TWI748776B - Method for recovering vanadium from nickel/iron/calcium/vanadium-containing concentrate - Google Patents
Method for recovering vanadium from nickel/iron/calcium/vanadium-containing concentrate Download PDFInfo
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本發明係關於一種回收釩的方法，尤其是一種自含鎳鐵高鈣釩渣中回收釩的方法。 The invention relates to a method for recovering vanadium, in particular to a method for recovering vanadium from nickel-iron-containing high-calcium vanadium slag.
含鎳鐵高鈣釩渣主要是發電廠、水泥廠、石化廠等燃燒石油焦後所產出的廢棄物，已知可以應用於水泥行業及石墨電極生產，亦可以用於在發電廠中當燃料；然而，該含鎳鐵高鈣釩渣中仍含有釩等有價金屬，因此自該含鎳鐵高鈣釩渣中回收有價金屬，即可以發揮該含鎳鐵高鈣釩渣之經濟效益。 Nickel-iron-containing high-calcium vanadium slag is mainly waste produced by burning petroleum coke in power plants, cement plants, petrochemical plants, etc. It is known to be used in the cement industry and graphite electrode production, and can also be used in power plants. Fuel; however, the nickel-iron-containing high-calcium vanadium slag still contains valuable metals such as vanadium. Therefore, the recovery of valuable metals from the nickel-iron-containing high-calcium vanadium slag can exert the economic benefits of the nickel-iron-containing high-calcium vanadium slag.
習知自含鎳鐵高鈣釩渣中回收釩的方法係可以藉由鈉化焙燒法來回收釩金屬；惟由於該含鎳鐵高鈣釩渣約包含以重量百分比計約10~20%的鈣，僅有少量的釩能夠與加入的鈉鹽結合而形成可以被回收的釩酸鈉，其回收率僅有約40~50%；再且，其中的鎳、鐵等金屬更會造成回收的釩的純度不佳。有鑑於此，仍需要提供一種自含鎳鐵高鈣釩渣中回收釩的方法。 The conventional method for recovering vanadium from nickel-iron-containing high-calcium vanadium slag is to recover vanadium metal by the sodium roasting method; however, because the nickel-iron-containing high-calcium vanadium slag contains about 10-20% by weight Calcium, only a small amount of vanadium can be combined with the added sodium salt to form sodium vanadate that can be recovered, and the recovery rate is only about 40-50%; moreover, the nickel, iron and other metals in it will even cause recycling The purity of vanadium is poor. In view of this, there is still a need to provide a method for recovering vanadium from nickel-iron-containing high-calcium vanadium slag.
為解決上述問題，本發明的目的是提供一種自含鎳鐵高鈣釩渣中回收釩的方法，係具有良好的釩回收率者。 In order to solve the above problems, the purpose of the present invention is to provide a method for recovering vanadium from nickel-iron-containing high-calcium vanadium slag, which has a good recovery rate of vanadium.
本發明的再一目的是提供一種自含鎳鐵高鈣釩渣中回收釩的方法，所回收之釩的純度良好者。 Another object of the present invention is to provide a method for recovering vanadium from nickel-iron-containing high-calcium vanadium slag, and the purity of the recovered vanadium is good.
本發明的自含鎳鐵高鈣釩渣中回收釩的方法，可以包含：提供一含鎳鐵高鈣釩渣，該含鎳鐵高鈣釩渣包含鎳、鐵、鈣、釩及矽，且該含鎳鐵高鈣釩渣的粒徑為100~250孔目；對該含鎳鐵高鈣釩渣進行磁性篩選，以得一非磁性項，該非磁性項包含鈣、釩及矽；以重量比為1：0.4之比例混合該非磁性項及一含鈉的鹼性化合物，得一混合物，使該混合物於900℃之溫度下進行一氧化焙燒反應3~4小時，得一焙燒物及二氧化碳氣體；及將該焙燒物浸入80℃的水中，並將該氧化焙燒反應所得的二氧化碳氣體通入浸有該焙燒物的水中，使該焙燒物所含有之釩以釩酸鈉的形式溶解於水中，得一釩貴液，該釩貴液包含釩酸鈉。 The method for recovering vanadium from nickel-iron-containing high-calcium vanadium slag of the present invention may include: providing a nickel-iron-containing high-calcium vanadium slag, the nickel-iron-containing high-calcium vanadium slag containing nickel, iron, calcium, vanadium and silicon, and The nickel-iron-containing high-calcium-vanadium slag has a particle size of 100-250 meshes; the nickel-iron-containing high-calcium-vanadium slag is magnetically screened to obtain a non-magnetic item, the non-magnetic item includes calcium, vanadium and silicon; Mix the non-magnetic term and a sodium-containing alkaline compound in a ratio of 1:0.4 to obtain a mixture, and subject the mixture to an oxidative roasting reaction at a temperature of 900°C for 3 to 4 hours to obtain a roasted product and carbon dioxide gas And immersing the calcined product in 80°C water, and passing the carbon dioxide gas obtained from the oxidation roasting reaction into the water immersed in the calcined product, so that the vanadium contained in the calcined product is dissolved in the water in the form of sodium vanadate, A vanadium noble solution is obtained, and the vanadium noble solution contains sodium vanadate.
