CN108285170B - Method for producing metastannic acid and stannic oxide by sulfuric acid method - Google Patents

Method for producing metastannic acid and stannic oxide by sulfuric acid method Download PDF

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CN108285170B
CN108285170B CN201810135124.9A CN201810135124A CN108285170B CN 108285170 B CN108285170 B CN 108285170B CN 201810135124 A CN201810135124 A CN 201810135124A CN 108285170 B CN108285170 B CN 108285170B
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acid
tin
sulfuric acid
metastannic
reaction
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CN108285170A (en
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苏瑞春
张旭
李发祥
李学鹏
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Yunnan Tin Industry Research Institute Co ltd
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Yunnan Tin Industry Research Institute Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C01G19/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

A method for producing metastannic acid and tin dioxide by a sulfuric acid method comprises the steps of putting sulfuric acid and tin into a closed container according to a proportion, wherein the liquid-solid mass ratio of a solution to tin is 5-14: 1, and the initial acidity of the sulfuric acid solution is 10-200 g/l; then, introducing oxygen into the closed container, pressurizing and heating to react tin and sulfuric acid to synthesize metastannic acid; and (3) performing closed reaction under the pressure of more than or equal to 0.5MPa at the reaction temperature of 90-200 ℃ for 2-8 hours, performing liquid-solid separation after the reaction, adding ammonium bicarbonate to the solid part, namely the metastannic acid intermediate product, neutralizing and washing, removing residual sulfuric acid, and performing centrifugal filtration and drying to obtain metastannic acid. And calcining metastannic acid to obtain the tin dioxide. The invention has low production cost, no three wastes generated in the process, energy saving and environmental protection. The prepared product has high purity.

