CN102168178A - Method for extracting vanadium again from tailing after extracting vanadium from vanadium tailing of converter - Google Patents
Method for extracting vanadium again from tailing after extracting vanadium from vanadium tailing of converter Download PDFInfo
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000002893 slag Substances 0.000 claims abstract description 28
- 238000002386 leaching Methods 0.000 claims abstract description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000605 extraction Methods 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 22
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 16
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 16
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 16
- 239000000706 filtrate Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 230000003647 oxidation Effects 0.000 claims description 14
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 7
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000013055 pulp slurry Substances 0.000 claims 4
- 230000003197 catalytic effect Effects 0.000 claims 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- KTYKZQRFFNXTQA-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].O.[Ta+5].[Ir+3] Chemical compound [O-2].[O-2].[O-2].[O-2].O.[Ta+5].[Ir+3] KTYKZQRFFNXTQA-UHFFFAOYSA-N 0.000 claims 1
- 230000004888 barrier function Effects 0.000 claims 1
- 238000005422 blasting Methods 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- 125000005287 vanadyl group Chemical group 0.000 claims 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 abstract description 18
- 229940041260 vanadyl sulfate Drugs 0.000 abstract description 18
- 229910000352 vanadyl sulfate Inorganic materials 0.000 abstract description 18
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 abstract description 14
- 239000002002 slurry Substances 0.000 abstract description 14
- 230000001590 oxidative effect Effects 0.000 abstract description 9
- 239000007800 oxidant agent Substances 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000012795 verification Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- BPNRRQFZIBQRMK-UHFFFAOYSA-N [O-2].[Ta+5].[Ir+3].[O-2].[O-2].[O-2] Chemical compound [O-2].[Ta+5].[Ir+3].[O-2].[O-2].[O-2] BPNRRQFZIBQRMK-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000010200 validation analysis Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VWBLQUSTSLXQON-UHFFFAOYSA-N N.[V+5] Chemical compound N.[V+5] VWBLQUSTSLXQON-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
从转炉钒渣提钒后的尾渣中再次提钒的方法，该方法包括用提钒后的转炉钒渣的尾渣、浸取剂硫酸和氧化剂硫酸亚铁混合，以制备矿浆液；将所得矿浆液置于无隔膜浸取槽中，以进行电催化氧化反应；对经电催化氧化反应后的矿浆液进行固液分离，得含硫酸氧钒的滤液等步骤。在得到含硫酸氧钒的滤液后，再通过常规的现有技术，或制备出硫酸氧钒或其水合物；也可制备出五氧化二钒，或进一步还原出钒。本发明能够更多地提取现有技术基本不能再所述尾渣中进一步提出的钒，是成本较低、资源化利用较好的方法。The method for extracting vanadium again from the tailings of converter vanadium slag after vanadium extraction, the method comprises mixing the tailings of converter vanadium slag after vanadium extraction, leaching agent sulfuric acid and oxidant ferrous sulfate to prepare ore slurry; The ore slurry is placed in a leaching tank without a diaphragm to carry out an electrocatalytic oxidation reaction; the ore slurry after the electrocatalytic oxidation reaction is subjected to solid-liquid separation to obtain a filtrate containing vanadyl sulfate. After the filtrate containing vanadyl sulfate is obtained, vanadyl sulfate or its hydrate can be prepared by conventional prior art; vanadium pentoxide can also be prepared, or vanadium can be further reduced. The invention can extract more vanadium which cannot be further extracted from the tailings in the prior art, and is a method with lower cost and better resource utilization.
Description
技术领域technical field
本发明涉及从转炉钒渣中提取钒的方法，尤其是从转炉钒渣提钒后的尾渣中再次提钒的方法。The invention relates to a method for extracting vanadium from converter vanadium slag, in particular to a method for extracting vanadium again from tailings after vanadium extraction from converter vanadium slag.
