TWI866146B - Methods for preparing vanadyl sulfate solution - Google Patents
Methods for preparing vanadyl sulfate solution Download PDFInfo
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- TWI866146B TWI866146B TW112112862A TW112112862A TWI866146B TW I866146 B TWI866146 B TW I866146B TW 112112862 A TW112112862 A TW 112112862A TW 112112862 A TW112112862 A TW 112112862A TW I866146 B TWI866146 B TW I866146B
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- vanadium
- sodium
- aqueous solution
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- oxysulfate
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- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 33
- 229910000352 vanadyl sulfate Inorganic materials 0.000 title abstract description 4
- 229940041260 vanadyl sulfate Drugs 0.000 title abstract 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 159
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 159
- 239000007864 aqueous solution Substances 0.000 claims abstract description 117
- 239000011734 sodium Substances 0.000 claims abstract description 98
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 93
- 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 claims abstract description 87
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 65
- 238000000605 extraction Methods 0.000 claims abstract description 64
- 239000000243 solution Substances 0.000 claims abstract description 62
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 86
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 42
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 229910052750 molybdenum Inorganic materials 0.000 claims description 20
- 239000011733 molybdenum Substances 0.000 claims description 20
- 239000012141 concentrate Substances 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- CFVBFMMHFBHNPZ-UHFFFAOYSA-N [Na].[V] Chemical compound [Na].[V] CFVBFMMHFBHNPZ-UHFFFAOYSA-N 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 239000003350 kerosene Substances 0.000 claims description 9
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 2
- -1 V5+ ion Chemical class 0.000 abstract description 14
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 28
- 229910052751 metal Inorganic materials 0.000 description 28
- 239000002184 metal Substances 0.000 description 28
- 238000012360 testing method Methods 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 21
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 16
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 12
- 239000012074 organic phase Substances 0.000 description 12
- 229910021645 metal ion Inorganic materials 0.000 description 11
- 239000008346 aqueous phase Substances 0.000 description 9
- 235000017550 sodium carbonate Nutrition 0.000 description 9
- 229910001415 sodium ion Inorganic materials 0.000 description 7
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 6
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 6
- 230000005611 electricity Effects 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 229910020700 Na3VO4 Inorganic materials 0.000 description 1
- 241001460678 Napo <wasp> Species 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- SNAMIIGIIUQQSP-UHFFFAOYSA-N bis(6-methylheptyl) hydrogen phosphate Chemical compound CC(C)CCCCCOP(O)(=O)OCCCCCC(C)C SNAMIIGIIUQQSP-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- IHIXIJGXTJIKRB-UHFFFAOYSA-N trisodium vanadate Chemical compound [Na+].[Na+].[Na+].[O-][V]([O-])([O-])=O IHIXIJGXTJIKRB-UHFFFAOYSA-N 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
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Abstract
Description
本發明係關於一種硫酸氧釩溶液的製備方法，尤其是一種以釩灰精礦作為原料以製備硫酸氧釩溶液方法。 The present invention relates to a method for preparing vanadium oxysulfate solution, in particular to a method for preparing vanadium oxysulfate solution using vanadium ash concentrate as a raw material.
由於地球上傳統能源的耗盡，目前世界各國都傾力發展能源技術，期許能夠更有效率地進行能源的利用。在能源技術領域中，儲能技術係重要的發展項目，其中儲能設備指的是透過儲能技術將所生產的電儲存起來，需要時再進行利用的一種裝置，其可以在離峰時段儲存電能，接著於尖峰時段將所儲存的電能輸出，能夠有效補足用電缺口。在儲能設備中，儲能電池係至關重要的部分，其中釩電池更是儲能電池中的明日之星。在釩電池中，電解液是釩電池不可或缺的核心，而硫酸氧釩又為製備釩電解液的主要原料，因此如何有效益地製備硫酸氧釩便成為釩電池產業的命脈所在。 Due to the exhaustion of traditional energy on the earth, countries around the world are currently working hard to develop energy technology in the hope of using energy more efficiently. In the field of energy technology, energy storage technology is an important development project. Energy storage equipment refers to a device that stores the electricity produced through energy storage technology and uses it when needed. It can store electricity during off-peak hours and then output the stored electricity during peak hours, which can effectively make up for the electricity gap. In energy storage equipment, energy storage batteries are a crucial part, and vanadium batteries are the rising star among energy storage batteries. In vanadium batteries, the electrolyte is the indispensable core of vanadium batteries, and vanadium oxysulfate is the main raw material for preparing vanadium electrolyte. Therefore, how to prepare vanadium oxysulfate efficiently becomes the lifeblood of the vanadium battery industry.
在當前領域中，硫酸氧釩溶液的製備方法大致可分為化學法及電解法，其中化學法係將五氧化二釩或偏釩酸銨與還原劑及硫酸混合而形成硫酸氧釩溶液，在製備過程中會產生氨氮作為副產物，不僅會造成環境汙染，昂貴的五氧化二釩及偏釩酸銨亦為嚴重的成本負擔；而電解法則是同樣以昂貴的五氧化二釩作為原料，利用濃度為98%的硫酸在高溫下溶解五氧化二釩，並且以無隔膜電解法進行電解而形成硫酸氧釩溶液，不僅同樣存在著原料成 本昂貴的問題，還伴隨著電解所需的大量電力及硫酸氧釩的純度不易提高的額外問題。 In the current field, the preparation methods of vanadium oxysulfate solution can be roughly divided into chemical method and electrolytic method. The chemical method is to mix vanadium pentoxide or ammonium metavanadate with a reducing agent and sulfuric acid to form vanadium oxysulfate solution. Ammonia nitrogen will be produced as a by-product during the preparation process, which will not only cause environmental pollution, but also the expensive vanadium pentoxide and ammonium metavanadate will be a serious cost burden; The electrolysis method also uses expensive vanadium pentoxide as a raw material, dissolving vanadium pentoxide in 98% sulfuric acid at high temperature, and then electrolyzing it using a diaphragmless electrolysis method to form a vanadium sulfate solution. Not only does it have the same problem of expensive raw material costs, but it also has the additional problem of a large amount of electricity required for electrolysis and the difficulty in improving the purity of vanadium sulfate.
有鑑於此，確實有必要開發硫酸氧釩溶液的製備方法，以解決原料成本昂貴、汙染及硫酸氧釩的純度問題。 In view of this, it is indeed necessary to develop a method for preparing vanadium oxysulfate solution to solve the problems of expensive raw material costs, pollution and purity of vanadium oxysulfate.
為解決上述問題，本發明的主要目的在於一種硫酸氧釩溶液的製備方法，能夠降低生產原料成本、降低汙染且製備高純度的硫酸氧釩者。 In order to solve the above problems, the main purpose of the present invention is to provide a method for preparing vanadium oxysulfate solution, which can reduce the cost of production raw materials, reduce pollution and prepare high-purity vanadium oxysulfate.
本發明全文所記載的元件及構件使用「一」或「一個」之量詞，僅是為了方便使用且提供本發明範圍的通常意義；於本發明中應被解讀為包括一個或至少一個，且單一的概念也包括複數的情況，除非其明顯意指其他意思。 The quantifiers "one" or "a" used in the components and parts described throughout the present invention are only for the convenience of use and to provide a general meaning of the scope of the present invention; in the present invention, they should be interpreted as including one or at least one, and the single concept also includes the plural case, unless it is obvious that it means otherwise.
