CN110453093B - A method for selective leaching of titanium from titanium-containing slag - Google Patents
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- 238000002386 leaching Methods 0.000 title claims abstract description 131
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 116
- 239000010936 titanium Substances 0.000 title claims abstract description 116
- 239000002893 slag Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010703 silicon Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims description 15
- 239000011575 calcium Substances 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 12
- 239000011777 magnesium Substances 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical group 0.000 claims description 3
- 230000036632 reaction speed Effects 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 12
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 239000012141 concentrate Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 2
- 229910017682 MgTi Inorganic materials 0.000 description 1
- 229910017855 NH 4 F Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004334 fluoridation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
- C22B34/124—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors
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Abstract
Description
技术领域technical field
本发明属于钛资源利用技术领域，涉及一种含钛炉渣选择性浸出钛的方法。The invention belongs to the technical field of titanium resource utilization, and relates to a method for selectively leaching titanium from titanium-containing slag.
背景技术Background technique
我国钛资源主要赋存在钒钛磁铁矿资源中，其中攀西地区钒钛磁铁矿资源储量达到96.6亿吨(含超低品位矿)，其中钛储量占全国钛储量的90.5％，居世界钛储量第一位。在目前的选矿技术条件下，攀西钒钛磁铁矿中约占52％的钛资源进入钒钛磁铁精矿产品中，约占24％的钛资源进入钛铁矿精矿产品中。钒钛磁铁精矿主要采用高炉法工艺回收其中的铁和钒，钛则进入高炉钛渣中，TiO2品位约25％左右，主要含钛矿物为钙钛矿，因其杂质种类多、含量大，难以经济回收利用；钒钛磁铁精矿经预还原-电炉冶炼后钛进入含钛电炉渣中，TiO2品位约40～60％，主要含钛矿物为黑钛石；钛铁矿精矿经电炉冶炼后钛进入电炉钛渣中，形成TiO2品位约72％左右、主要含钛矿物为黑钛石的电炉钛渣。含钛电炉渣和电炉钛渣中TiO2品位较高，含钛电炉渣与一般钛精矿中TiO2含量相当，电炉钛渣TiO2含量高于一般钛精矿中TiO2含量。因此，如何高效回收利用含钛炉渣中钛资源已成为提高我国攀西地区钛资源利用率的关键。my country's titanium resources are mainly hosted in vanadium-titanium-magnetite resources, of which the reserves of vanadium-titanium-magnetite resources in Panxi area reach 9.66 billion tons (including ultra-low-grade ore), of which titanium reserves account for 90.5% of the national titanium reserves, ranking first in the world. Titanium reserves first. Under the current beneficiation technology, about 52% of the titanium resources in Panxi vanadium titanomagnetite go into the vanadium titanomagnetite concentrate products, and about 24% of the titanium resources go into the ilmenite concentrate products. The iron and vanadium in the vanadium-titanium magnetite concentrate is mainly recovered by the blast furnace process, and the titanium enters the blast furnace titanium slag, with a TiO 2 grade of about 25%. , it is difficult to recycle and reuse; the vanadium-titanium magnetite concentrate is pre-reduced-electric furnace smelting, and the titanium enters the titanium-containing electric furnace slag, the TiO 2 grade is about 40-60%, and the main titanium-containing mineral is black titanium; ilmenite concentrate is processed by After electric furnace smelting, titanium enters into electric furnace titanium slag to form electric furnace titanium slag with TiO 2 grade of about 72% and the main titanium-containing mineral is black titanium stone. Titanium-containing EAF slag and EAF titanium slag have higher TiO 2 grades. Titanium-containing EAF slag has a TiO 2 content equivalent to that of ordinary titanium concentrates. The TiO 2 content of EAF titanium slag is higher than that of ordinary titanium concentrates. Therefore, how to efficiently recycle titanium resources in titanium-containing slag has become the key to improve the utilization rate of titanium resources in Panxi area of my country.