背景技术Background technique
钒（V）是重要的工业原料；转炉钒渣是以钒铁矿原料，用转炉炼钢产生的副产物，它同时也是提取钒的主要原料。用转炉钒渣为原料制取五氧化二钒（V2O5）既能够得到相关产业上可用的钒的氧化物，也能够方便地还原出钒。在用转炉钒渣中提取钒的方法中，直接酸浸法是一种污染较小的浸取提钒方法。其具体步骤包括：①用硫酸（H2SO4）与转炉钒渣混合制备矿浆液；②搅拌、静置以浸出硫酸氧钒（VOSO4）；③过滤；④在含硫酸氧钒的滤液中加入硫酸铵［(NH4)2SO4］（即氨盐沉钒法），以得到含多钒酸铵（NH4VO3）的沉淀物；⑤过滤、洗涤沉淀物，得纯净多钒酸铵；⑥在氧化气氛中煅烧多钒酸铵，得制品五氧化二钒（V2O5）的步骤。然而，传统的直接酸浸法却存在五氧化二钒的产率不高，即钒的提取率较低之不足。导致这一不足的关键是，在其第②步中硫酸氧钒浸出率较低。为提高关键步骤②中硫酸氧钒的浸出率，申请号为2011100487428、名称为《用电催化氧化浸取转炉钒渣的方法》，在直接酸浸法的基础上，在第②步中增加了电催化氧化，以确保能浸出更多的硫酸氧钒；并且，在该步骤中还进一步地增加了适量的氧化剂硫酸锰（MnSO4）。从而为最终提高五氧化二钒的浸取率提供了保证。然而，在包括该《用电催化氧化浸取转炉钒渣的方法》在内的现有提钒方法中，提钒后的转炉钒渣的尾渣内仍然有虽然不多、但又不可忽略的钒的残余。由于这些钒的残余是现有技术之方法不能提出的，且因其含量较低，所以，存在着想从提钒后的转炉钒渣尾渣中再次提钒时，成本较高的问题，于是，到目前为止，这些尾渣基本上都是作为废渣处理掉了。显然，从资源化利用角度来衡量，这仍然时一种浪费。Vanadium (V) is an important industrial raw material; converter vanadium slag is a by-product of vanadium iron ore raw material, which is produced by converter steelmaking, and it is also the main raw material for extracting vanadium. Using converter vanadium slag as raw material to produce vanadium pentoxide (V 2 O 5 ) can not only obtain the relevant industrially available vanadium oxides, but also can conveniently reduce vanadium. Among the methods for extracting vanadium from converter vanadium slag, the direct acid leaching method is a less polluting vanadium extraction method. The specific steps include: ① mix sulfuric acid (H 2 SO 4 ) with converter vanadium slag to prepare ore slurry; ② stir and stand to leach vanadyl sulfate (VOSO 4 ); ③ filter; ④ in the filtrate containing vanadyl sulfate Add ammonium sulfate [(NH 4 ) 2 SO 4 ] (i.e. ammonium salt vanadium precipitation method) to obtain a precipitate containing ammonium polyvanadate (NH 4 VO 3 ); ⑤ filter and wash the precipitate to obtain pure polyvanadate Ammonium; ⑥The step of calcining ammonium polyvanadate in an oxidizing atmosphere to obtain vanadium pentoxide (V 2 O 5 ). However, the traditional direct acid leaching method has the disadvantage that the yield of vanadium pentoxide is not high, that is, the extraction rate of vanadium is low. The key that causes this deficiency is that in its second step, the leaching rate of vanadyl sulfate is low. In order to improve the leaching rate of vanadyl sulfate in key step 2., the application number is 2011100487428, and the name is called "method for leaching converter vanadium slag with electrocatalytic oxidation". On the basis of direct acid leaching method, in 2. step, increased Electrocatalytic oxidation is used to ensure that more vanadyl sulfate can be leached; and an appropriate amount of oxidant manganese sulfate (MnSO 4 ) is further added in this step. Thereby, guarantee is provided for finally improving the leaching rate of vanadium pentoxide. However, in the existing methods of extracting vanadium including the "Method for Leaching Converter Vanadium Slag by Electrocatalytic Oxidation", there is still a small amount of but not negligible in the tailings of the converter vanadium slag after vanadium extraction vanadium remnants. Because these vanadium residues cannot be proposed by the methods of the prior art, and because of their low content, there is a problem that the cost is higher when wanting to extract vanadium again from the converter vanadium slag tailings after vanadium extraction, so, So far, these tailings have basically been disposed of as waste. Obviously, from the perspective of resource utilization, this is still a waste.
发明内容Contents of the invention
本发明的目的是，提供一种成本较低、资源化利用较好的从转炉钒渣提钒后的尾渣中再次提钒的方法。The object of the present invention is to provide a method for re-extracting vanadium from tailings after vanadium extraction from converter vanadium slag with low cost and good resource utilization.
