CN110054213B - Method for preparing sodium stannate by soda roasting of high-silicon type cassiterite concentrate - Google Patents
Method for preparing sodium stannate by soda roasting of high-silicon type cassiterite concentrate Download PDFInfo
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 94
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 title claims abstract description 82
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229940079864 sodium stannate Drugs 0.000 title claims abstract description 75
- 239000012141 concentrate Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000010703 silicon Substances 0.000 title claims description 29
- 229910052710 silicon Inorganic materials 0.000 title claims description 29
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 78
- 238000002386 leaching Methods 0.000 claims description 55
- 239000011734 sodium Substances 0.000 claims description 29
- 238000000227 grinding Methods 0.000 claims description 23
- 239000012535 impurity Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 9
- 238000005054 agglomeration Methods 0.000 claims description 7
- 230000002776 aggregation Effects 0.000 claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 21
- 238000011084 recovery Methods 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000000377 silicon dioxide Substances 0.000 abstract description 10
- RBMIHUQBGTUBMH-UHFFFAOYSA-N [Si].[Na].[Sn] Chemical compound [Si].[Na].[Sn] RBMIHUQBGTUBMH-UHFFFAOYSA-N 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000011135 tin Substances 0.000 description 52
- 239000000463 material Substances 0.000 description 26
- 229910052718 tin Inorganic materials 0.000 description 25
- 230000008569 process Effects 0.000 description 20
- 238000001914 filtration Methods 0.000 description 14
- 239000002893 slag Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 13
- 235000012239 silicon dioxide Nutrition 0.000 description 10
- 239000004615 ingredient Substances 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- FTAHXGPNHBWWDP-UHFFFAOYSA-N carbon monoxide Chemical compound [O+]#[C-].[O+]#[C-] FTAHXGPNHBWWDP-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Treatment Of Sludge (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
本发明公开了一种利用高硅锡石精矿苏打焙烧制备锡酸钠的方法，通过控制两段焙烧过程碳酸钠配比、焙烧温度、气氛等焙烧条件，调控苏打焙烧过程中二氧化锡、二氧化硅和碳酸钠之间的反应，抑制钠硅锡三元氧化物的形成，同时促进锡酸钠的生成，最终提高锡酸钠的转化率，将锡回收率提高至98.6％以上。The invention discloses a method for preparing sodium stannate by using high-silica cassiterite concentrate soda roasting to roast. The reaction between silica and sodium carbonate inhibits the formation of sodium-silicon-tin ternary oxide and promotes the formation of sodium stannate at the same time, which ultimately improves the conversion rate of sodium stannate and increases the tin recovery rate to more than 98.6%.
Description
Technical Field
The invention relates to a method for preparing sodium rare-earth oxide by using high-silicon type cassiterite concentrate, in particular to a method for improving the yield of sodium stannate in the soda roasting process of cassiterite concentrate by using a secondary roasting process, and belongs to the field of non-ferrous metal smelting and chemical engineering.
Background
Sodium stannate is a tin chemical product with the most extensive application, and is applied to various fields of electroplating, dyes, material processing and the like. The main preparation method of sodium stannate comprises an alkali precipitation method and a detinning method, and mainly takes metallic tin as a raw material to react with sodium hydroxide and an oxidant to prepare a sodium stannate solution, and then impurity removal, crystallization purification, separation and crystallization are carried out to obtain a product. The traditional sodium stannate preparation process has high cost, low yield and high requirement on equipment.
The cassiterite concentrate soda roasting method uses cassiterite concentrate as raw material, and adds sodium salts of sodium carbonate, etc. to promote the formation of sodium stannate under the action of reducing agent, and can obtain sodium stannate product by the processes of leaching, impurity-removing, purifying and separating. However, most of the original tin ore is closely associated and symbiotic with gangue minerals such as quartz, garnet and calcite, the grade of tin is continuously improved through multi-stage grinding-selecting, but the cassiterite concentrate still contains a certain proportion of gangue minerals, especially the content of quartz is high. The cassiterite concentrate can basically remove impurities such as sulfur, arsenic, lead, zinc and the like through an oxidation roasting and acid leaching two-step pretreatment process, and the element content of the cassiterite concentrate is less than 0.005 percent; however, the existing process can not remove the silicon dioxide in the cassiterite concentrate, and the content of the silicon dioxide in the concentrate is generally more than 10 percent.
