CN106179180A - A kind of solution of zinc sulfate defluorination material and preparation method - Google Patents
A kind of solution of zinc sulfate defluorination material and preparation method Download PDFInfo
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Abstract
The invention discloses a kind of zinc metallurgical process solution of zinc sulfate defluorination material and preparation method.What described defluorination material contained is mainly composed of containing aluminum, rare earth, ferrum, the oxide of magnesium elements.Its preparation method is: first put into by aluminium-hydroxide powder in ferrum magnesium salt mixed liquor, stirring adds alkali regulation pH, sucking filtration after standing, gained sample is added in rare earths salt, is again stirring for adding alkali regulation pH, then sucking filtration, sucking filtration post-drying, it is finally putting in high temperature resistance furnace, roasting under aeration condition, obtains described defluorination material.Preparation method of the present invention is simple, and product property is stable, and the high concentration fluorion in solution of zinc sulfate is had the strongest Selective adsorption and the highest adsorption capacity, and the most renewable by simple method.By this materials application in time removing the fluorion of solution of zinc sulfate middle and high concentration, can the most quickly reduce F concentration in solution, reduce entreprise cost, reduce the advantages such as environmental pollution.This material is suitable to heavy industrialization application.
Description
Technical field
The present invention relates to a kind of Purifying Zinc smelting process solution of zinc sulfate material and preparation method thereof, particularly to one
Solution of zinc sulfate defluorination material and preparation method.
Technical background
In the zinc sulfate electric effusion of zinc abstraction, Funing tablet is too high, will have a strong impact on Zinc electrolysis process: fluorion can destroy the moon
The oxide-film of pole surface of aluminum plate, increases pole plate consumption；Make between the zinc of precipitation and cathode aluminum plate, to form a kind of alloy, bond
Phenomenon, affects Eletrolytic zinc quality；Additionally, Funing tablet is too high in solution of zinc sulfate also can cause negative electrode stripping zinc difficulty, increase cost, fall
Low productivity effect, has a strong impact on the normal production of enterprise.Therefore, zinc abstraction industry must remove the fluorine in solution of zinc sulfate.
Absorption method fluorine removal, because of simple to operate, cheap, efficiency advantages of higher, obtains more in fluoride wastewater treatment
Application, wherein conventional de-fluoridation adsorbent includes zeolite, bentonite, hydroxyapatite, activated alumina etc..These adsorbents exist
Aqueous solution has preferable defluorination effect, but industrial sulphuric acid zinc solution system is sufficiently complex, containing plurality of impurity ions, inhale
Attached dose is very easy to be disturbed by other aniones, hinders its absorption to fluorion, thus make it in solution of zinc sulfate
Defluorination effect substantially reduce.The best results of activated alumina in above-mentioned various defluorinating agents, patent (CN102228746A)
Disclose and remove the method for fluorion in solution of zinc sulfate with activated alumina, but it has complex technical process, adsorption capacity
Less, fluorine removing rate is low, and aluminium oxide consumption is very big, the shortcoming such as cause follow-up filtering residue processing pressure heavier.Someone grinds before this
Study carefully and after being pyrolyzed by aluminium hydroxide, use acid treatment, then after high-temperature process, study it to the adsorption effect of fluorion in aqueous solution；With
Time, scientific investigations showed that, rare-earth elements of lanthanum and cerium are optimal to the affinity of fluorine, and the research of the most this kind of adsorbent the most gradually increases
Many.Such as, patent (CN104399430A) discloses and a kind of is applied to be electrolysed the compound defluorination material of fluorine removal in solution of zinc sulfate
Preparation method.This compound defluorination material is by high-temperature heating and soak with sulphuric acid pretreatment bamboo charcoal, then uses metal salt solution
Bamboo charcoal after impregnation process, through processing with alkali more after drying, makes metal salt precipitate in bamboo charcoal material hole.But should
The preparation process of material is complicated, and rare-earth salts consumption causes greatly high cost；And bamboo charcoal light weight, in material preparation and adsorption process
In, all it is difficult to be fully contacted with solution, causes operating difficulties；It addition, bamboo charcoal filtration washing warp again after metal salt solution impregnates
The process of base extraction, is easily caused the loss of the active component of load.