实现所述发明目的之方法是一种从转炉钒渣提钒后的尾渣中再次提钒的方法，与现有技术相同的方面是，该方法包括如下步骤：The method for realizing the purpose of the invention is a method for extracting vanadium again from the tailings after vanadium extraction from converter vanadium slag. The same aspect as the prior art is that the method includes the following steps:
（1）用提钒后的转炉钒渣的尾渣、浸取剂硫酸和氧化剂混合，以制备矿浆液；(1) Mix the tailings of converter vanadium slag after vanadium extraction, lixiviating agent sulfuric acid and oxidant to prepare ore slurry;
（2）将步骤（1）所得矿浆液置于无隔膜浸取槽中，接通电源，以进行电催化氧化反应；(2) The ore slurry obtained in step (1) is placed in a leaching tank without a diaphragm, and the power is turned on to carry out an electrocatalytic oxidation reaction;
（3）对经步骤（2）电催化氧化反应后的矿浆液进行固液分离，得含硫酸氧钒的滤液；(3) performing solid-liquid separation on the ore slurry after the electrocatalytic oxidation reaction in step (2) to obtain a filtrate containing vanadyl sulfate;
其改进之处是：在步骤（1）中，所述尾渣呈过100目（0.154mm）筛后的粉末状，所述硫酸的百分比浓度为10～30％，所述氧化剂为硫酸亚铁（FeSO4)；The improvements are as follows: in step (1), the tailings are in the form of powder sieved through a 100-mesh (0.154mm) sieve, the percentage concentration of the sulfuric acid is 10-30%, and the oxidant is ferrous sulfate (FeSO 4 );
其中，所述尾渣中所含钒∶硫酸∶硫酸亚铁＝0.208g∶80mL∶1～3g；Wherein, vanadium contained in the tailings: sulfuric acid: ferrous sulfate = 0.208g: 80mL: 1 ~ 3g;
在步骤（2）中，电催化氧化的阳极电流密度为200～400A/m2，浸取温度为40～80℃，浸取时间为3～5h。In step (2), the anode current density of the electrocatalytic oxidation is 200-400A/m 2 , the leaching temperature is 40-80° C., and the leaching time is 3-5 hours.
在得到含硫酸氧钒的滤液后，既可以再通过常规的去杂质、蒸发等工艺步骤，来制备出在相关产业上可用的硫酸氧钒或其水合物；也可以再通过常规的氨盐沉钒法和煅烧等工艺步骤，来制备出在相关产业上可用的五氧化二钒，乃至进一步还原出钒。After the filtrate containing vanadyl sulfate is obtained, the vanadyl sulfate or its hydrate that can be used in related industries can be prepared through conventional process steps such as impurity removal and evaporation; Vanadium method and calcination and other process steps to prepare vanadium pentoxide that can be used in related industries, and even further reduce vanadium.
从方案中可以看出，本发明是针对提钒后的转炉钒渣的尾渣中，所含剩余钒更少的特点，来对现有电催化氧化浸取提钒方法所作的改进。其主要改进处是，把混合时加入的氧化剂改成了硫酸亚铁——在步骤（2）的化学反应过程是，在矿浆液的酸性环境下，把硫酸亚铁氧化为其氧化性更强的硫酸铁，进而在电催化条件下更快、更多地把所述尾渣中已经不易浸出的钒，氧化成容易在现有后续步骤中浸出高价钒的硫酸氧钒。用硫酸亚铁而不直接用硫酸铁的好处是，前者价格远比后者低；且在把硫酸亚铁（FeSO4)转化为硫酸铁［Fe2(SO4)3］过程中，还可以利用这一过程来同时把所述尾渣中所含的二价铁离子，通过先转化为硫酸亚铁后，也一并转化为硫酸铁。这不但节省了加入原料的成本，而且还充分地利用了所述尾渣中的可用物（二价铁离子）。因此，本发明是一种成本较低、资源化利用较好的方法。It can be seen from the scheme that the present invention aims at the feature that the tailings of the converter vanadium slag after vanadium extraction contain less remaining vanadium, and improves the existing electrocatalytic oxidation leaching method for vanadium extraction. The main improvement is that the oxidant added during mixing is changed to ferrous sulfate—the chemical reaction process in step (2) is to oxidize ferrous sulfate to make it more oxidizing in the acidic environment of the ore slurry ferric sulfate, and then under the condition of electrocatalysis, the vanadium that has been difficult to leach in the tailings is oxidized faster and more into vanadyl sulfate that is easy to leach high-valent vanadium in the existing subsequent steps. The advantage of using ferrous sulfate instead of directly using ferric sulfate is that the price of the former is much lower than that of the latter; and in the process of converting ferrous sulfate (FeSO 4 ) into ferric sulfate [Fe 2 (SO 4 ) 3 ], it can also be This process is used to simultaneously convert the divalent iron ions contained in the tailings into ferrous sulfate and then into ferric sulfate. This not only saves the cost of adding raw materials, but also makes full use of the available substances (ferrous ions) in the tailings. Therefore, the present invention is a method with lower cost and better utilization of resources.