目前，钛工业主要产品为钛白粉和海绵钛，每年全球90％以上钛资源用于生产钛白粉，钛白粉生产方法主要有沸腾氯化法、硫酸法和氟化法。沸腾氯化法要求原料TiO2>90％、CaO<0.2％、MgO<1％，含钛炉渣中含有大量的杂质元素，特别是钙、镁杂质含量大，部分镁杂质固溶在黑钛石中，钙主要以硅酸盐形式存在，脱除困难，导致含钛炉渣难以作为氯化法钛白粉原料。含钛炉渣中含有大量的杂质元素，特别是Ca和Si元素。硫酸酸浸过程中这些Ca和Si元素与硫酸反应生成胶状的硫酸钙和原硅酸附着在未反应的颗粒表面，浸出液中大量的胶状物的存在不但会影响浸出反应的进一步进行，还会极度恶化钛液的过滤性能，且硫酸酸浸过程选择性差，导致大量的镁、铝、铁等元素溶解在浸出液中，对后续钛渣的除杂造成困难，浸出后废酸无法回收利用，易造成环境污染。氟化法浸出时，含钛炉渣中主要含钛物相为黑钛石或钙钛矿，因为含钛炉渣中的硅与钛元素在与含氟浸出剂反应后会转变为TiF6 2-和SiF6 2-离子，二者溶解行为接近，在溶液中分离TiF6 2-和SiF6 2-离子较困难。At present, the main products of the titanium industry are titanium dioxide and titanium sponge. More than 90% of the world's titanium resources are used to produce titanium dioxide every year. The production methods of titanium dioxide mainly include boiling chlorination, sulfuric acid and fluorination. The boiling chlorination method requires raw materials TiO 2 >90%, CaO<0.2%, MgO<1%, and titanium-containing slag contains a large amount of impurity elements, especially calcium and magnesium impurities, and some magnesium impurities are solid-dissolved in the black titanium stone. Among them, calcium mainly exists in the form of silicate, which is difficult to remove, which makes it difficult to use titanium-containing slag as a raw material for chlorination titanium dioxide. Titanium-containing slag contains a large amount of impurity elements, especially Ca and Si elements. During the sulfuric acid leaching process, these Ca and Si elements react with sulfuric acid to form colloidal calcium sulfate and orthosilicic acid, which adhere to the surface of unreacted particles. It will greatly deteriorate the filtration performance of the titanium solution, and the selectivity of the sulfuric acid leaching process is poor, resulting in a large amount of magnesium, aluminum, iron and other elements dissolved in the leaching solution, causing difficulties in the subsequent removal of impurities from the titanium slag, and the waste acid cannot be recycled after leaching. It is easy to cause environmental pollution. During leaching by fluorination method, the main titanium-containing phase in the titanium-containing slag is black titanium or perovskite, because the silicon and titanium elements in the titanium-containing slag will be transformed into TiF 6 2- and SiF 6 2- ions have similar dissolution behaviors, so it is difficult to separate TiF 6 2- and SiF 6 2- ions in solution.
综上所述，含钛炉渣因杂质含量高，无法满足沸腾氯化法原料要求，硫酸法选择性差，硅钛分离困难。开发一种不受杂质种类和含量影响的TiO2提取方法对含钛炉渣中钛资源的利用具有重要意义。To sum up, the titanium-containing slag cannot meet the raw material requirements of the boiling chlorination method due to the high impurity content, the sulfuric acid method has poor selectivity, and the separation of silicon and titanium is difficult. The development of a TiO2 extraction method that is not affected by the type and content of impurities is of great significance for the utilization of titanium resources in titanium-containing slag.
发明内容SUMMARY OF THE INVENTION
针对目前氟化浸出中硅元素钛元素一同进入钛液，造成后续液体中硅钛分离难的问题，本发明的目的在于提供一种含钛炉渣选择性浸出钛的方法，该工艺流程设计合理，操作简单，无环境污染。In view of the problem that silicon and titanium elements enter the titanium liquid together in the current fluoridation leaching, resulting in difficult separation of silicon and titanium in the subsequent liquid, the purpose of the present invention is to provide a method for selectively leaching titanium from titanium-containing slag, and the process flow design is reasonable, Simple operation and no environmental pollution.