Description

Method for producing metastannic acid and stannic oxide by sulfuric acid method
Technical Field
The invention belongs to the technical field of hydrometallurgy and chemical industry, and particularly relates to a production method of metastannic acid and stannic oxide.
Background
Metastannic acid (H)2SnO3) And wet process tin dioxide (SnO)2) Belongs to the same class of inorganic chemical products of tin and has wide industrial application. The method is mainly used for producing ceramics, enamel, glass, electronic devices, decorative materials and the like, and is also used for producing glaze, pigment, flame retardant, catalyst and other chemical agents.
The traditional wet method for producing metastannic acid and tin dioxide is a nitric acid method, and the method is characterized in that metal tin and concentrated nitric acid are directly reacted to produce metastannic acid and tin dioxide products under normal pressure, and the method has the following defects that ① tin dissolving reaction is carried out under normal pressure, tin and nitric acid react violently to generate a large amount of nitrogen oxides, the nitrogen oxides are difficult to absorb and treat and directly discharge to cause great pollution to the environment, the reaction of ② tin and nitric acid is an exothermic reaction, the released heat accelerates the decomposition of nitric acid, the consumption of nitric acid is increased, the production cost is high, and the like.
Chinese patent publication No. CN1657417A discloses a method for producing metastannic acid (tin dioxide) powder, which comprises adding oxygen into a closed container, controlling the reaction temperature and reaction time, and reacting tin with nitric acid, wherein the treatment method after the reaction is the same as that of the conventional wet method, the reaction residual liquid can be recycled, the content of nitrogen oxides in the reaction tail gas is low, and the nitrogen oxides can be directly discharged, thereby avoiding the absorption of the tail gas. However, the method has the defects of difficult control of the feeding process and high production cost of the nitric acid.
Disclosure of Invention
The invention aims to overcome the defects of nitrogen oxide gas generation and higher production cost of the existing nitric acid method, and provides a method for directly producing metastannic acid and tin dioxide by a sulfuric acid method, which has the advantages of low treatment cost, no three wastes generated in the technical process and high product purity.
The purpose of the invention is realized by the following technical scheme:
the method for producing metastannic acid by the sulfuric acid method comprises the steps of putting sulfuric acid and tin into a closed container according to a proportion, wherein the liquid-solid mass ratio of a solution to tin is 5-14: 1, and the initial acidity of the sulfuric acid solution is 10-200 g/l; then, introducing oxygen into the closed container, pressurizing and heating to react tin and sulfuric acid to synthesize metastannic acid; and (3) performing closed reaction under the pressure of more than or equal to 0.5MPa at the reaction temperature of 90-200 ℃ for 2-8 hours, performing liquid-solid separation after the reaction, adding ammonium bicarbonate to the solid part, namely the metastannic acid intermediate product, neutralizing and washing, removing residual sulfuric acid, and performing centrifugal filtration and drying to obtain metastannic acid.
The tin is tin powder or tin flower. After the tin reacts with the sulfuric acid, the leachate obtained by liquid-solid separation returns to the closed container to continue the metastannic acid synthesis reaction.
In the method, the metastannic acid is continuously calcined to obtain the tin dioxide.
By adopting the method, under the closed oxygen-introducing pressurizing condition, the metal tin firstly reacts with sulfuric acid to generate stannous sulfate, the stannous sulfate reacts with oxygen to generate metastannic acid, and the sulfuric acid is regenerated and can accelerate the dissolution of tin. Increasing pressure and heating can accelerate the reaction process and shorten the reaction time. The reaction formula is as follows:
Sn+H2SO4＝SnSO4+H2
2SnSO4+O2+4H2O＝2H2SnO3+2H2SO4。
the reaction system of the invention uses sulfuric acid to replace nitric acid, thereby effectively avoiding the problem of nitrogen oxide emission. And the consumption of the sulfuric acid is small, the residual acid is recycled, no waste liquid is discharged, and the energy-saving and environment-friendly effects are achieved. Compared with the nitric acid method production in the prior art, the production cost of the invention is greatly reduced.
Detailed Description
Example 1
A method for producing metastannic acid by a sulfuric acid method comprises the steps of preparing a sulfuric acid solution 2L with the acidity of 50g/l, adding the sulfuric acid solution into a 3L pressure kettle, adding 200g of tin flower, wherein the mass ratio of liquid to solid is 10:1, sealing the kettle, introducing oxygen to the pressure of 1.2MPa in the kettle, heating, controlling the reaction temperature to be 125 +/-5 ℃, reacting for 6 hours, carrying out liquid-solid separation after the reaction is finished to obtain reaction residual acid 1.9L and a reaction-synthesized intermediate metastannic acid, returning the reaction residual acid to the pressure kettle after the reaction residual acid contains 42.34g/l sulfate radicals and 0.016g/l Sn0, continuing the synthesis reaction after the sulfuric acid is supplemented, adding the obtained intermediate metastannic acid into ammonium bicarbonate for neutralization and washing, removing the residual sulfuric acid, carrying out centrifugal filtration and drying to obtain a metastannic acid product 282.82g, wherein the product quality is:
TABLE 1 product quality of metastannic acid (unit:%)
Number plate Metastannic acid Fe Heavy metals Ignition weightlessness PH Particle size
Standard of merit ≥88 ≤0.02 ≤0.1 10～12 5～7 0.125mm，≥98％
Product(s) 88.28 0.0043 0.0053 10.46 5.92 0.2～60μm
And continuously calcining the obtained metastannic acid to obtain the tin dioxide.
Example 2
A method for producing metastannic acid by a sulfuric acid method comprises the steps of preparing a sulfuric acid solution 2L with the acidity of 100g/l, adding the sulfuric acid solution into a 3L pressure kettle, adding 400g of tin powder, wherein the mass ratio of liquid to solid is 5:1, sealing and introducing oxygen to 2MPa, heating, controlling the reaction temperature to be 125 +/-5 ℃, reacting for 8 hours, carrying out liquid-solid separation after the reaction is finished to obtain reaction residual acid 1.9L and an intermediate metastannic acid product, adding 91.45g/l of sulfuric acid radical and Sn0.009g/l of the reaction residual acid, adding sulfuric acid into the reaction residual acid, returning to metastannic acid synthesis reaction, adding ammonium bicarbonate into the obtained intermediate metastannic acid for neutralization and washing, removing residual sulfuric acid, carrying out centrifugal filtration and drying to obtain a metastannic acid product 556.27g, wherein the product quality is as shown in:
TABLE 2 product quality of metastannic acid (unit:%)
Number plate Metastannic acid Fe Heavy metals Ignition weightlessness PH Particle size
Standard of merit ≥88 ≤0.02 ≤0.1 10～12 5～7 0.125mm，≥98％
Product(s) 89.02 0.0027 0.0076 10.69 6.18 0.2～60μm
And continuously calcining the obtained metastannic acid to obtain the tin dioxide.
Example 3
A method for producing metastannic acid by a sulfuric acid method comprises the steps of preparing a sulfuric acid solution 2L with acidity of 10g/l, adding the sulfuric acid solution into a 3L pressure kettle, adding 142g of tin flower, wherein the mass ratio of liquid to solid is 14:1, sealing a cover, introducing oxygen to 3MPa, heating, controlling the reaction temperature to be 195 +/-5 ℃, reacting for 5 hours, carrying out liquid-solid separation after the reaction is finished to obtain reaction residual acid 1.92L and an intermediate metastannic acid product, adding sulfuric acid to the reaction residual acid containing 6.92g/l sulfate radical and containing Sn0.0082g/l, returning metastannic acid to a metastannic acid synthesis reaction after the reaction residual acid is supplemented with sulfuric acid, adding ammonium bicarbonate to the obtained intermediate metastannic acid product for neutralization and washing, removing residual sulfuric acid, carrying out centrifugal filtration and drying to obtain a metastannic acid product 199.82 g:
TABLE 3 product quality of metastannic acid (unit:%)
Number plate Metastannic acid Fe Heavy metals Ignition weightlessness PH Particle size
Standard of merit ≥88 ≤0.02 ≤0.1 10～12 5～7 0.125mm，≥98％
Product(s) 88.52 0.0024 0.0051 10.35 5.88 0.2～60μm
And continuously calcining the obtained metastannic acid to obtain the tin dioxide.