下面结合具体实施方式对本发明作进一步的说明。The present invention will be further described below in combination with specific embodiments.
具体实施方式Detailed ways
从转炉钒渣提钒后的尾渣中再次提钒的方法，该方法包括如下步骤：A method for extracting vanadium again from tailings after vanadium extraction from converter vanadium slag, the method comprises the following steps:
（1）用提钒后的转炉钒渣的尾渣、浸取剂硫酸和氧化剂混合，以制备矿浆液；(1) Mix the tailings of converter vanadium slag after vanadium extraction, lixiviating agent sulfuric acid and oxidant to prepare ore slurry;
（2）将步骤（1）所得矿浆液置于无隔膜浸取槽中，接通电源，以进行电催化氧化反应；(2) The ore slurry obtained in step (1) is placed in a leaching tank without a diaphragm, and the power is turned on to carry out an electrocatalytic oxidation reaction;
（3）对经步骤（2）电催化氧化反应后的矿浆液进行固液分离，得含硫酸氧钒的滤液；(3) performing solid-liquid separation on the ore slurry after the electrocatalytic oxidation reaction in step (2) to obtain a filtrate containing vanadyl sulfate;
本发明内，在步骤（1）中，所述尾渣呈过100目筛后的粉末状，所述硫酸的百分比浓度为10～30％，所述氧化剂为硫酸亚铁；In the present invention, in step (1), the tailings are in the form of powder after passing through a 100-mesh sieve, the percentage concentration of the sulfuric acid is 10-30%, and the oxidant is ferrous sulfate;
其中，所述尾渣中所含钒∶硫酸∶硫酸亚铁＝0.208g∶80mL∶1～3g（产业化应用时，按照此配比换算）；Wherein, the vanadium contained in the tailings: sulfuric acid: ferrous sulfate = 0.208g: 80mL: 1-3g (converted according to this ratio for industrial application);
在步骤（2）中，电催化氧化的阳极电流密度为200～400A/m2，浸取温度为40～80℃，浸取时间为3～5h。In step (2), the anode current density of the electrocatalytic oxidation is 200-400A/m 2 , the leaching temperature is 40-80° C., and the leaching time is 3-5 hours.
进一步讲，为得到含量更多一些的含硫酸氧钒的滤液，在步骤（2）中，进行电催化氧化时的阳极采用（氧化活性较高的）铱钽氧化物涂层的DSA阳极，阴极采用（对阳极的腐蚀性较小的）钛阴极，极板间距15～20mm。Further speaking, in order to obtain the filtrate containing vanadyl sulfate with more content, in step (2), the anode when performing electrocatalytic oxidation adopts (higher oxidation activity) DSA anode coated with iridium tantalum oxide, and the cathode Titanium cathodes (less corrosive to the anode) are used, and the distance between the plates is 15-20mm.
更进一步地讲，在步骤（2）中进行电催化氧化时，同时向矿浆液中鼓入空气；该空气鼓入量以硫酸亚铁能尽量多地氧化为硫酸铁为度。本领域技术人员清楚，既然是进行电催化氧化，肯定是在其反应处于非密闭状态下（或曰，暴露于空气状态下）进行的。再同时向矿浆液中鼓入空气后，矿浆液中的硫酸亚铁就能够更快地氧化成氧化性更强的硫酸铁，也就同样能够更快地使所述尾渣中原来不易浸出的钒，氧化成容易在现有后续步骤中浸出高价钒的硫酸氧钒了。Furthermore, when electrocatalytic oxidation is carried out in step (2), air is blown into the ore slurry at the same time; the amount of air blowing is based on the degree that ferrous sulfate can be oxidized to ferric sulfate as much as possible. It is clear to those skilled in the art that since electrocatalytic oxidation is carried out, it must be carried out in a non-closed state (or in a state exposed to air). After blowing air into the ore slurry at the same time, the ferrous sulfate in the ore slurry can be oxidized into ferric sulfate with stronger oxidizability, which can also quickly make the original difficult-to-leach in the tailings Vanadium, oxidized to vanadyl sulfate which is easy to leach high-valent vanadium in the existing subsequent steps.
如在发明内容部分的方案中所说的，在得到含硫酸氧钒的滤液后，再通过常规工艺步骤，来制备出硫酸氧钒或其水合物，或者制备出五氧化二钒，乃至金属钒，因均属现有技术，在本案中不再进一步披露。As stated in the scheme of the summary of the invention, after obtaining the filtrate containing vanadyl sulfate, the conventional process steps are used to prepare vanadyl sulfate or its hydrate, or to prepare vanadium pentoxide, or even metal vanadium , as they are all prior art, no further disclosure will be made in this case.
