TW202239978A - Method for recovering vanadium from vanadium-containing lime byproduct - Google Patents
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本發明係關於一種回收釩金屬的方法，尤其是一種自含釩副產石灰中回收釩金屬的方法。The invention relates to a method for recovering vanadium metal, in particular to a method for recovering vanadium metal from vanadium-containing by-product lime.
石油焦（petroleum coke）為石油煉製（oil refining）過程中的副產品，由於石油焦具有燃燒熱（combustion heat）低的優點，可以作為發電、水泥等工業燃料。然而，由於石油焦所含有的硫元素，為避免石油焦在燃燒過程中產生之硫氧化物（sulfur oxides）的排出造成之空氣汙染，多會混合燃燒所產生的硫氧化物與石灰石（limestone，其主成分為碳酸鈣）以進行脫硫反應（desulfurization），此時所產生的副產品即為副產石灰（lime product）。Petroleum coke is a by-product of the oil refining process. Because of its low combustion heat, petroleum coke can be used as industrial fuel for power generation and cement. However, due to the sulfur contained in petroleum coke, in order to avoid air pollution caused by the emission of sulfur oxides (sulfur oxides) produced during the combustion of petroleum coke, the sulfur oxides produced by combustion will be mixed with limestone (limestone, Its main component is calcium carbonate) to carry out the desulfurization reaction (desulfurization), and the by-product produced at this time is the by-product lime (lime product).
副產石灰中含有大量含鈣化合物，其組成複雜，主要為硫酸鈣（calcium sulfate，CaSO 4）、氧化鈣（calcium oxide，CaO）及氫氧化鈣（calcium hydroxide，Ca(OH) 2）等，多半作為環保建材（green construction material）或混凝土添加劑（concrete additive）來使用，惟副產石灰中亦含有極為微量的釩等有價金屬（以重量百分比計約為0.1～2%），有鑒於此，若能夠自副產石灰中回收釩金屬，確實有助於提升副產石灰的經濟效益。 The by-product lime contains a large amount of calcium-containing compounds, and its composition is complex, mainly calcium sulfate (CaSO 4 ), calcium oxide (CaO) and calcium hydroxide (Ca(OH) 2 ), etc. It is mostly used as green construction material or concrete additive, but the by-product lime also contains a very small amount of valuable metals such as vanadium (about 0.1-2% by weight). In view of this, If vanadium metal can be recovered from by-product lime, it will indeed help to improve the economic benefits of by-product lime.
為解決上述問題，本發明的目的是提供一種自含釩副產石灰中回收釩金屬的方法，係能夠有效率地自含釩副產石灰中回收釩金屬者。In order to solve the above problems, the object of the present invention is to provide a method for recovering vanadium metal from vanadium-containing by-product lime, which can efficiently recover vanadium metal from vanadium-containing by-product lime.
本發明的次一目的是提供一種自含釩副產石灰中回收釩金屬的方法，係能夠降低自含釩副產石灰中回收釩金屬的成本者。Another object of the present invention is to provide a method for recovering vanadium metal from vanadium-containing by-product lime, which can reduce the cost of recovering vanadium metal from vanadium-containing by-product lime.
本發明的自含釩副產石灰中回收釩金屬的方法，可以包含：於0～5之pH值、25～80℃之溫度下，以一酸液浸漬一含釩副產石灰1～4小時，以得一濾餅及一酸浸液；及以一離子交換樹脂，自該酸浸液中回收釩金屬。The method for recovering vanadium metal from vanadium-containing by-product lime of the present invention may include: soaking a vanadium-containing by-product lime with an acid solution at a pH value of 0-5 and a temperature of 25-80°C for 1-4 hours , to obtain a filter cake and an acid leaching solution; and recovering vanadium metal from the acid leaching solution with an ion exchange resin.