Current adsorbing material being used for solution of zinc sulfate fluorine removal, there is adsorbance little, fluoride removing rate is low, selects fluorion
Property the highest, the problems such as zinc loss is high, the consumption causing adsorbent is big, follow-up filtering residue difficult treatment, causes entreprise cost to increase.
Summary of the invention
The present invention is directed to the deficiency of above-mentioned technology, it is provided that a kind of solution of zinc sulfate defluorination material and preparation method.
One solution of zinc sulfate defluorination material of the present invention；Described defluorination material includes following group by percentage to the quality
Point:
Al2O370.8%～83.5%；
Rare earth oxide 1.3%～3.8%；
Fe2O38.8%～16.1%；
MgO 6.4%～14.3%.
One solution of zinc sulfate defluorination material of the present invention；The BET specific surface area of described solution of zinc sulfate defluorination material
It is 200～238m2/g。
One solution of zinc sulfate defluorination material of the present invention；Described solution of zinc sulfate defluorination material is used for solution of zinc sulfate
When using fluorine removal, in solution of zinc sulfate, the loss rate of zinc is less than 1%.
The preparation method of the present invention a kind of solution of zinc sulfate defluorination material, comprises the steps:
Step one
Aluminium hydroxide is added after solution A stirs, obtain mixed liquor, regulate the pH to 8～10 of mixed liquor, quiet
Put, solid-liquid separation, obtain solid B, containing water solublity iron salt and water-soluble magnesium salt in described solution A；
Step 2
Step one gained solid B is added in solution C, after stirring, regulates pH to 8～10, stand, solid-liquid separation,
Obtain solid D, containing water-solubility rare-earth salt in described solution C；
Step 3
Step 2 gained solid D is placed in sintering furnace, is passed through gas, sinter at least 3 hours in 300～600 DEG C, obtain
Described solution of zinc sulfate defluorination material；The flow speed control of described gas is 0.2～0.8L/min.
Preferably, the preparation method of the present invention a kind of solution of zinc sulfate defluorination material, in step one, by solid-liquid
Mass ratio 1:3～8, adds aluminium hydroxide in solution A and stirs, obtain mixed liquor.Described hydroxide particle-size is-350
Mesh, preferably 150～350 mesh.
Preferably, the preparation method of the present invention a kind of solution of zinc sulfate defluorination material, in step one, mixed liquor
It is heated to 30～70 DEG C, under agitation, adds alkali liquor and adjust the pH to 8～10 of mixed liquor；After standing 8～16h, sucking filtration；
Obtain solid B.During stirring, controlling speed of agitator is 80～180r/min.
The preparation method of the present invention a kind of solution of zinc sulfate defluorination material, in step one:
At least one in iron sulfate, iron chloride, ferric nitrate of described water solublity iron salt；
At least one in magnesium sulfate, magnesium chloride, magnesium nitrate of described water-soluble magnesium salt.
Preferably, in described solution A, the concentration of ferrum element is 0.5～3mol/L；The concentration of magnesium elements be 0.5～
3mol/L。
Preferably, the preparation method of the present invention a kind of solution of zinc sulfate defluorination material, in step 2,
By solid-liquid mass ratio, solid: liquid=1:3～8, step one gained solid B is added in solution C, stirs
After, it is heated to 30～70 DEG C, under agitation, adds alkali liquor and adjust the pH to 8～10 of mixed liquor；After standing 8～16h, take out
Filter；Sucking filtration gained solid is dried under the conditions of 90～130 DEG C, obtains solid D.During stirring, controlling speed of agitator is 80～180r/
min.In described solution C, the concentration of rare earth element is 0.03～0.15mol/L.
Preferably, in step 2, water-solubility rare-earth salt is selected from least in Lanthanum (III) nitrate, cerous nitrate, cerium chloride
Kind.