本发明通过了实验室验证。制备含硫酸氧钒的滤液的过程，与具体实施方式中的步骤相同，在步骤（2）中进行电催化氧化时，其阳极和阴极，均采用效果更好的铱钽氧化物涂层的DSA阳极和钛阴极。由于在验证中发现，极板间距在15～20mm之间的效果没有明显差别，因此，在以下验证表中，极板间距的不同数值从略。验证效果的方法是，事先测定提钒后的转炉钒渣尾渣中的钒含量，其钒含量的测定采用钽试剂分光光度法进行测定。在步骤（3）固液分离后，再测定所得固体残渣中的钒含量（以下验证表中简称“残余V”）。The invention has passed laboratory verification. The process of preparing the filtrate containing vanadyl sulfate is the same as the steps in the specific embodiment. When the electrocatalytic oxidation is carried out in step (2), the anode and cathode are all made of DSA coated with iridium tantalum oxide with better effect anode and titanium cathode. Since it is found in the verification that there is no significant difference in the effect of the plate spacing between 15 and 20mm, in the following verification table, the different values of the plate spacing are omitted. The method to verify the effect is to measure the vanadium content in the converter vanadium slag tailings after vanadium extraction in advance, and the vanadium content is determined by tantalum reagent spectrophotometry. After the solid-liquid separation in step (3), measure the vanadium content in the obtained solid residue (hereinafter referred to as "residual V" in the verification table).
提钒后的转炉钒渣尾渣中钒含量的测定结果为1.04％。鉴于各验证例中硫酸用量均取80mL，因此，粉末状的提钒后的转炉钒渣尾渣也均取20g。验证时的其他参数见以下验证表。The vanadium content in the converter vanadium slag tailings after vanadium extraction was determined to be 1.04%. In view of the fact that the amount of sulfuric acid used in each verification example is 80mL, the powdery converter vanadium slag tailings after vanadium extraction are also taken as 20g. See the validation table below for other parameters during validation.
从验证中可以看出，在改用了硫酸亚铁的情况下，再通过电催化氧化（验证例2、4、9同时鼓入了空气），能使提钒后的转炉钒渣尾渣中钒含量，从原来的1.04％，最少降低到0.3055％（即浸取出了70.6％的钒），最多的降低到0.2723％（即浸取出了73.8％的钒）。从验证表中还可以看出，在本发明所述范围内，硫酸亚铁的用量越多，进一步浸取出金属钒的效果越好。其余优先数值在验证表中能够直观看出，故不赘述。It can be seen from the verification that when ferrous sulfate is used instead, electrocatalytic oxidation (air is blown in at the same time in verification examples 2, 4, and 9) can make the vanadium in the converter vanadium slag tailings The vanadium content, from the original 1.04%, was reduced to 0.3055% at least (70.6% vanadium was leached), and the most was reduced to 0.2723% (73.8% vanadium was leached). It can also be seen from the verification table that within the scope of the present invention, the more the amount of ferrous sulfate is, the better the effect of further leaching metal vanadium is. The remaining priority values can be seen intuitively in the verification table, so they will not be described in detail.
总之，从验证中可以看出，本发明的确成本较低、资源化利用较好的从转炉钒渣提钒后的尾渣中再次提钒的方法。In a word, it can be seen from the verification that the present invention is indeed a method for re-extracting vanadium from the tailing slag after vanadium extraction from converter vanadium slag with low cost and good resource utilization.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534229A (en) * | 2011-12-08 | 2012-07-04 | 重庆大学 | Method for selectively leaching vanadium from vanadium-bearing converter slag |
| CN102534229B (en) * | 2011-12-08 | 2013-03-27 | 重庆大学 | Method for selectively leaching vanadium from vanadium-bearing converter slag |
| CN103060843A (en) * | 2012-12-29 | 2013-04-24 | 中国科学院过程工程研究所 | Method for synchronously extracting vanadium and chromium by electrochemically decomposing vanadium slag in potassium hydroxide solution |
| CN103060843B (en) * | 2012-12-29 | 2017-09-29 | 中国科学院过程工程研究所 | A kind of method that electrochemical decomposition vanadium slag synchronously extracts vanadium chromium in potassium hydroxide solution |
| CN110117714A (en) * | 2019-05-29 | 2019-08-13 | 北京科技大学 | A kind of method of room temperature saturated oxalic acid solution Anodic electrolysis Leaching Vanadium |
| CN110117714B (en) * | 2019-05-29 | 2020-03-17 | 北京科技大学 | Method for leaching vanadium by anode electrolysis in normal-temperature saturated oxalic acid solution |
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