據此，本發明的自含釩副產石灰中回收釩金屬的方法，藉由以該酸液浸漬該含釩副產石灰，可以使該含釩副產石灰中的含鈣化合物沉澱而形成該濾餅，進而與溶有釩離子的酸浸液分離，因此可以輕鬆地藉由該離子交換樹脂，使該酸浸液中的釩離子還原形成釩金屬，可以達成提升回收釩金屬之效率的功效。Accordingly, in the method for recovering vanadium metal from vanadium-containing by-product lime of the present invention, by impregnating the vanadium-containing by-product lime with the acid solution, the calcium-containing compound in the vanadium-containing by-product lime can be precipitated to form the The filter cake is further separated from the acid leaching solution in which vanadium ions are dissolved, so the ion exchange resin can be used to easily reduce the vanadium ions in the acid leaching solution to form vanadium metal, which can achieve the effect of improving the efficiency of vanadium metal recovery .
本發明的自含釩副產石灰中回收釩金屬的方法，其中，該含釩副產石灰可以包含以重量百分比計為0.1～5%的含釩化合物、70～90%的含鈣化合物，其餘比例為不可避免之雜質；其中，該含鈣化合物可以包含40～60%的硫酸鈣、25～30%的氧化鈣、10～30%的氫氧化鈣，且該酸液可以包含以重量百分比計為45～65%的硫酸、30～50%的過氧化氫，其餘比例為不可避免之雜質。如此，使該含釩副產石灰中的氧化鈣及氫氧化鈣均能夠與該酸液中的硫酸反應形成硫酸鈣而沉澱，且該含釩副產石灰中的釩離子則能夠藉由過氧化氫的氧化作用而形成正五價的釩離子（V 5+），可以提升與該離子交換樹脂的反應效率，達成提升回收釩金屬之效率的功效。 The method for recovering vanadium metal from vanadium-containing by-product lime of the present invention, wherein, the vanadium-containing by-product lime may contain 0.1-5% of vanadium-containing compounds, 70-90% of calcium-containing compounds, and the rest The proportion is unavoidable impurity; wherein, the calcium-containing compound can contain 40-60% calcium sulfate, 25-30% calcium oxide, 10-30% calcium hydroxide, and the acid solution can contain It is 45-65% sulfuric acid, 30-50% hydrogen peroxide, and the rest is unavoidable impurities. In this way, the calcium oxide and calcium hydroxide in the vanadium-containing by-product lime can react with the sulfuric acid in the acid solution to form calcium sulfate and precipitate, and the vanadium ions in the vanadium-containing by-product lime can be The hydrogen oxidizes to form positive pentavalent vanadium ions (V 5+ ), which can improve the reaction efficiency with the ion exchange resin and achieve the effect of improving the efficiency of recovering vanadium metal.
本發明的自含釩副產石灰中回收釩金屬的方法，其中，可以於pH值＜2的環境中浸漬該含釩副產石灰。如此，藉由浸漬pH值的調整，可以使釩離子的浸出率達90%以上。In the method for recovering vanadium metal from vanadium-containing by-product lime of the present invention, the vanadium-containing by-product lime can be impregnated in an environment with a pH value<2. In this way, by adjusting the pH value of impregnation, the leaching rate of vanadium ions can reach more than 90%.
本發明的自含釩副產石灰中回收釩金屬的方法，其中，可以浸漬該含釩副產石灰2～4小時。如此，藉由浸漬時間的調整，可以使釩離子的浸出率達90%以上。In the method for recovering vanadium metal from vanadium-containing by-product lime of the present invention, the vanadium-containing by-product lime can be soaked for 2-4 hours. In this way, by adjusting the immersion time, the leaching rate of vanadium ions can reach more than 90%.
本發明的自含釩副產石灰中回收釩金屬的方法，其中，可以於50～80℃之溫度下浸漬該含釩副產石灰。藉由浸漬溫度的調整，可以使釩離子的浸出率達90%以上。In the method for recovering vanadium metal from vanadium-containing by-product lime of the present invention, the vanadium-containing by-product lime can be impregnated at a temperature of 50-80°C. By adjusting the immersion temperature, the leaching rate of vanadium ions can reach more than 90%.