Preferably, described alkali liquor is selected from ammonia (mass concentration is 20%～36%), sodium carbonate liquor, potassium carbonate
Solution, sodium bicarbonate solution, potassium bicarbonate solution, sodium acetate solution, potassium acetate solution, sal volatile, ammonium bicarbonate soln
In at least one.
Preferably, in step 3,
Step 2 gained solid D is placed in sintering furnace, is passed through noble gas, with the heating rate liter of 4～10 DEG C/min
Temperature, to 350-450 DEG C of roasting 3-5 hour, obtains described solution of zinc sulfate defluorination material.The flow speed control of described gas is 0.6
～0.8L/min.Described noble gas is nitrogen, the one in argon.
One solution of zinc sulfate defluorination material of the present invention, can be utilized with repetitive cycling by regeneration, described regeneration technology
For:
(1) with deionized water, the defluorination material after absorption is repeatedly washed, filter, dry；
(2) sample after drying is put into and is impregnated 2～3h in low concentration (0.1～0.4mol/L) NaOH solution, uses subsequently
The sulfuric acid solution of 0.1～0.3mol/L neutralizes, and the time is 0.5～1h.Filter, dry, seal and preserve or be re-used in fluorine removal.
Advantage
The present invention is by first obtaining the mixture of Al-Fe-Mg (OH) x, the most again at the table of Al-Fe-Mg (OH) x mixture
Face further precipitation rare earth element hydroxide；By roasting, obtain internal predominantly Al2O3、Fe2O3, MgO, outside uniformly point
It is furnished with the solution of zinc sulfate defluorination material of rare earth oxide；Its appropriate each component and the synergism of preparation technology, obtain
With low cost, except F beneficial and the extremely low defluorination material of Zn damage amount.It is compared with existing solution of zinc sulfate defluorination material
There is following clear superiority:
(1) resulting materials good stability of the present invention, is not disturbed by other ions, has the strongest absorbability；Absorption
The consumption of agent is few (in the case of reaching identical defluorination effect, consumption is about the 1/5 of other defluorinating agents), the place of subsequent adsorbtion slag
Reason amount also significantly reduces.
(2) (BET method analysis, its specific surface area is 200～238m to the material specific surface area prepared by the present invention relatively greatly2/
g.), can be fully contacted with fluorine-containing solution of zinc sulfate, there is higher fluorine removing rate.
(3) material preparation process of the present invention is simple, will not introduce impurity, and cause zinc hardly during fluorine removal
Loss (loss rate is only about 1%).
(4) present invention is developed solution of zinc sulfate defluorination material is renewable to be reused, and it economizes on resources, and has good
Good economic benefit.
Detailed description of the invention:
Embodiment 1
(1) first by aluminium-hydroxide powder that 1kg granularity is 150 mesh according to solid-to-liquid ratio 1:4, putting into 4L concentration is 0.3mol/L
Iron sulfate and 0.3mol/L magnesium sulfate mixed solution in, be thoroughly mixed；
(2) mixed solution in step (1) is heated to 40 DEG C, is stirred under the conditions of rotating speed is 80r/min, simultaneously
Add ammonia regulation pH to 9.2, stand 8h, sucking filtration；
(3) gained sample is added to the lanthanum nitrate hexahydrate of 0.05mol/L by solid-to-liquid ratio 1:4, repeat the behaviour of step (2)
Make step, the sample after sucking filtration is dried under the conditions of 105 DEG C 3h；
(4) sample after drying is inserted in high temperature resistance furnace, and controlling heating rate is 4 DEG C/min, simultaneously with 0.4L/
The speed of min is passed through nitrogen, is warming up to 350 DEG C, roasting 3h under this temperature conditions, obtains zinc sulfate of the present invention after being down to room temperature
Solution defluorination material；Its BET specific surface area specific surface area 200.777m2/g。
(5) with the material prepared process fluorinion concentration be 125mg/L, pH be the solution of zinc sulfate 80min of 5.1, add
Amount is 10g/L, and after absorption, fluorinion concentration is down to 65mg/L.In solution of zinc sulfate, zinc loss is 0.7%.
