CN112456545A - Method for preparing sodium stannate trihydrate by using tin stripping waste liquid - Google Patents
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- 239000007788 liquid Substances 0.000 title claims abstract description 100
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 87
- SFXJSNATBHJIDS-UHFFFAOYSA-N disodium;dioxido(oxo)tin;trihydrate Chemical compound O.O.O.[Na+].[Na+].[O-][Sn]([O-])=O SFXJSNATBHJIDS-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000002699 waste material Substances 0.000 title claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 claims abstract description 52
- 239000003513 alkali Substances 0.000 claims abstract description 32
- 239000013078 crystal Substances 0.000 claims abstract description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 105
- 239000000243 solution Substances 0.000 claims description 64
- 229940079864 sodium stannate Drugs 0.000 claims description 37
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 35
- 238000000926 separation method Methods 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 28
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- 239000012670 alkaline solution Substances 0.000 claims description 24
- 239000012535 impurity Substances 0.000 claims description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- -1 iron ion Chemical class 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 150000005837 radical ions Chemical class 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 16
- 238000002360 preparation method Methods 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000004458 analytical method Methods 0.000 abstract description 6
- 238000009713 electroplating Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 229940071182 stannate Drugs 0.000 abstract description 3
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 2
- 229910052718 tin Inorganic materials 0.000 description 62
- 238000003756 stirring Methods 0.000 description 21
- 239000000047 product Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910001868 water Inorganic materials 0.000 description 11
- 238000001914 filtration Methods 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 3
- 239000005750 Copper hydroxide Substances 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 229910001128 Sn alloy Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229910001956 copper hydroxide Inorganic materials 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 235000014413 iron hydroxide Nutrition 0.000 description 3
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000510672 Cuminum Species 0.000 description 1
- 235000007129 Cuminum cyminum Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910020209 Na2Sn(OH)6 Inorganic materials 0.000 description 1
- 229910020212 Na2SnO3 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 125000005402 stannate group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
Abstract
The invention belongs to the technical field of preparation methods of alkali metal stannate, and particularly discloses a method for preparing sodium stannate trihydrate by using tin stripping waste liquid, which comprises the following steps: the tin stripping waste liquid is used as a raw material, and after crude tin hydroxide-high-purity tin hydroxide twice conversion, sodium stannate trihydrate is synthesized, so that the operation is simple, the process is environment-friendly, the production cost is low, the market competitiveness is strong, the obtained product is white to colorless crystals, the purity is high, the components are single, the free alkali is low, all indexes can reach the analytical purity standard, and the requirements of various industries such as chemical analysis, chemical synthesis and electroplating can be met.
Description
Technical Field
The invention belongs to the technical field of preparation methods of alkali metal stannate, and particularly relates to a method for preparing sodium stannate trihydrate by using tin stripping waste liquid.
Background
Sodium stannate is a tin-containing alkaline inorganic compound, usually with three crystal waters, of the formula Na2SnO3·3H2O or Na2Sn(OH)6Easy absorption of CO in air2To NaCO3And Sn (OH)4. Sodium stannate trihydrate is a basic tin chemical raw material and is widely applied to various industries such as electroplating, chemical analysis, catalysis, synthesis of tin chemical products and the like.
Chinese patent CN103172109A discloses a method for preparing sodium stannate by using tin-stripping wastewater: uniformly mixing the tin mud with strong base and water to form a blank; controlling the temperature to be 90-600 ℃, roasting the blank for 2-4 hours, cooling and crushing to form a dry material; mixing the dry materials with water to form a first leaching solution, stirring for reaction, and then carrying out solid-liquid separation on the first leaching solution to obtain a first filtrate and first sediments; evaporating, concentrating, crystallizing and cleaning the first filtrate to obtain a crude sodium stannate product; and drying the sodium stannate crude product to obtain a sodium stannate product. The invention has the advantages of mild preparation conditions, greatly reduced roasting temperature of the prior art, greatly reduced energy consumption, simplified leaching process, improved leaching rate of tin, obvious economic benefit and good development prospect, high energy consumption and high treatment cost of flue gas generated by roasting because the process needs high-temperature roasting.