本發明的硫酸氧釩溶液的製備方法，可以包含：一熔融混合步驟，將一含釩原料與一鈉鹽混合，並且在700℃~900℃下熔融混合，以形成一含釩及鈉材料，該含釩原料為釩灰精礦，且該釩灰精礦含有15~30重量%的釩、10~20重量%的鐵、10~20重量%的鎳，以及0.1~0.5重量%的鉬；一粗萃取步驟，將該含釩及鈉材料以70℃~90℃的水進行粗萃取，以形成一含釩及鈉水溶液；一還原步驟，將該含釩及鈉水溶液的酸鹼值調整為pH0.5~2.0，且將一還原劑加入該含釩及鈉水溶液中，使該含釩及鈉水溶液中的正五價釩離子被還原為正四價釩離子，以得到一經還原含釩及鈉水溶液；及一分離步驟，利用一萃取液對於該經還原含釩及鈉水溶液進行萃取，以得到一含釩萃取液，並且利用硫酸對該含釩萃取液進行反萃取以得到該硫酸氧釩溶液。 The preparation method of the vanadium oxysulfate solution of the present invention may include: a melting and mixing step, mixing a vanadium-containing raw material with a sodium salt, and melting and mixing them at 700° C. to 900° C. to form a vanadium- and sodium-containing material, wherein the vanadium-containing raw material is vanadium ash concentrate, and the vanadium ash concentrate contains 15 to 30% by weight of vanadium, 10 to 20% by weight of iron, 10 to 20% by weight of nickel, and 0.1 to 0.5% by weight of molybdenum; a crude extraction step, crudely extracting the vanadium- and sodium-containing material with water at 70° C. to form A vanadium and sodium aqueous solution; a reduction step, adjusting the pH value of the vanadium and sodium aqueous solution to pH 0.5-2.0, and adding a reducing agent to the vanadium and sodium aqueous solution to reduce the pentavalent vanadium ions in the vanadium and sodium aqueous solution to tetravalent vanadium ions to obtain a reduced vanadium and sodium aqueous solution; and a separation step, extracting the reduced vanadium and sodium aqueous solution with an extracting liquid to obtain a vanadium-containing extract, and back-extracting the vanadium-containing extract with sulfuric acid to obtain the vanadium oxysulfate solution.
據此，本發明的硫酸氧釩溶液的製備方法，藉由將含釩原料與鈉鹽熔融混合而形成水溶性的釩鈉化合物，接著以熱水進行粗萃取後，利用 還原劑將水溶液中的正五價釩離子還原為正四價釩離子，最後分別利用萃取液及硫酸進行萃取及反萃取而得到該硫酸氧釩溶液，無須使用昂貴的五氧化二釩或偏釩酸銨作為原料即可以製備硫酸氧釩溶液，且在製備過程中不會產生氨氣汙染，為本發明之功效。如此，藉由使用釩灰精礦作為該含釩原料，無須使用昂貴的五氧化二釩或偏釩酸銨作為原料即可以製備硫酸氧釩溶液，能夠大幅降低製備硫酸氧釩溶液的成本。 According to the present invention, the method for preparing vanadium oxysulfate solution is to melt and mix vanadium-containing raw materials and sodium salt to form a water-soluble vanadium sodium compound, and then use hot water for crude extraction, and then use a reducing agent to reduce the pentavalent vanadium ions in the aqueous solution to tetravalent vanadium ions, and finally use the extract and sulfuric acid for extraction and back extraction respectively to obtain the vanadium oxysulfate solution. The vanadium oxysulfate solution can be prepared without using expensive vanadium pentoxide or ammonium metavanadate as raw materials, and no ammonia pollution will be generated during the preparation process, which is the effect of the present invention. Thus, by using vanadium ash concentrate as the vanadium-containing raw material, vanadium oxysulfate solution can be prepared without using expensive vanadium pentoxide or ammonium metavanadate as raw materials, which can significantly reduce the cost of preparing vanadium oxysulfate solution.
本發明的硫酸氧釩溶液的製備方法，其中，該含釩原料與該鈉鹽的重量比係介於1：0.3~1：0.6之間。如此，將該含釩原料與該鈉鹽以此比例熔融混合，能夠提高後續的釩的金屬萃取率。 The method for preparing vanadium oxysulfate solution of the present invention, wherein the weight ratio of the vanadium-containing raw material to the sodium salt is between 1:0.3 and 1:0.6. Thus, the vanadium-containing raw material and the sodium salt are melt-mixed in this ratio, which can improve the subsequent vanadium metal extraction rate.
本發明的硫酸氧釩溶液的製備方法，其中，該鈉鹽係下列所構成的群組的其中至少一者：碳酸鈉、氫氧化鈉或硫酸鈉。如此，選用該些鈉鹽與該含釩原料熔融混合，能夠提高後續的釩的金屬萃取率。 The method for preparing vanadium oxysulfate solution of the present invention, wherein the sodium salt is at least one of the following groups: sodium carbonate, sodium hydroxide or sodium sulfate. Thus, the selection of these sodium salts and the vanadium-containing raw material for melting and mixing can improve the subsequent vanadium metal extraction rate.
本發明的硫酸氧釩溶液的製備方法，其中，該還原劑為聯胺、草酸、次磷酸鈉或硫代硫酸鈉。如此，能夠有效提升含釩及鈉水溶液中的正四價釩離子的轉化率。 The method for preparing vanadium oxysulfate solution of the present invention, wherein the reducing agent is hydrazine, oxalic acid, sodium hypophosphite or sodium thiosulfate. In this way, the conversion rate of positive tetravalent vanadium ions in the aqueous solution containing vanadium and sodium can be effectively improved.
本發明的硫酸氧釩溶液的製備方法，其中，該還原劑的添加量為該含釩及鈉水溶液中的含釩量ppm的0.1~0.5倍。如此，能夠有效提升含釩及鈉水溶液中的正四價釩離子的轉化率。 The preparation method of the vanadium oxysulfate solution of the present invention, wherein the amount of the reducing agent added is 0.1 to 0.5 times the ppm of the vanadium content in the vanadium and sodium aqueous solution. In this way, the conversion rate of positive tetravalent vanadium ions in the vanadium and sodium aqueous solution can be effectively improved.
本發明的硫酸氧釩溶液的製備方法，其中，該還原步驟更包含將該含釩及鈉水溶液的酸鹼值調整為介於0.5~2.0之間。如此，能夠有效提升含釩及鈉水溶液中的正四價釩離子的轉化率。 The method for preparing vanadium oxysulfate solution of the present invention, wherein the reduction step further comprises adjusting the pH value of the vanadium and sodium aqueous solution to between 0.5 and 2.0. In this way, the conversion rate of positive tetravalent vanadium ions in the vanadium and sodium aqueous solution can be effectively improved.
本發明的硫酸氧釩溶液的製備方法，其中，該萃取液包含二(2-乙基己基)磷酸酯、磷酸三正丁酯及磺化煤油。如此，能夠有效使經還原含釩及鈉水溶液中的正四價釩離子分配於該萃取液中。 The preparation method of the vanadium oxysulfate solution of the present invention, wherein the extract contains di(2-ethylhexyl) phosphate, tri-n-butyl phosphate and sulfonated kerosene. In this way, the positive tetravalent vanadium ions in the reduced vanadium and sodium aqueous solution can be effectively distributed in the extract.
本發明的硫酸氧釩溶液的製備方法，其中，該分離步驟更包含：利用水將該經還原含釩及鈉水溶液進行稀釋，以形成一稀釋後的經還原含釩及鈉水溶液，其中該稀釋後的經還原含釩及鈉水溶液中的正四價釩離子的濃度係介於10g/L~50g/L之間；及利用該萃取液對於該稀釋後的經還原含釩及鈉水溶液進行萃取，以得到該含釩萃取液。如此，能夠提高正四價釩離子的萃取率，並且將正四價釩離子與其他金屬離子進行分離，而得到高純度的硫酸氧釩水溶液。 The preparation method of vanadium oxysulfate solution of the present invention, wherein the separation step further comprises: diluting the reduced vanadium and sodium aqueous solution with water to form a diluted reduced vanadium and sodium aqueous solution, wherein the concentration of positive tetravalent vanadium ions in the diluted reduced vanadium and sodium aqueous solution is between 10g/L and 50g/L; and extracting the diluted reduced vanadium and sodium aqueous solution with the extracting liquid to obtain the vanadium-containing extracting liquid. In this way, the extraction rate of positive tetravalent vanadium ions can be improved, and positive tetravalent vanadium ions can be separated from other metal ions to obtain a high-purity vanadium oxysulfate aqueous solution.