The silicon dioxide is an acidic oxide with stable property, and the silicon dioxide can easily react to generate sodium silicate with low melting point when the temperature is higher than 700 ℃ in the presence of sodium salt; in the process of roasting the cassiterite concentrate soda, silicon dioxide, cassiterite and sodium carbonate are easy to carry out chemical combination reaction to generate silicon-tin-sodium ternary oxide, the melting point of the ternary oxide is only about 700 ℃, the ternary oxide is tightly wrapped on the surface of the cassiterite, and the generation reaction of sodium stannate is inhibited. In addition, the ternary oxides of sodium, silicon and tin are insoluble in weak acid and alkali solution, and the leaching recovery rate of tin is greatly reduced in the subsequent leaching process, so that in the existing process for preparing sodium stannate by roasting cassiterite concentrate with soda, the conversion rate of tin is only about 85% (patent numbers ZL201210412835.9 and ZL201210411593.1), and part of tin remains in leaching residues in the form of ternary oxides of sodium, silicon and tin, thereby causing the waste of tin resources.
Disclosure of Invention
In order to solve the adverse effects of low conversion recovery rate of sodium stannate, large tin loss and the like caused by the generation of sodium stannate by silicon dioxide in the process of preparing the sodium stannate by roasting the high-silicon cassiterite concentrate as the raw material soda, the invention aims to provide the method for inhibiting the generation of sodium stannate ternary oxide in the roasting process of the high-silicon cassiterite concentrate soda by utilizing the secondary reduction roasting process so as to improve the conversion rate of the sodium stannate and reduce the tin loss.
In order to achieve the technical purpose, the invention provides a method for preparing sodium stannate by roasting high-silicon cassiterite concentrate soda, which comprises the following steps:
1) the high-silicon cassiterite concentrate and sodium carbonate are subjected to primary burdening according to the molar ratio of Na (Sn + Si) to 2.1: 1-2.6: 1, and after uniform mixing and grinding, agglomeration and drying are carried out, and then the mixture is placed in CO-CO2Roasting at 750-850 ℃ in mixed atmosphere for primary roasting, cooling and crushing a roasted product, then putting the crushed product into a sodium hydroxide solution for grinding and leaching, and performing solid-liquid separation to obtain a sodium stannate solution and primary leaching residues; wherein, CO-CO2The volume ratio of carbon monoxide in the mixed atmosphere is 10-15%;
2) mixing the primary leaching residue and sodium carbonate according to the molar ratio of Na (Sn + Si) being 3: 1-3.5: 1 for the second time, uniformly mixing, grinding, agglomerating, drying, and placing in CO-CO2Roasting at 750-850 ℃ in mixed atmosphere for secondary roasting, cooling and crushing a roasted product, then putting the crushed product into a sodium hydroxide solution for grinding and leaching, and performing solid-liquid separation to obtain a sodium stannate solution and secondary leaching residues; wherein, CO-CO2The volume ratio of carbon monoxide in the mixed atmosphere is 5-10%;
3) concentrating and crystallizing the sodium stannate solutions obtained in the steps 1) and 2) step by step to obtain the sodium stannate.
In the preferred scheme, the high-silicon cassiterite concentrate is pretreated by oxidizing roasting and acid leaching impurity removal. The high-silicon cassiterite concentrate is subjected to conventional oxidizing roasting-acid leaching impurity removal in the prior art in advance, so that the content of impurity elements such as iron, calcium, aluminum, magnesium and the like is lower than 0.01%, and the rest main impurities are silicon dioxide, and the content of the silicon dioxide is higher than 8%.
