CN106179180B - 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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- CN106179180B CN106179180B CN201610830900.8A CN201610830900A CN106179180B CN 106179180 B CN106179180 B CN 106179180B CN 201610830900 A CN201610830900 A CN 201610830900A CN 106179180 B CN106179180 B CN 106179180B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
Abstract
The invention discloses a kind of zinc metallurgical process solution of zinc sulfate defluorination material and preparation methods.The main component that the defluorination material contains be containing aluminium, rare earth, iron, magnesium elements oxide.Preparation method are as follows: be first put into aluminium-hydroxide powder in iron magnesium salts mixed liquor, stirring plus alkali adjust pH, it is filtered after standing, gained sample is added in rare-earth salt solution, is again stirring for plus alkali adjusts pH, then filter, it is dried after suction filtration, it is finally putting into high temperature resistance furnace, is roasted under aeration condition, obtain the defluorination material.Preparation method of the present invention is simple, and product property is stablized, and has very strong Selective adsorption and very high adsorption capacity to the high concentration fluorine ion in solution of zinc sulfate, and i.e. renewable by simple method.When the material is applied to the fluorine ion of removal solution of zinc sulfate middle and high concentration, it effectively can quickly reduce F concentration in solution, reduce entreprise cost, the advantages such as reduce environmental pollution.The material is suitable for heavy industrialization application.
Description
Technical field
The present invention relates to a kind of purification zinc metallurgical process solution of zinc sulfate materials and preparation method thereof, in particular to a kind of
Solution of zinc sulfate defluorination material and preparation method.
Technical background
Funing tablet is excessively high in the sulfuric acid Zinc sulfate electrolyte of zinc abstraction, and will seriously affect Zinc electrolysis process: fluorine ion can destroy yin
The oxidation film of pole surface of aluminum plate increases pole plate consumption;Make to form a kind of alloy between the zinc and cathode aluminum plate that are precipitated, bond
Phenomenon influences Eletrolytic zinc quality;In addition, the excessively high cathode stripping zinc that also will cause of Funing tablet is difficult in solution of zinc sulfate, increase cost, drop
Low productivity effect seriously affects the normal production of enterprise.Therefore, the fluorine in solution of zinc sulfate must be removed in zinc abstraction industry.
Absorption method fluorine removal because it is easy to operate, cheap, high-efficient the advantages that, obtained in fluoride wastewater treatment more
Using wherein common de-fluoridation adsorbent includes zeolite, bentonite, hydroxyapatite, activated alumina etc..These adsorbents exist
There is preferable defluorination effect, but industrial sulphuric acid zinc solution system is sufficiently complex, containing plurality of impurity ions, inhales in aqueous solution
Attached dose is very easy to the interference by other anion, it is hindered thus to make it in solution of zinc sulfate the absorption of fluorine ion
Defluorination effect be substantially reduced.The effect of activated alumina is best in above-mentioned various defluorinating agents, patent (CN102228746A)
The method with fluorine ion in activated alumina removing solution of zinc sulfate is disclosed, but it is with complex technical process, adsorption capacity
The disadvantages of smaller, fluorine removing rate is low, and aluminium oxide dosage is very big, causes subsequent filter residue processing pressure heavier.Someone grinds before this
Study carefully and handled after being pyrolyzed aluminium hydroxide with acid, then studies its adsorption effect to fluorine ion in aqueous solution after high-temperature process;Together
When, scientific investigations showed that, rare-earth elements of lanthanum and cerium are best to the compatibility of fluorine, therefore the research of this kind of adsorbent also gradually increases
It is more.For example, patent (CN104399430A) discloses a kind of compound defluorination material applied to fluorine removal in electrolysis solution of zinc sulfate
Preparation method.The compound defluorination material is then to use metal salt solution by high-temperature heating and sulfuric acid dipping pretreatment bamboo charcoal
Bamboo charcoal after impregnation, is handled with alkali again after drying, makes metal salt precipitate in bamboo charcoal material hole.But it should
The preparation process of material is complicated, and rare-earth salts dosage causes greatly cost excessively high;And bamboo charcoal is light, in material preparation and adsorption process
In, it is not easy to come into full contact with solution, causes operating difficulties;In addition, bamboo charcoal filtration washing after metal salt solution impregnates passes through again
The process of base extraction easily leads to the loss of the active component of load.
Current adsorbent material is used for solution of zinc sulfate fluorine removal, it is small that there are adsorbances, and fluoride removing rate is low, selects fluorine ion
Property not high, the problems such as zinc loss is high, cause the dosage of adsorbent big, the processing of subsequent filter residue is difficult, and entreprise cost is caused to increase.