本發明的硫酸氧釩溶液的製備方法，其中，該萃取液與該經還原含釩及鈉水溶液的體積比係介於1：1~1：1.5之間。如此，能夠提高正四價釩離子的萃取率，並且將正四價釩離子與其他金屬離子進行分離，而得到高純度的硫酸氧釩水溶液。 The method for preparing vanadium oxysulfate solution of the present invention, wherein the volume ratio of the extract to the reduced vanadium and sodium aqueous solution is between 1:1 and 1:1.5. In this way, the extraction rate of tetravalent vanadium ions can be increased, and tetravalent vanadium ions can be separated from other metal ions to obtain a high-purity vanadium oxysulfate aqueous solution.
本發明的硫酸氧釩溶液的製備方法，其中，該硫酸的濃度係介於3M~7M之間。如此，能夠提高正四價釩離子的萃取率，並且將正四價釩離子與其他金屬離子進行分離，而得到高純度的硫酸氧釩水溶液。 The preparation method of the vanadium oxysulfate solution of the present invention, wherein the concentration of the sulfuric acid is between 3M and 7M. In this way, the extraction rate of tetravalent vanadium ions can be improved, and the tetravalent vanadium ions can be separated from other metal ions to obtain a high-purity vanadium oxysulfate aqueous solution.
本發明的硫酸氧釩溶液的製備方法，更包含：一純化步驟，利用空氣對該硫酸氧釩溶液進行通氣或鼓泡(bubbling)，以及將該硫酸氧釩溶液通過一吸附型樹脂。如此，能夠將硫酸氧釩水溶液進一步純化，提升硫酸氧釩水溶液的純度。 The preparation method of the vanadium oxysulfate solution of the present invention further includes: a purification step, using air to ventilate or bubble the vanadium oxysulfate solution, and passing the vanadium oxysulfate solution through an adsorption resin. In this way, the vanadium oxysulfate aqueous solution can be further purified to improve the purity of the vanadium oxysulfate aqueous solution.
本發明的硫酸氧釩溶液的製備方法，其中，該空氣的流率係介於3公升/分鐘~6公升/分鐘之間。如此，可以有效提升該純化步驟的效率，以提升硫酸氧釩水溶液的純度。 In the method for preparing vanadium oxysulfate solution of the present invention, the air flow rate is between 3 liters/minute and 6 liters/minute. In this way, the efficiency of the purification step can be effectively improved to improve the purity of the vanadium oxysulfate aqueous solution.
〔本發明〕 [The present invention]
S1:熔融混合步驟 S1: Melt mixing step
S2:粗萃取步驟 S2: Crude extraction step
S3:還原步驟 S3: Restoration step
S4:分離步驟 S4: Separation step
S5:純化步驟 S5: Purification step
〔第1圖〕本發明的一實施例的硫酸氧釩溶液的製備方法的流程圖。 [Figure 1] A flow chart of a method for preparing a vanadium oxysulfate solution according to an embodiment of the present invention.
為讓本發明之上述及其他目的、特徵及優點能更明顯易懂，下文特舉本發明之較佳實施例，並配合所附圖式作詳細說明。 In order to make the above and other purposes, features and advantages of the present invention more clearly understood, the following specifically cites a preferred embodiment of the present invention and provides a detailed description in conjunction with the attached drawings.
如第1圖所示，本發明的硫酸氧釩溶液製備方法例如可以包含一熔融混合步驟S1、粗萃取步驟S2、一還原步驟S3及一分離步驟S4。 As shown in Figure 1, the method for preparing vanadium oxysulfate solution of the present invention may include, for example, a melt mixing step S1, a crude extraction step S2, a reduction step S3 and a separation step S4.
在該熔融混合步驟S1中，工者可以將一含釩原料與一鈉鹽以1：0.3~1：0.6的重量比混合，在介於700℃~900℃之間(例如，750℃)的溫度下熔融混合，並且將混合後的熔融物1-2℃/分鐘的降溫速率降至室溫，從而形成一含釩及鈉材料。在本實施例中，工者可以將該含釩原料與該鈉鹽預先進行粉碎，使其粒徑介於1-0.5mm之間，以提高後續在高溫熔融混合而形成該含釩及鈉材料的效率及品質；該含釩原料可以為一釩灰精礦(vanadium ore)，其中該釩灰精礦例如可以含有15~30重量%的釩、10~20重量%的鐵、10~20重量%的鎳，以及0.1~0.5重量%的鉬。該鈉鹽可以為碳酸鈉(sodium carbonate，Na2CO3)、氫氧化鈉(sodium hydroxide，NaOH)、硫酸鈉(sodium sulfate，Na2SO4)等鈉鹽。 In the melt mixing step S1, the worker may mix a vanadium-containing raw material and a sodium salt in a weight ratio of 1:0.3 to 1:0.6, melt mix them at a temperature between 700° C. and 900° C. (e.g., 750° C.), and cool the mixed melt to room temperature at a cooling rate of 1-2° C./min, thereby forming a vanadium- and sodium-containing material. In this embodiment, the worker may pre-crush the vanadium-containing raw material and the sodium salt to a particle size between 1 and 0.5 mm, so as to improve the efficiency and quality of the subsequent high-temperature melting and mixing to form the vanadium-containing and sodium-containing material; the vanadium-containing raw material may be a vanadium ore concentrate, wherein the vanadium ore concentrate may contain, for example, 15 to 30% by weight of vanadium, 10 to 20% by weight of iron, 10 to 20% by weight of nickel, and 0.1 to 0.5% by weight of molybdenum. The sodium salt may be sodium carbonate (Na 2 CO 3 ), sodium hydroxide (NaOH), sodium sulfate (Na 2 SO 4 ) and the like.
舉例而言，在該含釩原料中含有鐵且該鈉鹽為碳酸鈉的情況下，上述反應可以下列化學式表示：2Fe-V+3Na 2 CO 3+4O 2→2Na 3 VO 4+Fe 2 O 3+3CO 2。 For example, when the vanadium-containing raw material contains iron and the sodium salt is sodium carbonate, the above reaction can be represented by the following chemical formula: 2 Fe - V + 3 Na2CO3 + 4O2 → 2 Na3VO4 + Fe2O3 + 3CO2 .
接著，在該粗萃取步驟S2中，工者可以將該含釩及鈉材料以溫度介於70℃~90℃之間(例如，80℃)的熱水進行粗萃取，使該含釩及鈉材料中的水溶性成分溶於熱水中，以形成一含釩及鈉水溶液。舉例而言，該含釩及鈉材料與熱水的重量比可以介於1：1~1：4之間，而能夠提高金屬萃 取的效率。 Next, in the crude extraction step S2, the worker may crudely extract the vanadium-and-sodium-containing material with hot water at a temperature between 70°C and 90°C (e.g., 80°C), so that the water-soluble components in the vanadium-and-sodium-containing material are dissolved in the hot water to form a vanadium-and-sodium aqueous solution. For example, the weight ratio of the vanadium-and-sodium-containing material to the hot water may be between 1:1 and 1:4, which can improve the efficiency of metal extraction.
