TWI761256B - Method for recycling metals from concentrate with nickel and aluminum - Google Patents
Method for recycling metals from concentrate with nickel and aluminum Download PDFInfo
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- TWI761256B TWI761256B TW110125149A TW110125149A TWI761256B TW I761256 B TWI761256 B TW I761256B TW 110125149 A TW110125149 A TW 110125149A TW 110125149 A TW110125149 A TW 110125149A TW I761256 B TWI761256 B TW I761256B
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Abstract
Description
本發明係關於一種回收金屬的方法，尤其是一種自鎳鋁精礦中回收金屬的方法。 The present invention relates to a method for recovering metals, especially a method for recovering metals from nickel-aluminum concentrates.
隨著石化工業的蓬勃發展，連帶使得應用於石油加氫脫硫的觸媒大量使用，該觸媒以氧化鋁(Al2O3)作為載體，並附著有活性金屬(例如，鎳金屬)，但是該觸媒於作用過程中，會吸附鐵、釩、磷等大量元素，而形成失去效用之含釩鉬廢觸媒(即，RDS)，該含釩鉬廢觸媒中仍含有釩、鉬、鎳、鋁等多種有價金屬，因此工者係可以自該含釩鉬廢觸媒中續回收有價金屬，發揮該含釩鉬廢觸媒之經濟效益。舉例而言，中華民國公告第I542701號專利案及中華民國公告第I635184號專利案均揭示自RDS廢觸媒中回收釩等有價金屬。 With the vigorous development of the petrochemical industry, the catalyst for the hydrodesulfurization of petroleum has been widely used. However, in the process of action, the catalyst will adsorb a large number of elements such as iron, vanadium, phosphorus, etc., and form a waste catalyst containing vanadium and molybdenum (ie, RDS) that has no effect. The waste catalyst containing vanadium and molybdenum still contains vanadium, molybdenum and molybdenum. , nickel, aluminum and other valuable metals, so workers can continue to recover valuable metals from the vanadium-containing molybdenum waste catalyst, and exert the economic benefits of the vanadium-molybdenum-containing waste catalyst. For example, the Republic of China Announcement Patent No. I542701 and the Republic of China Announcement Patent No. I635184 both disclose the recovery of valuable metals such as vanadium from RDS waste catalysts.
在依前述專利案所揭示之方法，自RDS廢觸媒中回收釩等有價金屬之後，另可以獲得一鎳鋁精礦，其仍包含釩、鉬、鎳等有價金屬，若要自該鎳鋁精礦中回收該些有價金屬，習知自鎳鋁精礦中回收金屬的方法係將該鎳鋁精礦混合一鈉鹽或一鈣鹽，以自該鎳鋁精礦中回收釩及鉬。然而，由於該鎳鋁精礦中含有大量的鋁，故在回收釩、鉬之後剩下的鎳會與鋁結合而難以分離，且包含鎳及鋁的鎳鋁合金的經濟價值不高，因此仍需要提供一種 新穎的自鎳鋁精礦中回收金屬的方法。 According to the method disclosed in the aforementioned patent case, after recovering valuable metals such as vanadium from the RDS waste catalyst, another nickel-aluminum concentrate can be obtained, which still contains valuable metals such as vanadium, molybdenum, and nickel. The valuable metals are recovered from the concentrate. The conventional method for recovering metals from the nickel-aluminum concentrate is to mix the nickel-aluminum concentrate with a sodium salt or a calcium salt to recover vanadium and molybdenum from the nickel-aluminum concentrate. However, since the nickel-aluminum concentrate contains a large amount of aluminum, the remaining nickel after the recovery of vanadium and molybdenum will be combined with aluminum and difficult to separate, and the economic value of nickel-aluminum alloy containing nickel and aluminum is not high, so it is still difficult to separate. need to provide a Novel method for metal recovery from nickel-aluminum concentrates.
為解決上述問題，本發明的目的是提供一種自鎳鋁精礦中回收金屬的方法，係能夠以鎳鋁精礦作為原料，以獲得具有經濟價值的鎳鉬鐵合金者。 In order to solve the above-mentioned problems, the purpose of the present invention is to provide a method for recovering metals from nickel-aluminum concentrate, which can use nickel-aluminum concentrate as a raw material to obtain a nickel-molybdenum-iron alloy with economic value.