In the preferred scheme, the high-silicon cassiterite concentrate is uniformly mixed with sodium carbonate and ground until the granularity of 100 percent is less than 0.1 mm. The raw materials are all ground to proper granularity in advance, so that good contact among material particles can be ensured, and the solid-phase reaction can be smoothly and quickly carried out in the roasting process.
In a preferable scheme, the time for one-time roasting is 30-60 min.
In a preferable scheme, the primary leaching residue and sodium carbonate are uniformly mixed and ground until the granularity of 100 percent is less than 0.1 mm.
In a preferable scheme, the secondary roasting time is 30-60 min.
Preferably, the pH value of the sodium hydroxide solution in the steps 1) and 2) is 10.5-12.5.
The solid-liquid separation process of the present invention may be a conventional filtration separation.
The concentration and fractional crystallization processes of the present invention are conventional in the art.
In order to realize the technical purpose, the method for preparing the sodium stannate by roasting the high-silicon type cassiterite concentrate soda comprises the following specific steps:
1) the high-silicon cassiterite concentrate and sodium carbonate are subjected to primary burdening and mixing according to the molar ratio of Na (Sn + Si) to 2.1: 1-2.6: 1, are ground to 100 percent and smaller than-0.1 mm, are agglomerated and dried, and are placed in a CO-CO (carbon monoxide-carbon monoxide) environment2Roasting in the atmosphere for the first time, wherein the roasting temperature is 750-850 ℃, the roasting time is 30-60 min, and the volume ratio of carbon monoxide in the roasting atmosphere is 10-15%; after baking and sintering, crushing the cooled material, grinding and soaking in a sodium hydroxide solution (the pH value of the sodium hydroxide solution is 10.5-12.5), and then filtering and separating to obtain a sodium stannate solution and primary leaching residues;
2) will be oneMixing the secondary leaching residue and sodium carbonate according to the molar ratio of Na (Sn + Si) of 3: 1-3.5: 1 for the second time, uniformly mixing, grinding until the powder is 100% and less than-0.1 mm, agglomerating, drying, and placing in a CO-CO container2Roasting in the atmosphere for two-stage roasting at the secondary roasting temperature of 750-800 ℃ for 30-60 min, crushing the cooled material after roasting with the volume proportion of carbon monoxide of 5-10% in the roasting atmosphere, grinding and soaking in a sodium hydroxide solution (the pH value of the sodium hydroxide solution is 10.5-12.5), and then filtering and separating to obtain a sodium stannate solution and secondary leaching residues;
3) after two-stage roasting-grinding and soaking, sodium stannate solution is concentrated, crystallized step by step, filtered and separated twice to obtain sodium stannate product.
In the prior art, in the soda roasting process of the high-silicon type cassiterite concentrate, a sodium silicate binary compound and a sodium-silicon-tin ternary oxide are inevitably formed, the two substances are low-melting-point substances, and a local liquid phase is formed in the roasting process and wraps the surfaces of cassiterite particles to inhibit the subsequent reaction. In addition, sodium silicon tin ternary oxide is extremely difficult to dissolve in an alkalescent system, is not beneficial to separation and recovery of tin, and is a main reason for tin loss in the soda roasting process. The key point of the technical scheme is that the ratio of the sodium, silicon and tin elements in the mixed raw material of the high-silicon cassiterite concentrate and the sodium carbonate is effectively regulated and controlled, and the temperature and atmosphere optimization in the multi-stage roasting process are combined, so that the unexpected discovery can well inhibit the production of sodium, silicon and tin ternary oxides in the soda roasting process of the high-silicon cassiterite concentrate, promote the generation of sodium stannate, further improve the conversion rate of the sodium stannate and realize the high-efficiency recovery of the tin elements.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1) the technical scheme of the invention can obviously improve the conversion rate of sodium stannate in the soda roasting process of the cassiterite concentrate, and the comprehensive recovery rate of tin is improved to more than 98.6 percent.