本发明提供以下技术方案：一种含钛炉渣选择性浸出钛的方法，包括以下步骤：The present invention provides the following technical solutions: a method for selectively leaching titanium from titanium-containing slag, comprising the following steps:
S1.将含钛炉渣破碎并细磨；得到预定细度的含钛炉渣；S1. Crush and finely grind the titanium-containing slag; obtain a titanium-containing slag with a predetermined fineness;
S2.将细磨后的含钛炉渣进行第一段浸出反应，将浸出后的料浆进行固液分离，得到浸出液和含钛浸出渣；S2. The first-stage leaching reaction is performed on the finely ground titanium-containing slag, and the leached slurry is subjected to solid-liquid separation to obtain a leaching solution and a titanium-containing leaching slag;
所述的第一段浸出反应采用高铵低氟体系选择性浸出含钛炉渣中的硅元素，硅元素以含氟配离子的形式溶解在浸出液中，其他元素以固态形式存在于含钛浸出渣中，达到预先脱硅的目的；The first-stage leaching reaction uses a high-ammonium and low-fluorine system to selectively leaching silicon in the titanium-containing slag, the silicon is dissolved in the leaching solution in the form of fluorine-containing complex ions, and other elements exist in the titanium-containing leaching slag in a solid form. , to achieve the purpose of pre-desilication;
S3.将步骤S2所得含钛浸出渣进行第二段浸出反应，将浸出后的料浆进行固液分离，获得浸出钛液和残渣；S3. The second stage leaching reaction is carried out on the titanium-containing leaching residue obtained in step S2, and the leached slurry is subjected to solid-liquid separation to obtain leached titanium liquid and residue;
所述的第二段浸出反应采用低铵高氟体系选择性浸出含钛浸出渣中的钛元素，钛元素以含氟配离子的形式溶解在浸出钛液中，钙、镁、铝、铁等元素以沉淀的形式残留在残渣中。The second-stage leaching reaction adopts a low-ammonium and high-fluorine system to selectively leaches the titanium element in the titanium-containing leaching residue. Elements remain in the residue in the form of precipitates.
优选的方案，步骤S1中，所述的含钛炉渣中TiO2含量大于40％，细磨粒度小于0.074mm占80％以上。In a preferred solution, in step S1, the content of TiO 2 in the titanium-containing slag is greater than 40%, and the fine grinding particle size is less than 0.074 mm, accounting for more than 80%.
优选的方案，步骤S2中，所述的第一段浸出采用的氟化浸出剂，[NH4 +]/[F-]摩尔比值为1～3，[F-]浓度为5～10mol/L，pH值为7～14，pH值反应[H+]浓度，决定含钛原料的浸出反应快慢，决定浸出效率。In a preferred solution, in step S2, the fluorinated leaching agent used in the first stage leaching has a [NH 4 + ]/[F − ] molar ratio of 1 to 3, and a [F − ] concentration of 5 to 10 mol/L , pH value is 7～14, pH value reacts [H + ] concentration, decides the leaching reaction speed of titanium-containing raw material, decides leaching efficiency.
优选的方案，步骤S2中，所述的第一段浸出过程，固液比为10～200g/L，浸出温度在20～160℃，浸出时间在10～180min。In a preferred solution, in step S2, in the first stage of the leaching process, the solid-liquid ratio is 10-200 g/L, the leaching temperature is 20-160°C, and the leaching time is 10-180 min.
优选的方案，步骤S3中，所述的第二段浸出采用的氟化浸出剂，[NH4 +]/[F-]摩尔比值为0～1，[F-]浓度为5～20mol/L，pH值为-1～7，pH值反应[H+]浓度，决定含钛原料的浸出反应快慢，决定浸出效率。In a preferred solution, in step S3, the fluorinated leaching agent used in the second stage leaching has a [NH 4 + ]/[F − ] molar ratio of 0 to 1, and a [F − ] concentration of 5 to 20 mol/L , the pH value is -1 to 7, and the pH value reacts to the [H + ] concentration, which determines the speed of the leaching reaction of titanium-containing raw materials and determines the leaching efficiency.
优选的方案，步骤S3中，所述的第二段浸出过程，固液比为10～200g/L，浸出温度在20～160℃，浸出时间在10～180min。In a preferred solution, in step S3, in the second stage of the leaching process, the solid-liquid ratio is 10-200 g/L, the leaching temperature is 20-160°C, and the leaching time is 10-180 min.
本发明技术方案的原理为：The principle of the technical solution of the present invention is:
本发明浸出过程分为两段进行，第一段浸出目的为选择性浸出硅，预先脱除硅元素，第二段浸出的目的为选择性浸出钛元素，使钛元素与其他杂质元素分离。两段浸出可以有效避免TiF6 2-和SiF6 2-离子同时存在于浸出液中，解决了氟化浸出液中钛硅分离难的问题。The leaching process of the present invention is carried out in two stages. The purpose of the first stage of leaching is to selectively leaching silicon and preliminarily remove silicon element, and the purpose of the second stage of leaching is to selectively leaching titanium element to separate titanium element from other impurity elements. The two-stage leaching can effectively avoid the simultaneous existence of TiF 6 2- and SiF 6 2- ions in the leaching solution, and solve the problem of difficult separation of titanium and silicon in the fluorinated leaching solution.
