of complex acid process sulfuric acid reaches
97.30%。
Embodiment 2
By the spent acid in production process of titanium pigment, its main component, it is calculated as in mass ratio: H2SO420.51%, FeSO4
9.13%, Al2(SO4)3 0.66% MgSO42.16%, TiO20.36%, calcine tail gas through countercurrent spray rotary kiln, utilize calcining
The waste heat concentrate of tail gas is to H2SO428%, then reclaimed after metatitanic acid by flocculating setting, obtain limpid spent acid；Spent acid is joined
In a complex acid groove, being slow added into the concentrated sulfuric acid that sulfuric acid mass fraction is 98%, the spent acid of every 5t 28% adds 1.53t
The concentrated sulfuric acid, the two mixes, and obtains nitration mixture.Then carrying out Slow cooling cooling, curing, the speed of cooling is 8 DEG C/h, eventually
Point temperature 60 C, is cooled to outlet temperature post curing 2h, and whole nitration mixture are squeezed into filter press and carried out separation of solid and liquid, and isolated is once
Complex acid filtrate.Its sulfuric acid mass fraction is 50.00%, and iron content mass fraction is 0.85%, free sulfuric acid in the condensed slag obtained
Mass fraction is 8.64%, and condensed slag is mixed for sand acid and fired standby sulfuric acid or bodied ferric sulfate production.One time complex acid filtrate is the quickest
Adding sulfuric acid mass fraction is the concentrated sulfuric acid of 98%, and a complex acid filtrate of every 5t 50% adds the 1.73t concentrated sulfuric acid, and cooling is with ripe
Change condition is with a complex acid, and curing terminates, and adding system content is 5ppm flocculant, after sedimentation separation 30min, i.e. obtains secondary
Complex acid clear liquid, its sulfuric acid mass fraction is 63.74%, and iron content mass fraction is 0.15%, and this acid is for titanium dioxide acidolysis or phosphorus
The acid workshop section such as chemical industry extraction.Thick slurry is back to a complex acid workshop section and continues complex acid.The rate of recovery of complex acid process sulfuric acid reaches
97.36%。
Embodiment 3
By the spent acid in production process of titanium pigment, its main component, it is calculated as in mass ratio: H2SO4 20.51%, FeSO4
9.13%, Al2(SO4)3 0.66% MgSO42.16%, TiO20.36%, calcine tail gas through countercurrent spray rotary kiln, utilize calcining
The waste heat concentrate of tail gas is to H2SO432%, then reclaimed after metatitanic acid by flocculating setting, obtain limpid spent acid；Spent acid is joined
In a complex acid groove, being slow added into the concentrated sulfuric acid that sulfuric acid mass fraction is 98%, the spent acid of every 5t 28% adds 1.33t
The concentrated sulfuric acid, the two mixes, and obtains nitration mixture.Then carrying out Slow cooling cooling, curing, the speed of cooling is 8 DEG C/h, eventually
Point temperature 60 C, is cooled to outlet temperature post curing 3h, and whole nitration mixture are squeezed into filter press and carried out separation of solid and liquid, and isolated is once
Complex acid filtrate.Its sulfuric acid mass fraction is 48.14%, and one time complex acid filtrate iron content mass fraction is 1.04%, the concentration obtained
In slag, free sulfuric acid mass fraction is 8.43%, and condensed slag is mixed for sand acid and fired standby sulfuric acid or bodied ferric sulfate production.Once join
Acidleach liquid rapidly joins the concentrated sulfuric acid that sulfuric acid mass fraction is 98% again, and a complex acid filtrate of every 5t 48.14% adds 2.17t
The concentrated sulfuric acid, cooling and cooking conditions are with a complex acid, and curing terminates, and adding system content is the flocculant of 10ppm, sedimentation separation
After 30min, i.e. obtaining secondary complex acid clear liquid, its sulfuric acid mass fraction is 65.00%, and iron content mass fraction is 0.14%, this acid
For the acid workshop section such as titanium dioxide acidolysis or phosphorous chemical industry extraction.Thick slurry is back to a complex acid workshop section and continues complex acid.Complex acid process
The rate of recovery of sulfuric acid reaches 97.30%.
Comparative example 1
By the spent acid in production process of titanium pigment, its main component, it is calculated as in mass ratio: H2SO420.51%, FeSO4
9.13%, Al2(SO4)3 0.66% MgSO42.16%, TiO20.36%, calcine tail gas through countercurrent spray rotary kiln, utilize calcining
The waste heat concentrate of tail gas is to H2SO428%, then reclaimed after metatitanic acid by flocculating setting, obtain limpid spent acid；Spent acid is joined
In a complex acid groove, being slowly added to the concentrated sulfuric acid that sulfuric acid mass fraction is 98%, it is dense that the spent acid of every 5t 28% adds 3.59t
Sulfuric acid, the two mixes, and obtains nitration mixture.Then carrying out Slow cooling cooling, curing, the amplitude of gradient cooling is 8 DEG C/h,
Outlet temperature 60 DEG C, is cooled to outlet temperature post curing 1h, and whole nitration mixture are squeezed into filter press and carried out separation of solid and liquid, and isolated is filtered
Acid, this acid filtering sulfuric acid mass fraction is 63.74%, and iron content mass fraction is 0.15%.Free sulfuric acid matter in the condensed slag obtained
Amount mark is 31.68%.The rate of recovery of complex acid process sulfuric acid reaches 88.79%.