Claims (4)

1. The method for producing metastannic acid by the sulfuric acid method is characterized by comprising the following steps: putting sulfuric acid and tin into a closed container according to a ratio, wherein the liquid-solid mass ratio of the solution to the tin is 5-14: 1, and the initial acidity of the sulfuric acid solution is 10-200 g/l; then, introducing oxygen into the closed container, pressurizing and heating to react tin and sulfuric acid to synthesize metastannic acid; the reaction formula is as follows:
Sn+H2SO4＝SnSO4+H2；
2SnSO4+O2+4H2O＝2H2SnO3+2H2SO4；
and (3) performing closed reaction under the pressure of more than or equal to 0.5MPa at the reaction temperature of 90-200 ℃ for 2-8 hours, performing liquid-solid separation after the reaction, adding ammonium bicarbonate to the solid part, namely the metastannic acid intermediate product, neutralizing and washing, removing residual sulfuric acid, and performing centrifugal filtration and drying to obtain metastannic acid.
2. The method for producing metastannic acid according to the sulfuric acid process of claim 1, wherein the tin is tin powder or tin flower.
3. The method for producing metastannic acid according to claim 1, wherein after the reaction of tin with sulfuric acid, the leachate obtained by the liquid-solid separation is returned to the closed vessel to continue the metastannic acid synthesis reaction.
4. A process for producing tin dioxide using metastannic acid obtained by the process according to claim 1, 2 or 3, characterized in that metastannic acid is calcined to obtain tin dioxide.
CN201810135124.9A 2018-02-09 2018-02-09 Method for producing metastannic acid and stannic oxide by sulfuric acid method Active CN108285170B (en)

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CN110156069B (en) * 2019-05-30 2021-11-23 云南锡业研究院有限公司 Method for preparing indium oxide superfine powder
CN111573715A (en) * 2020-06-16 2020-08-25 云南锡业研究院有限公司 Method for preparing stannic oxide by using tin oxide slag
CN112441611A (en) * 2020-12-07 2021-03-05 云南锡业锡化工材料有限责任公司 Method for preparing tin dioxide by using sponge tin and anode mud
CN113060758B (en) * 2021-05-07 2023-03-24 云南锡业研究院有限公司 Method for preparing stannic oxide and stannate by using tin-copper slag

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