Chinese patent CN103086421A discloses a method for preparing sodium stannate by using oxidizing slag and anode mud generated during stannous sulfate production, which comprises the steps of putting the oxidizing slag and anode mud generated during stannous sulfate production into sodium carbonate solution to perform sulfate radical removal reaction to obtain low-sulfate radical material, carrying out synthetic reaction of the low-sulfate radical material with sodium hydroxide, sodium nitrate and water to obtain crude sodium stannate, dissolving the crude sodium stannate in water, leaching to remove impurities, and concentrating and crystallizing the solution from which the impurities are removed. The method utilizes the oxidizing slag and the anode mud as raw materials to prepare the sodium stannate, avoids the process of putting the raw materials into the sodium stannate production after the raw materials are sent to a tin smelting plant to be processed into refined tin, improves the recovery rate of tin metal, realizes the comprehensive utilization of the tin metal materials in the company, and saves energy; the production process and equipment are simple and easy to implement, the production cost of the sodium stannate is greatly reduced, the tin metal realizes 'green circulation' in branch companies, but the process needs to add the sodium nitrate for ingredient oxidation, and the production process is not environment-friendly.
Chinese patent CN101544397A discloses a method for producing sodium stannate by using tin and tin alloy, the preparation method of the method is: (1) carrying out chemical reaction on tin and tin alloy, sodium hydroxide and an oxidant in a reaction kettle at the temperature of 300-550 ℃ to obtain granular crude sodium stannate; the reaction process is that sodium hydroxide and oxidant are gradually added into the molten tin and tin alloy until the reaction is complete; (2) dissolving granular crude sodium stannate with water; (3) refining and purifying the solution; (4) the sodium stannate solution obtained by refining and purifying is concentrated, separated and dried to obtain the finished product, and the process has high reaction temperature, high requirement on equipment and difficult popularization.
It can be seen from the prior art that the production process of producing sodium stannate by using tin-containing waste as raw material is long, the product quality is unstable, and the technology is difficult to be applied in industrial production.
In the prior art, refined tin ingots are used as raw materials for producing sodium stannate, an alkaline hydrolysis method and a chlorine method are mainly adopted, nitrogen oxide emission exists in the production process of the alkaline hydrolysis method, the process is not environment-friendly, the chlorine method production process can cause harm to the working environment and workers due to the existence of chlorine, a large amount of strong acid and strong base are used in the production process, the corrosion to equipment is serious, products are easy to pollute, and the requirements of finished products can be met through a plurality of complicated impurity removal processes. The sodium stannate produced by the existing method has high water content and can be provided for customers after being dried, crushed and screened, the drying and crushing process can not only increase the contact time of the sodium stannate and air, but also bring great harm to human bodies due to sodium stannate dust generated in the drying and crushing process.
Chinese patent CN103641156A discloses a preparation method of low free alkali reagent grade sodium stannate, which comprises the steps of firstly reacting stannum flower, sodium hydroxide and ozone at the temperature of 90-110 ℃ until the concentration of free sodium hydroxide in reaction liquid is 50-100 g/L; adding reagent-grade hydrated tin hydroxide, adjusting the concentration of free sodium hydroxide in the solution to 5-20g/L, introducing ozone again until the solution is colorless and transparent, and filtering; adding the filtrate into a concentration reaction kettle, evaporating and concentrating under the condition that the stirring speed is 10-30 r/min until most of crystals are separated out from the solution, discharging to a centrifugal machine, and centrifuging to obtain crystals, namely the finished product of sodium stannate. The preparation method is simple to operate, the process is environment-friendly, the obtained product is white to colorless crystals, the purity is high, the components are single, the free alkali is low, and all indexes can reach the analytical pure standard, but the process has low reaction rate of synthesizing the sodium stannate solution by using ozone, metallic tin and sodium hydroxide, long synthesis time and high production cost, has low market competitiveness of the product, and is difficult to realize mass production, so that the development of the process for producing the high-quality sodium stannate crystals at low cost is a matter of cumin for related scientific and technological workers.
