CN112717873A - Preparation method and application of aluminum-based nickel-lanthanum-loaded defluorination material - Google Patents
Preparation method and application of aluminum-based nickel-lanthanum-loaded defluorination material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 48
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 44
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006115 defluorination reaction Methods 0.000 title claims abstract description 14
- DOARWPHSJVUWFT-UHFFFAOYSA-N lanthanum nickel Chemical compound [Ni].[La] DOARWPHSJVUWFT-UHFFFAOYSA-N 0.000 title claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 81
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 44
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 41
- 239000011701 zinc Substances 0.000 claims abstract description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 230000020477 pH reduction Effects 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 230000006641 stabilisation Effects 0.000 claims abstract description 9
- 238000011105 stabilization Methods 0.000 claims abstract description 9
- 238000003723 Smelting Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 98
- 238000003756 stirring Methods 0.000 claims description 70
- 239000007788 liquid Substances 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 40
- 239000011259 mixed solution Substances 0.000 claims description 38
- 239000003513 alkali Substances 0.000 claims description 35
- 239000002244 precipitate Substances 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 19
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 16
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 239000011737 fluorine Substances 0.000 abstract description 38
- 229910052731 fluorine Inorganic materials 0.000 abstract description 38
- 238000001556 precipitation Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 abstract description 3
- 229910018626 Al(OH) Inorganic materials 0.000 abstract 4
- 229910018661 Ni(OH) Inorganic materials 0.000 abstract 3
- 229910052746 lanthanum Inorganic materials 0.000 abstract 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 36
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 32
- 239000011859 microparticle Substances 0.000 description 20
- 238000003795 desorption Methods 0.000 description 18
- 239000002893 slag Substances 0.000 description 18
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 12
- 239000011247 coating layer Substances 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 6
- 239000000292 calcium oxide Substances 0.000 description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 6
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 6
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 4
- 238000002386 leaching Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- LRYUTWLWUDBDMW-UHFFFAOYSA-N [La].[F] Chemical compound [La].[F] LRYUTWLWUDBDMW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- -1 fluorine ions Chemical class 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- 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
- B01J20/06—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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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/28016—Particle form
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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Abstract
本发明公开了一种铝基载镍镧除氟材料的制备方法及应用，制备方法包括如下步骤：在硫酸溶液中溶解Al2(SO4)3；进一步溶解Ni2(SO4)3；进一步溶解La2(SO4)3；加入碱液至生成Al(OH)3沉淀；进一步加入碱液至生成Ni(OH)3，并均匀包覆在Al(OH)3微小沉淀颗粒上；进一步加入碱液至生成La(OH)3，并均匀附着在被Ni(OH)3包覆的Al(OH)3微小沉淀颗粒上；快速加入碱液使未被Ni(OH)3包裹或包裹效果不好的Al(OH)3颗粒溶解；过滤，得到的滤渣烘干之后，放入硫酸溶液中进行弱酸酸化稳定处理。本发明方法制备得到的铝基载镍镧除氟材料可以实现锌冶炼系统中氟的高效脱除。
The invention discloses a preparation method and application of an aluminum-based nickel-loaded lanthanum defluorination material. The preparation method includes the following steps: dissolving Al 2 (SO 4 ) 3 in a sulfuric acid solution; further dissolving Ni 2 (SO 4 ) 3 ; Dissolve La 2 (SO 4 ) 3 ; add lye solution to form Al(OH) 3 precipitation; further add lye solution to form Ni(OH) 3 , and evenly coat on Al(OH) 3 micro-precipitated particles; further add The lye solution generates La(OH) 3 and evenly adheres to the Al(OH) 3 micro-precipitated particles coated by Ni(OH) 3 ; adding the lye solution quickly makes it not covered by Ni(OH) 3 or the coating effect is not good. The good Al(OH) 3 particles are dissolved; filtered, and after the obtained filter residue is dried, it is put into a sulfuric acid solution for weak acid acidification and stabilization treatment. The aluminum-based nickel-carrying lanthanum defluorination material prepared by the method of the invention can realize the efficient removal of fluorine in the zinc smelting system.
Description
Technical Field
The invention relates to the field of zinc hydrometallurgy, in particular to a preparation method and application of an aluminum-based nickel-loaded lanthanum fluoride removal material.