第一段浸出过程浸出剂选用高铵低氟的[NH4 +]/[F-]体系，浸出过程中主要发生硅酸盐的分解的反应：The leaching agent of the first stage of leaching process is [NH 4 + ]/[F - ] system with high ammonium and low fluorine, and the decomposition reaction of silicate mainly occurs during the leaching process:
2CaO·MgO·2SiO2(s)+2CaO·Al2O3·2SiO2(s)+56H+ (aq)+6NH4 + (aq)+78F- (aq) 2CaO·MgO·2SiO 2(s) +2CaO·Al 2 O 3 ·2SiO 2(s) +56H + (aq) +6NH 4 + (aq) +78F - (aq)
＝8SiF6 2- (aq)+CaMg2Al2F12(s)+2(NH4)3AlF6(s)+3CaF2(s)+28H2O(aq) (1)=8SiF 6 2- (aq) +CaMg 2 Al 2 F 12(s) +2(NH 4 ) 3 AlF 6(s) +3CaF 2(s) +28H 2 O (aq) (1)
含钛炉渣中的硅元素转变为SiF6 2-离子溶解在浸出液中，其他元素以沉淀的形式存在于含钛浸出渣中，达到预先脱硅的目的。The silicon element in the titanium-containing slag is transformed into SiF 6 2- ions and dissolved in the leaching solution, and other elements exist in the titanium-containing leaching slag in the form of precipitation to achieve the purpose of pre-desiliconization.
第二段浸出过程浸出剂选用低铵高氟的[NH4 +]/[F-]体系，浸出过程中主要发生含钛矿物的分解的反应：The leaching agent of the second stage leaching process is [NH 4 + ]/[F - ] system with low ammonium and high fluorine. During the leaching process, the decomposition reaction of titanium-containing minerals mainly occurs:
Fe2TiO5(s)+10H+ (aq)+6NH4 + (aq)+18F- (aq)＝TiF6 2- (aq)+2(NH4)3FeF6(s)+5H2O(aq) (2)Fe 2 TiO 5(s) +10H + (aq) +6NH 4 + (aq) +18F - (aq) =TiF 6 2- (aq) +2(NH 4 ) 3 FeF 6(s) +5H 2 O (aq) (2)
Al2TiO5(s)+10H+ (aq)+6NH4 + (aq)+18F- (aq)＝TiF6 2- (aq)+2(NH4)3AlF6(s)+5H2O(aq) (3)Al 2 TiO 5(s) +10H + (aq) +6NH 4 + (aq) +18F - (aq) =TiF 6 2- (aq) +2(NH 4 ) 3 AlF 6(s) +5H 2 O (aq) (3)
Al2TiO5(s)+MgTi2O5(s)+20H+ (aq)+4NH4 + (aq)+30F- (aq) Al 2 TiO 5(s) +MgTi 2 O 5(s) +20H + (aq) +4NH 4 + (aq) +30F - (aq)
＝3TiF6 2- (aq)+NH4MgAlF6(s)+(NH4)3AlF6(s)+10H2O(aq) (4)=3TiF 6 2- (aq) +NH 4 MgAlF 6(s) +(NH 4 ) 3 AlF 6(s) +10H 2 O (aq) (4)
CaTiO3(s)+6H+ (aq)+8F- (aq)＝TiF6 2- (aq)+CaF2(s)+3H2O(aq) (5)CaTiO 3(s) +6H + (aq) +8F - (aq) =TiF 6 2- (aq) +CaF 2(s) +3H 2 O (aq) (5)
浸出时含钛炉渣中钛元素与氟化物反应生成TiF6 2-离子溶解在浸出液中，铁、钙、镁、铝元素与氟化物反应生成(NH4)3FeF6、CaMg2Al2F12、(NH4)3AlF6、NH4MgAlF6、CaF2沉淀残留在浸出渣中，达到选择性浸出钛元素的目的。During leaching, the titanium element in the titanium-containing slag reacts with the fluoride to form TiF 6 2- ions are dissolved in the leaching solution, and the iron, calcium, magnesium and aluminum elements react with the fluoride to form (NH 4 ) 3 FeF 6 , CaMg 2 Al 2 F 12 , (NH 4 ) 3 AlF 6 , NH 4 MgAlF 6 , and CaF 2 precipitates remain in the leaching residue to achieve the purpose of selective leaching of titanium elements.