Disclosure of Invention
In order to solve the problems, the invention provides a method for preparing sodium stannate trihydrate from tin stripping waste liquid, which uses the tin stripping waste liquid as a raw material, has short production process flow, simple operation and environment-friendly process, can prepare the sodium stannate trihydrate with electroplating grade and reagent grade without drying and crushing, and has the following specific technical scheme:
the invention aims to provide a method for preparing sodium stannate trihydrate by using tin stripping waste liquid, which has the technical points that: the method for preparing the sodium stannate trihydrate by using the tin stripping waste liquid comprises the following steps:
adding tin stripping waste liquid into a reaction kettle, then adding a sodium carbonate solution to adjust the pH value of the tin stripping waste liquid to 0-0.5, then adding liquid alkali to adjust the pH value of the tin stripping waste liquid to 5-8, and then carrying out first solid-liquid separation to obtain a crude tin hydroxide solid;
step two, adding alkali liquor into the reaction kettle in the step one, mixing the alkali liquor with the crude tin hydroxide solid prepared in the step one, heating to 110 ℃, reacting for 1-6 hours, performing second solid-liquid separation after the reaction is finished to obtain tin-containing alkaline solution, adding a composite impurity removing agent into the tin-containing alkaline solution to remove impurities, performing third solid-liquid separation to obtain pure tin-containing alkaline solution, introducing carbon dioxide into the pure tin-containing alkaline solution to adjust the pH value to 8.5-10, performing fourth solid-liquid separation, and washing to obtain high-purity tin hydroxide solid;
step three, adding liquid caustic soda into the reaction kettle in the step two to mix with the high-purity tin hydroxide solid prepared in the step two, heating to 110 ℃, reacting for 2-4 hours, adding a composite impurity removing agent after the reaction is finished, removing impurities, and performing fifth solid-liquid separation to remove the solid to obtain a pure sodium stannate solution;
and step four, adding the pure sodium stannate solution prepared in the step three into a concentration reaction kettle for reaction, carrying out evaporation concentration at the rotating speed of 10-30rmp until most of crystals in the solution are separated out, stopping concentration, discharging to a centrifugal machine, and centrifuging to obtain crystals, namely the sodium stannate trihydrate.
In the method for preparing sodium stannate trihydrate by using the tin stripping waste liquid, the tin stripping waste liquid in the first step comprises 10-25 wt% of acid radical ion mass fraction, 1-5 wt% of chloride ion mass fraction, 0.2-5 wt% of COD mass fraction, 2-10 wt% of Sn mass fraction, 1-5 wt% of copper ion mass fraction and 1-5 wt% of iron ion mass fraction.
In the method for preparing sodium stannate trihydrate by using the tin stripping waste liquid, the acid radical ions are nitrate ions or sulfate ions.
In the method for preparing sodium stannate trihydrate by using the tin stripping waste liquid, the composite impurity removing agent in the second step and the third step is a mixture of hydrogen peroxide and activated carbon.
In the method for preparing sodium stannate trihydrate by using the tin stripping waste liquid, the ratio of the amount of the two-liquid caustic soda substance to the amount of the crude tin hydroxide substance in the steps is 4-8: 1.
In the method for preparing the sodium stannate trihydrate by using the tin stripping waste liquid, the adding amount of the hydrogen peroxide in the second step is 0.1-0.5 wt% of the weight of the tin-containing alkaline solution, and the adding amount of the active carbon is 0.5-1 wt% of the weight of the tin-containing alkaline solution.
In the method for preparing the sodium stannate trihydrate by using the tin stripping waste liquid, the addition amount of the hydrogen peroxide in the third step is 0.1-0.5 wt% of the sum of the weights of the liquid alkali and the high-purity tin hydroxide solid, and the addition amount of the active carbon is 0.5-1 wt% of the sum of the weights of the liquid alkali and the high-purity tin hydroxide solid.
In the method for preparing sodium stannate trihydrate by using the tin stripping waste liquid, the alkali liquor in the first step, the second step and the third step is sodium hydroxide solution with the mass fraction of 30-32 wt%.
Compared with the prior art, the invention has the beneficial effects that:
the invention relates to a method for preparing sodium stannate trihydrate from tin stripping waste liquid, which synthesizes crude tin hydroxide from the tin stripping waste liquid, sodium carbonate solution and caustic soda solution, then the crude product of tin hydroxide is further reacted with flake caustic soda, pure water and carbon dioxide to prepare high-purity tin hydroxide, the high-purity tin hydroxide and liquid caustic soda are utilized to synthesize pure sodium stannate solution, and finally, in the process of concentrating and crystallizing the sodium stannate trihydrate solution, by controlling the stirring speed and the concentration of free alkali, the sodium stannate trihydrate crystals which can reach the analytical purity standard without drying and crushing are obtained, the method is simple to operate, environment-friendly in process, low in production cost, high in market competitiveness, high in purity, single in component, low in free alkali and capable of meeting the requirement of various industries such as chemical analysis, chemical synthesis and electroplating, and the obtained product is white to colorless crystals.