Background
Along with the continuous exploitation of mineral resources, zinc ores tend to be poor, fine and impure, so that zinc concentrate produced by flotation is low in grade and high in impurity content, and particularly the fluorine content is higher and higher. In the zinc smelting process, the cathode aluminum plate can be corroded due to too high concentration of fluorine ions in the electrolyte, the passive film on the cathode plate is damaged, so that the separated zinc and the aluminum plate are adhered, the zinc stripping is difficult, the consumption of the cathode plate is increased, and the electrolytic process can not be normally carried out. In addition, fluorine accelerates corrosion of steel members, increases wear of equipment such as pumps and mixers, and increases production costs. Therefore, many researchers have conducted a great deal of research in succession, and the efforts are being made to achieve efficient removal of fluorine from zinc leachate. However, most of the existing defluorinating agents cannot be applied to acidic zinc-containing leachate, and the problems of metal dissolution of the defluorinating agent, high zinc precipitation rate, small particle size of the defluorinating agent, difficulty in filtration, high treatment cost and the like exist in the using process. Therefore, the development of a technology for efficiently removing fluorine in a zinc smelting system at low cost is urgently needed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method and application of an aluminum-based nickel-loaded lanthanum fluoride removal material, which can realize the high-efficiency removal of fluorine in a zinc smelting system.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a preparation method of an aluminum-based nickel-lanthanum-loaded defluorination material comprises the following steps:
s1, adding Al at the temperature of 25-90 DEG C2(SO4)3Slowly adding into sulfuric acid solution, and stirring to make Al2(SO4)3Dissolving to obtain a mixed solution A;
s2, slowly adding Ni into the mixed solution A obtained in the step S1 at the temperature of 25-90 DEG C2(SO4)3And stirring to form Ni2(SO4)3Dissolving to obtain a mixed solution B;
s3, slowly adding La into the mixed solution B obtained in the step S2 at the temperature of 25-90 DEG C2(SO4)3And stirring to make La2(SO4)3Dissolving to obtain a mixed solution C;
s4, slowly adding alkali liquor into the mixed solution C obtained in the step S3 at the temperature of 25-90 ℃ under strong stirring until the pH value is 2.5-5, and slowly generating Al (OH) in the mixed solution C3Precipitating to finally obtain a solid-liquid mixture A;
s5, slowly adding alkali liquor into the solid-liquid mixture A obtained in the step S4 at the temperature of 25-90 ℃ under strong stirring until the pH value is 5-7, wherein Ni in the solid-liquid mixture A3+Slowly precipitate to form Ni (OH)3And is uniformly coated on Al (OH)3Obtaining a solid-liquid mixture B on the tiny precipitate particles;
s6, slowly adding alkali liquor into the solid-liquid mixture B obtained in the step S5 at the temperature of 25-90 ℃ under strong stirring until the pH value is 7-9, wherein La in the solid-liquid mixture B3+Slowly precipitate to generate La (OH)3And is uniformly attached to the coating Ni (OH)3Coated Al (OH)3Obtaining a solid-liquid mixture C on the tiny precipitate particles;
s7, reducing the stirring speed, and quickly adding the mixture into the solid-liquid mixture CAdding alkaline solution until pH is 12-13, and Ni (OH) is not added3Wrapping or coating of Al (OH) with poor results3Dissolving the particles to obtain a solid-liquid mixture D;
and S8, filtering the solid-liquid mixture D obtained in the step S7, drying the obtained filter residue, putting the filter residue into a sulfuric acid solution with the pH value of 5-5.5 and the temperature of 25-90 ℃ for weak acid acidification stabilization treatment, and filtering to obtain the final aluminum-based nickel-loaded lanthanum fluoride removal material after the treatment.
Further, in step S1, the concentration of the sulfuric acid solution is 1-20 g/L; volume of sulfuric acid solution and Al2(SO4)3The mass ratio of (A) to (B) is 8-15:1, the volume unit is L, and the mass unit is g.
Further, the stirring speed in the steps S1, S2 and S3 is 20-200 r/min.
Further, in step S1, step S2, and step S3, Al is added2(SO4)3：Ni2(SO4)3：La2(SO4)3The mass ratio of (A) to (B) is 50-300: 5-30:1.
Further, in the steps S4, S5 and S6, the alkali solution added is NaOH solution, KOH solution or Na solution2CO3One of the solutions, pH 10-12.
Further, in the steps S4, S5 and S6, the speed of strong stirring is 200r/min-1000 r/min.
Further, the stirring speed in step S7 is lower than the stirring speeds in steps S4, S5, and S6, and is 50r/min or more and 200r/min or less.
Further, in step S7, the alkali solution is one of NaOH solution and KOH solution, and the concentration is 0.5-10 g/L.
The aluminum-based nickel-lanthanum-loaded fluorine removal material prepared by the preparation method can be used as a fluorine removal agent to be applied to fluorine removal of a zinc smelting system.
The invention has the beneficial effects that:
(1) the method has the advantages of wide raw material source, low cost and simple process, and the prepared aluminum-based nickel-loaded lanthanum fluorine removal material is low in price, good in fluorine removal effect and renewable in fluorine removal agent.
(2) In the method, the aluminum-based nickel-lanthanum-loaded defluorination material is subjected to acidification treatment, is suitable for defluorination of a zinc smelting system, and has high defluorination efficiency and small zinc loss.