Comparative example 1
(1) being inserted in high temperature resistance furnace by the aluminium hydroxide that 1kg granularity is 150 mesh, controlling heating rate is 4 DEG C/min,
Being passed through nitrogen with the speed of 0.4L/min simultaneously, be warming up to 350 DEG C, under this temperature conditions, roasting 3h, is cooled to room temperature.Its
BET specific surface area specific surface area is 130.258m2/g。
(2) with baked aluminium hydroxide process fluorinion concentration be 124mg/L, pH be the solution of zinc sulfate of 5.1
80min, dosage is 10g/L, and after absorption, fluorinion concentration is down to 90mg/L.In solution of zinc sulfate, zinc loss is 1.6%.
Comparative example 2
(1) first by aluminium-hydroxide powder that 1kg granularity is 180 mesh according to solid-to-liquid ratio 1:4, putting into 4L concentration is 0.3mol/L
Ferric nitrate and 0.3mol/L magnesium sulfate mixed solution in, be thoroughly mixed；
(2) mixed solution in step (1) is heated to 50 DEG C, is stirred under the conditions of rotating speed is 100r/min, with
Time add sodium carbonate regulation pH to 9, stand 8h, sucking filtration；
(3) gained sample is added to the lanthanum nitrate hexahydrate of 0.05mol/L by solid-to-liquid ratio 1:4, repeat the behaviour of step (2)
Make step, the sample after sucking filtration is dried under the conditions of 120 DEG C 4h；Its BET specific surface area specific surface area is 39.807m2/g。
(4) with the material prepared process fluorinion concentration be 124mg/L, pH be the solution of zinc sulfate 80min of 5.1, add
Amount is 10g/L, and after absorption, fluorinion concentration is down to 105mg/L.In solution of zinc sulfate, zinc loss is 1.4%.
Comparative example 3
(1) first by aluminium-hydroxide powder that 1kg granularity is 200 mesh according to solid-to-liquid ratio 1:4, putting into 4L concentration is 0.3mol/L
Iron sulfate, in the mixed solution that formed of the magnesium nitrate of 0.3mol/L, the cerous nitrate of 0.05mol/L, after being thoroughly mixed
Add sodium carbonate regulation pH to 8.9, stand 10h, sucking filtration；Sample after sucking filtration is dried under the conditions of 110 DEG C 3h；
(2) sample after drying is inserted in high temperature resistance furnace, and controlling heating rate is 5 DEG C/min, is warming up to 350 DEG C,
Roasting 3h under this temperature conditions, obtains solution of zinc sulfate defluorination material after being down to room temperature；
(3) with the material prepared process fluorinion concentration be 125mg/L, pH be the solution of zinc sulfate 80min of 5.2, add
Amount is 10g/L, and after absorption, fluorinion concentration is down to 79mg/L.In solution of zinc sulfate, zinc loss is 1.6%.
Embodiment 2
(1) first by aluminium-hydroxide powder that 1kg granularity is 230 mesh according to solid-to-liquid ratio 1:5, putting into 5L concentration is 1mol/L's
In the magnesium sulfate mixed solution of iron sulfate and 1.2mol/L, it is thoroughly mixed；
(2) mixed solution in step (1) is heated to 60 DEG C, is stirred under the conditions of rotating speed is 120r/min, with
Time add ammonia regulation pH to 9.5, stand 12h, sucking filtration；
(3) gained sample is added to the lanthanum nitrate hexahydrate of 0.1mol/L by solid-to-liquid ratio 1:5, repeat the behaviour of step (2)
Make step, the sample after sucking filtration is dried under the conditions of 120 DEG C 4h；
(4) sample after drying is inserted in high temperature resistance furnace, and controlling heating rate is 6 DEG C/min, simultaneously with 0.6L/
The speed of min is passed through nitrogen, is warming up to 400 DEG C, roasting 4h under this temperature conditions, obtains zinc sulfate of the present invention after being down to room temperature
Solution defluorination material；
(5) with the material prepared process fluorinion concentration be 127mg/L, pH be the solution of zinc sulfate 80min of 5.2, add
Amount is 10g/L, and after absorption, fluorinion concentration is down to 56mg/L.In solution of zinc sulfate, zinc loss is 0.6%.