本發明的次一目的是提供一種自鎳鋁精礦中回收金屬的方法，可以提升所獲得的鎳鉬鐵合金中的純度者。 Another object of the present invention is to provide a method for recovering metal from nickel-aluminum concentrate, which can improve the purity of the obtained nickel-molybdenum-iron alloy.
本發明的自鎳鋁精礦中回收金屬的方法，可以包含：提供一鎳鋁精礦，該鎳鋁精礦包含鎳、鋁、釩、鉬及磷；混合該鎳鋁精礦、氧化鈣、碳及純鐵，得一混合物；使該混合物於一大氣環境中進行一初煉反應，得一重項；及使該重項於一富氧環境中進行一精煉反應，得一鎳鉬鐵合金；其中，該初煉反應係於1450~1850℃之溫度下進行1~4小時，該精煉反應係於一精煉爐的一反應室中進行，於該反應室中，以體積百分比計，氧氣佔所有氣體的100%，且該精煉反應係於1450~1850℃之溫度下進行1~4小時。 The method for recovering metal from nickel-aluminum concentrate of the present invention may include: providing a nickel-aluminum concentrate, the nickel-aluminum concentrate comprising nickel, aluminum, vanadium, molybdenum and phosphorus; mixing the nickel-aluminum concentrate, calcium oxide, carbon and pure iron to obtain a mixture; make the mixture carry out a primary refining reaction in an atmospheric environment to obtain a heavy item; and make the heavy item undergo a refining reaction in an oxygen-rich environment to obtain a nickel-molybdenum-iron alloy; wherein , the primary refining reaction is carried out at a temperature of 1450~1850 ° C for 1~4 hours, and the refining reaction is carried out in a reaction chamber of a refining furnace. In the reaction chamber, in terms of volume percentage, oxygen accounts for all the gas 100%, and the refining reaction is carried out at a temperature of 1450~1850°C for 1~4 hours.
據此，本發明的自鎳鋁精礦中回收金屬的方法，藉由混合氧化鈣、碳及純鐵等輔料，使該鎳鋁精礦於該大氣環境中進行該初煉反應，而可以去除該鎳鋁精礦中的鋁，續於該富氧環境中進行該精煉反應，進而可以去除該鎳鋁精礦中的釩及磷，該鎳鋁精礦中僅存的鎳與鉬，則能夠與該輔料中的純鐵共同形成該鎳鉬鐵合金，該鎳鉬鐵合金後續可以作為煉鋼的原料(如可以用於形成抗腐蝕性佳、強度良好，且價格較高的316不鏽鋼)，為本發明之功效。 Accordingly, in the method for recovering metals from nickel-aluminum concentrate of the present invention, by mixing auxiliary materials such as calcium oxide, carbon and pure iron, the nickel-aluminum concentrate is subjected to the primary refining reaction in the atmospheric environment, and the removal of The aluminum in the nickel-aluminum concentrate continues to carry out the refining reaction in the oxygen-rich environment, thereby removing vanadium and phosphorus in the nickel-aluminum concentrate, and the only remaining nickel and molybdenum in the nickel-aluminum concentrate can be The nickel-molybdenum-iron alloy is formed together with the pure iron in the auxiliary material, and the nickel-molybdenum-iron alloy can be used as a raw material for steelmaking (for example, it can be used to form 316 stainless steel with good corrosion resistance, good strength, and high price), which is the The power of invention.
本發明的自鎳鋁精礦中回收金屬的方法，其中，該鎳鋁精礦可以包含以重量百分比計為30~45%的鋁、0.1~1%的釩、0.1~1%的鉬、3~ 8%的鎳、0.1~1%的磷，其餘比例為雜質。 The method for recovering metal from nickel-aluminum concentrate of the present invention, wherein the nickel-aluminum concentrate may contain 30-45% by weight of aluminum, 0.1-1% of vanadium, 0.1-1% of molybdenum, 3 ~ 8% nickel, 0.1~1% phosphorus, and the rest are impurities.