(3) In the method, the diameter range of the micro particles is controlled by the stirring speed, so that the problem that the adsorbent is difficult to filter and recover is solved.
Drawings
FIG. 1 is a schematic structural diagram of an aluminum-based lanthanum-nickel-supported fluoride removal material microparticle in an embodiment of the present invention;
FIG. 2 is a flow chart of the preparation of the aluminum-based lanthanum-nickel-supported fluoride removal material in the embodiment of the invention;
FIG. 3 is a flow chart of a process for removing fluorine from a neutral zinc leaching solution according to an embodiment of the present invention.
Detailed Description
The invention will be further described with reference to the accompanying drawings. It should be noted that the present embodiment is premised on the technical solution, and detailed description and specific implementation are given, but the scope of protection of the present invention is not limited to the present embodiment.
Example 1
A preparation method of an aluminum-based nickel-lanthanum-loaded fluorine removal material is shown in figure 2 and comprises the following steps:
(1) stirring at 60 deg.C and 100r/min to obtain 50g Al2(SO4)3Slowly adding into 2g/L sulfuric acid solution with a liquid-solid ratio (L/g) of 8:1 to obtain Al2(SO4)3And (4) dissolving.
(2) Slowly adding 5g of Ni into the mixed solution obtained in the step (1) at the temperature of 60 ℃ and the stirring speed of 100r/min2(SO4)3Make Ni2(SO4)3And (4) dissolving.
(3) Slowly adding 1g of La into the mixed solution obtained in the step (2) at the temperature of 60 ℃ and the stirring speed of 100r/min2(SO4)3Let La2(SO4)3And (4) dissolving.
(4) Adding the mixture obtained in the step (3) into the mixed solution at the temperature of 60 ℃ and the stirring speed of 400r/min,slowly adding alkali liquor to control the pH value of the solution to be 4 so as to enable Al in the solution to be in the range of3+Slow formation of Al (OH)3Precipitation, the aluminum hydroxide microparticles shown in fig. 1 are formed.
(5) Slowly adding alkali liquor into the solid-liquid mixture obtained in the step (4) at the temperature of 60 ℃ and the stirring speed of 400r/min to control the pH value of the solution to be 7 so as to enable Ni in the solution to be in contact with the solution3+Slowly precipitate to form Ni (OH)3And is uniformly coated on Al (OH)3On the fine precipitated particles, a coating layer of nickel hydroxide microparticles shown in fig. 1 is formed.
(6) Slowly adding alkali liquor into the solid-liquid mixture obtained in the step (5) at the temperature of 60 ℃ and the stirring speed of 400r/min to control the pH of the solution to be 8.5 so as to ensure that the La in the solution3+Slowly precipitate to generate La (OH)3And is uniformly attached to the coating Ni (OH)3Coated Al (OH)3On the fine precipitated particles, a coating layer of lanthanum hydroxide microparticles shown in fig. 1 was formed.
(7) On the basis of the step (6), reducing the stirring speed to 100r/min, quickly adding alkali liquor to control the pH value of the solution to be 13, and adding Ni (OH) which is not coated on the solution3Wrapping or coating of Al (OH) with poor results3The particles dissolve away.
(8) And (3) filtering and drying the solid-liquid mixture obtained in the step (7), and then putting the solid-liquid mixture into a sulfuric acid solution with the pH value of 5 and the temperature of 60 ℃ for weak acid acidification and stabilization treatment. Filtering to obtain the aluminum-based nickel-loaded lanthanum fluoride removal material.
The prepared aluminum-based nickel-lanthanum-loaded fluorine removal material is applied to a fluorine removal process of zinc neutral leachate as shown in figure 3. Specifically, 1L of zinc-containing leachate is taken, 2g of aluminum-based nickel-loaded lanthanum fluoride removal material is added, stirring is carried out for 1h at 200r/min, then, the obtained product is filtered to obtain fluoride removal slag and fluoride removal liquid, 150g/L sodium hydroxide solution is added into the fluoride removal slag for desorption and regeneration, the desorption slag is returned to the zinc-containing leachate to be used as the fluoride removal material to participate in fluoride removal, and the desorption liquid is subjected to zinc precipitation by calcium carbonate with the excessive amount of 1.5 times and fluorine precipitation by calcium oxide with the excessive amount of 1.5 times. The results are shown in Table 1.
Example 2
A preparation method of an aluminum-based nickel-lanthanum-loaded fluorine removal material is shown in figure 2 and comprises the following steps:
(1) stirring at 70 deg.C and 100r/min to obtain 100g Al2(SO4)3Slowly adding into 2g/L sulfuric acid solution with a liquid-solid ratio (L/g) of 8:1 to obtain Al2(SO4)3And (4) dissolving.