本發明的自含釩副產石灰中回收釩金屬的方法，其中，該含釩副產石灰的粒徑可以為20～70 mesh，較佳可以為50 mesh以上。如此，藉由該粒徑的調整，可以提升該含釩副產石灰與該酸液的反應面積，進而可以提升釩離子的浸出率。In the method for recovering vanadium metal from vanadium-containing by-product lime of the present invention, the particle size of the vanadium-containing by-product lime can be 20-70 mesh, preferably more than 50 mesh. In this way, by adjusting the particle size, the reaction area between the vanadium-containing by-product lime and the acid solution can be increased, thereby increasing the leaching rate of vanadium ions.
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，作詳細說明如下：In order to make the above and other purposes, features and advantages of the present invention more comprehensible, the preferred embodiments of the present invention are specifically cited below, together with the accompanying drawings, as follows:
請參照第1圖所示，其為本發明自含釩副產石灰中回收釩金屬的方法的一實施例，該方法可以包含一酸浸步驟S1及一離子交換步驟S2，藉此可以將存在於一含釩副產石灰中的釩，以釩金屬的形式回收。Please refer to Fig. 1, which is an embodiment of the method for recovering vanadium metal from vanadium-containing by-product lime of the present invention. The method may include an acid leaching step S1 and an ion exchange step S2, whereby existing Vanadium in a vanadium-containing by-product lime is recovered as vanadium metal.
詳而言之，該含釩副產石灰係為了處理石油焦燃燒所產生的硫氧化物所形成者，其中包含含釩化合物、含鈣化合物等化合物。於本實施例中，該含釩副產石灰可以包含以重量百分比計為0.1～5%的含釩化合物、70～90%的含鈣化合物，其餘比例為不可避免之雜質。又，該含鈣化合物可以包含以重量百分比計為40～60%的硫酸鈣、25～30%的氧化鈣、10～30%的氫氧化鈣。Specifically, the vanadium-containing by-product lime is formed to treat sulfur oxides produced by burning petroleum coke, and includes compounds such as vanadium-containing compounds and calcium-containing compounds. In this embodiment, the vanadium-containing by-product lime may contain 0.1-5% by weight of vanadium-containing compounds, 70-90% of calcium-containing compounds, and the rest are unavoidable impurities. In addition, the calcium-containing compound may contain 40-60% of calcium sulfate, 25-30% of calcium oxide, and 10-30% of calcium hydroxide by weight percentage.
於該酸浸步驟S1中，係以一酸液浸漬該含釩副產石灰，使該含釩副產石灰中的含鈣化合物可以沉澱而形成一濾餅，而能夠藉由過濾而與溶於該酸液中的釩離子得以分離，為便於後續說明，將溶有該釩離子的酸液稱為一酸浸液。In the acid leaching step S1, the vanadium-containing by-product lime is impregnated with an acid solution, so that the calcium-containing compound in the vanadium-containing by-product lime can precipitate to form a filter cake, which can be dissolved in the The vanadium ions in the acid solution are separated. For the convenience of subsequent description, the acid solution in which the vanadium ions are dissolved is called an acid dipping solution.