Drawings
FIG. 1 is a flow chart of a method for preparing sodium stannate trihydrate from tin stripping waste liquid according to the invention.
Detailed description of the invention
A method for preparing sodium stannate trihydrate by using tin stripping waste liquid comprises the following steps:
adding tin-stripping waste liquid into a reaction kettle, slowly adding sodium carbonate into the tin-stripping waste liquid in order to prevent the reaction kettle from overflowing, adjusting the pH value of the tin-stripping waste liquid to 0-0.5, preferably 0.5, keeping the reaction temperature at normal temperature, further preventing the phenomenon that carbon dioxide gas generated in acid-base neutralization overflows due to the fact that solid precipitate colloid is not easily released, adding liquid alkali to adjust the pH value of the tin-stripping waste liquid to 5-8, and then carrying out first solid-liquid separation to obtain crude tin hydroxide solid;
the tin stripping waste liquid comprises 10-25 wt% of acid radical ions (nitrate ions or sulfate ions), 1-5 wt% of chloride ions, 0.2-5 wt% of COD, 2-10 wt% of Sn, 1-5 wt% of copper ions and 1-5 wt% of iron ions.
Step two, adding alkali liquor into the reaction kettle in the step one to mix with the crude tin hydroxide solid prepared in the step one, wherein the ratio of the amount of the alkali liquor substance to the amount of the crude tin hydroxide substance is 4-8:1, heating to 110 ℃, preferably to 105 ℃, and reacting for 1-6h, wherein the heating reaction principle is as follows: and converting tin into soluble stannate so as to realize separation with other metal impurities such as copper, iron and the like, and performing secondary solid-liquid separation after the reaction is finished to obtain the tin-containing alkaline solution. Adding a composite impurity removing agent into the tin-containing alkaline solution for impurity removal, carrying out solid-liquid separation for the third time to obtain a pure tin-containing alkaline solution, introducing carbon dioxide into the pure tin-containing alkaline solution to adjust the pH value to 8.5-10, carrying out solid-liquid separation for the fourth time, recycling the liquid obtained by solid-liquid separation into a sodium carbonate solution in the crude tin hydroxide preparation procedure in the step two, and washing to obtain a high-purity tin hydroxide solid;
step three, adding liquid caustic soda into the reaction kettle in the step two to mix with the high-purity tin hydroxide solid prepared in the step two, heating to 110 ℃, reacting for 2-4 hours, adding a composite impurity removing agent after the reaction is finished to remove impurities, further removing pollution caused by equipment corrosion and the like, and then performing fifth solid-liquid separation to remove solids to obtain a pure sodium stannate solution;
and step four, adding the pure sodium stannate solution prepared in the step three into a concentration reaction kettle for reaction, carrying out evaporation concentration at the rotating speed of 10-30rmp until most of crystals in the solution are separated out, stopping concentration, discharging to a centrifugal machine, and centrifuging to obtain crystals, namely the sodium stannate trihydrate.
The composite impurity removing agent in the second step and the third step is a mixture of hydrogen peroxide and active carbon. In the second step, the adding amount of the hydrogen peroxide is 0.1 to 0.5 weight percent of the weight of the tin-containing alkaline solution, and the adding amount of the active carbon is 0.5 to 1 weight percent of the weight of the tin-containing alkaline solution. In the third step, the addition amount of the hydrogen peroxide is 0.1 to 0.5 weight percent of the sum of the solid weights of the liquid alkali and the high-purity tin hydroxide, and the addition amount of the active carbon is 0.5 to 1 weight percent of the sum of the solid weights of the liquid alkali and the high-purity tin hydroxide.
In the method for preparing the sodium stannate trihydrate by using the tin stripping waste liquid, the alkali liquor in the first step, the second step and the third step is a sodium hydroxide solution with the mass fraction of 30-32 wt%, wherein the sodium hydroxide solution is prepared by dissolving solid sodium hydroxide solid in water.