(2) Slowly adding 10g of Ni into the mixed solution obtained in the step (1) at the temperature of 70 ℃ and the stirring speed of 100r/min2(SO4)3Make Ni2(SO4)3And (4) dissolving.
(3) Slowly adding 2g of La into the mixed solution obtained in the step (2) at the temperature of 70 ℃ and the stirring speed of 100r/min2(SO4)3Let La2(SO4)3And (4) dissolving.
(4) Slowly adding alkali liquor into the mixed solution obtained in the step (3) at the temperature of 70 ℃ and the stirring speed of 500r/min to control the pH value of the solution to be 4 so as to enable Al in the solution to be in the range of3+Slow formation of Al (OH)3Precipitation, the aluminum hydroxide microparticles shown in fig. 1 are formed.
(5) Slowly adding alkali liquor into the solid-liquid mixture obtained in the step (4) at the temperature of 70 ℃ and the stirring speed of 500r/min to control the pH value of the solution to be 7 so as to enable Ni in the solution to be in contact with the solution3+Slowly precipitate to form Ni (OH)3And is uniformly coated on Al (OH)3On the fine precipitated particles, a coating layer of nickel hydroxide microparticles shown in fig. 1 is formed.
(6) Slowly adding alkali liquor into the solid-liquid mixture obtained in the step (5) at the temperature of 70 ℃ and the stirring speed of 500r/min to control the pH of the solution to be 8.5 so as to ensure that the La in the solution3+Slowly precipitate to generate La (OH)3And is uniformly attached to the coating Ni (OH)3Coated Al (OH)3On the fine precipitated particles, a coating layer of lanthanum hydroxide microparticles in fig. 1 is formed.
(7) On the basis of the step (6), reducing the stirring speed to 100r/min, quickly adding alkali liquor to control the pH value of the solution to be 13, and adding Ni (OH) which is not coated on the solution3Wrapping or coating of Al (OH) with poor results3The particles dissolve away.
(8) And (3) filtering and drying the solid-liquid mixture obtained in the step (7), and then putting the solid-liquid mixture into a sulfuric acid solution with the pH value of 5 and the temperature of 70 ℃ for weak acid acidification and stabilization treatment. Filtering to obtain the aluminum-based nickel-loaded lanthanum fluoride removal material.
The prepared aluminum-based nickel-lanthanum-loaded fluorine removal material is applied to a fluorine removal process of zinc neutral leachate as shown in figure 3. Specifically, 1L of zinc-containing leachate is taken, 2g of aluminum-based nickel-loaded lanthanum fluoride removal material is added, stirring is carried out for 1h at 200r/min, then, the obtained product is filtered to obtain fluoride removal slag and fluoride removal liquid, 150g/L sodium hydroxide solution is added into the fluoride removal slag for desorption and regeneration, the desorption slag is returned to the zinc-containing leachate to be used as the fluoride removal material to participate in fluoride removal, and the desorption liquid is subjected to zinc precipitation by calcium carbonate with the excessive amount of 1.5 times and fluorine precipitation by calcium oxide with the excessive amount of 1.5 times. The results are shown in Table 1.
Example 3
A preparation method of an aluminum-based nickel-lanthanum-loaded fluorine removal material is shown in figure 2 and comprises the following steps:
(1) stirring at 80 deg.C and 150r/min to obtain 200g Al2(SO4)3Slowly adding into 2g/L sulfuric acid solution with a liquid-solid ratio of 10:1 to obtain Al2(SO4)3And (4) dissolving.
(2) Slowly adding 40g of Ni into the mixed solution obtained in the step (1) at the temperature of 80 ℃ and the stirring speed of 150r/min2(SO4)3Make Ni2(SO4)3And (4) dissolving.
(3) Slowly adding 3g of La into the mixed solution obtained in the step (2) at the temperature of 80 ℃ and the stirring speed of 150r/min2(SO4)3Let La2(SO4)3And (4) dissolving.
(4) Slowly adding alkali liquor to the mixed solution obtained in the step (3) at the temperature of 80 ℃ and the stirring speed of 600r/min to control the pH value of the solution to be 4 so as to enable Al in the solution to be in the range of3+Slow formation of Al (OH)3Precipitating to form the aluminum hydroxide microparticles shown in figure 1.
(5) Slowly adding alkali liquor into the solid-liquid mixture obtained in the step 4 at the temperature of 80 ℃ and the stirring speed of 600r/min to control the pH value of the solution to be 7 so as to enable Ni in the solution to be in a stable state3+Slowly precipitate to form Ni (OH)3And are all combinedCoating is evenly on Al (OH)3On the fine precipitated particles, a coating layer of nickel hydroxide microparticles shown in fig. 1 is formed.