值得注意的是，該酸液可以包含以重量百分比計為45～65%的硫酸（sulfuric acid，H 2SO 4），如此可以使氧化鈣及氫氧化鈣分別依下列式一及式二而形成硫酸鈣，因此可以使該濾餅中的硫酸鈣的純度得以提升。 CaO＋H 2SO 4＋H 2O→Ca(OH) 2＋H 2SO 4→CaSO 4＋2H 2O （式一） Ca(OH) 2＋H 2SO 4→CaSO 4＋2H 2O （式二） It is worth noting that the acid solution may contain 45-65% by weight of sulfuric acid (sulfuric acid, H 2 SO 4 ), so that calcium oxide and calcium hydroxide can be formed according to the following formula 1 and formula 2 respectively Calcium sulfate, so the purity of calcium sulfate in the filter cake can be improved. CaO＋H 2 SO 4 ＋H 2 O→Ca(OH) 2 ＋H 2 SO 4 →CaSO 4 ＋2H 2 O (Formula 1) Ca(OH) 2 ＋H 2 SO 4 →CaSO 4 ＋2H 2 O (Formula 2)
再且，該酸液可以另包含以重量百分比計為30～50%的過氧化氫（hydrogen peroxide，H 2O 2），因而在以該酸液浸漬該含釩副產石灰時，該酸液中的過氧化氫可以使該含釩副產石灰中的正二價、正三價、正四價的釩離子形成正五價的釩離子（V 5+）。較佳地，於本實施例中，該酸液為半導體晶圓（semiconductor wafer）產業所產生的廢酸液，而另包含不可避免之雜質，惟該些雜質不會影響釩金屬的回收，進而不僅可以降低釩金屬的回收成本，亦可以降低半導體晶圓產業的廢液處理成本。 Furthermore, the acid solution may further contain 30-50% by weight of hydrogen peroxide (hydrogen peroxide, H 2 O 2 ), so when the acid solution is used to impregnate the vanadium-containing by-product lime, the acid solution The hydrogen peroxide in the vanadium-containing by-product lime can make the positive divalent, positive trivalent and positive tetravalent vanadium ions in the vanadium-containing by-product lime form positive pentavalent vanadium ions (V 5+ ). Preferably, in this embodiment, the acid solution is the waste acid solution produced by the semiconductor wafer industry, and contains unavoidable impurities, but these impurities will not affect the recovery of vanadium metal, and then Not only can the recycling cost of vanadium metal be reduced, but also the waste liquid treatment cost of the semiconductor wafer industry can be reduced.
又，藉由調整該酸浸步驟S1的浸漬pH值、浸漬溫度及/或浸漬時間，均可以提升釩離子的浸出率（leaching rate），舉例而言，該浸漬pH值可以介於0～5之間，該浸漬溫度可以介於25～80℃之間，且該浸漬時間可以介於1～4小時之間，較佳地，該浸漬pH值可以＜2，該浸漬溫度可以為50℃以上，且該浸漬時間可以為2小時以上，如此均可以有效提升釩離子的浸出率達90%以上。In addition, by adjusting the immersion pH value, immersion temperature and/or immersion time of the acid leaching step S1, the leaching rate of vanadium ions can be increased. For example, the immersion pH value can be between 0-5 Between, the immersion temperature can be between 25-80°C, and the immersion time can be between 1-4 hours, preferably, the immersion pH value can be <2, and the immersion temperature can be above 50°C , and the immersion time can be more than 2 hours, so that the leaching rate of vanadium ions can be effectively improved to more than 90%.
再者，在進行該酸浸步驟S1之前，為提升該含釩副產石灰與該酸液的反應面積，可以預先粉碎該含釩副產石灰，使其粒徑介於20～70 mesh之間，較佳可以使其粒徑為50 mesh以上，進而可以有效提升釩離子的浸出率達99%以上。Furthermore, before performing the acid leaching step S1, in order to increase the reaction area between the vanadium-containing by-product lime and the acid solution, the vanadium-containing by-product lime can be crushed in advance so that the particle size is between 20-70 mesh , preferably with a particle size of more than 50 mesh, which can effectively increase the leaching rate of vanadium ions to more than 99%.