2) According to the technical scheme, the sodium carbonate dosage, the roasting temperature and the atmosphere lamp parameters in the two-stage roasting process are regulated and controlled, so that the formation of sodium-silicon-tin ternary oxide is inhibited, the conversion of sodium stannate is promoted, other additives, expensive organic sodium salts and the like are not used, and the production cost is reduced.
3) The technical scheme of the invention has the advantages of simple operation, low energy consumption and low cost, and is easy to realize industrial production.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1:
using cassiterite concentrate (Sn content 70.0%, SiO)211.7 percent) and sodium carbonate (analytically pure) are taken as raw materials, the first-stage ingredients are mixed according to the proportion of Na (Sn + Si) of 2.5:1, ground to 100 percent and less than-0.1 mm after being uniformly mixed, then agglomerated and dried, and subjected to first-stage roasting, the roasting temperature is 850 ℃, the roasting time is 60min, the CO content in the roasting atmosphere is 15 percent, the materials are crushed after the roasting and sintering, and are ground and soaked in a sodium hydroxide solution with the pH value of 12.5, and filtered to obtain a sodium stannate solution and first leaching slag; and then, carrying out secondary batching on the leaching residues and sodium carbonate according to the ratio of Na (Sn + Si) of 3.1:1, grinding the mixture to 100 percent and less than-0.1 mm after uniformly mixing, then carrying out agglomeration, drying, carrying out secondary roasting, wherein the roasting temperature is 750 ℃, the roasting time is 30min, and the CO content in the roasting atmosphere is 5 percent, crushing the material after roasting and sintering, grinding and leaching the material in a sodium hydroxide solution with the pH value of 10.5, filtering to obtain a sodium stannate solution and secondary leaching residues, separating the two times to obtain a sodium stannate leaching solution, purifying and removing impurities, concentrating and crystallizing, and the like to obtain a sodium stannate product. The recovery of tin was 98.6%.
Example 2:
using cassiterite concentrate (Sn content 70.0%, SiO)211.7 percent) and sodium carbonate (analytically pure) are taken as raw materials, the first-stage ingredients are ground to 100 percent less than-0.1 mm after being uniformly mixed according to the proportion of Na (Sn + Si) of 2.1:1, then the mixture is agglomerated and dried, the mixture is roasted for the first time, the roasting temperature is 750 ℃, the roasting time is 30min, the CO content in the roasting atmosphere is 10 percent, the material is crushed after the roasting is finished, the crushed material is ground and soaked in sodium hydroxide solution with the pH value of 11.5, and sodium stannate solution and first leaching slag are obtained after the filtration; then leaching outPerforming secondary burdening on the slag and sodium carbonate according to the ratio of Na (Sn + Si) of 3.5:1, grinding the mixture to 100 percent and less than-0.1 mm after uniformly mixing, then agglomerating, drying, performing secondary roasting, wherein the roasting temperature is 800 ℃, the roasting time is 60min, the CO content in the roasting atmosphere is 10 percent, crushing the material after the roasting is finished, grinding and soaking the crushed material in a sodium hydroxide solution with the pH value of 10.5, filtering to obtain a sodium stannate solution and secondary leaching slag, separating the two times to obtain a sodium stannate leaching solution, purifying and removing impurities, concentrating and crystallizing and the like to obtain a sodium stannate product. The recovery of tin was 99.3%.