(6) Slowly adding alkali liquor into the solid-liquid mixture obtained in the step 5 at the temperature of 80 ℃ and the stirring speed of 600r/min to control the pH of the solution to be 8.5 so as to ensure that the La in the solution3+Slowly precipitate to generate La (OH)3And is uniformly attached to the coating Ni (OH)3Coated Al (OH)3On the fine precipitated particles, a coating layer of lanthanum hydroxide microparticles shown in fig. 1 was formed.
(7) On the basis of the step (6), reducing the stirring speed to 150r/min, quickly adding alkali liquor to control the pH value of the solution to be 13, and adding Ni (OH) which is not coated on the solution3Wrapping or coating of Al (OH) with poor results3The particles dissolve away.
(8) And (3) filtering and drying the mixed solution obtained in the step (7), and then putting the mixed solution into a sulfuric acid solution with the pH value of 5 and the temperature of 80 ℃ for weak acid acidification and stabilization treatment. Filtering to obtain the aluminum-based nickel-loaded lanthanum fluoride removal material.
The prepared aluminum-based nickel-lanthanum-loaded fluorine removal material is applied to a fluorine removal process of zinc neutral leachate as shown in figure 3. Specifically, 1L of zinc-containing leachate is taken, 2g of aluminum-based nickel-loaded lanthanum fluoride removal material is added, stirring is carried out for 1h at 200r/min, then, the obtained product is filtered to obtain fluoride removal slag and fluoride removal liquid, 150g/L sodium hydroxide solution is added into the fluoride removal slag for desorption and regeneration, the desorption slag is returned to the zinc-containing leachate to be used as the fluoride removal material to participate in fluoride removal, and the desorption liquid is subjected to zinc precipitation by calcium carbonate with the excessive amount of 1.5 times and fluorine precipitation by calcium oxide with the excessive amount of 1.5 times. The results are shown in Table 1.
Example 4
A preparation method of an aluminum-based nickel-lanthanum-loaded fluorine removal material is shown in figure 2 and comprises the following steps:
(1) stirring at 90 deg.C and 150r/min to obtain 400g of Al2(SO4)3Slowly adding into 2g/L sulfuric acid solution with liquid-solid ratio (L/g) of 10:1 to obtain Al2(SO4)3And (4) dissolving.
(2) Slowly adding 50g of Ni into the mixed solution obtained in the step (1) at the temperature of 90 ℃ and the stirring speed of 150r/min2(SO4)3Make Ni2(SO4)3And (4) dissolving.
(3) Slowly adding 4g of La into the mixed solution obtained in the step (2) at the temperature of 90 ℃ and the stirring speed of 150r/min2(SO4)3Let La2(SO4)3And (4) dissolving.
(4) Slowly adding alkali liquor into the mixed solution obtained in the step (3) at the temperature of 90 ℃ and the stirring speed of 700r/min to control the pH value of the solution to be 4 so as to enable Al in the solution to be in the range of3+Slow formation of Al (OH)3Precipitation, the aluminum hydroxide microparticles shown in fig. 1 are formed.
(5) Slowly adding alkali liquor into the solid-liquid mixture obtained in the step (4) at the temperature of 90 ℃ and the stirring speed of 700r/min to control the pH value of the solution to be 7 so as to enable Ni in the solution to be in contact with the solution3+Slowly precipitate to form Ni (OH)3And is uniformly coated on Al (OH)3On the fine precipitated particles, a coating layer of nickel hydroxide microparticles shown in fig. 1 is formed.
(6) Slowly adding alkali liquor into the solid-liquid mixture obtained in the step (5) at the temperature of 90 ℃ and the stirring speed of 700r/min to control the pH of the solution to be 8.5 so as to ensure that the La in the solution3+Slowly precipitate to generate La (OH)3And is uniformly attached to the coating Ni (OH)3Coated Al (OH)3On the fine precipitated particles, a coating layer of lanthanum hydroxide microparticles shown in fig. 1 was formed.
(7) On the basis of the step (3), reducing the stirring speed to 150r/min, quickly adding alkali liquor to control the pH value of the solution to be 13, and adding Ni (OH) which is not coated on the solution3Wrapping or coating of Al (OH) with poor results3The particles dissolve away.
(8) And (3) filtering and drying the solid-liquid mixture obtained in the step (7), and then putting the solid-liquid mixture into a sulfuric acid solution with the pH value of 5 and the temperature of 90 ℃ for weak acid acidification and stabilization treatment. Filtering to obtain the aluminum-based nickel-loaded lanthanum fluoride removal material.