The technical solutions in the embodiments of the present invention will be clearly and completely described below so that those skilled in the art can better understand the advantages and features of the present invention, and thus the scope of the present invention will be more clearly defined. The embodiments described herein are only a few embodiments of the present invention, rather than all embodiments, and all other embodiments that can be derived by one of ordinary skill in the art without inventive faculty based on the embodiments described herein are intended to fall within the scope of the present invention.
Example 1
1. Preparation of crude tin hydroxide:
adding the nitric acid type tin stripping waste liquid into a reaction kettle, starting stirring, slowly adding a sodium bicarbonate solution, stopping adding the sodium carbonate solution when the pH value is 0, adding liquid alkali (30-32% sodium hydroxide solution) to adjust the pH value to 6.0, stopping stirring, standing and settling for 2 hours, starting a filter press to perform solid-liquid separation, and obtaining a solid which is a crude product of tin hydroxide (tin hydroxide containing a small amount of copper hydroxide and iron hydroxide) through separation;
2. preparing high-purity tin hydroxide:
adding liquid caustic soda (30-32% sodium hydroxide solution) into a reaction kettle, starting stirring, and slowly adding the crude tin hydroxide, wherein the mass ratio of the liquid caustic soda to the crude tin hydroxide is 4: 1, heating to 100 ℃, reacting for 3 hours, then carrying out solid-liquid separation to obtain a tin-containing alkaline solution and a copper oxide and iron oxide solid, adding the tin-containing alkaline solution into a reaction kettle, starting stirring, introducing carbon dioxide gas to enable the pH of the solution to be 9.0, and then carrying out solid-liquid separation to obtain a sodium carbonate solution and high-purity tin hydroxide;
3. preparation of sodium stannate trihydrate:
adding liquid alkali (30-32% of sodium hydroxide solution) into a reaction kettle, starting stirring, adding high-purity tin hydroxide, heating to 100 ℃ for reaction for 2 hours, adding water to enable the specific gravity of the solution to be 1.20, adding hydrogen peroxide and activated carbon according to the volume ratio of 0.1% for reaction for 8 hours, filtering to obtain a pure sodium stannate solution, adding the pure sodium stannate solution obtained by filtering into a concentration reaction kettle, adjusting the stirring speed of a stirrer to be 20 revolutions per minute, evaporating and concentrating until a large amount of crystals are separated out, putting the crystals into a centrifugal machine for centrifugal dehydration to obtain sodium stannate trihydrate, and performing analytical test to obtain sodium stannate trihydrate, wherein the tin content is 43.3%, the free alkali content is 0.6%, and the analytical purity standard is met.
Example 2
1. Preparation of crude tin hydroxide:
adding sulfuric acid type tin-stripping waste liquid into a reaction kettle, starting stirring, slowly adding a sodium bicarbonate solution, stopping adding a sodium carbonate solution when the pH value is 0.4, adding liquid alkali (30-32% sodium hydroxide solution) to adjust the pH value to 6.5, stopping stirring, standing and settling for 4 hours, starting a filter press for solid-liquid separation, and obtaining a solid product which is crude tin hydroxide (tin hydroxide containing a small amount of copper hydroxide and iron hydroxide) through separation;
2. preparing high-purity tin hydroxide:
adding liquid caustic soda (30-32% sodium hydroxide solution) into a reaction kettle, starting stirring, and slowly adding the crude tin hydroxide, wherein the mass ratio of the liquid caustic soda to the crude tin hydroxide is 5: 1, heating to 105 ℃, reacting for 4 hours, then carrying out solid-liquid separation to obtain a tin-containing alkaline solution and a copper oxide and iron oxide solid, adding the tin-containing alkaline solution into a reaction kettle, starting stirring, introducing carbon dioxide gas to enable the pH of the solution to be 9.5, and then carrying out solid-liquid separation to obtain a sodium carbonate solution and high-purity tin hydroxide;
3. preparation of sodium stannate trihydrate:
adding liquid alkali (30-32% of sodium hydroxide solution) into a reaction kettle, starting stirring, adding high-purity tin hydroxide, heating to 105 ℃ for reaction for 4 hours, adding water to enable the specific gravity of the solution to be 1.24, adding hydrogen peroxide and active carbon according to the volume ratio of 0.3%, reacting for 12 hours, filtering to obtain a pure sodium stannate solution, adding the pure sodium stannate solution obtained by filtering into a concentration reaction kettle, adjusting the stirring speed of a stirrer to be 30 revolutions per minute, evaporating and concentrating until a large amount of crystals are separated out, putting the crystals into a centrifugal machine for centrifugal dehydration to obtain sodium stannate trihydrate, and performing analytical test to obtain sodium stannate trihydrate, wherein the tin content is 43.6%, the free alkali content is 0.5%, and the analytical purity standard is met.