Summary of the invention
The deficiency of the present invention in view of the above technology provides a kind of solution of zinc sulfate defluorination material and preparation method.
A kind of solution of zinc sulfate defluorination material of the present invention;The defluorination material includes following groups 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%.
A kind of solution of zinc sulfate defluorination material of the present invention;The BET specific surface area of the solution of zinc sulfate defluorination material
For 200~238m2/g。
A kind of solution of zinc sulfate defluorination material of the present invention;The solution of zinc sulfate is used for solution of zinc sulfate with defluorination material
When with fluorine removal, the loss late of zinc is less than 1% in solution of zinc sulfate.
A kind of preparation method of solution of zinc sulfate defluorination material of the present invention, includes the following steps:
Step 1
Aluminium hydroxide is added in solution A after mixing evenly, mixed liquor is obtained, adjusts the pH to 8~10 of mixed liquor, it is quiet
It sets, is separated by solid-liquid separation, obtain solid B, contain water-soluble iron salts and water-soluble magnesium salt in the solution A;
Step 2
Step 1 obtained solid B is added in solution C, after mixing evenly, pH to 8~10 is adjusted, stands, be separated by solid-liquid separation,
Solid D is obtained, contains water-solubility rare-earth salt in the solution C;
Step 3
Step 2 obtained solid D is placed in sintering furnace, gas is passed through, is sintered at least 3 hours, obtains in 300~600 DEG C
The solution of zinc sulfate defluorination material;The flow control of the gas is 0.2~0.8L/min.
Preferably, a kind of preparation method of solution of zinc sulfate defluorination material of the present invention, in step 1, by solid-liquid
Aluminium hydroxide is added in solution A and stirs evenly, obtains mixed liquor by mass ratio 1:3~8.The hydroxide particle-size is -350
Mesh, preferably 150~350 mesh.
Preferably, a kind of preparation method of solution of zinc sulfate defluorination material of the present invention, in step 1, mixed liquor
30~70 DEG C are heated to, under agitation, the pH to 8~10 of lye adjustment mixed liquor is added;After standing 8~16h, filter;
Obtain solid B.When stirring, control speed of agitator is 80~180r/min.
A kind of preparation method of solution of zinc sulfate defluorination material of the present invention, in step 1:
The water-soluble iron salts are selected from least one of ferric sulfate, iron chloride, ferric nitrate;
The water-soluble magnesium salt is selected from least one of magnesium sulfate, magnesium chloride, magnesium nitrate.
Preferably, the concentration of ferro element is 0.5~3mol/L in the solution A;The concentration of magnesium elements be 0.5~
3mol/L。
Preferably, a kind of preparation method of solution of zinc sulfate defluorination material of the present invention, in step 2,
By solid-liquid mass ratio, solid: step 1 obtained solid B is added in solution C, stirs evenly by liquid=1:3~8
Afterwards, 30~70 DEG C are heated to, under agitation, the pH to 8~10 of lye adjustment mixed liquor is added;After standing 8~16h, take out
Filter;It filters obtained solid to dry under the conditions of 90~130 DEG C, obtains solid D.When stirring, control speed of agitator is 80~180r/
min.In the solution C, the concentration of rare earth element is 0.03~0.15mol/L.
Preferably, in step 2, water-solubility rare-earth salt in lanthanum nitrate, cerous nitrate, cerium chloride at least one
Kind.
Preferably, the lye is selected from ammonium hydroxide (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
At least one of.
Preferably, in step 3,
Step 2 obtained solid D is placed in sintering furnace, inert gas is passed through, with the heating rate liter of 4~10 DEG C/min
Temperature to 350-450 DEG C roasting 3-5 hours, obtain the solution of zinc sulfate defluorination material.The flow control of the gas is 0.6
~0.8L/min.The inert gas is nitrogen, one of argon gas.
A kind of solution of zinc sulfate defluorination material of the present invention, can be with repeated recycling utilize, the regeneration technology by regeneration
Are as follows:
(1) defluorination material after absorption is repeatedly washed with deionized water, is filtered, drying;
(2) sample after drying is put into 2~3h of dipping in low concentration (0.1~0.4mol/L) NaOH solution, then used
The sulfuric acid solution of 0.1~0.3mol/L neutralizes, and the time is 0.5~1h.Filtering, drying, is sealed or is re-used in fluorine removal.