The prepared aluminum-based nickel-lanthanum-loaded fluorine removal material is applied to a fluorine removal process of zinc neutral leachate as shown in figure 3. Specifically, 1L of zinc-containing leachate is taken, 2g of aluminum-based nickel-loaded lanthanum fluoride removal material is added, stirring is carried out for 1h at 200r/min, then, the obtained product is filtered to obtain fluoride removal slag and fluoride removal liquid, 150g/L sodium hydroxide solution is added into the fluoride removal slag for desorption and regeneration, the desorption slag is returned to the zinc-containing leachate to be used as the fluoride removal material to participate in fluoride removal, and the desorption liquid is subjected to zinc precipitation by calcium carbonate with the excessive amount of 1.5 times and fluorine precipitation by calcium oxide with the excessive amount of 1.5 times. The results are shown in Table 1.
Example 5
A preparation method of an aluminum-based nickel-lanthanum-loaded fluorine removal material is shown in figure 2 and comprises the following steps:
(1) stirring at 25 deg.C and 20r/min to obtain 50g Al2(SO4)3Slowly adding into 2g/L sulfuric acid solution with a liquid-solid ratio of L/g of 8:1 to obtain Al2(SO4)3And (4) dissolving.
(2) Slowly adding 5g of Ni into the mixed solution obtained in the step (1) at the temperature of 25 ℃ and the stirring speed of 20r/min2(SO4)3Make Ni2(SO4)3And (4) dissolving.
(3) Slowly adding 1g of La into the mixed solution obtained in the step (2) at the temperature of 25 ℃ and the stirring speed of 20r/min2(SO4)3Let La2(SO4)3And (4) dissolving.
(4) Slowly adding alkali liquor into the mixed solution obtained in the step (3) at the temperature of 25 ℃ and the stirring speed of 200r/min to control the pH of the solution to be 2.5 so as to enable Al in the solution to be in the range of3+Slow formation of Al (OH)3Precipitating to form the aluminum hydroxide microparticles shown in figure 1.
(5) Slowly adding alkali liquor into the solid-liquid mixture obtained in the step 4 at the temperature of 25 ℃ and the stirring speed of 200r/min to control the pH value of the solution to be 5 so as to enable Ni in the solution to be in a stable state3+Slowly precipitate to form Ni (OH)3And is uniformly coated on Al (OH)3On the fine precipitated particles, a coating layer of nickel hydroxide microparticles shown in fig. 1 is formed.
(6) Slowly adding alkali liquor into the solid-liquid mixture obtained in the step 5 at the temperature of 25 ℃ and the stirring speed of 200r/min to control the pH of the solution to be 7 so as to ensure that the La in the solution3+Slowly precipitate to generate La (OH)3And is uniformly attached to the coating Ni (OH)3Coated Al (OH)3On the fine precipitated particles, a coating layer of lanthanum hydroxide microparticles shown in fig. 1 was formed.
(7) On the basis of the step (6), reducing the stirring speed to 50r/min, quickly adding alkali liquor to control the pH value of the solution to be 12, and adding Ni (OH) which is not coated on the solution3Wrapping or coating of Al (OH) with poor results3The particles dissolve away.
(8) And (3) filtering and drying the mixed solution obtained in the step (7), and then putting the mixed solution into a sulfuric acid solution with the pH value of 5 and the temperature of 25 ℃ for weak acid acidification and stabilization treatment. Filtering to obtain the aluminum-based nickel-loaded lanthanum fluoride removal material.
The prepared aluminum-based nickel-lanthanum-loaded fluorine removal material is applied to a zinc neutral leaching solution fluorine removal process shown in figure 3: taking 1L of zinc-containing leachate, adding 2g of aluminum-based nickel-loaded lanthanum fluoride removal material, stirring for 1h at 200r/min, filtering to obtain fluoride removal slag and fluoride removal liquid, adding 150g/L sodium hydroxide solution into the fluoride removal slag for desorption regeneration, returning the desorption slag to the zinc-containing leachate as the fluoride removal material to participate in fluoride removal, and precipitating zinc by using 1.5 times of excessive calcium carbonate and 1.5 times of excessive calcium oxide in the desorption liquid. The results are shown in Table 1.
Example 6
A preparation method of an aluminum-based nickel-lanthanum-loaded fluorine removal material is shown in figure 2 and comprises the following steps:
(1) stirring at 90 deg.C and 200r/min to obtain 300g of Al2(SO4)3Slowly adding into 2g/L sulfuric acid solution with a liquid-solid ratio of L/g of 15:1 to obtain Al2(SO4)3And (4) dissolving.
(2) Slowly adding 30g of Ni into the mixed solution obtained in the step (1) at the temperature of 90 ℃ and the stirring speed of 200r/min2(SO4)3Make Ni2(SO4)3And (4) dissolving.
(3) Slowly adding 1g of La into the mixed solution obtained in the step (2) at the temperature of 90 ℃ and the stirring speed of 200r/min2(SO4)3Let La2(SO4)3And (4) dissolving.