Example 3
1. Preparation of crude tin hydroxide:
adding the nitric acid type tin stripping waste liquid into a reaction kettle, starting stirring, slowly adding a sodium bicarbonate solution, stopping adding the sodium carbonate solution when the pH value is 0.5, adding liquid alkali (30-32% sodium hydroxide solution) to adjust the pH value to 7.0, stopping stirring, standing and settling for 6 hours, starting a filter press for solid-liquid separation, and obtaining a solid product which is crude tin hydroxide (tin hydroxide containing a small amount of copper hydroxide and iron hydroxide) through separation;
2. preparing high-purity tin hydroxide:
adding liquid caustic soda (30-32% sodium hydroxide solution) into a reaction kettle, starting stirring, and slowly adding the crude tin hydroxide, wherein the mass ratio of the liquid caustic soda to the crude tin hydroxide is 8:1, heating to 110 ℃, reacting for 6 hours, then carrying out solid-liquid separation to obtain a tin-containing alkaline solution and a copper oxide and iron oxide solid, adding the tin-containing alkaline solution into a reaction kettle, starting stirring, introducing carbon dioxide gas to enable the pH of the solution to be 10.0, and then carrying out solid-liquid separation to obtain a sodium carbonate solution and high-purity tin hydroxide;
3. preparation of sodium stannate trihydrate:
adding liquid alkali (30-32% of sodium hydroxide solution) into a reaction kettle, starting stirring, adding high-purity tin hydroxide, heating to 100 ℃ for reaction for 6 hours, adding water to enable the specific gravity of the solution to be 1.25, adding hydrogen peroxide according to the volume ratio of 0.5% to react with activated carbon for 16 hours, filtering to obtain a pure sodium stannate solution, adding the pure sodium stannate solution obtained by filtering into a concentration reaction kettle, adjusting the stirring speed of a stirrer to be 10 r/min, evaporating and concentrating until a large amount of crystals are separated out, putting the crystals into a centrifugal machine for centrifugal dehydration to obtain sodium stannate trihydrate, and performing analytical test to obtain sodium stannate trihydrate, wherein the tin content is 44%, the free alkali content is 0.4%, and the analytical purity standard is met.
Examples of the experiments
By examining the sodium stannate trihydrate obtained in examples 1, 2 and 3, the technical indexes are shown in table 1:
table 1 sodium stannate trihydrate quality specifications: is based on
TABLE 2 existing national standard for sodium stannate trihydrate GB/T26040-
As can be seen from the above, the indexes of the sodium stannate trihydrate product prepared by the invention are superior to the first-grade indexes of national sodium stannate trihydrate.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. A method for preparing sodium stannate trihydrate by using tin stripping waste liquid is characterized by comprising the following steps: the method for preparing the sodium stannate trihydrate by using the tin stripping waste liquid comprises the following steps:
adding tin stripping waste liquid into a reaction kettle, then adding a sodium carbonate solution to adjust the pH value of the tin stripping waste liquid to 0-0.5, then adding liquid alkali to adjust the pH value of the tin stripping waste liquid to 5-8, and then carrying out first solid-liquid separation to obtain a crude tin hydroxide solid;
step two, adding alkali liquor into the reaction kettle in the step one, mixing the alkali liquor with the crude tin hydroxide solid prepared in the step one, heating to 110 ℃, reacting for 1-6 hours, performing second solid-liquid separation after the reaction is finished to obtain tin-containing alkaline solution, adding a composite impurity removing agent into the tin-containing alkaline solution to remove impurities, performing third solid-liquid separation to obtain pure tin-containing alkaline solution, introducing carbon dioxide into the pure tin-containing alkaline solution to adjust the pH value to 8.5-10, performing fourth solid-liquid separation, and washing to obtain high-purity tin hydroxide solid;
step three, adding liquid caustic soda into the reaction kettle in the step two to mix with the high-purity tin hydroxide solid prepared in the step two, heating to 110 ℃, reacting for 2-4 hours, adding a composite impurity removing agent after the reaction is finished, removing impurities, and performing fifth solid-liquid separation to remove the solid to obtain a pure sodium stannate solution;
and step four, adding the pure sodium stannate solution prepared in the step three into a concentration reaction kettle for reaction, carrying out evaporation concentration at the rotating speed of 10-30rmp until most of crystals in the solution are separated out, stopping concentration, discharging to a centrifugal machine, and centrifuging to obtain crystals, namely the sodium stannate trihydrate.