據此，本發明的自含鎳鐵高鈣釩渣中回收釩的方法，藉由磁性篩選移除該鎳鐵高鈣釩渣中的鎳及鐵，再藉由將二氧化碳氣體通入浸有該焙燒物的水中，使該焙燒物所含有的釩能夠以釩酸鈉的形式溶解於水中，不僅可以有效將釩的回收率提升至85%以上，更可以防止鎳及鐵以碳酸鎳及碳酸亞鐵的形式溶於水中，並與釩共同被回收，達成提升釩的回收率及提升釩回收物的純度等功效。 Accordingly, the method for recovering vanadium from nickel-iron-containing high-calcium vanadium slag of the present invention removes the nickel and iron in the nickel-iron high-calcium vanadium slag by magnetic screening, and then passes carbon dioxide gas into the slag impregnated with the nickel and iron. In the water of the calcined product, the vanadium contained in the calcined product can be dissolved in the water in the form of sodium vanadate, which not only effectively increases the recovery rate of vanadium to more than 85%, but also prevents nickel and iron from being converted into nickel carbonate and subcarbonate. The form of iron is dissolved in water and is recovered together with vanadium to achieve the effects of increasing the recovery rate of vanadium and the purity of the recovered vanadium.
再且，藉由將該氧化焙燒反應所得的二氧化碳氣體通入浸有該焙燒物的水中，不僅可以減少該氧化焙燒反應所產生的二氧化碳氣體排出造成的空氣汙染，亦無須自外部引入二氧化碳氣體而可以降低釩的回收成本。 Moreover, by passing the carbon dioxide gas obtained from the oxidation roasting reaction into the water immersed in the roasted product, not only can the air pollution caused by the emission of carbon dioxide gas generated by the oxidation roasting reaction be reduced, but also there is no need to introduce carbon dioxide gas from the outside. Can reduce the recovery cost of vanadium.
本發明的自含鎳鐵高鈣釩渣中回收釩的方法，其中，該含鎳鐵高鈣釩渣較佳可以包含以重量百分比計為1~5%的鎳、3~10%的鐵、10~20%的鈣、3~10%的釩及1~10%的矽，其餘比例為雜質；當該含鎳鐵高鈣釩渣中的鈣含量過高時，將會影響釩與鈉的結合而不易形成可溶於水中的釩酸 鈉，無法有效提升釩的回收率；當該含鎳鐵高鈣釩渣中的鎳及鐵含量過高時，則會導致鎳及鐵以碳酸鎳及碳酸亞鐵的形式，與形成釩酸鈉的釩共同溶於水中，因而影響釩回收物的純度。 In the method for recovering vanadium from nickel-iron-containing high-calcium vanadium slag of the present invention, the nickel-iron-containing high-calcium vanadium slag may preferably contain 1 to 5% of nickel, 3 to 10% of iron, 10-20% calcium, 3-10% vanadium and 1-10% silicon, the remaining proportion is impurities; when the calcium content in the nickel-iron high-calcium vanadium slag is too high, it will affect the vanadium and sodium Combining difficult to form vanadic acid soluble in water Sodium cannot effectively increase the recovery rate of vanadium; when the nickel and iron content in the nickel-iron high-calcium vanadium slag is too high, the nickel and iron will be formed in the form of nickel carbonate and ferrous carbonate and form sodium vanadate The vanadium dissolves in water together, thus affecting the purity of vanadium recovery.