為了確認含釩原料與鈉鹽的比例對於粗萃取效果的影響，遂進行以下試驗： In order to confirm the effect of the ratio of vanadium-containing raw materials to sodium salt on the crude extraction effect, the following test was conducted:
(A)鈉鹽比例對於粗萃取效果的影響 (A) Effect of sodium salt ratio on crude extraction effect
本試驗係將100公克的釩灰精礦與碳酸鈉分別以1：0.3~1：0.6的重量比進行混合，並且在750℃的溫度下熔融混合而形成該含釩及鈉材料；其中，該釩灰精礦含有25.1%的釩、12.2%的鐵、12.3%的鎳及0.2%的鉬。接著，以300毫升的80℃熱水對該含釩及鈉材料進行粗萃取，並且以感應耦合電漿質譜法(ICP-MS)檢測萃取後的熱水中的金屬含量；其中，金屬萃取率的定義為〔(萃取後於熱水中含有的金屬重量)/(該釩灰精礦中的原始金屬重量)〕＊100。請參照第1表所示，各組樣品中的釩及鉬的金屬萃取率均遠高於鐵及鎳；此外，在釩灰精礦與碳酸鈉的重量比大於1：0.4的組別(即，第A2~A4組)中，釩及鉬的金屬萃取率均高於90%。 In this test, 100 grams of vanadium ash concentrate and sodium carbonate were mixed in a weight ratio of 1:0.3 to 1:0.6, and melted and mixed at a temperature of 750°C to form the vanadium- and sodium-containing material; wherein the vanadium ash concentrate contains 25.1% vanadium, 12.2% iron, 12.3% nickel and 0.2% molybdenum. Then, the vanadium- and sodium-containing material was crudely extracted with 300 ml of 80°C hot water, and the metal content in the hot water after extraction was detected by inductively coupled plasma mass spectrometry (ICP-MS); wherein the metal extraction rate was defined as [(the weight of metal contained in the hot water after extraction)/(the original weight of metal in the vanadium ash concentrate)]*100. Please refer to Table 1. The metal extraction rates of vanadium and molybdenum in each group of samples are much higher than those of iron and nickel. In addition, in the group where the weight ratio of vanadium ash concentrate to sodium carbonate is greater than 1:0.4 (i.e., Groups A2 to A4), the metal extraction rates of vanadium and molybdenum are higher than 90%.
接著，為了確認鈉鹽的種類對於粗萃取效果的影響，遂進行以下試驗。另外，由於在試驗(A)中，在釩灰精礦與碳酸鈉的重量比為1：0.5 的組別中，釩及鉬的金屬萃取率已分別高達98.8%及99.3%，係第A1~A4組中金屬萃取效率最佳的組別。因此，以下試驗係以釩灰精礦與鈉鹽的重量比為1：0.5的比例進行。 Next, in order to confirm the effect of the type of sodium salt on the crude extraction effect, the following test was conducted. In addition, in test (A), in the group with a weight ratio of vanadium ash concentrate to sodium carbonate of 1:0.5, the metal extraction rates of vanadium and molybdenum were as high as 98.8% and 99.3% respectively, which was the group with the best metal extraction efficiency in groups A1 to A4. Therefore, the following test was conducted with a weight ratio of vanadium ash concentrate to sodium salt of 1:0.5.
(B)鈉鹽種類對於粗萃取效果的影響 (B) The effect of sodium salt types on crude extraction efficiency
本試驗係分別將100公克的釩灰精礦與碳酸鈉/氫氧化鈉以1：0.5的重量比進行混合，並且在750℃的溫度下熔融混合而形成該含釩及鈉材料；其中，該釩灰精礦含有25.1%的釩、12.2%的鐵、12.3%的鎳及0.2%的鉬。接著，以300毫升的80℃熱水對該含釩及鈉材料進行粗萃取，並且以感應耦合電漿質譜法(ICP-MS)檢測萃取後的熱水中的金屬含量；其中，金屬萃取率的定義為〔(萃取後於熱水中含有的金屬重量)/(該釩灰精礦中的原始金屬重量)〕＊100。請參照第2表所示，無論鈉鹽係使用碳酸鈉或氫氧化鈉，均可以有效溶出釩灰精礦中的釩及鉬，顯示本發明的硫酸氧釩溶液製備方法對於各種鈉鹽具有良好的適用性。 In this test, 100 grams of vanadium ash concentrate and sodium carbonate/sodium hydroxide were mixed in a weight ratio of 1:0.5, and melted and mixed at a temperature of 750°C to form the vanadium- and sodium-containing material; wherein the vanadium ash concentrate contains 25.1% vanadium, 12.2% iron, 12.3% nickel and 0.2% molybdenum. Then, the vanadium- and sodium-containing material was crudely extracted with 300 ml of 80°C hot water, and the metal content in the hot water after extraction was detected by inductively coupled plasma mass spectrometry (ICP-MS); wherein the metal extraction rate was defined as [(the weight of metal contained in the hot water after extraction)/(the original weight of metal in the vanadium ash concentrate)]*100. Please refer to Table 2. Whether the sodium salt is sodium carbonate or sodium hydroxide, vanadium and molybdenum in vanadium ash concentrate can be effectively dissolved, indicating that the vanadium oxysulfate solution preparation method of the present invention has good applicability to various sodium salts.
在該還原步驟S3中，工者可以利用一質子酸將該含釩及鈉水溶液的酸鹼值調整至介於0.5~2.0之間。該質子酸可以為鹽酸(hydrochloric acid，HCl)、硫酸(sulfuric acid，H2SO4)等。接著，保持此酸性酸鹼值，並且將一還原劑加入該含釩及鈉水溶液中，以將該含釩及鈉水溶液中的金屬離子進行還原反應，從而將該含釩及鈉水溶液中的正五價釩離子(例如， H3VO4中的V5+)還原為正四價釩離子(例如，VOSO4中的V4+)，並且得到一經還原含釩及鈉水溶液。在本實施例中，該還原劑的添加量可以為該含釩及鈉水溶液中的含釩量ppm的0.1~0.5倍；其中，該還原劑可以為聯胺(hydrazine，N2H4)、草酸(oxalic acid，C2H2O4)、次磷酸鈉(sodium hypophosphite，NaPO2H2)、硫代硫酸鈉(sodium thiosulfate，Na2S2O3)等。 In the reduction step S3, the worker may use a proton acid to adjust the pH value of the vanadium-sodium aqueous solution to between 0.5 and 2.0. The proton acid may be hydrochloric acid (HCl), sulfuric acid ( H2SO4 ), etc. Then, the acidic pH value is maintained, and a reducing agent is added to the vanadium-sodium aqueous solution to reduce the metal ions in the vanadium-sodium aqueous solution, thereby reducing the positive pentavalent vanadium ions (e.g., V5 + in H3VO4 ) in the vanadium-sodium aqueous solution to positive tetravalent vanadium ions (e.g., V4 + in VOSO4 ), and obtaining a reduced vanadium-sodium aqueous solution. In this embodiment, the amount of the reducing agent added may be 0.1-0.5 times the ppm of the vanadium content in the vanadium-and-sodium aqueous solution; wherein the reducing agent may be hydrazine (N 2 H 4 ), oxalic acid (C 2 H 2 O 4 ), sodium hypophosphite (NaPO 2 H 2 ), sodium thiosulfate (Na 2 S 2 O 3 ), etc.