2. The method for preparing sodium stannate trihydrate from the tin stripping waste liquid according to claim 1, which is characterized in that: the tin stripping waste liquid in the first step comprises 10-25 wt% of acid radical ion mass fraction, 1-5 wt% of chloride ion mass fraction, 0.2-5 wt% of COD mass fraction, 2-10 wt% of Sn mass fraction, 1-5 wt% of copper ion mass fraction and 1-5 wt% of iron ion mass fraction.
3. The method for preparing sodium stannate trihydrate from the tin stripping waste liquid according to claim 2, which is characterized in that: the acid radical ion is one of nitrate ion or sulfate ion.
4. The method for preparing sodium stannate trihydrate from the tin stripping waste liquid according to claim 1, which is characterized in that: the composite impurity removing agent in the second step and the third step is a mixture of hydrogen peroxide and active carbon.
5. The method for preparing sodium stannate trihydrate from the tin stripping waste liquid according to claim 1, which is characterized in that: the ratio of the amount of the two-liquid caustic soda material to the amount of the crude tin hydroxide material in the step is 4-8: 1.
6. The method for preparing sodium stannate trihydrate from the tin stripping waste liquid according to claim 4, which is characterized in that: in the second step, the addition amount of the hydrogen peroxide is 0.1 to 0.5 weight percent of the weight of the tin-containing alkaline solution, and the addition amount of the active carbon is 0.5 to 1 weight percent of the weight of the tin-containing alkaline solution.
7. The method for preparing sodium stannate trihydrate from the tin stripping waste liquid according to claim 4, which is characterized in that: in the third step, the addition amount of the hydrogen peroxide is 0.1 to 0.5 weight percent of the sum of the weights of the liquid alkali and the high-purity tin hydroxide solid, and the addition amount of the active carbon is 0.5 to 1 weight percent of the sum of the weights of the liquid alkali and the high-purity tin hydroxide solid.
8. The method for preparing sodium stannate trihydrate from the tin stripping waste liquid according to claim 1, which is characterized in that: the alkali liquor in the first step, the second step and the third step is sodium hydroxide solution with the mass fraction of 30-32 wt%.
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| CN115232985A (en) * | 2022-07-01 | 2022-10-25 | 清远市中宇环保实业有限公司 | Novel alkaline leaching-crystallization preparation process for tin in tin-containing sludge |
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| CN101532096A (en) * | 2009-04-01 | 2009-09-16 | 深圳市危险废物处理站有限公司 | A recovery method of tin in tin-stripping waste liquid |
| CN103451452A (en) * | 2013-09-11 | 2013-12-18 | 广东致远新材料有限公司 | Method for recovering tin from tin-containing waste liquid |
| CN105329936A (en) * | 2015-12-02 | 2016-02-17 | 柳州华锡铟锡材料有限公司 | Preparation method for sodium stannate product with whiteness larger than 95 degrees |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101532096A (en) * | 2009-04-01 | 2009-09-16 | 深圳市危险废物处理站有限公司 | A recovery method of tin in tin-stripping waste liquid |
| CN103451452A (en) * | 2013-09-11 | 2013-12-18 | 广东致远新材料有限公司 | Method for recovering tin from tin-containing waste liquid |
| CN105329936A (en) * | 2015-12-02 | 2016-02-17 | 柳州华锡铟锡材料有限公司 | Preparation method for sodium stannate product with whiteness larger than 95 degrees |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115232985A (en) * | 2022-07-01 | 2022-10-25 | 清远市中宇环保实业有限公司 | Novel alkaline leaching-crystallization preparation process for tin in tin-containing sludge |
| CN115232985B (en) * | 2022-07-01 | 2024-01-16 | 清远市中宇环保实业有限公司 | Alkaline leaching-crystallization preparation process of tin in tin-containing sludge |
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