本发明的有益技术效果：Beneficial technical effects of the present invention:
本发明可以实现含钛炉渣中硅元素的预先脱除和钛元素的选择性高效浸出，浸出钛液中杂质种类和含量少，有利于后续钛液中杂质元素的去除。该工艺流程设计合理，操作简单，无环境污染。The invention can realize the pre-removal of silicon element in the titanium-containing slag and the selective and efficient leaching of titanium element, and the types and contents of impurities in the leached titanium liquid are small, which is beneficial to the subsequent removal of impurity elements in the titanium liquid. The technological process has reasonable design, simple operation and no environmental pollution.
附图说明Description of drawings
图1为本发明实施例1的工艺流程图。FIG. 1 is a process flow diagram of Embodiment 1 of the present invention.
具体实施方式Detailed ways
下面通过实施例来进一步说明本发明的具体实施方式，但本发明的具体实施方式不局限于以下实施例。The specific embodiments of the present invention will be further described below through examples, but the specific embodiments of the present invention are not limited to the following examples.
在本发明实施例中，如无特别说明，采用的手段均为本领域常规的手段，采用的试剂均可通过常规的商业途径获取。In the embodiments of the present invention, unless otherwise specified, the methods used are conventional methods in the art, and the used reagents can be obtained through conventional commercial channels.
以下通过具体实施例和附图对本发明技术方案进行详细的阐述。The technical solutions of the present invention will be described in detail below through specific embodiments and accompanying drawings.
实施例1Example 1
以含钛炉渣(47.35％TiO2、16.08％SiO2、12.10％Al2O3、9.97％CaO、9.88％MgO)为原料，原料粒度为-74μm占80.47％。第一段浸出过程的浸出剂中NH4 +/F-摩尔比值为2，[F]浓度为10mol/L，pH值为8.5，固液比为100g/L，浸出温度为100℃，浸出时间为60min，硅元素浸出率为99.28％，钛、镁、铝、钙浸出率均为0。第二浸出过程的浸出剂中NH4 +/F-摩尔比值为0.4，[F]浓度为10mol/L，pH值为-0.48，固液比为100g/L，浸出温度为120℃，浸出时间为60min，钛浸出率为98.56％，钙、镁和铝浸出率均为0，具体工艺流程如图1所示。Titanium-containing slag (47.35%TiO 2 , 16.08% SiO 2 , 12.10% Al 2 O 3 , 9.97% CaO, 9.88% MgO) was used as raw material, and the particle size of the raw material was -74 μm, accounting for 80.47%. In the first leaching process, the NH 4 + /F - molar ratio is 2, the [F] concentration is 10 mol/L, the pH is 8.5, the solid-liquid ratio is 100 g/L, the leaching temperature is 100 °C, and the leaching time For 60min, the leaching rate of silicon element was 99.28%, and the leaching rate of titanium, magnesium, aluminum and calcium were all 0. In the leaching agent of the second leaching process, the molar ratio of NH 4 + /F - was 0.4, the [F] concentration was 10 mol/L, the pH value was -0.48, the solid-liquid ratio was 100 g/L, the leaching temperature was 120°C, and the leaching time was For 60min, the titanium leaching rate was 98.56%, and the calcium, magnesium and aluminum leaching rates were all 0. The specific process flow is shown in Figure 1.