本發明的自含鎳鐵高鈣釩渣中回收釩的方法，其中，該含鎳鐵高鈣釩渣的粒徑較佳可以為100孔目；如此，可以防止過細的含鎳鐵高鈣釩渣在磁性篩選時發生飛散而有所損失。 In the method for recovering vanadium from nickel-iron-containing high-calcium vanadium slag of the present invention, the particle size of the nickel-iron-containing high-calcium vanadium slag can preferably be 100 meshes; in this way, it can prevent excessively fine nickel-iron-containing high-calcium vanadium The slag scatters and loses during the magnetic screening.
本發明的自含鎳鐵高鈣釩渣中回收釩的方法，其中，該含鈉的鹼性化合物為氫氧化鈉、碳酸鈉或氯化鈉；如此，使該含鈉的鹼性化合物能夠有效地與該磁性粉末中的釩進行反應。 The method for recovering vanadium from nickel-iron-containing high-calcium vanadium slag of the present invention, wherein the sodium-containing alkaline compound is sodium hydroxide, sodium carbonate or sodium chloride; in this way, the sodium-containing alkaline compound can be effective Ground reacts with vanadium in the magnetic powder.
本發明的自含鎳鐵高鈣釩渣中回收釩的方法，其中，較佳可以將二氧化碳氣體通入浸有該焙燒物的水中，使浸有該焙燒物的水的酸鹼值為8~9；如此，使該焙燒物中以釩酸鈣形式存在的鈣，能夠有效地與二氧化碳反應而形成碳酸鈣，進而釋放釩酸鈣中的釩，使釩能夠與該含鈉的鹼性化合物形成釩酸鈉。 In the method for recovering vanadium from nickel-iron-containing high-calcium vanadium slag of the present invention, it is preferable to pass carbon dioxide gas into the water immersed in the roasted product so that the acid-base value of the water immersed in the roasted product is 8~ 9; In this way, the calcium in the calcined product in the form of calcium vanadate can effectively react with carbon dioxide to form calcium carbonate, and then release the vanadium in the calcium vanadate, so that vanadium can form with the sodium-containing basic compound Sodium vanadate.
S1:磁性篩選步驟 S1: Magnetic screening step
S2:鈉化焙燒步驟 S2: Sodium roasting step
S3:熱水傾出步驟 S3: Hot water pouring step
〔第1圖〕自含鎳鐵高鈣釩渣中回收釩的方法流程圖。 [Figure 1] Flow chart of the method for recovering vanadium from nickel-iron-containing high-calcium vanadium slag.
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：本發明所述之「含鎳鐵高鈣釩渣」除包含鎳、鐵、鈣之外，另可以包含釩等高價金屬。舉例而言，該含鎳鐵高鈣釩渣大致可以包含以重量 百分比計為1~5%的鎳(nickel，Ni)、3~10%的鐵(iron，Fe)、10~20%的鈣(calcium，Ca)、3~10%的釩(vanadium，V)及1~10%的矽(silicon，Si)，其餘比例為雜質，此為本發明所屬技術領域中具有通常知識者可以理解，於此不加以限制。 In order to make the above and other objects, features and advantages of the present invention more comprehensible, the following is a detailed description of the preferred embodiments of the present invention, together with the accompanying drawings: In addition to nickel, iron, and calcium, "iron-high-calcium vanadium slag" may also contain expensive metals such as vanadium. For example, the nickel-iron-containing high-calcium vanadium slag can roughly contain by weight The percentage is calculated as 1~5% nickel (nickel, Ni), 3~10% iron (iron, Fe), 10~20% calcium (calcium, Ca), 3~10% vanadium (vanadium, V) And 1-10% silicon (Si), the remaining proportion is impurities, which can be understood by those with ordinary knowledge in the technical field to which the present invention belongs, and is not limited here.
請參照第1圖所示，本發明自含鎳鐵高鈣釩渣中回收釩的方法的一實施例係可以包含：一磁性篩選步驟S1、一鈉化焙燒步驟S2及一熱水傾出步驟S3。 Please refer to Figure 1, an embodiment of the method for recovering vanadium from nickel-iron-containing high-calcium vanadium slag according to the present invention may include: a magnetic screening step S1, a sodiumization roasting step S2, and a hot water decanting step S3.
詳而言之，於該磁性篩選步驟S1中，工者係能夠對該含鎳鐵高鈣釩渣進行磁性篩選(magnetic separation)，使該含鎳鐵高鈣釩渣中的磁性物質受到磁力的作用而分離得一磁性項(magnetic phase)及一非磁性項(non-magnetic phase)，該磁性項主要可以包含鎳及鐵，該非磁性項則至少可以包含鈣、釩及矽。 In detail, in the magnetic screening step S1, the worker can perform magnetic separation on the nickel-iron-containing high-calcium-vanadium slag, so that the magnetic substance in the nickel-iron-containing high-calcium-vanadium slag is subjected to magnetic force. It separates into a magnetic phase and a non-magnetic phase. The magnetic phase can mainly include nickel and iron, and the non-magnetic phase can include at least calcium, vanadium, and silicon.