舉例而言，在該質子酸選用硫酸，且該還原劑選用聯胺的情況下，上述反應可以下列化學式表示：2Na 3 VO 4+3H 2 SO 4→2H 3 VO 4+3Na 2 SO 4 For example, when sulfuric acid is used as the protonic acid and hydrazine is used as the reducing agent, the above reaction can be represented by the following chemical formula: 2 Na 3 VO 4 +3 H 2 SO 4 →2 H 3 VO 4 +3 Na 2 SO 4
2H 3 VO 4+2N 2 H 4+2H 2 SO 4→2VOSO 4+2N 2+3H 2+6H 2 O 2 H 3 VO 4 +2 N 2 H 4 +2 H 2 SO 4 →2 VOSO 4 +2 N 2 +3 H 2 +6 H 2 O
為了確認該還原劑的添加量對於釩離子的還原效果的影響，遂進行以下試驗： In order to confirm the effect of the amount of the reducing agent added on the reduction effect of vanadium ions, the following test was conducted:
(C)還原劑的添加量對於釩離子的還原效果的影響 (C) The effect of the amount of reducing agent added on the reduction effect of vanadium ions
本試驗係利用硫酸(重量百分濃度為50%)將含釩及鈉水溶液的酸鹼值調整至0.5；其中，該含釩及鈉水溶液中的釩離子濃度為155.7g/L、鉬離子濃度為0.9g/L、鐵離子濃度為0.1g/L、鎳離子濃度為0.006g/L，而鈉離子濃度為138g/L。接著，以聯胺作為還原劑，將該含釩及鈉水溶液中的正五價釩離子還原為正四價釩離子，其中聯胺的添加量為該含釩及鈉水溶液中的含釩量ppm的0.1~0.5倍。在加入一定量的聯胺後，以氧化還原滴定法(以0.1N重铬酸鉀作為滴定液，滴定到反趨點)檢測該含釩及鈉水溶液中的正四價釩離子的轉化率；其中，正四價釩離子的轉化率的定義為〔(加入聯胺後的該經還原含釩及鈉水溶液中的正四價釩離子的莫耳數)/(加入聯胺前的該含釩及鈉水溶液中的正五價釩離子的莫耳數)〕×100。請參照第3表所示，當聯胺的添加量為該含釩及鈉水溶液中的釩離子的莫耳數的0.2倍以上時，正四價釩離子的轉化率可以達到90%以上；其中，第C3組的效率最佳， 聯胺的添加量僅為該含釩及鈉水溶液中的釩離子的莫耳數的0.3倍即可以達到99.8%的正四價釩離子的轉化率。 This test uses sulfuric acid (50% by weight) to adjust the pH value of the vanadium and sodium aqueous solution to 0.5; wherein the vanadium ion concentration in the vanadium and sodium aqueous solution is 155.7 g/L, the molybdenum ion concentration is 0.9 g/L, the iron ion concentration is 0.1 g/L, the nickel ion concentration is 0.006 g/L, and the sodium ion concentration is 138 g/L. Then, hydrazine is used as a reducing agent to reduce the pentavalent vanadium ions in the vanadium and sodium aqueous solution to tetravalent vanadium ions, wherein the amount of hydrazine added is 0.1 to 0.5 times the ppm of the vanadium content in the vanadium and sodium aqueous solution. After adding a certain amount of hydrazine, the conversion rate of tetravalent vanadium ions in the vanadium-containing and sodium-containing aqueous solution is detected by redox titration (using 0.1N potassium dichromate as a titrant, titrating to the reversal point); wherein the conversion rate of tetravalent vanadium ions is defined as [(the molar number of tetravalent vanadium ions in the reduced vanadium-containing and sodium-containing aqueous solution after adding hydrazine)/(the molar number of pentavalent vanadium ions in the vanadium-containing and sodium-containing aqueous solution before adding hydrazine)]×100. Please refer to Table 3. When the amount of hydrazine added is more than 0.2 times the molar number of vanadium ions in the vanadium and sodium aqueous solution, the conversion rate of positive tetravalent vanadium ions can reach more than 90%. Among them, the efficiency of Group C3 is the best. The amount of hydrazine added is only 0.3 times the molar number of vanadium ions in the vanadium and sodium aqueous solution, which can achieve a conversion rate of 99.8% of positive tetravalent vanadium ions.
接著，為了確認還原劑的種類對於釩離子的還原效果的影響，遂進行以下試驗。另外，由於在試驗(C)中，在還原劑的添加量為該含釩及鈉水溶液中的釩離子的莫耳數的0.3倍的組別(即，第C3組)中，四價釩離子的轉化率高達99.8%，係第C1~C5組中四價釩離子的轉化效率最佳的組別。因此，以下試驗係以還原劑的添加量為該含釩及鈉水溶液中的釩離子的莫耳數的0.3倍的條件進行。 Next, in order to confirm the effect of the type of reducing agent on the reduction effect of vanadium ions, the following test was conducted. In addition, in test (C), in the group (i.e., group C3) where the amount of reducing agent added was 0.3 times the molar number of vanadium ions in the vanadium and sodium aqueous solution, the conversion rate of tetravalent vanadium ions reached 99.8%, which was the group with the best conversion efficiency of tetravalent vanadium ions in groups C1 to C5. Therefore, the following test was conducted under the condition that the amount of reducing agent added was 0.3 times the molar number of vanadium ions in the vanadium and sodium aqueous solution.
(D)還原劑種類對於四價釩離子的轉化率的影響 (D) The effect of reducing agent type on the conversion rate of tetravalent vanadium ions
本試驗係利用硫酸(重量百分濃度為98%)將含釩及鈉水溶液的酸鹼值調整至0.5；其中，該含釩及鈉水溶液中的釩離子濃度為155.7g/L、鉬離子濃度為0.9g/L、鐵離子濃度為0.1g/L、鎳離子濃度為0.006g/L，而鈉離子濃度為138g/L。接著，分別以聯胺、草酸、次磷酸鈉及硫代硫酸鈉作為還原劑，將該含釩及鈉水溶液中的正五價釩離子還原為正四價釩離子，其中各還原劑的添加量為該含釩及鈉水溶液中的含釩量ppm的0.3倍。在加入一定量的還原劑後，以氧化還原滴定法(以0.1N重铬酸鉀作為滴定液，滴定到反趨點)檢測該含釩及鈉水溶液中的正四價釩離子的轉化率；其中，正四 價釩離子的轉化率的定義為〔(加入還原劑後的該經還原含釩及鈉水溶液中的正四價釩離子的莫耳數)/(加入還原劑前的該含釩及鈉水溶液中的正五價釩離子的莫耳數)〕×100。請參照第4表所示，第D1~D4組的正四價釩離子的轉化率均高達95%以上，顯示本發明的硫酸氧釩溶液製備方法對於各種還原劑具有良好的適用性。 In this test, the pH value of the vanadium and sodium aqueous solution is adjusted to 0.5 using sulfuric acid (98% by weight); the vanadium ion concentration in the vanadium and sodium aqueous solution is 155.7g/L, the molybdenum ion concentration is 0.9g/L, the iron ion concentration is 0.1g/L, the nickel ion concentration is 0.006g/L, and the sodium ion concentration is 138g/L. Next, hydrazine, oxalic acid, sodium hypophosphite and sodium thiosulfate are used as reducing agents to reduce pentavalent vanadium ions in the vanadium and sodium aqueous solution to tetravalent vanadium ions, wherein the amount of each reducing agent added is 0.3 times the ppm of the vanadium content in the vanadium and sodium aqueous solution. After adding a certain amount of reducing agent, the conversion rate of positive tetravalent vanadium ions in the vanadium and sodium aqueous solution is detected by redox titration (using 0.1N potassium dichromate as titrant, titrated to the reversal point); wherein, the conversion rate of positive tetravalent vanadium ions is defined as [(the molar number of positive tetravalent vanadium ions in the reduced vanadium and sodium aqueous solution after adding reducing agent)/(the molar number of positive pentavalent vanadium ions in the vanadium and sodium aqueous solution before adding reducing agent)] × 100. Please refer to Table 4, the conversion rates of positive tetravalent vanadium ions in groups D1 to D4 are all as high as 95% or more, indicating that the preparation method of vanadium oxysulfate solution of the present invention has good applicability to various reducing agents.
接著，為了確認酸鹼值對於釩離子的還原效果的影響，遂進行以下試驗。另外，由於在試驗(D)中，選用聯胺作為還原劑的四價釩離子的轉化率高達99.8%，係第D1~D4組中四價釩離子的轉化效率最佳的組別。因此，以下試驗係以第D1組的條件進行。 Next, in order to confirm the effect of acid-base value on the reduction effect of vanadium ions, the following test was conducted. In addition, since the conversion rate of tetravalent vanadium ions using hydrazine as the reducing agent in test (D) was as high as 99.8%, it was the group with the best conversion efficiency of tetravalent vanadium ions in groups D1 to D4. Therefore, the following test was conducted under the conditions of group D1.