实施例2Example 2
以含钛炉渣(72.52％TiO2、5.39％SiO2、2.75％Al2O3、1.38％CaO、8.25％MgO)为原料，原料粒度为-74μm占84.25％。第一段浸出过程的浸出剂中NH4 +/F-摩尔比值为2，[F]浓度为8mol/L，pH值为8.5，固液比为100g/L，浸出温度为100℃，浸出时间为60min，硅元素浸出率为98.48％，钛、镁、铝、钙浸出率均为0。第二浸出过程的浸出剂中NH4 +/F-摩尔比值为0.4，[F]浓度为12mol/L，pH值为-0.60，固液比为100g/L，浸出温度为140℃，浸出时间为60min，钛浸出率为98.84％，钙、镁和铝浸出率均为0。Titanium-containing slag (72.52%TiO 2 , 5.39% SiO 2 , 2.75% Al 2 O 3 , 1.38% CaO, 8.25% MgO) was used as raw material, and the particle size of the raw material was -74 μm, accounting for 84.25%. The molar ratio of NH 4 + /F - in the leaching agent in the first leaching process is 2, the [F] concentration is 8mol/L, the pH value is 8.5, the solid-liquid ratio is 100g/L, the leaching temperature is 100℃, and the leaching time is For 60min, the leaching rate of silicon element was 98.48%, and the leaching rate of titanium, magnesium, aluminum and calcium were all 0. In the leaching agent of the second leaching process, the molar ratio of NH 4 + /F - is 0.4, the [F] concentration is 12 mol/L, the pH value is -0.60, the solid-liquid ratio is 100 g/L, the leaching temperature is 140°C, and the leaching time is For 60min, the leaching rate of titanium was 98.84%, and the leaching rates of calcium, magnesium and aluminum were all 0.
实施例3Example 3
以含钛炉渣(72.52％TiO2、5.39％SiO2、2.75％Al2O3、1.38％CaO、8.25％MgO)为原料，原料粒度为-74μm占84.25％。第一段浸出过程的浸出剂中NH4 +/F-摩尔比值为2.5，[F]浓度为8mol/L，pH值为9.5，固液比为100g/L，浸出温度为100℃，浸出时间为60min，硅元素浸出率为99.33％，钛、镁、铝、钙浸出率均为0。第二浸出过程的浸出剂中NH4 +/F-摩尔比值为0.3，[F]浓度为12mol/L，pH值为-0.65，固液比为100g/L，浸出温度为120℃，浸出时间为60min，钛浸出率为98.98％，钙、镁和铝浸出率均为0。Titanium-containing slag (72.52%TiO 2 , 5.39% SiO 2 , 2.75% Al 2 O 3 , 1.38% CaO, 8.25% MgO) was used as raw material, and the particle size of the raw material was -74 μm, accounting for 84.25%. In the first leaching process, the molar ratio of NH 4 + /F - in the leaching agent is 2.5, the [F] concentration is 8mol/L, the pH value is 9.5, the solid-liquid ratio is 100g/L, the leaching temperature is 100℃, and the leaching time is For 60min, the leaching rate of silicon element was 99.33%, and the leaching rate of titanium, magnesium, aluminum and calcium were all 0. In the leaching agent of the second leaching process, the molar ratio of NH 4 + /F - was 0.3, the [F] concentration was 12 mol/L, the pH value was -0.65, the solid-liquid ratio was 100 g/L, the leaching temperature was 120 °C, and the leaching time was For 60min, the leaching rate of titanium was 98.98%, and the leaching rates of calcium, magnesium and aluminum were all 0.
对比例Comparative ratio
以含钛炉渣(主要成分为47.35％TiO2、16.08％SiO2、12.10％Al2O3、9.97％CaO、9.88％MgO)为原料。原料粒度为-74μm占80.47％，选取NH4F作浸出剂，浸出剂中NH4 +/F-摩尔比值为1，[F]浓度为12mol/L，固液比为100g/L，浸出温度为140℃，浸出时间为60min。钛浸出率为5.4％，硅浸出率为36.4％，钙、镁和铝浸出率均为0。Titanium-containing slag (main components: 47.35% TiO 2 , 16.08% SiO 2 , 12.10% Al 2 O 3 , 9.97% CaO, 9.88% MgO) was used as the raw material. The particle size of the raw material is -74 μm, accounting for 80.47%, and NH 4 F is selected as the leaching agent. The NH 4 + /F - molar ratio in the leaching agent is 1, the [F] concentration is 12 mol/L, the solid-liquid ratio is 100 g/L, and the leaching temperature The temperature was 140 °C, and the leaching time was 60 min. The titanium leaching rate was 5.4%, the silicon leaching rate was 36.4%, and the calcium, magnesium and aluminum leaching rates were all 0.
以上所述仅是本发明的优选实施方式，本发明的保护范围并不仅局限于上述实施例。对于本技术领域的技术人员来说，在不脱离本发明技术构思前提下所得到的改进和变换也应视为本发明的保护范围。The above are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited to the above embodiments. For those skilled in the art, improvements and transformations obtained without departing from the technical concept of the present invention should also be regarded as the protection scope of the present invention.
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