值得注意的是，在該磁性篩選步驟S1之前，較佳可以使該含鎳鐵高鈣釩渣形成粒徑介於100~250孔目(mesh)的顆粒，當該含鎳鐵高鈣釩渣的粒徑過大時，將無法於該磁性篩選步驟S1中有效分離鎳及鐵，進而影響後續所回收的釩的純度，而當該含鎳鐵高鈣釩渣的粒徑太小時，則可能會於該磁性篩選步驟S1大量地飛散，影響能夠回收之釩的總量；於本實施例中，係使該含鎳鐵高鈣釩渣形成粒徑為100孔目的顆粒。 It is worth noting that before the magnetic screening step S1, the nickel-iron-containing high-calcium vanadium slag can preferably be formed into particles with a particle size of 100 to 250 mesh (mesh), when the nickel-iron-containing high-calcium vanadium slag When the particle size of the nickel-iron-containing high-calcium vanadium slag is too large, it will not be able to effectively separate nickel and iron in the magnetic screening step S1, which will affect the purity of the subsequently recovered vanadium. In the magnetic screening step S1, a large amount of scattering affects the total amount of vanadium that can be recovered; in this embodiment, the nickel-iron-containing high-calcium vanadium slag is formed into particles with a particle size of 100 meshes.
於該鈉化焙燒步驟S2中，工者能夠優先混合該含鎳鐵高鈣釩渣及一含鈉的鹼性化合物(sodium-containing alkaline compound)，以得一混合物；舉例而言，該含鈉的鹼性化合物可以為氫氧化鈉(sodium hydroxide，NaOH)、碳酸氫鈉(sodium bicarbonate，NaHCO3)或氯化鈉(sodium chloride，NaCl)，但不以此為限。於本實施例中，工者係能夠以重量比為1：0.4之比例混合該非磁性項及該含鈉的鹼性化合物，而獲得該混合物(換言之，每公 斤的非磁性項可以混合400克的含鈉的鹼性化合物)。 In the sodium-containing roasting step S2, the worker can preferentially mix the nickel-iron-containing high-calcium vanadium slag and a sodium-containing alkaline compound to obtain a mixture; for example, the sodium-containing alkaline compound The basic compound can be sodium hydroxide (NaOH), sodium bicarbonate (NaHCO 3 ) or sodium chloride (sodium chloride, NaCl), but is not limited to this. In this embodiment, the worker can mix the non-magnetic item and the sodium-containing alkaline compound in a weight ratio of 1:0.4 to obtain the mixture (in other words, 400 grams of non-magnetic item can be mixed per kilogram Basic compounds containing sodium).
接著，工者可以使該混合物於高溫下進行一氧化焙燒反應(oxidizing roasting reaction)，即可以獲得一焙燒物(roasted product)。於本實施例中，工者係能夠於900℃之溫度下進行該氧化焙燒反應3~4小時，以獲得該焙燒物。 Next, the worker can subject the mixture to an oxidizing roasting reaction at a high temperature to obtain a roasted product. In this embodiment, the worker can perform the oxidative roasting reaction at a temperature of 900° C. for 3 to 4 hours to obtain the roasted product.