Advantage
The present invention passes through the mixture for first obtaining Al-Fe-Mg (OH) x, then again in the table of Al-Fe-Mg (OH) x mixture
The further deposition of rare-earth element hydroxide in face;By roasting, obtain internal being mainly Al2O3、Fe2O3, MgO, it is external uniformly point
It is furnished with the solution of zinc sulfate defluorination material of rare earth oxide;The synergistic effect of its appropriate each component and preparation process, obtains
It is low in cost, except F beneficial and Zn damage measures extremely low defluorination material.It is compared with existing solution of zinc sulfate defluorination material
With following clear superiority:
(1) resulting materials stability of the present invention is good, not by the interference of other ions, has very strong adsorption capacity;Absorption
The dosage of agent is few (in the case where reaching identical defluorination effect, dosage is 1/5 of other defluorinating agents or so), the place of subsequent adsorbtion slag
Reason amount also significantly reduces.
(2) present invention prepared by material specific surface area it is larger (BET method analysis, specific surface area be 200~238m2/
g.), it can be come into full contact with fluorine-containing solution of zinc sulfate, fluorine removing rate with higher.
(3) material preparation process of the present invention is simple, will not introduce impurity during fluorine removal, and hardly cause zinc
It loses (loss late is only 1% or so).
(4) the renewable reuse of solution of zinc sulfate defluorination material that the present invention is developed, economizes on resources, and has good
Good economic benefit.
Specific embodiment:
Embodiment 1
(1) first by aluminium-hydroxide powder that 1kg granularity is 150 mesh according to solid-to-liquid ratio 1:4, being put into 4L concentration is 0.3mol/L
Ferric 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 revolving speed is 80r/min, simultaneously
Add ammonium hydroxide to adjust pH to 9.2, stand 8h, filters;
(3) gained sample is added by solid-to-liquid ratio 1:4 into the lanthanum nitrate hexahydrate of 0.05mol/L, repeats the behaviour of step (2)
Make step, filtered sample is dried into 3h under the conditions of 105 DEG C;
(4) by the sample merging high temperature resistance furnace after drying, control heating rate is 4 DEG C/min, while with 0.4L/
The rate of min is passed through nitrogen, is warming up to 350 DEG C, roasts 3h under the conditions of the temperature, is cooled to room temperature to obtain zinc sulfate of the present invention
Solution defluorination material;Its BET specific surface area specific surface area 200.777m2/g。
It (5) is 125mg/L with the material processing fluorinion concentration of preparation, the solution of zinc sulfate 80min that pH is 5.1 is added
Amount is 10g/L, and fluorinion concentration is down to 65mg/L after absorption.Zinc loss is 0.7% in solution of zinc sulfate.
Comparative example 1
(1) aluminium hydroxide that 1kg granularity is 150 mesh being placed in high temperature resistance furnace, control heating rate is 4 DEG C/min,
Nitrogen is passed through with the rate of 0.4L/min simultaneously, 350 DEG C is warming up to, roasts 3h under the conditions of the temperature, be cooled to room temperature.Its
BET specific surface area specific surface area is 130.258m2/g。
It (2) is 124mg/L, the solution of zinc sulfate that pH is 5.1 with baked aluminium hydroxide processing fluorinion concentration
80min, dosage 10g/L, fluorinion concentration is down to 90mg/L after absorption.Zinc loss is 1.6% in solution of zinc sulfate.
Comparative example 2
(1) first by aluminium-hydroxide powder that 1kg granularity is 180 mesh according to solid-to-liquid ratio 1:4, being put 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 revolving speed is 100r/min, together
When add sodium carbonate adjust pH to 9, stand 8h, filter;
(3) gained sample is added by solid-to-liquid ratio 1:4 into the lanthanum nitrate hexahydrate of 0.05mol/L, repeats the behaviour of step (2)
Make step, filtered sample is dried into 4h under the conditions of 120 DEG C;Its BET specific surface area specific surface area is 39.807m2/g。
It (4) is 124mg/L with the material processing fluorinion concentration of preparation, the solution of zinc sulfate 80min that pH is 5.1 is added
Amount is 10g/L, and fluorinion concentration is down to 105mg/L after absorption.Zinc loss is 1.4% in solution of zinc sulfate.
Comparative example 3
(1) first by aluminium-hydroxide powder that 1kg granularity is 200 mesh according to solid-to-liquid ratio 1:4, being put into 4L concentration is 0.3mol/L
Ferric sulfate, the magnesium nitrate of 0.3mol/L, in mixed solution composed by the cerous nitrate of 0.05mol/L, after being thoroughly mixed
Add sodium carbonate to adjust pH to 8.9, stand 10h, filters;Filtered sample is dried into 3h under the conditions of 110 DEG C;
(2) by the sample merging high temperature resistance furnace after drying, control heating rate is 5 DEG C/min, is warming up to 350 DEG C,
3h is roasted under the conditions of the temperature, is cooled to room temperature to obtain solution of zinc sulfate defluorination material;
It (3) is 125mg/L with the material processing fluorinion concentration of preparation, the solution of zinc sulfate 80min that pH is 5.2 is added
Amount is 10g/L, and fluorinion concentration is down to 79mg/L after absorption.Zinc loss is 1.6% in solution of zinc sulfate.