Example 3:
using cassiterite concentrate (Sn content 72.0%, SiO)28.1 percent of sodium stannate and sodium carbonate (analytically pure) are taken as raw materials, the first-stage ingredients are mixed according to the proportion of Na (Sn + Si) of 2.5:1, ground to 100 percent and less than-0.1 mm after being uniformly mixed, then agglomerated and dried, and subjected to first-stage roasting, the roasting temperature is 795 ℃, the roasting time is 45min, the CO content in the roasting atmosphere is 10.5 percent, the materials are crushed after being roasted and sintered, ground and soaked in sodium hydroxide solution with the pH value of 11.5, and filtered to obtain sodium stannate solution and first leaching slag; and then, carrying out secondary burdening on the leaching residue and sodium carbonate according to the ratio of Na (Sn + Si) of 3.2:1, uniformly mixing, grinding until the content of Na is less than-0.1 mm after being uniformly mixed, then carrying out agglomeration, drying, carrying out secondary roasting, carrying out roasting at the roasting temperature of 825 ℃, the roasting time of 60min and the CO content in the roasting atmosphere of 10%, crushing the materials after the roasting is finished, carrying out grinding and leaching in a sodium hydroxide solution with the pH of 12.5, filtering to obtain a sodium stannate solution and secondary leaching residue, separating twice to obtain a sodium stannate leaching solution, purifying, removing impurities, concentrating, crystallizing and the like, and obtaining a sodium stannate product. The recovery of tin was 99.2%.
Example 4:
using cassiterite concentrate (Sn content 72.0%, SiO)28.1 percent of sodium stannate and sodium carbonate (analytically pure) are taken as raw materials, the first-stage ingredients are mixed according to the proportion of Na (Sn + Si) of 2.2:1, ground to 100 percent and less than-0.1 mm after being uniformly mixed, then agglomerated and dried, and then first-stage roasting is carried out, the roasting temperature is 850 ℃, the roasting time is 30min, the CO content in the roasting atmosphere is 13.5 percent, the materials are crushed after the roasting and sintering, and are ground and soaked in a sodium hydroxide solution with the pH value of 10.5, and the sodium stannate solution and first-stage leaching slag are obtained after filtering; then will beAnd (2) carrying out secondary burdening on the leaching residues and sodium carbonate according to the ratio of Na (Sn + Si) to 1, uniformly mixing, grinding until the content of Na is less than-0.1 mm to 100%, then agglomerating, drying, carrying out secondary roasting, carrying out roasting at the roasting temperature of 775 ℃ for 30min and the CO content in the roasting atmosphere of 10%, crushing the materials after roasting is finished, carrying out grinding and leaching in a sodium hydroxide solution with the pH of 10.5, filtering to obtain a sodium stannate solution and secondary leaching residues, separating twice to obtain a sodium stannate leaching solution, purifying to remove impurities, concentrating and crystallizing, and the like to obtain a sodium stannate product. The recovery of tin was 99.0%.
Comparative example 1
Using cassiterite concentrate (Sn content 72.0%, SiO)28.1 percent) and sodium carbonate (analytically pure) are taken as raw materials, the ingredients are mixed according to the proportion of Na (Sn + Si) to 2.2:1, the mixture is ground to 100 percent and is smaller than-0.1 mm after being uniformly mixed, then agglomeration and drying are carried out, roasting is carried out, the roasting temperature is 850 ℃, the roasting time is 60min, the CO content in the roasting atmosphere is 13.5 percent, the materials are crushed after roasting, the materials are ground and soaked in a sodium hydroxide solution with the pH value of 10.5, a sodium stannate solution and secondary leaching slag are obtained through filtration, the two times of separation are carried out to obtain a sodium stannate leaching solution, and the treatments of purification, impurity removal, concentration, crystallization and the like are carried. The recovery of tin was 74.0%.