於該熱水傾出步驟S3中，工者可以將該焙燒物浸入80℃的水中，並將二氧化碳氣體通入浸有該焙燒物的水中，使浸有該焙燒物的水的酸鹼值可以為鹼性(例如使浸有該焙燒物的水的酸鹼值為8~9之間)，使該焙燒物所含有之釩可以溶解於水中，續經由過濾即可以分離獲得一釩貴液及一矽鈣渣，該釩貴液含有釩酸鈉(sodium vanadate(V)，Na3VO4)如此即可以有效地自該含鎳鐵高鈣釩渣中回收釩。於本實施例中，由於該混合物進行該氧化焙燒反應時，同時會產生二氧化碳氣體，因此可以將所產生的二氧化碳氣體通入浸有該焙燒物的水中，如此不僅可以減少該氧化焙燒反應所產生的二氧化碳氣體排出造成的空氣汙染，亦無須自外部引入二氧化碳氣體而可以降低釩的回收成本。 In the hot water pouring step S3, the worker can immerse the roasted product in 80°C water, and pass carbon dioxide gas into the water immersed in the roasted product, so that the pH of the water immersed in the roasted product can be It is alkaline (for example, the acid-base value of the water immersed in the roasted product is between 8-9), so that the vanadium contained in the roasted product can be dissolved in the water, and then filtered to obtain a vanadium precious liquid and A calcium silicate slag, the vanadium precious solution contains sodium vanadate (V) (Na 3 VO 4 ) so that vanadium can be effectively recovered from the nickel-iron-containing high-calcium vanadium slag. In this embodiment, because the mixture produces carbon dioxide gas during the oxidative roasting reaction, the carbon dioxide gas produced can be passed into the water immersed in the roasted product, which can not only reduce the generation of the oxidative roasting reaction The air pollution caused by the discharge of carbon dioxide gas does not require the introduction of carbon dioxide gas from the outside, which can reduce the recovery cost of vanadium.
為證實藉由該自含鎳鐵高鈣釩渣中回收釩的方法，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2.2%的鎳、4.1%的鐵、14.5%的鈣、5.0%的釩及2.5%的矽，其餘比例為雜質的含鎳鐵高鈣釩渣進行以下試驗： In order to verify that the method of recovering vanadium from nickel-iron-containing high-calcium vanadium slag can indeed effectively recover valuable metals such as vanadium, it was taken to contain 2.2% nickel, 4.1% iron, and 14.5% calcium by weight. , 5.0% of vanadium, 2.5% of silicon, and the remaining proportion of impurities in nickel-iron-containing high-calcium vanadium slag for the following tests:
(A)含鎳鐵高鈣釩渣的粒徑對磁性篩選步驟的影響 (A) The influence of the particle size of the nickel-iron-containing high-calcium vanadium slag on the magnetic screening step
本試驗係使該含鎳鐵高鈣釩渣分別形成如第1、2表所示的30、50、100、200及250等不同孔目的顆粒後，對各組的含鎳鐵高鈣釩渣進行磁性篩選，並分析所獲得的磁性項與非磁性項中的鎳、鐵、鈣、釩及矽的含量。 In this experiment, the nickel-iron-containing high-calcium-vanadium slag was formed into particles of 30, 50, 100, 200, and 250 with different pores as shown in Tables 1 and 2, and the nickel-iron-containing high-calcium vanadium slag Carry out magnetic screening and analyze the content of nickel, iron, calcium, vanadium and silicon in the obtained magnetic items and non-magnetic items.
第1表、本試驗各組的磁性項的分析結果
請參照第1、2表所示，在進行磁性篩選之後，第A1、A2組的非磁性項中仍包含大量的鎳及鐵，而第A4、A5組的磁性項與非磁性項的百分比總和分別為99.2%及98.8%，顯示其顆粒過小在磁性篩選時發生飛散而有所損失，因此後續試驗係以第A3組的含鎳鐵高鈣釩渣所得的非磁性項進行測試(其包含以重量百分比計為0.08%的鎳、0.21%的鐵、14.49%的鈣、4.99%的釩及2.44%的矽，其餘比例為雜質)。 Please refer to Tables 1 and 2, after the magnetic screening, the non-magnetic items of groups A1 and A2 still contain a large amount of nickel and iron, while the percentages of the magnetic items and non-magnetic items of groups A4 and A5 are the sum of the percentages Respectively 99.2% and 98.8%, indicating that the particles are too small to fly and lose during magnetic screening. Therefore, the follow-up test is based on the non-magnetic items obtained from the nickel-iron-containing high-calcium vanadium slag of group A3 (which includes The weight percentages are 0.08% nickel, 0.21% iron, 14.49% calcium, 4.99% vanadium and 2.44% silicon, and the remaining proportion is impurities).
(B)氧化焙燒反應時間的優化 (B) Optimization of oxidation roasting reaction time
本試驗係取1000克的前述第A3組的含鎳鐵高鈣釩渣所得的非磁性項，混合400克的碳酸鈉，於900℃之溫度下進行該氧化焙燒反應，反應時間如第3表所示，分別為1、2、3或4小時，接著將所獲得的焙燒物浸入80℃的水中，並通入二氧化碳氣體(維持浸有該焙燒物的水的酸鹼值為8~9)，過濾獲得該釩貴液之後，分析該釩貴液中的鎳、鐵、鈣、釩及矽的含量。 This experiment is to take 1000 grams of the non-magnetic items obtained from the aforementioned group A3 nickel-iron-containing high-calcium vanadium slag, mix 400 grams of sodium carbonate, and carry out the oxidative roasting reaction at a temperature of 900°C. The reaction time is shown in Table 3. As shown, it is 1, 2, 3, or 4 hours respectively, and then the obtained roasted product is immersed in 80°C water, and carbon dioxide gas is introduced (maintain the pH value of the water in which the roasted product is immersed is 8-9) After filtering the vanadium precious liquid, the content of nickel, iron, calcium, vanadium and silicon in the vanadium precious liquid is analyzed.