此外，為提升該濾餅中的硫酸鈣的純度，可以再以該酸液二度浸漬該濾餅，使該濾餅中尚未形成硫酸鈣的氧化鈣及氫氧化鈣可以同樣依上述式一及式二而形成硫酸鈣，因此可以有效提升該濾餅中的硫酸鈣的純度。In addition, in order to improve the purity of the calcium sulfate in the filter cake, the filter cake can be impregnated with the acid solution for the second time, so that the calcium oxide and calcium hydroxide that have not yet formed calcium sulfate in the filter cake can be obtained according to the above formula one and Formula two and form calcium sulfate, therefore can effectively promote the purity of the calcium sulfate in this filter cake.
於該離子交換步驟S2中，係以一離子交換樹脂，自該酸浸液中回收釩金屬。舉例而言，該離子交換樹脂為D201樹脂、D290樹脂或947樹脂，D201樹脂與D290樹脂均為大孔結構的苯乙烯─二乙烯苯共聚體上帶有季銨基（-N(CH 3) 3OH）的陰離子交換樹脂，947樹脂則為一萃淋樹脂（extraction resin），此為本發明所屬技術領域中具有通常知識者可以理解，於此不再贅述。 In the ion exchange step S2, an ion exchange resin is used to recover vanadium metal from the acid dipping solution. For example, the ion exchange resin is D201 resin, D290 resin or 947 resin, both D201 resin and D290 resin are macroporous styrene-divinylbenzene copolymers with quaternary ammonium groups (-N(CH 3 ) 3 OH ) anion exchange resin, 947 resin is an extraction resin (extraction resin), which can be understood by those with ordinary knowledge in the technical field of the present invention, and will not be repeated here.
為證實藉由該自含釩副產石灰中回收釩金屬的方法，確實能夠有效回收釩等有價金屬，遂取包含以重量百分比計為25%的鈣（calcium，Ca）、8%的硫（sulfur，S）及0.1%的釩（vanadium，V）的含釩副產石灰，及包含52%的硫酸及45%的過氧化氫的廢酸液，以進行以下試驗：In order to prove that the method for recovering vanadium metal from vanadium-containing by-product lime can effectively recover valuable metals such as vanadium, a calcium (Ca) containing 25% by weight and 8% sulfur ( sulfur, S) and 0.1% vanadium (vanadium, V) vanadium-containing by-product lime, and waste acid solution containing 52% sulfuric acid and 45% hydrogen peroxide for the following tests:
（A）粒徑的影響(A) Effect of particle size
本試驗係以具有如第1表所示之粒徑的含釩副產石灰進行測試，於pH值為0、溫度為60℃的環境中，以該廢酸液進行浸漬2小時，之後分析所得的酸浸液中的釩含量，進而換算出釩的浸出率。This test is carried out with vanadium-containing by-product lime with the particle size shown in Table 1. In an environment with a pH value of 0 and a temperature of 60°C, the waste acid solution is used for immersion for 2 hours, and then the obtained results are analyzed. The vanadium content in the acid leaching solution is converted to the vanadium leaching rate.
第1表、本試驗各組的釩的浸出率
請參照第1表所示，該含釩副產石灰的粒徑為30 mesh時，其釩的浸出率即可以達90%以上（第A2組），而該含釩副產石灰的粒徑達50 mesh以上時，其釩的浸出率更可以達99%以上（第A3～A5組）。Please refer to Table 1, when the particle size of the vanadium-containing by-product lime is 30 mesh, the leaching rate of vanadium can reach more than 90% (Group A2), and the particle size of the vanadium-containing by-product lime reaches When it is more than 50 mesh, the leaching rate of vanadium can reach more than 99% (groups A3-A5).
（B）浸漬pH值的影響(B) Effect of impregnation pH
本試驗係以粒徑為50 mesh的含釩副產石灰進行測試，於如第2表所示的pH值下，且溫度為60℃的環境中，以該廢酸液進行浸漬2小時，之後分析所得的酸浸液中的釩含量，進而換算出釩的浸出率。This test is carried out with vanadium-containing by-product lime with a particle size of 50 mesh. At the pH value shown in Table 2 and at a temperature of 60°C, the waste acid solution is used for immersion for 2 hours, and then Analyze the vanadium content in the obtained acid leaching solution, and then convert the vanadium leaching rate.