Comparative example 2:
using cassiterite concentrate (Sn content 70.0%, SiO)211.7 percent) and sodium carbonate (analytically pure) are taken as raw materials, the first-stage ingredients are mixed according to the proportion of Na (Sn + Si) of 2.5:1, ground to 100 percent and less than-0.1 mm after being uniformly mixed, then agglomerated and dried, and subjected to first-stage roasting at the roasting temperature of 850 ℃ for 60min in the roasting atmosphere of air, the materials are crushed after the roasting, ground and soaked in a sodium hydroxide solution with the pH value of 12.5, and filtered to obtain a sodium stannate solution and primary leaching slag; then, the leached slag and sodium carbonate are secondarily mixed according to the ratio of Na (Sn + Si) of 3.1:1, the mixture is evenly mixed and ground to 100 percent of the mixture to be less than-0.1 mm, then the mixture is agglomerated and dried, the mixture is secondly roasted at the roasting temperature of 750 ℃ for 30min in the air atmosphere, the material is crushed after roasting and sintering, the crushed material is ground and leached in a sodium hydroxide solution with the pH value of 10.5, the sodium stannate solution and the secondary leached slag are obtained by filtration, and the stannic acid is obtained by separating the two timesAnd (3) carrying out treatment on the sodium leaching solution, purifying and removing impurities, concentrating and crystallizing, and the like to obtain a sodium stannate product. The recovery of tin was 53.2%.
Comparative example 3:
using cassiterite concentrate (Sn content 70.0%, SiO)211.7 percent) and sodium carbonate (analytically pure) are taken as raw materials, the first-stage ingredients are mixed according to the proportion of Na (Sn + Si) of 2.5:1, ground to 100 percent and less than-0.1 mm after being uniformly mixed, then agglomerated and dried, and subjected to first-stage roasting, the roasting temperature is 850 ℃, the roasting time is 60min, the CO content in the roasting atmosphere is 35 percent, the materials are crushed after roasting, and are ground and soaked in a sodium hydroxide solution with the pH value of 12.5, and the sodium stannate solution and the first leaching slag are obtained after filtering; and then, carrying out secondary batching on the leaching residues and sodium carbonate according to the ratio of Na (Sn + Si) of 3.1:1, grinding the mixture to 100 percent of the mixture to be less than-0.1 mm after uniformly mixing, then carrying out agglomeration, drying, carrying out secondary roasting at the roasting temperature of 750 ℃ for 30min and the CO content in the roasting atmosphere of 2.5 percent, crushing the material after roasting and sintering, grinding and leaching the material in a sodium hydroxide solution with the pH of 10.5, filtering to obtain a sodium stannate solution and secondary leaching residues, separating the two times to obtain a sodium stannate leaching solution, purifying and removing impurities, concentrating and crystallizing, and the like to obtain a sodium stannate product. The recovery of tin was 34.2%.
Comparative example 4:
using cassiterite concentrate (Sn content 70.0%, SiO)211.7 percent) and sodium carbonate (analytically pure) are taken as raw materials, the first-stage ingredients are mixed according to the proportion of Na (Sn + Si) of 2.0:1, ground to 100 percent and less than-0.1 mm after being uniformly mixed, then agglomerated and dried, and subjected to first-stage roasting, the roasting temperature is 850 ℃, the roasting time is 60min, the CO content in the roasting atmosphere is 15 percent, the materials are crushed after the roasting and sintering, and are ground and soaked in a sodium hydroxide solution with the pH value of 12.5, and filtered to obtain a sodium stannate solution and first leaching slag; then, the leaching slag and sodium carbonate are secondarily mixed according to the ratio of Na (Sn + Si) of 3.0:1, the mixture is evenly mixed and ground to 100 percent of the mixture to be less than-0.1 mm, then agglomeration and drying are carried out, two-stage roasting is carried out, the roasting temperature is 750 ℃, the roasting time is 30min, the CO content in the roasting atmosphere is 5 percent, the material is crushed after roasting and sintering, the material is ground and leached in sodium hydroxide solution with the pH value of 10.5, filtering is carried out to obtain sodium stannate solution and secondary leaching slag, and the two times of leaching are carried outSeparating to obtain sodium stannate leachate, purifying to remove impurities, concentrating, crystallizing, and the like to obtain a sodium stannate product. The recovery of tin was 60.8%.