請參照第3表所示，該氧化焙燒反應的時間介於1~4小時之間時，釩的回收率均可以達到80%以上，而該氧化焙燒反應的時間為3~4小時之間時，釩的回收效果最佳，回收率達86.0%。 Please refer to Table 3, when the oxidation roasting reaction time is between 1 and 4 hours, the recovery rate of vanadium can reach more than 80%, and the oxidation roasting reaction time is between 3 and 4 hours. , The recovery effect of vanadium is the best, with a recovery rate of 86.0%.
(C)碳酸鈉添加量的優化 (C) Optimization of sodium carbonate addition
本試驗係取1000克的前述第A3組的含鎳鐵高鈣釩渣所得的非磁性項，混合如第4表所示的不同比例的碳酸鈉，於900℃之溫度下進行該氧化焙燒反應3小時，接著將所獲得的焙燒物浸入80℃的水中，並通入二氧化碳氣體(維持浸有該焙燒物的水的酸鹼值為8~9)，過濾獲得該釩貴液之後，分析該釩貴液中的鎳、鐵、鈣、釩及矽的含量。 In this experiment, 1000 grams of the non-magnetic items obtained from the nickel-iron-containing high-calcium vanadium slag of the aforementioned group A3 were mixed with different proportions of sodium carbonate as shown in Table 4, and the oxidative roasting reaction was carried out at a temperature of 900°C. After 3 hours, the calcined product obtained was immersed in water at 80°C, and carbon dioxide gas was introduced (to maintain the pH value of the water in which the calcined product was immersed in 8-9). After filtering to obtain the vanadium precious liquid, analyze the The content of nickel, iron, calcium, vanadium and silicon in vanadium precious liquid.
請參照第4表所示，碳酸鈉的添加比例介於1：0.3~0.5之間時，釩的回收率均可以達到80%以上，其中以碳酸鈉的添加比例為1：0.4時，釩的回收效果最佳，回收率達86.0%。 Please refer to Table 4, when the addition ratio of sodium carbonate is between 1:0.3~0.5, the recovery rate of vanadium can reach more than 80%. Among them, when the addition ratio of sodium carbonate is 1:0.4, the recovery rate of vanadium The recovery effect is the best, with a recovery rate of 86.0%.
(D)氧化焙燒反應溫度的優化 (D) Optimization of oxidation roasting reaction temperature
本試驗係取1000克的前述第A3組的含鎳鐵高鈣釩渣所得的非磁性項，混合400克的碳酸鈉，於如第5表所示的不同溫度下進行該氧化焙燒反應3小時，接著將所獲得的焙燒物浸入80℃的水中，並通入二氧化碳氣體(維持浸有該焙燒物的水的酸鹼值為8~9)，過濾獲得該釩貴液之後，分析該釩貴液中的鎳、鐵、鈣、釩及矽的含量。 In this experiment, 1000 grams of the non-magnetic items obtained from the nickel-iron-containing high-calcium vanadium slag of the aforementioned group A3 were mixed with 400 grams of sodium carbonate, and the oxidative roasting reaction was carried out for 3 hours at different temperatures as shown in Table 5. Then, the obtained roasted product was immersed in 80°C water, and carbon dioxide gas was introduced (to maintain the acid-base value of the water in which the roasted product was immersed in 8-9). After the vanadium precious liquid was obtained by filtration, the vanadium precious liquid was analyzed. The content of nickel, iron, calcium, vanadium and silicon in the liquid.
請參照第5表所示，該氧化焙燒反應的溫度介於800~1000℃之間時，釩的回收率均可以達到80%以上，而該氧化焙燒反應的溫度為900℃時，釩的回收效果最佳，回收率達86.0%。 Please refer to Table 5, when the oxidation roasting reaction temperature is between 800 and 1000 ℃, the recovery rate of vanadium can reach more than 80%, and when the oxidation roasting reaction temperature is 900 ℃, the recovery of vanadium The effect is the best, with a recovery rate of 86.0%.