(E)酸鹼值對於四價釩離子的轉化率的影響 (E) Effect of pH on the conversion rate of tetravalent vanadium ions
本試驗係利用硫酸(重量百分濃度為98%)將含釩及鈉水溶液的酸鹼值分別調整至0.5、1.0、1.5及2.0；其中，該含釩及鈉水溶液中的釩離子濃度為155.7g/L、鉬離子濃度為0.9g/L、鐵離子濃度為0.1g/L、鎳離子濃度為0.006g/L，而鈉離子濃度為138g/L。接著，以聯胺作為還原劑，將該含釩及鈉水溶液中的正五價釩離子還原為正四價釩離子，其中聯胺的添加量為該含釩及鈉水溶液中的含釩量ppm的0.3倍。在加入一定量的聯胺後，以氧化還原滴定法(以0.1N重铬酸鉀作為滴定液，滴定到反趨點)檢測該含釩及鈉水溶液中的正四價釩離子的轉化率；其中，正四價釩離子的轉化率的 定義為〔(加入聯胺後的該經還原含釩及鈉水溶液中的正四價釩離子的莫耳數)/(加入聯胺前的該含釩及鈉水溶液中的正五價釩離子的莫耳數)〕×100。請參照第5表所示，第E1~E4組的正四價釩離子的轉化率均高達90%以上，且隨著酸鹼值的降低而提高。 In this test, the pH values of the vanadium and sodium aqueous solutions were adjusted to 0.5, 1.0, 1.5 and 2.0 respectively using sulfuric acid (98% by weight); wherein the vanadium ion concentration in the vanadium and sodium aqueous solutions was 155.7 g/L, the molybdenum ion concentration was 0.9 g/L, the iron ion concentration was 0.1 g/L, the nickel ion concentration was 0.006 g/L, and the sodium ion concentration was 138 g/L. Then, hydrazine is used as a reducing agent to reduce the pentavalent vanadium ions in the vanadium and sodium aqueous solution to tetravalent vanadium ions, wherein the amount of hydrazine added is 0.3 times the ppm of the vanadium content in the vanadium and sodium aqueous solution. After adding a certain amount of hydrazine, the conversion rate of the tetravalent vanadium ions in the vanadium and sodium aqueous solution is detected by redox titration (using 0.1N potassium dichromate as a titrant, titrating to the reversal point); wherein the conversion rate of the tetravalent vanadium ions is defined as [(the molar number of the tetravalent vanadium ions in the reduced vanadium and sodium aqueous solution after the addition of hydrazine)/(the molar number of the pentavalent vanadium ions in the vanadium and sodium aqueous solution before the addition of hydrazine)]×100. Please refer to Table 5. The conversion rates of tetravalent vanadium ions in groups E1 to E4 are all above 90%, and increase with decreasing acid-base values.
根據試驗(A)及(B)的試驗結果，釩及鉬的金屬萃取率均高於90%，表示鉬離子與釩離子均會存在於該含釩及鈉水溶液中。因此，為了確認該還原步驟S3中所使用的還原劑是否會一併還原該含釩及鈉水溶液中的鉬離子，並且判斷還原劑對於鉬離子與釩離子各自的還原效果的差異，遂進行以下試驗： 在該分離步驟S4中，工者可以利用水(例如，逆滲透水、蒸餾水、去離子水等)將該經還原含釩及鈉水溶液進行稀釋以形成一稀釋後的經還原含釩及鈉水溶液；其中，該稀釋後的經還原含釩及鈉水溶液中的正四價釩離子的濃度係介於10g/L~50g/L之間。接著，工者可以利用一萃取液對於該稀釋後的經還原含釩及鈉水溶液進行萃取，使該稀釋後的經還原含釩及鈉水溶液中的正四價釩離子分配於該萃取液中，從而得到一含釩萃取液。該萃取液可以包含二(2-乙基己基)磷酸酯(C16H35O4P，di(2-ethylhexyl)phosphate，別名P204或磷酸二異辛酯)、磷酸三正丁酯(C12H27O4P，tributyl phosphate)及磺化煤油，其中二(2-乙基己基)磷酸酯 與磷酸三正丁酯的總量係落在該萃取液的50重量%以下。在本實施例中，該萃取液(有機相)與該稀釋後的經還原含釩及鈉水溶液(水相)的體積比可以介於1：1~1：1.5之間(例如，介於1：1.1~1：1.3之間)，使正四價釩離子分配於該萃取液中的效率更佳。 According to the test results of tests (A) and (B), the metal extraction rates of vanadium and molybdenum were both higher than 90%, indicating that both molybdenum ions and vanadium ions were present in the aqueous solution containing vanadium and sodium. Therefore, in order to confirm whether the reducing agent used in the reduction step S3 will also reduce the molybdenum ions in the vanadium and sodium aqueous solution, and to determine the difference in the reducing effect of the reducing agent on the molybdenum ions and the vanadium ions, the following test is performed: In the separation step S4, the worker can use water (for example, reverse osmosis water, distilled water, deionized water, etc.) to dilute the reduced vanadium and sodium aqueous solution to form a diluted reduced vanadium and sodium aqueous solution; wherein the concentration of tetravalent vanadium ions in the diluted reduced vanadium and sodium aqueous solution is between 10 g/L and 50 g/L. Then, the worker may use an extracting liquid to extract the diluted reduced vanadium-containing and sodium-containing aqueous solution, so that the positive tetravalent vanadium ions in the diluted reduced vanadium-containing and sodium-containing aqueous solution are distributed in the extracting liquid, thereby obtaining a vanadium-containing extracting liquid. The extracting liquid may contain di(2-ethylhexyl)phosphate (C 16 H 35 O 4 P, di(2-ethylhexyl)phosphate, also known as P204 or diisooctyl phosphate), tri-n-butyl phosphate (C 12 H 27 O 4 P, tributyl phosphate) and sulfonated kerosene, wherein the total amount of di(2-ethylhexyl)phosphate and tri-n-butyl phosphate is less than 50% by weight of the extracting liquid. In this embodiment, the volume ratio of the extract (organic phase) to the diluted reduced vanadium-and-sodium aqueous solution (aqueous phase) may be between 1:1 and 1:1.5 (e.g., between 1:1.1 and 1:1.3), so that the efficiency of the distribution of positive tetravalent vanadium ions in the extract is better.
接著，工者可以利用濃度介於3M~7M的硫酸對該含釩萃取液進行反萃取，使該含釩萃取液中的正四價釩離子分配於硫酸中，即可以得到該硫酸氧釩水溶液。在本實施例中，硫酸與該含釩萃取液的體積比可以介於1：2~1：4之間，使正四價釩離子分配於硫酸中且形成該硫酸氧釩水溶液的效率更佳。 Then, the worker can use sulfuric acid with a concentration between 3M and 7M to strip the vanadium-containing extract so that the tetravalent vanadium ions in the vanadium-containing extract are distributed in the sulfuric acid, and the vanadium oxysulfate aqueous solution can be obtained. In this embodiment, the volume ratio of sulfuric acid to the vanadium-containing extract can be between 1:2 and 1:4, so that the tetravalent vanadium ions are distributed in the sulfuric acid and the efficiency of forming the vanadium oxysulfate aqueous solution is better.
為了確認該經還原含釩及鈉水溶液中的正四價釩離子的濃度對於正四價釩離子的萃取效率的影響，遂進行以下試驗： In order to confirm the effect of the concentration of tetravalent vanadium ions in the reduced vanadium and sodium aqueous solution on the extraction efficiency of tetravalent vanadium ions, the following test was conducted:
(F)釩離子濃度對於萃取效率的影響 (F) Effect of vanadium ion concentration on extraction efficiency
本試驗係選用第C3組的待測樣品，將經過聯胺還原後的該經還原含釩及鈉水溶液分別進行稀釋，使該稀釋後的經還原含釩及鈉水溶液中的正四價釩離子的濃度分別為10g/L、20g/L、30g/L、40g/L及50g/L。接著，利用包含二(2-乙基己基)磷酸酯(P204)、磷酸三正丁酯(TBP)及磺化煤油的該萃取液(P204：TBP：磺化煤油=30%：20%：50%，以重量計)，在該萃取液(有機相)與該稀釋後的經還原含釩及鈉水溶液(水相)的體積比為1：1.2的條件下進行萃取。接著，利用濃度為5M的硫酸對於有機相進行反萃取，並且以感應耦合電漿質譜法(ICP-MS)檢測萃取後的硫酸中的金屬萃取率；其中，金屬萃取率的定義為〔(萃取後於硫酸中含有的金屬重量)/(第C3組的待測樣品中的原始金屬重量)〕×100。請參照第6表所示，第F1~F5組的正四價釩離子的萃取率均高達90%以上，且隨著該稀釋後的經還原含釩及鈉水溶液中的正四價釩離子的濃度的降低而提高；另外，其餘金屬離 子(即，鉬離子及鈉離子)的萃取率幾乎為0，顯示本發明的硫酸氧釩溶液製備方法確實能夠有效將正四價釩離子與其他金屬離子進行分離，並且得到高純度的硫酸氧釩水溶液。 This test uses the sample of group C3 to dilute the reduced vanadium and sodium aqueous solution after hydrazine reduction, so that the concentration of positive tetravalent vanadium ions in the diluted reduced vanadium and sodium aqueous solution is 10g/L, 20g/L, 30g/L, 40g/L and 50g/L, respectively. Then, the extraction is carried out using the extract containing di(2-ethylhexyl) phosphate (P204), tri-n-butyl phosphate (TBP) and sulfonated kerosene (P204:TBP:sulfonated kerosene=30%:20%:50%, by weight), under the condition that the volume ratio of the extract (organic phase) to the diluted reduced vanadium and sodium aqueous solution (aqueous phase) is 1:1.2. Then, the organic phase was stripped using 5M sulfuric acid, and the metal extraction rate in the sulfuric acid after extraction was detected by inductively coupled plasma mass spectrometry (ICP-MS); wherein the metal extraction rate was defined as [(metal weight contained in sulfuric acid after extraction)/(original metal weight in the sample to be tested in group C3)]×100. Please refer to Table 6. The extraction rate of tetravalent vanadium ions in groups F1 to F5 is as high as 90% or more, and increases with the decrease in the concentration of tetravalent vanadium ions in the diluted reduced vanadium and sodium aqueous solution. In addition, the extraction rate of the remaining metal ions (i.e., molybdenum ions and sodium ions) is almost 0, indicating that the preparation method of vanadium oxysulfate solution of the present invention can effectively separate tetravalent vanadium ions from other metal ions and obtain a high-purity vanadium oxysulfate aqueous solution.