(4) At the temperature of 90 ℃, the stirring speed is 1000r/min to the step (3)Slowly adding alkali liquor to control the pH value of the solution to be 5.0 so as to enable Al in the solution to be in the mixed solution3+Slow formation of Al (OH)3Precipitating to form the aluminum hydroxide microparticles shown in figure 1.
(5) Slowly adding alkali liquor into the solid-liquid mixture obtained in the step 4 at the temperature of 90 ℃ and the stirring speed of 1000r/min to control the pH value of the solution to be 7 so as to enable Ni in the solution to be in a stable state3+Slowly precipitate to form Ni (OH)3And is uniformly coated on Al (OH)3On the fine precipitated particles, a coating layer of nickel hydroxide microparticles shown in fig. 1 is formed.
(6) Slowly adding alkali liquor into the solid-liquid mixture obtained in the step 5 at the temperature of 90 ℃ and the stirring speed of 1000r/min to control the pH of the solution to be 9 so as to ensure that the La in the solution3+Slowly precipitate to generate La (OH)3And is uniformly attached to the coating Ni (OH)3Coated Al (OH)3On the fine precipitated particles, a coating layer of lanthanum hydroxide microparticles shown in fig. 1 was formed.
(7) On the basis of the step (6), reducing the stirring speed to 200r/min, quickly adding alkali liquor to control the pH value of the solution to be 13, and adding Ni (OH) which is not coated on the solution3Wrapping or coating of Al (OH) with poor results3The particles dissolve away.
(8) And (3) filtering and drying the mixed solution obtained in the step (7), and then putting the mixed solution into a sulfuric acid solution with the pH value of 5.5 and the temperature of 25 ℃ for weak acid acidification and stabilization treatment. Filtering to obtain the aluminum-based nickel-loaded lanthanum fluoride removal material.
The prepared aluminum-based nickel-lanthanum-loaded fluorine removal material is applied to a zinc neutral leaching solution fluorine removal process shown in figure 3: taking 1L of zinc-containing leachate, adding 2g of aluminum-based nickel-loaded lanthanum fluoride removal material, stirring for 1h at 200r/min, filtering to obtain fluoride removal slag and fluoride removal liquid, adding 200g/L sodium hydroxide solution into the fluoride removal slag for desorption regeneration, returning the desorption slag to the zinc-containing leachate as the fluoride removal material to participate in fluoride removal, and precipitating zinc by using 2.0 times of excessive calcium carbonate and 2.0 times of excessive calcium oxide in the desorption liquid. The results are shown in Table 1.
TABLE 1 defluorination test results for aluminum-based supported nickel lanthanum defluorination material
Note: the effect of the regenerative fluorine removal agent is that 2g of the regenerative fluorine removal agent is applied to 1L of solution containing 131mg/L of fluorine.
Various other changes and modifications to the above-described embodiments and concepts will become apparent to those skilled in the art from the above description, and all such changes and modifications are intended to be included within the scope of the present invention as defined in the appended claims.
Claims (10)
1. A preparation method of an aluminum-based nickel-lanthanum-loaded defluorination material is characterized by comprising the following steps:
s1, adding Al at the temperature of 25-90 DEG C2(SO4)3Slowly adding into sulfuric acid solution, and stirring to make Al2(SO4)3Dissolving to obtain a mixed solution A;
s2, slowly adding Ni into the mixed solution A obtained in the step S1 at the temperature of 25-90 DEG C2(SO4)3And stirring to form Ni2(SO4)3Dissolving to obtain a mixed solution B;
s3, slowly adding La into the mixed solution B obtained in the step S2 at the temperature of 25-90 DEG C2(SO4)3And stirring to make La2(SO4)3Dissolving to obtain a mixed solution C;
s4, slowly adding alkali liquor into the mixed solution C obtained in the step S3 at the temperature of 25-90 ℃ under strong stirring until the pH value is 2.5-5, and slowly generating Al (OH) in the mixed solution C3Precipitating to finally obtain a solid-liquid mixture A;
s5, slowly adding alkali liquor into the solid-liquid mixture A obtained in the step S4 at the temperature of 25-90 ℃ under strong stirring until the pH value is 5-7, wherein Ni in the solid-liquid mixture A3+Slowly precipitate to form Ni (OH)3And is uniformly coated on Al (OH)3Obtaining a solid-liquid mixture B on the tiny precipitate particles;
s6, mixing the solid and the liquid obtained in the step S5 at the temperature of 25-90 ℃ under strong stirringAdding alkali liquor slowly to pH 7-9, and adding La in solid-liquid mixture B3+Slowly precipitate to generate La (OH)3And is uniformly attached to the coating Ni (OH)3Coated Al (OH)3Obtaining a solid-liquid mixture C on the tiny precipitate particles;
s7, reducing stirring speed, and quickly adding alkali liquor into the solid-liquid mixture C until the pH value is 12-13 and the solid-liquid mixture C is not coated with Ni (OH)3Wrapping or coating of Al (OH) with poor results3Dissolving the particles to obtain a solid-liquid mixture D;
and S8, filtering the solid-liquid mixture D obtained in the step S7, drying the obtained filter residue, putting the filter residue into a sulfuric acid solution with the pH value of 5-5.5 and the temperature of 25-90 ℃ for weak acid acidification stabilization treatment, and filtering to obtain the final aluminum-based nickel-loaded lanthanum fluoride removal material after the treatment.