(E)通入二氧化碳的效果 (E) The effect of introducing carbon dioxide
本試驗係取1000克的前述第A3組的含鎳鐵高鈣釩渣所得的非磁性項，混合400克的碳酸鈉，於900℃溫度下進行該氧化焙燒反應3小時，接著將所獲得的焙燒物浸入80℃的水中，如第6表所示在有無通入二氧化碳氣體的狀況下進行反應，過濾獲得該釩貴液之後，分析該釩貴液中的釩的含量。 In this experiment, 1000 grams of the non-magnetic items obtained from the nickel-iron-containing high-calcium vanadium slag of the aforementioned group A3 were mixed with 400 grams of sodium carbonate, and the oxidative roasting reaction was carried out at 900°C for 3 hours, and then the obtained The calcined product was immersed in 80°C water, and the reaction was carried out with or without carbon dioxide gas as shown in Table 6. After the vanadium noble solution was obtained by filtration, the vanadium content in the vanadium noble solution was analyzed.
請參照第6表所示，未通入二氧化碳的第E2組的釩的回收率遠低於有通入二氧化碳的第E1組，顯示二氧化碳的通入確實有助於使該焙燒物中以釩酸鈣形式存在的鈣，能夠形成碳酸鈣，進而釋放釩酸鈣中的釩，使釩能夠與該含鈉的鹼性化合物形成釩酸鈉，進而提升釩的回收率。 Please refer to Table 6, the recovery rate of vanadium in the E2 group without carbon dioxide is much lower than that of the E1 group with carbon dioxide, which shows that the introduction of carbon dioxide does help to make vanadic acid in the roasted material. Calcium in the form of calcium can form calcium carbonate, thereby releasing vanadium in calcium vanadate, enabling vanadium to form sodium vanadate with the sodium-containing alkaline compound, thereby increasing the recovery rate of vanadium.
(F)含鎳鐵高鈣釩渣的粒徑對釩回收純度的影響 (F) The effect of the particle size of nickel-iron-containing high-calcium vanadium slag on the purity of vanadium recovery
本試驗係如第7表所示，分別取1000克的前述的A1組的含鎳鐵高鈣釩渣所得的非磁性項(包含以重量百分比計為0.27%的鎳、0.81%的鐵、14.49%的鈣、4.99%的釩及2.45%的矽，其餘比例為雜質)及第A3組的含鎳鐵高鈣釩渣所得的非磁性項(包含以重量百分比計為0.08%的鎳、0.21%的鐵、14.49%的鈣、4.99%的釩及2.44%的矽，其餘比例為雜質)，混合400克的碳酸鈉，於900℃之溫度下進行該氧化焙燒反應3小時，接著將所獲得的焙燒物浸入80℃的水中，並通入二氧化碳氣體(維持浸有該焙燒物的水的酸鹼值為8~9)，過濾獲得該釩貴液之後，分析該釩貴液中的鎳、鐵、鈣、釩及矽的含量。 This test system is shown in Table 7. The non-magnetic items (including 0.27% nickel, 0.81% iron, and 14.49% by weight) obtained from the above-mentioned A1 group of nickel-containing iron high-calcium vanadium slag were taken respectively. % Calcium, 4.99% vanadium and 2.45% silicon, the remaining proportion is impurities) and the non-magnetic items obtained from the A3 group of nickel-iron-containing high-calcium vanadium slag (including 0.08% nickel and 0.21% by weight Iron, 14.49% calcium, 4.99% vanadium and 2.44% silicon, the remaining proportion is impurities), 400 grams of sodium carbonate are mixed, the oxidative roasting reaction is carried out at a temperature of 900 ℃ for 3 hours, and then the obtained The calcined product is immersed in 80℃ water, and carbon dioxide gas is introduced (to maintain the pH value of the water in which the calcined product is immersed is 8-9). After the vanadium precious liquid is obtained by filtration, the nickel and iron in the vanadium precious liquid are analyzed. , Calcium, vanadium and silicon content.