Embodiment 2
(1) first by aluminium-hydroxide powder that 1kg granularity is 230 mesh according to solid-to-liquid ratio 1:5, being put into 5L concentration is 1mol/L's
In the magnesium sulfate mixed solution of ferric 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 revolving speed is 120r/min, together
When add ammonium hydroxide adjust pH to 9.5, stand 12h, filter;
(3) gained sample is added by solid-to-liquid ratio 1:5 into the lanthanum nitrate hexahydrate of 0.1mol/L, repeats the behaviour of step (2)
Make step, filtered sample is dried into 4h under the conditions of 120 DEG C;
(4) by the sample merging high temperature resistance furnace after drying, control heating rate is 6 DEG C/min, while with 0.6L/
The rate of min is passed through nitrogen, is warming up to 400 DEG C, roasts 4h under the conditions of the temperature, is cooled to room temperature to obtain zinc sulfate of the present invention
Solution defluorination material;
It (5) is 127mg/L with the material processing fluorinion concentration of preparation, the solution of zinc sulfate 80min that pH is 5.2 is added
Amount is 10g/L, and fluorinion concentration is down to 56mg/L after absorption.Zinc loss is 0.6% in solution of zinc sulfate.
Embodiment 3
(1) first by aluminium-hydroxide powder that 1kg granularity is 250 mesh according to solid-to-liquid ratio 1:7, being put into 7L concentration is 2.1mol/L
Ferric 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 revolving speed is 140r/min, together
When add potassium carbonate adjust pH to 10, stand 14h, filter;
(3) gained sample is added by solid-to-liquid ratio 1:7 into the lanthanum nitrate hexahydrate of 0.15mol/L, repeats the behaviour of step (2)
Make step, filtered sample is dried into 4h under the conditions of 120 DEG C;
(3) by the sample merging high temperature resistance furnace after drying, control heating rate is 8 DEG C/min, while with 0.6L/
The rate of min is passed through nitrogen, is warming up to 450 DEG C, roasts 3h under the conditions of the temperature, is cooled to room temperature to obtain zinc sulfate of the present invention
Solution defluorination material;Its BET specific surface area specific surface area is 238.415m2/g;
It (4) is 124mg/L with the material processing fluorinion concentration of preparation, the solution of zinc sulfate 80min that pH is 5.2 is added
Amount is 10g/L, and fluorinion concentration is down to 45mg/L after absorption.Zinc loss is 0.8% in solution of zinc sulfate.
Comparative example 4
(1) first by aluminium-hydroxide powder that 1kg granularity is 250 mesh according to solid-to-liquid ratio 1:7, being put 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 revolving speed is 160r/min, together
When add ammonium hydroxide adjust pH to 10.1, stand 14h, filter;3h is dried under the conditions of 120 DEG C;
(3) by the sample merging high temperature resistance furnace after drying, control heating rate is 8 DEG C/min, while with 0.7L/
The rate of min is passed through argon gas, is warming up to 450 DEG C, roasts 5h under the conditions of the temperature, is cooled to room temperature to obtain zinc sulfate of the present invention
Solution defluorination material;
It (4) is 125mg/L with the material processing fluorinion concentration of preparation, the solution of zinc sulfate 80min that pH is 5.0 is added
Amount is 10g/L, and fluorinion concentration is down to 58mg/L after absorption.Zinc loss is 1.2% in solution of zinc sulfate.Pass through comparative example 4
With embodiment 3 as can be seen that when largely using rare earth element, when it is used in combination with aluminium oxide, increased there are zinc loss
Risk.
Embodiment 4
It takes from the defluorination material after fluorine removal in embodiment 3, is regenerated by following regeneration technologies
(1) defluorination material after absorption is repeatedly washed with deionized water, is filtered, drying;
(2) sample after drying is put into 2~3h of dipping in low concentration (0.1~0.4mol/L) NaOH solution, then used
The sulfuric acid solution of 0.1~0.3mol/L neutralizes, and the time is 0.5~1h.Filtering, drying obtain regeneration defluorination material.
Regenerated defluorination material processing Funing tablet is 124mg/L, the solution of zinc sulfate that pH is 5.1, dosage 10g/L,
Fluorinion concentration is down to 60mg/L after absorption.Solution of zinc sulfate loss late is 0.9%.