2. The method according to claim 1, wherein in step S1, the concentration of the sulfuric acid solution is 1 to 20 g/L; volume of sulfuric acid solution and Al2(SO4)3The mass ratio of (A) to (B) is 8-15:1, the volume unit is L, and the mass unit is g.
3. The method according to claim 1, wherein the stirring speed in each of the steps S1, S2 and S3 is 20 to 200 r/min.
4. The method of claim 1, wherein Al is added in steps S1, S2, and S32(SO4)3：Ni2(SO4)3：La2(SO4)3The mass ratio of (A) to (B) is 50-300: 5-30:1.
5. The method of claim 1, wherein the alkali solution added in step S4, step S5, and step S6 is NaOH solution, KOH solution, or Na solution2CO3One of the solutions, pH 10-12.
6. The method of claim 1, wherein the speed of the intensive stirring is 200 to 1000r/min in steps S4, S5, and S6.
7. The production method according to claim 6, wherein the stirring speed in step S7 is lower than the stirring speeds in steps S4, S5, and S6, and is 50r/min or more and 200r/min or less.
8. The method of claim 1, wherein in step S7, the alkali solution is one of NaOH solution and KOH solution, and the concentration is 0.5-10 g/L.
9. The aluminum-based nickel-lanthanum-loaded defluorination material prepared by the preparation method of any one of the claims 1 to 8.
10. The use of the aluminum-based nickel-lanthanum-loaded defluorination material prepared by the preparation method of any one of claims 1 to 8 in defluorination of zinc smelting systems.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1954906A (en) * | 2005-10-28 | 2007-05-02 | 中国科学院生态环境研究中心 | A composite metal oxide fluorine removal adsorbent |
| CN101972658A (en) * | 2010-11-19 | 2011-02-16 | 昆明理工大学 | Carbonyl sulfide hydrolysis catalyst taking rare-earth hydrotalcite as precursor and preparation method thereof |
| CN102732722A (en) * | 2012-05-21 | 2012-10-17 | 贵州顶效开发区宏达金属综合回收有限公司 | Zinc hydrometallurgy method for removing fluorine and chlorine by extraction |
| US20140314951A1 (en) * | 2011-11-24 | 2014-10-23 | Indian Institute Of Technology | Multilayer organic-templated-boehmite-nanoarchitecture for water purification |
| CN106512936A (en) * | 2016-11-11 | 2017-03-22 | 镇江市高等专科学校 | Hydrothermal method for preparing fluoride removal adsorbent and application thereof |
| CN111422926A (en) * | 2020-04-10 | 2020-07-17 | 浙江帕瓦新能源股份有限公司 | A core-shell structure Al/La co-doped high-nickel ternary precursor, a preparation method thereof, and a positive electrode material |
-
2020
- 2020-12-16 CN CN202011487903.9A patent/CN112717873A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1954906A (en) * | 2005-10-28 | 2007-05-02 | 中国科学院生态环境研究中心 | A composite metal oxide fluorine removal adsorbent |
| CN101972658A (en) * | 2010-11-19 | 2011-02-16 | 昆明理工大学 | Carbonyl sulfide hydrolysis catalyst taking rare-earth hydrotalcite as precursor and preparation method thereof |
| US20140314951A1 (en) * | 2011-11-24 | 2014-10-23 | Indian Institute Of Technology | Multilayer organic-templated-boehmite-nanoarchitecture for water purification |
| CN102732722A (en) * | 2012-05-21 | 2012-10-17 | 贵州顶效开发区宏达金属综合回收有限公司 | Zinc hydrometallurgy method for removing fluorine and chlorine by extraction |
| CN106512936A (en) * | 2016-11-11 | 2017-03-22 | 镇江市高等专科学校 | Hydrothermal method for preparing fluoride removal adsorbent and application thereof |
| CN111422926A (en) * | 2020-04-10 | 2020-07-17 | 浙江帕瓦新能源股份有限公司 | A core-shell structure Al/La co-doped high-nickel ternary precursor, a preparation method thereof, and a positive electrode material |
Non-Patent Citations (1)
| Title |
|---|
| 杨腾蛟等: "湿法炼锌硫酸锌溶液脱除氟氯方法探讨", 《有色冶金节能》 * |
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