Embodiment 3
(1) first by aluminium-hydroxide powder that 1kg granularity is 250 mesh according to solid-to-liquid ratio 1:7, putting into 7L concentration is 2.1mol/L
Iron sulfate and 2.5mol/L magnesium chloride mixture solution in, be thoroughly mixed；
(2) mixed solution in step (1) is heated to 60 DEG C, is stirred under the conditions of rotating speed is 140r/min, with
Time add potassium carbonate regulation pH to 10, stand 14h, sucking filtration；
(3) gained sample is added to the lanthanum nitrate hexahydrate of 0.15mol/L by solid-to-liquid ratio 1:7, repeat the behaviour of step (2)
Make step, the sample after sucking filtration is dried under the conditions of 120 DEG C 4h；
(3) sample after drying is inserted in high temperature resistance furnace, and controlling heating rate is 8 DEG C/min, simultaneously with 0.6L/
The speed of min is passed through nitrogen, is warming up to 450 DEG C, roasting 3h under this temperature conditions, obtains zinc sulfate of the present invention after being down to room temperature
Solution defluorination material；Its BET specific surface area specific surface area is 238.415m2/g；
(4) with the material prepared process fluorinion concentration be 124mg/L, pH be the solution of zinc sulfate 80min of 5.2, add
Amount is 10g/L, and after absorption, fluorinion concentration is down to 45mg/L.In solution of zinc sulfate, zinc loss is 0.8%.
Comparative example 4
(1) first by aluminium-hydroxide powder that 1kg granularity is 250 mesh according to solid-to-liquid ratio 1:7, putting into 7L concentration is 0.2mol/L
Lanthanum nitrate hexahydrate in, be thoroughly mixed；
(2) mixed solution in step (1) is heated to 70 DEG C, is stirred under the conditions of rotating speed is 160r/min, with
Time add ammonia regulation pH to 10.1, stand 14h, sucking filtration；3h is dried under the conditions of 120 DEG C；
(3) sample after drying is inserted in high temperature resistance furnace, and controlling heating rate is 8 DEG C/min, simultaneously with 0.7L/
The speed of min is passed through argon, is warming up to 450 DEG C, roasting 5h under this temperature conditions, obtains zinc sulfate of the present invention after being down to room temperature
Solution defluorination material；
(4) with the material prepared process fluorinion concentration be 125mg/L, pH be the solution of zinc sulfate 80min of 5.0, add
Amount is 10g/L, and after absorption, fluorinion concentration is down to 58mg/L.In solution of zinc sulfate, zinc loss is 1.2%.By comparative example 4
During with embodiment 3 it can be seen that use rare earth element in a large number, when it is used in combination with aluminium oxide, have what zinc loss strengthened
Risk.
Embodiment 4
Take the defluorination material after fluorine removal from embodiment 3, regenerate by following regeneration technology
(1) with deionized water, the defluorination material after absorption is repeatedly washed, filter, dry；
(2) sample after drying is put into and is impregnated 2～3h in low concentration (0.1～0.4mol/L) NaOH solution, uses subsequently
The sulfuric acid solution of 0.1～0.3mol/L neutralizes, and the time is 0.5～1h.Filter, dry, obtain regenerating defluorination material.
Regeneration defluorination material process Funing tablet be 124mg/L, pH be the solution of zinc sulfate of 5.1, dosage is 10g/L,
After absorption, fluorinion concentration is down to 60mg/L.Solution of zinc sulfate loss rate is 0.9%.