Comparative example 2
Carry out with reference to CN101774557A, by the spent acid in production process of titanium pigment, its main component, count in mass ratio
For: H2SO420.51%, FeSO49.13%, Al2(SO4)3 0.66% MgSO42.16%, TiO20.36%, through countercurrent spray
Rotary kiln calcining tail gas, the waste heat concentrate of utilization calcining tail gas to H2SO428%, then reclaimed after metatitanic acid by flocculating setting, obtain
Limpid spent acid；Spent acid is joined in a complex acid groove, is slowly added to the concentrated sulfuric acid that sulfuric acid mass fraction is 98%, 5t
The spent acid of 28% adds the 3.84t concentrated sulfuric acid, and the two mixes, and obtains nitration mixture.Then Slow cooling cooling, curing are carried out, ladder
The amplitude of degree cooling is 8 DEG C/h, and outlet temperature 60 DEG C is cooled to outlet temperature post curing 1h, and whole nitration mixture are squeezed into filter press and entered
Row separation of solid and liquid, isolated acid filtering, this acid filtering sulfuric acid mass fraction is 66.35%, and iron content mass fraction is 0.13%.Obtain
Condensed slag in free sulfuric acid mass fraction be 33.67%.The rate of recovery of complex acid process sulfuric acid reaches 86.00%.Complex acid for the second time
Adopt above 6.69 tons of gained 66.35% sulfuric acid, add the concentrated sulfuric acid 14.48 tons that sulfuric acid mass fraction is 98%, obtain sulfuric acid matter
Amount mark is 21.17 tons of the sulfuric acid of 88%.Above in the spent acid that 5 tons of sulfuric acid concentrations are 28% of same quality, add the sulfuric acid of 88%
6.13 tons, operating by above-mentioned curing, obtaining acid filtering sulfuric acid mass fraction is 67.39%, and iron content mass fraction is 0.12%, obtains
Condensed slag in free sulfuric acid mass fraction be 35.16%, the rate of recovery of complex acid process sulfuric acid reaches 88.29%.
Claims (4)
1. the recoverying and utilizing method of a titanium white waste acid, it is characterised in that comprise the following steps:
A, spent acid pre-concentration and titanium reclaim: titanium white waste acid utilizes rotary kiln waste heat from tail gas pre-concentration to the mass percent of sulfuric acid be
25%-32%, then carries out recovery Pd operation, obtains titanium white waste acid clear liquid；
B, a complex acid: titanium white waste acid clear liquid step A obtained, add the mixing of concentrated sulfuric acid complex acid, controls sulfuric acid in nitration mixture
Mass percent is 45%-50%, then lowers the temperature, crystallization, curing, and separation of solid and liquid obtains a complex acid filtrate and condensed slag；
C, secondary complex acid: complex acid filtrate step B obtained, add the mixing of concentrated sulfuric acid complex acid, controls sulfuric acid in nitration mixture
Mass percent is 60%-65%, then lowers the temperature, crystallization, curing, and sedimentation separation obtains gelled acid clear liquid and thick oar, and thick slurry is returned
It is back to a complex acid workshop section.
The recoverying and utilizing method of a kind of titanium white waste acid the most according to claim 1, it is characterised in that add body in step C
It is that content 5-10ppm flocculant assists sedimentation separation.
The recoverying and utilizing method of a kind of titanium white waste acid the most according to claim 1 and 2, it is characterised in that in step B, C
Rate of temperature fall is 5-10 DEG C/h, and the curing time is 1-3h.
The recoverying and utilizing method of a kind of titanium white waste acid the most according to claim 1 and 2, it is characterised in that in step B, C
Cooling final temperature is 60-65 DEG C.
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| CN106315521B (en) * | 2016-08-18 | 2018-10-23 | 四川龙蟒钛业股份有限公司 | The recoverying and utilizing method of titanium white waste acid |
| CN107986244A (en) * | 2017-12-11 | 2018-05-04 | 珠海绿水环保科技有限公司 | A kind of recovery method of the Waste Sulfuric Acid of metal ion |
| CN108529666B (en) * | 2018-02-28 | 2021-03-09 | 安徽迪诺环保新材料科技有限公司 | Method for preparing lithium titanate from inorganic titanium source, product and application |
| CN109941970A (en) * | 2019-04-24 | 2019-06-28 | 成都先进金属材料产业技术研究院有限公司 | Utilize the method for aluminum aluminum sulfate concentration titanium white waste acid |
| 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 |
| CN113387334B (en) * | 2021-06-16 | 2022-10-28 | 龙佰四川钛业有限公司 | Concentration and purification method of titanium dioxide waste acid by sulfuric acid process |
| CN113772633A (en) * | 2021-09-09 | 2021-12-10 | 东华工程科技股份有限公司 | Mixed acid system and method for removing ferrous sulfate in titanium white waste acid |
| CN115974123B (en) * | 2022-12-09 | 2024-04-12 | 四川大学 | Method for recycling sulfuric acid and valuable metals in titanium white waste acid |
| CN116495775A (en) * | 2023-04-27 | 2023-07-28 | 南通三圣石墨设备科技股份有限公司 | High-efficiency solid-liquid separation method of metatitanic acid slurry |
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Address after: 618200 Deyang city of Sichuan province Mianzhu new industrial zone longmang Chemical Industrial Zone Patentee after: Longbai Sichuan Titanium Co., Ltd Address before: 618200 Deyang city of Sichuan province Mianzhu new industrial zone longmang Chemical Industrial Zone Patentee before: SICHUAN LOMON TITANIUM Co.,Ltd. |