第2表、本試驗各組的釩的浸出率
請參照第2表所示，pH值＜2時，釩的浸出率即可以達90%以上（第B1、B2組），而pH值為0時，釩的浸出率更可以達99%以上（第B1組）。Please refer to Table 2, when the pH value is less than 2, the leaching rate of vanadium can reach more than 90% (groups B1 and B2), and when the pH value is 0, the leaching rate of vanadium can reach more than 99% ( Group B1).
（C）浸漬時間的影響(C) Effect of immersion time
本試驗係以粒徑為50 mesh的含釩副產石灰進行測試，於pH值為0、溫度為60℃的環境中，以該廢酸液進行浸漬如第3表所示之時間，之後分析所得的酸浸液中的釩含量，進而換算出釩的浸出率。This test is carried out with vanadium-containing by-product lime with a particle size of 50 mesh. In an environment with a pH value of 0 and a temperature of 60°C, the waste acid solution is used for immersion for the time shown in Table 3, and then analyzed The vanadium content in the obtained pickling solution is then converted to obtain the vanadium leaching rate.
第3表、本試驗各組的釩的浸出率
請參照第3表所示，時間為2小時以上時，釩的浸出率即可以達99%以上（第C1～C3組），惟考量經濟效應，浸漬時間以2小時為佳。Please refer to Table 3. When the time is more than 2 hours, the leaching rate of vanadium can reach more than 99% (groups C1-C3). However, considering the economic effect, the immersion time is preferably 2 hours.
（D）浸漬溫度的影響(D) Effect of impregnation temperature
本試驗係以粒徑為50 mesh的含釩副產石灰進行測試，於pH值為0，且如第4表所示的溫度下，以該廢酸液進行浸漬2小時，之後分析所得的酸浸液中的釩含量，進而換算出釩的浸出率。In this test, vanadium-containing by-product lime with a particle size of 50 mesh was used to test it. At a pH value of 0 and at the temperature shown in Table 4, the waste acid solution was soaked for 2 hours, and then the resulting acid was analyzed. The vanadium content in the leaching solution is then converted to the vanadium leaching rate.
第4表、本試驗各組的釩的浸出率
請參照第4表所示，溫度為50℃以上時，釩的浸出率即可以達90%以上（第D3～D6組），而溫度達60℃以上時，釩的浸出率更可以達99%以上（第D4～D6組），惟考量經濟效應，浸漬溫度以60℃為佳。Please refer to Table 4, when the temperature is above 50°C, the leaching rate of vanadium can reach more than 90% (groups D3-D6), and when the temperature is above 60°C, the leaching rate of vanadium can reach 99%. For the above (groups D4~D6), but considering the economic effect, the best immersion temperature is 60°C.
（E）離子交換樹脂的選用(E) Selection of ion exchange resin
以如第5表所示的離子交換樹脂，於S/V值（柱內單位時間內流經單位體積樹脂的平均液量）為2.5、pH值為6.8的條件下，吸附前述第D4組的酸浸液中的釩，並換算釩的吸附率。With the ion exchange resin shown in Table 5, under the conditions of S/V value (the average liquid volume flowing through a unit volume of resin per unit time in the column) of 2.5 and a pH value of 6.8, adsorb the aforementioned group D4 Vanadium in the acid leaching solution, and convert the adsorption rate of vanadium.
第5表、本試驗各組的釩的吸附率
請參照第5表所示，測試的三種離子交換樹脂的釩的吸附率都可以達95%以上，由以D201為佳（第E1組）。Please refer to Table 5, the vanadium adsorption rate of the three tested ion exchange resins can reach more than 95%, and D201 is the best (group E1).