請參照第7表所示，第F2組的釩回收率為84.0%，略低於的 F1組的釩回收率；惟可以發現的F2組的釩貴液中仍含有以碳酸鎳(nickel(II)carbonate，NiCO3)及碳酸亞鐵(iron(II)carbonate，FeCO3)的形式殘存的鎳及鐵，在後續自該釩貴液中回收呈現釩酸鈉形式的釩之時，將會一併回收碳酸鎳及碳酸亞鐵，而影響釩的回收純度。 Please refer to Table 7, the vanadium recovery rate of group F2 is 84.0%, which is slightly lower than the vanadium recovery rate of group F1; however, it can be found that the vanadium liquid of group F2 still contains nickel carbonate (nickel(II) The remaining nickel and iron in the form of )carbonate, NiCO 3 ) and ferrous carbonate (iron(II)carbonate, FeCO 3 ) will be recovered in the subsequent recovery of vanadium in the form of sodium vanadate from the vanadium precious liquid. It also recovers nickel carbonate and ferrous carbonate, which affects the recovery purity of vanadium.
綜上所述，本發明的自含鎳鐵高鈣釩渣中回收釩的方法，藉由磁性篩選移除該鎳鐵高鈣釩渣中的鎳及鐵，再藉由將二氧化碳氣體通入浸有該焙燒物的水中，使該焙燒物所含有的釩能夠以釩酸鈉的形式溶解於水中，不僅可以有效將釩的回收率提升至85%以上，更可以防止鎳及鐵以碳酸鎳及碳酸亞鐵的形式溶於水中，並與釩共同被回收，達成提升釩的回收率及提升釩回收物的純度等功效。 In summary, the method for recovering vanadium from nickel-iron high-calcium vanadium slag of the present invention removes the nickel and iron in the nickel-iron high-calcium vanadium slag by magnetic screening, and then passes carbon dioxide gas into the leaching method. In the water with the calcined product, the vanadium contained in the calcined product can be dissolved in the water in the form of sodium vanadate, which not only can effectively increase the recovery rate of vanadium to more than 85%, but also prevents nickel and iron from being mixed with nickel carbonate. The form of ferrous carbonate is dissolved in water and is recovered together with vanadium to achieve the effects of increasing the recovery rate of vanadium and the purity of the recovered vanadium.
再且，本發明的自含鎳鐵高鈣釩渣中回收釩的方法，藉由將二氧化碳氣體通入浸有該焙燒物的水中，可以使該焙燒物中以釩酸鈣形式存在的鈣，能夠有效地與二氧化碳反應而形成碳酸鈣，進而釋放釩酸鈣中的釩，使釩能夠與該含鈉的鹼性化合物形成釩酸鈉，可以更進一步地提升釩的回收率。 Furthermore, in the method for recovering vanadium from nickel-iron-containing high-calcium vanadium slag of the present invention, by passing carbon dioxide gas into the water immersed in the roasted product, the calcium in the roasted product can be made in the form of calcium vanadate. It can effectively react with carbon dioxide to form calcium carbonate, and then release vanadium in calcium vanadate, so that vanadium can form sodium vanadate with the sodium-containing alkaline compound, which can further improve the recovery rate of vanadium.
此外，本發明的自含鎳鐵高鈣釩渣中回收釩的方法，藉由將該氧化焙燒反應所產生二氧化碳氣體通入浸有該焙燒物的水中，不僅可以減少該氧化焙燒反應所產生的二氧化碳氣體排出造成的空氣汙染，亦無須自外部引入二氧化碳氣體而可以降低釩的回收成本，可以達成減少污染產生及降低回收成本等功效。 In addition, the method for recovering vanadium from nickel-iron-containing high-calcium vanadium slag of the present invention, by passing the carbon dioxide gas generated by the oxidation roasting reaction into the water immersed in the roasted product, not only can reduce the production of the oxidation roasting reaction The air pollution caused by the discharge of carbon dioxide gas does not require the introduction of carbon dioxide gas from the outside, which can reduce the recovery cost of vanadium, and can achieve the effects of reducing pollution generation and reducing recovery costs.
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 using the above-mentioned preferred embodiments, it is not intended to limit the present invention. Anyone who is familiar with the art without departing from the spirit and scope of the present invention may make various changes and modifications relative to the above-mentioned embodiments. The technical scope of the invention is protected. Therefore, the scope of protection of the invention shall be subject to the scope of the attached patent application.
S1:磁性篩選步驟 S1: Magnetic screening step
S2:鈉化焙燒步驟 S2: Sodium roasting step
S3:熱水傾出步驟 S3: Hot water pouring step
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| CN107287431A (en) * | 2017-06-22 | 2017-10-24 | 河钢股份有限公司承德分公司 | A kind of method for reclaiming vanadium in vanadium containing steel slag element |
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