By embodiment and comparative example as can be seen that the defluorination material developed of the present invention, in appropriate each component and preparation
Under the synergistic effect of technique, unexpected effect has been obtained.
Claims (10)
1. a kind of solution of zinc sulfate defluorination material;It is characterized in that, solution of zinc sulfate with defluorination material by percentage to the quality
Including following components:
Al2O370.8%~83.5%;
Rare earth oxide 1.3%~3.8%;
Fe2O38.8%~16.1%;
MgO 6.4%~14.3%;
The solution of zinc sulfate is prepared with defluorination material by following step:
Step 1
Aluminium hydroxide is added in solution A after mixing evenly, mixed liquor is obtained, adjusts the pH to 8~10 of mixed liquor, is stood, Gu
Liquid separation obtains solid B, contains water-soluble iron salts and water-soluble magnesium salt in the solution A;
Step 2
Step 1 obtained solid B is added in solution C, after mixing evenly, pH to 8~10 is adjusted, stands, be separated by solid-liquid separation, obtain
Solid D contains water-solubility rare-earth salt in the solution C;
Step 3
Step 2 obtained solid D is placed in sintering furnace, gas is passed through, is sintered at least 3 hours in 300~600 DEG C, is obtained described
Solution of zinc sulfate defluorination material;The flow control of the gas is 0.2~0.8L/min.
2. a kind of solution of zinc sulfate defluorination material according to claim 1;It is characterized by: the solution of zinc sulfate is used
The BET specific surface area of defluorination material is 200~238m2/g。
3. a kind of solution of zinc sulfate defluorination material according to claim 2;It is characterized by: the solution of zinc sulfate is used
When defluorination material is used for solution of zinc sulfate fluorine removal, the loss late of zinc is less than 1% in solution of zinc sulfate.
4. a kind of solution of zinc sulfate defluorination material according to claim 1, it is characterised in that: in step 1, by solid-liquid
Aluminium hydroxide is added in solution A and stirs evenly, obtains mixed liquor by mass ratio 1:3~8;
The hydroxide particle-size is -350 mesh;
The water-soluble iron salts are selected from least one of ferric sulfate, iron chloride, ferric nitrate;
The water-soluble magnesium salt is selected from least one of magnesium sulfate, magnesium chloride, magnesium nitrate.
5. a kind of solution of zinc sulfate defluorination material according to claim 1, it is characterised in that: in step 1, mixed liquor
30~70 DEG C are heated to, under agitation, the pH to 8~10 of lye adjustment mixed liquor is added;After standing 8~16h, filter;
Obtain solid B;When stirring, control speed of agitator is 80~180r/min.
6. a kind of solution of zinc sulfate defluorination material according to claim 1, it is characterised in that: solution described in step 1
The concentration of ferro element is 0.5~3mol/L in A, and the concentration of magnesium elements is 0.5~3mol/L.
7. a kind of solution of zinc sulfate defluorination material according to claim 1, it is characterised in that: in step 2,
By solid-liquid mass ratio, solid: step 1 obtained solid B is added in solution C, after mixing evenly, adds by liquid=1:3~8
Heat is to 30~70 DEG C, under agitation, the pH to 8~10 of lye adjustment mixed liquor is added;After standing 8~16h, filter;It takes out
Filter obtained solid is dried under the conditions of 90~130 DEG C, obtains solid D;When stirring, control speed of agitator is 80~180r/min;
In the solution C, the concentration of rare earth element is 0.03~0.15mol/L.
8. a kind of solution of zinc sulfate defluorination material according to claim 1, it is characterised in that:
In step 2, water-solubility rare-earth salt is selected from least one of lanthanum nitrate, cerous nitrate, cerium chloride.
9. a kind of solution of zinc sulfate defluorination material according to claim 7, it is characterised in that:
In step 2, it is molten that the lye is selected from ammonium hydroxide, sodium carbonate liquor, solution of potassium carbonate, sodium bicarbonate solution, saleratus
At least one of liquid, sodium acetate solution, potassium acetate solution, sal volatile, ammonium bicarbonate soln.
10. a kind of solution of zinc sulfate defluorination material according to claim 1, it is characterised in that:
In step 3,
Step 2 obtained solid D is placed in sintering furnace, gas is passed through, 350- is warming up to the heating rate of 4~10 DEG C/min
450 DEG C roasting 3-5 hours, obtain the solution of zinc sulfate defluorination material;The flow control of the gas is 0.6~0.8L/
Min, the gas are selected from nitrogen, one of argon gas.
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