接著，為了確認該萃取液(有機相)與該稀釋後的經還原含釩及鈉水溶液(水相)的體積比對於正四價釩離子的萃取效率的影響，遂進行以下試驗： Next, in order to confirm the effect of the volume ratio of the extract (organic phase) to the diluted reduced vanadium and sodium aqueous solution (aqueous phase) on the extraction efficiency of tetravalent vanadium ions, the following test was conducted:
(G)有機相與水相的體積比對於萃取效率的影響 (G) Effect of the volume ratio of organic phase to aqueous phase on extraction efficiency
本試驗係選用第C3組的待測樣品，將經過聯胺還原後的該經還原含釩及鈉水溶液分別進行稀釋，使該稀釋後的經還原含釩及鈉水溶液中的正四價釩離子的濃度為30g/L。接著，利用包含二(2-乙基己基)磷酸酯(P204)、磷酸三正丁酯(TBP)及磺化煤油的該萃取液(P204：TBP：磺化煤油=30%：20%：50%，以重量計)，在該萃取液(有機相)與該稀釋後的經還原含釩及鈉水溶液(水相)的體積比分別為1：1、1：1.1、1：1.2、1：1.3、1：1.4及1：1.5的條件下進行萃取。接著，利用濃度為5M的硫酸對於有機相進行反萃取，並且以感應耦合電漿質譜法(ICP-MS)檢測萃取後的硫 酸中的金屬萃取率；其中，金屬萃取率的定義為〔(萃取後於硫酸中含有的金屬重量)/(第C3組的待測樣品中的原始金屬重量)〕×100。請參照第7表所示，第G1~G6組的正四價釩離子的萃取率均高達95%以上，且隨著該萃取液(有機相)與該稀釋後的經還原含釩及鈉水溶液(水相)的體積比增加而提高；其中，第H3組的效率最佳，該萃取液(有機相)與該稀釋後的經還原含釩及鈉水溶液(水相)的體積比僅為1：2即可以達到98.5%的正四價釩離子的萃取率。另外，其餘金屬離子(即，鉬離子及鈉離子)的萃取率幾乎為0，顯示本發明的硫酸氧釩溶液製備方法確實能夠有效將正四價釩離子與其他金屬離子進行分離，並且得到高純度的硫酸氧釩水溶液。 This test uses the sample of group C3 to be tested. The reduced vanadium and sodium aqueous solution after hydrazine reduction is diluted respectively so that the concentration of positive tetravalent vanadium ions in the diluted reduced vanadium and sodium aqueous solution is 30 g/L. Then, the extraction is performed using the extract containing di(2-ethylhexyl) phosphate (P204), tri-n-butyl phosphate (TBP) and sulfonated kerosene (P204:TBP:sulfonated kerosene=30%:20%:50%, by weight) under the conditions that the volume ratio of the extract (organic phase) to the diluted reduced vanadium and sodium aqueous solution (aqueous phase) is 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4 and 1:1.5 respectively. Then, the organic phase was stripped with 5M sulfuric acid, and the metal extraction rate in the sulfuric acid after extraction was detected by inductively coupled plasma mass spectrometry (ICP-MS); the metal extraction rate was defined as [(metal weight contained in sulfuric acid after extraction)/(original metal weight in the sample to be tested in group C3)] × 100. As shown in Table 7, the extraction rates of tetravalent vanadium ions of Groups G1 to G6 are all as high as over 95%, and increase with the volume ratio of the extract (organic phase) to the diluted reduced vanadium-containing and sodium aqueous solution (aqueous phase). Among them, Group H3 has the best efficiency, and the extraction rate of tetravalent vanadium ions can reach 98.5% when the volume ratio of the extract (organic phase) to the diluted reduced vanadium-containing and sodium aqueous solution (aqueous phase) is only 1:2. In addition, the extraction rate of the remaining metal ions (i.e., molybdenum ions and sodium ions) is almost 0, indicating that the method for preparing the vanadium oxysulfate solution of the present invention can effectively separate positive tetravalent vanadium ions from other metal ions and obtain a high-purity vanadium oxysulfate aqueous solution.
接著，為了確認硫酸濃度對於正四價釩離子的萃取效率的影響，遂進行以下試驗： Next, in order to confirm the effect of sulfuric acid concentration on the extraction efficiency of tetravalent vanadium ions, the following test was conducted:
(H)硫酸濃度對於萃取效率的影響 (H) Effect of sulfuric acid concentration on extraction efficiency
本試驗係選用第C3組的待測樣品，將經過聯胺還原後的該經 還原含釩及鈉水溶液分別進行稀釋，使該稀釋後的經還原含釩及鈉水溶液中的正四價釩離子的濃度為30g/L。接著，利用包含二(2-乙基己基)磷酸酯(P204)、磷酸三正丁酯(TBP)及磺化煤油的該萃取液(P204：TBP：磺化煤油=30%：20%：50%，以重量計)，在該萃取液(有機相)與該稀釋後的經還原含釩及鈉水溶液(水相)的體積比為1：1.2的條件下進行萃取。接著，利用濃度分別為3M、4M、5M、6M及7M的硫酸對於有機相進行反萃取，並且以感應耦合電漿質譜法(ICP-MS)檢測萃取後的硫酸中的金屬萃取率；其中，金屬萃取率的定義為〔(萃取後於硫酸中含有的金屬重量)/(第C3組的待測樣品中的原始金屬重量)〕×100。請參照第8表所示，第H1~H5組的正四價釩離子的萃取率均高達90%以上，且隨著硫酸濃度的增加而提高；其中，第I3組的效率最佳，硫酸濃度僅為5M即可以達到97.5%的正四價釩離子的萃取率。另外，其餘金屬離子(即，鉬離子及鈉離子)的萃取率幾乎為0，顯示本發明的硫酸氧釩溶液製備方法確實能夠有效將正四價釩離子與其他金屬離子進行分離，並且得到高純度的硫酸氧釩水溶液。 This test uses the sample of group C3 to be tested. The reduced vanadium and sodium aqueous solution after hydrazine reduction is diluted respectively so that the concentration of positive tetravalent vanadium ions in the diluted reduced vanadium and sodium aqueous solution is 30 g/L. Then, the extraction is performed using the extract containing di(2-ethylhexyl) phosphate (P204), tri-n-butyl phosphate (TBP) and sulfonated kerosene (P204:TBP:sulfonated kerosene = 30%:20%:50%, by weight) under the condition that the volume ratio of the extract (organic phase) to the diluted reduced vanadium and sodium aqueous solution (aqueous phase) is 1:1.2. Then, the organic phase was stripped using sulfuric acid of concentrations of 3M, 4M, 5M, 6M and 7M, and the metal extraction rate in the sulfuric acid after extraction was detected by inductively coupled plasma mass spectrometry (ICP-MS); wherein the metal extraction rate is defined as [(weight of metal contained in sulfuric acid after extraction)/(weight of original metal in the sample to be tested in group C3)] × 100. Please refer to Table 8, the extraction rates of positive tetravalent vanadium ions in groups H1 to H5 are all as high as over 90%, and increase with the increase of sulfuric acid concentration; among them, group I3 has the best efficiency, and the extraction rate of positive tetravalent vanadium ions can reach 97.5% at a sulfuric acid concentration of only 5M. In addition, the extraction rate of the remaining metal ions (i.e., molybdenum ions and sodium ions) is almost 0, indicating that the method for preparing the vanadium oxysulfate solution of the present invention can effectively separate positive tetravalent vanadium ions from other metal ions and obtain a high-purity vanadium oxysulfate aqueous solution.