（F）一次酸浸後的硫酸鈣純度(F) Calcium sulfate purity after one acid leaching
分析第D4組的濾餅可知，其中包含以重量百分比計為22.8%的鈣、12.5%的硫，且釩的含量已無法測得，換言之，第D4組的濾餅中的硫鈣比為54.82%，相較於含釩副產石灰的硫鈣比（32.0%）有所提升，且其硫酸鈣的純度推估約為68.52%。Analysis of the filter cake of group D4 shows that it contains 22.8% calcium and 12.5% sulfur by weight percentage, and the content of vanadium cannot be measured. In other words, the ratio of sulfur to calcium in the filter cake of group D4 is 54.82 %, compared with the sulfur-calcium ratio (32.0%) of vanadium-containing by-product lime, it has been improved, and the purity of calcium sulfate is estimated to be about 68.52%.
（G）二次酸浸後的硫酸鈣純度(G) Calcium sulfate purity after secondary acid leaching
將第D4組的濾餅重新粉碎至粒徑為50 mesh，續於pH值為0、溫度為60℃的環境中，以該廢酸液進行浸漬2小時，之後再次取得濾餅後重新進行分析。The filter cake of group D4 was crushed again to a particle size of 50 mesh, and then immersed in the waste acid solution for 2 hours in an environment with a pH value of 0 and a temperature of 60°C, and then the filter cake was obtained again and analyzed again .
經二次酸浸後的濾餅包含以重量百分比計為22.2%的鈣、16.9%的硫，換言之，二次酸浸後的濾餅中的硫鈣比為76.13%，相較於試驗（F）中一次酸浸後的濾餅的硫鈣比（54.82%）亦有所提升，且其硫酸鈣的純度推估約為95.16%。The filter cake after the secondary acid leaching contains 22.2% calcium and 16.9% sulfur by weight percentage. In other words, the sulfur-calcium ratio in the filter cake after the secondary acid leaching is 76.13%, compared with the test (F ), the sulfur-calcium ratio (54.82%) of the filter cake after one acid leaching also increased, and the purity of calcium sulfate was estimated to be about 95.16%.
（H）二次酸浸液的再利用(H) Reuse of secondary pickling solution
將試驗（G）所得的二次酸浸液回收，以該廢酸液將其pH值調整為0，續於pH值為0、溫度為60℃的環境中，浸漬粒徑為50 mesh的含釩副產石灰2小時，再分析釩的浸出率及濾餅的硫鈣比，其結果顯示釩的浸出率約為99.2%，且濾餅的硫鈣比約為54.55%，顯示回收的二次酸浸液亦具有良好的釩金屬回收效果。Recover the secondary acid leaching solution obtained in the test (G), adjust the pH value of the waste acid solution to 0, continue to impregnate the 50 mesh particle size in an environment with a pH value of 0 and a temperature of 60° Lime was produced by vanadium for 2 hours, and the leaching rate of vanadium and the sulfur-calcium ratio of the filter cake were analyzed again. The results showed that the leaching rate of vanadium was about 99.2%, and the sulfur-calcium ratio of the filter cake was about 54.55%. The acid leaching solution also has a good recovery effect of vanadium metal.
（I）過氧化氫的作用(I) The role of hydrogen peroxide
以濃度為50%的硫酸水溶液，於pH值為0、溫度為60℃的環境中，浸漬粒徑為50 mesh的含釩副產石灰2小時，測試所得之酸浸液的釩的浸出率約為97.4%；再以947樹脂進行吸附後可知釩的吸附率為90.9%，低於試驗（D）中第D4組的釩的浸出率（99.0%）及試驗（E）中第E3組的釩的吸附率（95.9%），顯示包含過氧化氫的酸液確實有助於提升釩金屬的回收效果。With a concentration of 50% sulfuric acid aqueous solution, in an environment with a pH value of 0 and a temperature of 60°C, impregnate vanadium-containing by-product lime with a particle size of 50 mesh for 2 hours, and the vanadium leaching rate of the obtained acid leaching solution is about After adsorption with 947 resin, it can be seen that the adsorption rate of vanadium is 90.9%, which is lower than the leaching rate (99.0%) of vanadium in group D4 in test (D) and the vanadium in group E3 in test (E). The adsorption rate (95.9%) shows that the acid solution containing hydrogen peroxide really helps to improve the recovery effect of vanadium metal.