By embodiment and comparative example it can be seen that the defluorination material developed of the present invention, in appropriate each component and preparation
Under the synergism of technique, obtain beyond thought effect.
Claims (10)
1. a solution of zinc sulfate defluorination material；It is characterized in that, solution of zinc sulfate is with defluorination material by percentage to the quality
Including following component:
Al2O370.8%～83.5%；
Rare earth oxide 1.3%～3.8%；
Fe2O38.8%～16.1%；
MgO 6.4%～14.3%.
A kind of solution of zinc sulfate defluorination material the most according to claim 1；It is characterized in that: described solution of zinc sulfate is used
The BET specific surface area of defluorination material is 200～238m2/g。
A kind of solution of zinc sulfate defluorination material the most according to claim 2；It is characterized in that: described solution of zinc sulfate is used
Defluorination material is when solution of zinc sulfate fluorine removal, and in solution of zinc sulfate, the loss rate of zinc is less than 1%.
4. prepare the method for solution of zinc sulfate defluorination material described in claim 1-3 any one for one kind, it is characterised in that bag
Include following step:
Step one
Aluminium hydroxide is added after solution A stirs, obtain mixed liquor, the pH to 8～10 of regulation mixed liquor, stand, Gu
Liquid separates, and obtains solid B, containing water solublity iron salt and water-soluble magnesium salt in described solution A；
Step 2
Step one gained solid B is added in solution C, after stirring, regulate pH to 8～10, stand, solid-liquid separation, obtain
Solid D, containing water-solubility rare-earth salt in described solution C；
Step 3
Step 2 gained solid D is placed in sintering furnace, is passed through gas, sinter at least 3 hours in 300～600 DEG C, obtain described
Solution of zinc sulfate defluorination material；The flow speed control of described gas is 0.2～0.8L/min.
The preparation method of a kind of solution of zinc sulfate defluorination material the most according to claim 4, it is characterised in that: step one
In, by solid-liquid mass ratio 1:3～8, aluminium hydroxide is added in solution A and stirs, obtain mixed liquor；
Described hydroxide particle-size is-350 mesh；
At least one in iron sulfate, iron chloride, ferric nitrate of described water solublity iron salt；
At least one in magnesium sulfate, magnesium chloride, magnesium nitrate of described water-soluble magnesium salt.
The preparation method of a kind of solution of zinc sulfate defluorination material the most according to claim 5, it is characterised in that: step one
In, mixed liquor is heated to 30～70 DEG C, under agitation, adds alkali liquor and adjusts the pH to 8～10 of mixed liquor；Stand 8～16h
After, sucking filtration；Obtain solid B；During stirring, controlling speed of agitator is 80～180r/min.
The preparation method of a kind of solution of zinc sulfate defluorination material the most according to claim 4, it is characterised in that: step one
Described in solution A the concentration of ferrum element be 0.5～3mol/L, the concentration of magnesium elements is 0.5～3mol/L.
The preparation method of a kind of solution of zinc sulfate defluorination material the most according to claim 4, it is characterised in that: step 2
In,
By solid-liquid mass ratio, solid: liquid=1:3～8, step one gained solid B is added in solution C, after stirring, adds
Heat is to 30～70 DEG C, under agitation, adds alkali liquor and adjusts the pH to 8～10 of mixed liquor；After standing 8～16h, sucking filtration；Take out
Filter gained solid is dried under the conditions of 90～130 DEG C, obtains solid D.During stirring, controlling speed of agitator is 80～180r/min；
In described solution C, the concentration of rare earth element is 0.03～0.15mol/L.
The preparation method of a kind of solution of zinc sulfate defluorination material the most according to claim 4, it is characterised in that:
In step 2, at least one in Lanthanum (III) nitrate, cerous nitrate, cerium chloride of water-solubility rare-earth salt；
In step 2, described alkali liquor is molten selected from ammonia, sodium carbonate liquor, solution of potassium carbonate, sodium bicarbonate solution, potassium bicarbonate
At least one in liquid, sodium acetate solution, potassium acetate solution, sal volatile, ammonium bicarbonate soln.