如第1圖所示，本發明的硫酸氧釩溶液製備方法可以進一步包 含一純化步驟S5。在該純化步驟S5中，工者可以將該分離步驟S4後所得到的該硫酸氧釩水溶液以流率(flow rate)介於3公升/分鐘~6公升/分鐘之間的空氣進行通氣/鼓泡(bubbling)，以去除該硫酸氧釩水溶液中的油分(殘留有機項)。在本實施例中，該通氣/鼓泡步驟可以進行1~2小時，較佳為2小時以上，以將該硫酸氧釩水溶液中的油分完全去除。接著，工者可以將經過該通氣/鼓泡步驟後的該硫酸氧釩水溶液通過一吸附型樹脂(例如，高分子類多孔吸附樹脂)，以去除該硫酸氧釩水溶液中的懸浮物或雜質，從而將該硫酸氧釩水溶液進一步純化而得到純度更高的該硫酸氧釩水溶液。 As shown in FIG. 1 , the method for preparing vanadium oxysulfate solution of the present invention may further include a purification step S5. In the purification step S5, the worker may ventilate/bubble the vanadium oxysulfate aqueous solution obtained after the separation step S4 with air at a flow rate between 3 liters/minute and 6 liters/minute to remove the oil (residual organic matter) in the vanadium oxysulfate aqueous solution. In this embodiment, the ventilating/bubbling step may be performed for 1 to 2 hours, preferably for more than 2 hours, to completely remove the oil in the vanadium oxysulfate aqueous solution. Next, the worker can pass the vanadium sulfate aqueous solution after the ventilation/bubbling step through an adsorption resin (e.g., a polymer porous adsorption resin) to remove suspended matter or impurities in the vanadium sulfate aqueous solution, thereby further purifying the vanadium sulfate aqueous solution to obtain a vanadium sulfate aqueous solution with a higher purity.
為了確認空氣的流率對於純化效果的影響，遂進行以下試驗： In order to confirm the effect of air flow rate on purification effect, the following test was conducted:
(I)氣體對於純化效果的影響 (I) The impact of gas on purification effect
本試驗係選用第F3組的待測樣品，在經過該萃取液及硫酸的萃取及反萃取後，將所得到的該硫酸氧釩水溶液分別以流率為3公升/分鐘、4公升/分鐘、5公升/分鐘及6公升/分鐘的空氣進行通氣/鼓泡，接著將經過該通氣/鼓泡步驟後的該硫酸氧釩水溶液通過HP268高分子類多孔吸附樹脂後，以感應耦合電漿質譜法(ICP-MS)檢測經過純化後的該硫酸氧釩水溶液中的各成分濃度。請參照第9表所示，第I1~I4組的其餘金屬離子(即，鉬離子及鈉離子)的濃度皆為0或趨近於0，而油脂的濃度亦在0.005g/L以下，顯示本發明的硫酸氧釩溶液製備方法的純化步驟S5確實可以進一步純化該硫酸氧釩水溶液，將該分離步驟S4中所使用的油性成分有效去除，而得到純度更高的硫酸氧釩水溶液。 This test uses the test samples of group F3. After extraction and stripping with the extract and sulfuric acid, the obtained vanadium oxysulfate aqueous solution is ventilated/bubbled with air at flow rates of 3 liters/minute, 4 liters/minute, 5 liters/minute and 6 liters/minute, respectively. Then, the vanadium oxysulfate aqueous solution after the venting/bubbling step is passed through HP268 polymer porous adsorption resin, and the concentration of each component in the purified vanadium oxysulfate aqueous solution is detected by inductively coupled plasma mass spectrometry (ICP-MS). Please refer to Table 9. The concentrations of the remaining metal ions (i.e., molybdenum ions and sodium ions) in Groups I1 to I4 are all 0 or close to 0, and the concentration of oil is also below 0.005 g/L, indicating that the purification step S5 of the vanadium oxysulfate solution preparation method of the present invention can indeed further purify the vanadium oxysulfate aqueous solution, effectively remove the oily components used in the separation step S4, and obtain a vanadium oxysulfate aqueous solution with higher purity.
綜上所述，本發明的硫酸氧釩溶液的製備方法，藉由將含釩原料與鈉鹽熔融混合而形成水溶性的釩鈉化合物，接著以熱水進行粗萃取後，利用還原劑將水溶液中的正五價釩離子還原為正四價釩離子，最後分別利用萃取液及硫酸進行萃取及反萃取而得到該硫酸氧釩溶液，無須使用昂貴的五氧化二釩或偏釩酸銨作為原料即可以製備硫酸氧釩溶液，且在製備過程中不會產生氨氣汙染，為本發明之功效。並且，藉由使用釩灰精礦作為該含釩原料，無須使用昂貴的五氧化二釩或偏釩酸銨作為原料即可以製備硫酸氧釩溶液，能夠大幅降低製備硫酸氧釩溶液的成本。 In summary, the method for preparing vanadium oxysulfate solution of the present invention comprises the following steps: melting and mixing a vanadium-containing raw material and a sodium salt to form a water-soluble vanadium sodium compound, and then performing a crude extraction with hot water. Then, a reducing agent is used to reduce the pentavalent vanadium ions in the aqueous solution to tetravalent vanadium ions. Finally, the extract and sulfuric acid are used to perform extraction and stripping, respectively, to obtain the vanadium oxysulfate solution. The vanadium oxysulfate solution can be prepared without using expensive vanadium pentoxide or ammonium metavanadate as a raw material, and no ammonia pollution is generated during the preparation process, which is the effect of the present invention. Furthermore, by using vanadium ash concentrate as the vanadium-containing raw material, vanadium oxysulfate solution can be prepared without using expensive vanadium pentoxide or ammonium metavanadate as raw materials, which can significantly reduce the cost of preparing vanadium oxysulfate solution.
雖然本發明已利用上述較佳實施例揭示，然其並非用以限定本發明，任何熟習此技藝者在不脫離本發明之精神和範圍之內，相對上述實施例進行各種更動與修改仍屬本發明所保護之技術範疇，因此本發明之保護範圍當包含後附之申請專利範圍所記載的文義及均等範圍內之所有變更。 Although the present invention has been disclosed using the above preferred embodiments, they are not intended to limit the present invention. Any person skilled in the art may make various changes and modifications to the above embodiments within the spirit and scope of the present invention, and the changes and modifications are still within the technical scope protected by the present invention. Therefore, the protection scope of the present invention shall include all changes within the meaning and equivalent scope recorded in the attached patent application scope.
S1:熔融混合步驟 S1: Melt mixing step
S2:粗萃取步驟 S2: Crude extraction step
S3:還原步驟 S3: Restoration step
S4:分離步驟 S4: Separation step
S5:純化步驟 S5: Purification step
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| CN114436328B (en) * | 2022-03-14 | 2023-03-28 | 中国科学院过程工程研究所 | Method for preparing vanadyl sulfate electrolyte from sodium vanadate-containing solution |
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