綜上所述，本發明的自含釩副產石灰中回收釩金屬的方法中，藉由以該酸液浸漬該含釩副產石灰，可以使該含釩副產石灰中的含鈣化合物沉澱而形成該濾餅，進而與溶有釩離子的酸浸液分離，因此可以輕鬆地藉由該離子交換樹脂，使該酸浸液中的釩離子還原形成釩金屬，可以達成提升回收釩金屬之效率的功效。In summary, in the method for recovering vanadium metal from vanadium-containing by-product lime of the present invention, the calcium-containing compound in the vanadium-containing by-product lime can be precipitated by impregnating the vanadium-containing by-product lime with the acid solution The filter cake is formed, and then separated from the acid leaching solution in which vanadium ions are dissolved. Therefore, the ion exchange resin can be used to easily reduce the vanadium ions in the acid leaching solution to form vanadium metal, which can achieve the goal of improving the recovery of vanadium metal. The efficacy of efficiency.
再且，本發明的自含釩副產石灰中回收釩金屬的方法中，藉由該酸液中包含硫酸及過氧化氫，使該含釩副產石灰中的硫酸鈣、氧化鈣及氫氧化鈣均能夠與該酸液中的硫酸反應形成硫酸鈣而沉澱，該含釩副產石灰中的釩則能夠藉由過氧化氫的氧化作用而形成正五價的釩離子（V 5+），可以提升與該離子交換樹脂的反應效率，達成提升回收釩金屬之效率的功效。 Furthermore, in the method for recovering vanadium metal from vanadium-containing by-product lime of the present invention, the calcium sulfate, calcium oxide and hydroxide in the vanadium-containing by-product lime are oxidized by sulfuric acid and hydrogen peroxide contained in the acid solution. Calcium can react with sulfuric acid in the acid solution to form calcium sulfate and precipitate, and the vanadium in the vanadium-containing by-product lime can form positive pentavalent vanadium ions (V 5+ ) through the oxidation of hydrogen peroxide. The reaction efficiency with the ion exchange resin can be improved, and the effect of improving the efficiency of recovering vanadium metal can be achieved.
此外，本發明的自含釩副產石灰中回收釩金屬的方法中，藉由該酸液為半導體晶圓產業所產生的廢酸液，不僅可以降低釩金屬的回收成本，亦可以降低半導體晶圓產業的廢液處理成本。In addition, in the method for recovering vanadium metal from vanadium-containing by-product lime according to the present invention, since the acid solution is waste acid solution produced in the semiconductor wafer industry, not only the recovery cost of vanadium metal can be reduced, but also the cost of semiconductor crystal wafers can be reduced. Waste liquid treatment costs in circular industries.
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視後附之申請專利範圍所界定者為準。Although the present invention has been disclosed by using the above-mentioned preferred embodiments, it is not intended to limit the present invention. It is still within the scope of this invention for anyone skilled in the art to make various changes and modifications relative to the above-mentioned embodiments without departing from the spirit and scope of the present invention. The technical scope protected by the invention, therefore, the scope of protection of the present invention should be defined by the scope of the appended patent application.
S1:酸浸步驟 S2:離子交換步驟 S1: acid leaching step S2: ion exchange step
［第1圖］ 本發明之一實施例的自含釩副產石灰中回收釩金屬的方法之流程圖。[Fig. 1] A flowchart of a method for recovering vanadium metal from vanadium-containing by-product lime according to an embodiment of the present invention.
S1:酸浸步驟 S1: acid leaching step
S2:離子交換步驟 S2: ion exchange step
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