The preparation method of a kind of solution of zinc sulfate defluorination material the most according to claim 4, it is characterised in that:
In step 3,
Step 2 gained solid D is placed in sintering furnace, is passed through noble gas, is warming up to the heating rate of 4～10 DEG C/min
350-450 DEG C of roasting 3-5 hour, obtains described solution of zinc sulfate defluorination material；The flow speed control of described gas be 0.6～
0.8L/min；Described noble gas is nitrogen, the one in argon.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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Cited By (4)
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| CN108220598A (en) * | 2018-01-16 | 2018-06-29 | 昆明理工大学 | A kind of method of fluorine in removing solution of zinc sulfate |
| WO2018184686A1 (en) * | 2017-04-06 | 2018-10-11 | Montanuniversität Leoben | Method for removing fluoride from a zinc-containing solution or suspension, defluoridated zinc sulfate solution and use thereof, and method for producing zinc and hydrogen fluoride or hydrofluoric acid |
| CN111139367A (en) * | 2019-12-30 | 2020-05-12 | 江西赣锋循环科技有限公司 | Method for deeply removing fluorine from LiCl solution recovered from waste battery |
| CN113842871A (en) * | 2021-10-19 | 2021-12-28 | 山东建筑大学 | Anti-interference defluorination adsorbent and preparation method thereof |
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| CN104826588A (en) * | 2015-04-29 | 2015-08-12 | 长沙清能环保科技有限公司 | Preparation and regeneration method of fluorine removing material on basis of coal-based coke powder |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018184686A1 (en) * | 2017-04-06 | 2018-10-11 | Montanuniversität Leoben | Method for removing fluoride from a zinc-containing solution or suspension, defluoridated zinc sulfate solution and use thereof, and method for producing zinc and hydrogen fluoride or hydrofluoric acid |
| CN110475878A (en) * | 2017-04-06 | 2019-11-19 | 莱奥本矿业大学 | Method for removing fluoride from the solution containing zinc or suspension, solution of zinc sulfate of defluorinate and application thereof and the method for being used to prepare zinc and hydrogen fluoride or hydrofluoric acid |
| KR20190138654A (en) * | 2017-04-06 | 2019-12-13 | 몬탄우니베지퇴트 레오벤 | A method for removing fluoride from a zinc containing solution or suspension, a fluorinated zinc sulfate solution and its use, and a method for producing zinc and a method for producing hydrogen fluoride or hydrofluoric acid |
| KR102384599B1 (en) * | 2017-04-06 | 2022-04-07 | 몬탄우니베지퇴트 레오벤 | Method for the removal of fluoride from zinc containing solutions or suspensions, defluorinated zinc sulfate solution and uses thereof, and methods for the production of zinc and methods for the production of hydrogen fluoride or hydrofluoric acid |
| US11512368B2 (en) | 2017-04-06 | 2022-11-29 | Montanuniversität Leoben | Method for removing fluoride from a zinc-containing solution or suspension, defluoridated zinc sulfate solution and use thereof, and method for producing zinc and hydrogen fluoride or hydrofluoric acid |
| AU2017408055B2 (en) * | 2017-04-06 | 2023-05-04 | Montanuniversität Leoben | Method for removing fluoride from a zinc-containing solution or suspension, defluoridated zinc sulfate solution and use thereof, and method for producing zinc and hydrogen fluoride or hydrofluoric acid |
| CN108220598A (en) * | 2018-01-16 | 2018-06-29 | 昆明理工大学 | A kind of method of fluorine in removing solution of zinc sulfate |
| CN111139367A (en) * | 2019-12-30 | 2020-05-12 | 江西赣锋循环科技有限公司 | Method for deeply removing fluorine from LiCl solution recovered from waste battery |
| CN113842871A (en) * | 2021-10-19 | 2021-12-28 | 山东建筑大学 | Anti-interference defluorination adsorbent and preparation method thereof |
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