Claims (7)
1. A method for preparing sodium stannate by soda roasting of high-silicon cassiterite concentrate is characterized by comprising the following steps: the method comprises the following steps:
1) the high-silicon cassiterite concentrate and sodium carbonate are subjected to primary burdening according to the molar ratio of Na (Sn + Si) to 2.1: 1-2.6: 1, and after uniform mixing and grinding, agglomeration and drying are carried out, and then the mixture is placed in CO-CO2Roasting at 750-850 ℃ in mixed atmosphere for primary roasting, cooling and crushing a roasted product, then putting the crushed product into a sodium hydroxide solution for grinding and leaching, and performing solid-liquid separation to obtain a sodium stannate solution and primary leaching residues; wherein, CO-CO2The volume ratio of carbon monoxide in the mixed atmosphere is 10-15%;
2) mixing the primary leaching residue and sodium carbonate according to the molar ratio of Na (Sn + Si) being 3: 1-3.5: 1 for the second time, uniformly mixing, grinding, agglomerating, drying, and placing in CO-CO2Roasting at 750-850 ℃ in mixed atmosphere for secondary roasting, cooling and crushing a roasted product, then putting the crushed product into a sodium hydroxide solution for grinding and leaching, and performing solid-liquid separation to obtain a sodium stannate solution and secondary leaching residues; wherein, CO-CO2The volume ratio of carbon monoxide in the mixed atmosphere is 5-10%;
3) concentrating and crystallizing the sodium stannate solutions obtained in the steps 1) and 2) step by step to obtain the sodium stannate.
2. The method for preparing sodium stannate by soda roasting of high-silicon cassiterite concentrate according to claim 1, characterized in that: and carrying out oxidation roasting-acid leaching impurity removal pretreatment on the high-silicon cassiterite concentrate.
3. The method for preparing sodium stannate by soda roasting of high-silicon cassiterite concentrate according to claim 1, characterized in that: the high-silicon cassiterite concentrate is uniformly mixed with sodium carbonate and ground until the granularity of 100 percent is less than 0.1 mm.
4. The method for preparing sodium stannate by soda roasting of high-silicon cassiterite concentrate according to claim 1, characterized in that: the time of the primary roasting is 30-60 min.
5. The method for preparing sodium stannate by soda roasting of high-silicon cassiterite concentrate according to claim 1, characterized in that: mixing the first leaching residue with sodium carbonate, and grinding to particle size of 100% less than 0.1 mm.
6. The method for preparing sodium stannate by soda roasting of high-silicon cassiterite concentrate according to claim 1, characterized in that: the secondary roasting time is 30-60 min.
7. The method for preparing sodium stannate by soda roasting of high-silicon cassiterite concentrate according to claim 1, characterized in that: the pH value of the sodium hydroxide solution in the steps 1) and 2) is 10.5-12.5.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BG33057A1 (en) * | 1981-11-24 | 1982-12-15 | Maneva | Method for obtaining of sodium stannate |
| CN102923764A (en) * | 2012-10-25 | 2013-02-13 | 中南大学 | Method for preparing sodium stannate from stannic oxide and sodium salt in reduction roasting manner |
| CN104152675A (en) * | 2014-07-21 | 2014-11-19 | 中南大学 | Method for preparing metallic tin and sodium silicate by utilizing high-silicon type cassiterite concentrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BG33057A1 (en) * | 1981-11-24 | 1982-12-15 | Maneva | Method for obtaining of sodium stannate |
| CN102923764A (en) * | 2012-10-25 | 2013-02-13 | 中南大学 | Method for preparing sodium stannate from stannic oxide and sodium salt in reduction roasting manner |
| CN104152675A (en) * | 2014-07-21 | 2014-11-19 | 中南大学 | Method for preparing metallic tin and sodium silicate by utilizing high-silicon type cassiterite concentrate |
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| Title |
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| DIRECT PREPAPRATION OF SODIUM STANNATE FROM TIN CONCENTRATES;Wang Lichuan等;《J.CENT-SOUTH INST. MIN. METALL》;19870831;第18卷(第4期);第427-431页 * |
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