本發明的自鎳鋁精礦中回收金屬的方法，其中，能夠以1：0.1~1：0.6之重量比混合該鎳鋁精礦及氧化鈣，較佳係能夠以1：0.3~1：0.6之重量比混合該鎳鋁精礦及氧化鈣。如此，藉由氧化鈣可以藉由該初煉反應與該鎳鋁精礦中的鋁進行反應而形成鋁酸鈣，可以有效地去除該鎳鋁精礦中的鋁，進而降低該重項中的鋁含量。 In the method for recovering metal from nickel-aluminum concentrate of the present invention, the nickel-aluminum concentrate and calcium oxide can be mixed in a weight ratio of 1:0.1-1:0.6, preferably, the nickel-aluminum concentrate can be mixed in a weight ratio of 1:0.3-1:0.6 Mix the nickel-aluminum concentrate and calcium oxide in a weight ratio. In this way, calcium oxide can react with the aluminum in the nickel-aluminum concentrate through the primary refining reaction to form calcium aluminate, which can effectively remove the aluminum in the nickel-aluminum concentrate, thereby reducing the heavy item. aluminum content.
本發明的自鎳鋁精礦中回收金屬的方法，其中，能夠以1：0.01~1：0.1之重量比混合該鎳鋁精礦及碳，較佳係能夠以1：0.05~1：0.1之重量比混合該鎳鋁精礦及碳。如此，該鎳鋁精礦中包含鎳、釩、鉬等元素的化合物(例如，NiO、Ni2O3等鎳氧化物、VO、V2O3、VO2及V2O5等釩氧化物及MoO2、MoO3等鉬氧化物)可以被碳還原形成鎳、釩、鉬等金屬，如此經還原形成的鎳、釩、鉬等金屬可以與鐵共同形成該重項(比重約為6~10)，而與鋁酸鈣(比重約為3)有效分層。 In the method for recovering metal from nickel-aluminum concentrate of the present invention, the nickel-aluminum concentrate and carbon can be mixed in a weight ratio of 1:0.01-1:0.1, preferably, the nickel-aluminum concentrate can be mixed in a weight ratio of 1:0.05-1:0.1 The nickel-aluminum concentrate and carbon are mixed in a weight ratio. In this way, the nickel - aluminum concentrate contains compounds of elements such as nickel, vanadium, and molybdenum (for example, nickel oxides such as NiO and Ni2O3 , vanadium oxides such as VO , V2O3 , VO2 , and V2O5) . and MoO 2 , MoO 3 and other molybdenum oxides) can be reduced by carbon to form metals such as nickel, vanadium, and molybdenum, so the metals such as nickel, vanadium, and molybdenum formed by reduction can form the heavy item together with iron (the specific gravity is about 6~ 10), while effectively delaminating with calcium aluminate (specific gravity about 3).
本發明的自鎳鋁精礦中回收金屬的方法，其中，能夠以1：0.05~1：0.2之重量比混合該鎳鋁精礦及純鐵，較佳係能夠以1：0.1~1：0.2之重量比混合該鎳鋁精礦及純鐵。如此，在該重項中的釩與磷發生氧化而形成釩磷精礦後，該重項中殘留的鎳與鉬可以與純鐵中的鐵共同形成後續可以作為煉鋼的原料的鎳鉬鐵合金；並且，由於包含鐵的重項與鋁酸鈣的比重相差較大(包含鐵的重項的比重約為6~10)，使鋁酸鈣(比重約為3)較容易與包含鐵的重項分層，避免在回收該重項時誤一併回收到未完全分層的鋁酸鈣。 In the method for recovering metals from nickel-aluminum concentrate of the present invention, wherein the nickel-aluminum concentrate and pure iron can be mixed in a weight ratio of 1:0.05~1:0.2, preferably, the nickel-aluminum concentrate and pure iron can be mixed in a weight ratio of 1:0.1~1:0.2 Mix the nickel-aluminum concentrate and pure iron in a weight ratio. In this way, after the vanadium and phosphorus in the heavy item are oxidized to form a vanadium-phosphorus concentrate, the residual nickel and molybdenum in the heavy item can be combined with the iron in the pure iron to form a nickel-molybdenum-iron alloy that can be used as a raw material for steelmaking subsequently. ; And, since the specific gravity of the heavy item containing iron and calcium aluminate is quite different (the specific gravity of the heavy item containing iron is about 6~10), the calcium aluminate (specific gravity is about 3) is easier to be compared with the heavy item containing iron. Items are delaminated to avoid the accidental recovery of incompletely delaminated calcium aluminate when recycling the heavy items.
本發明的自鎳鋁精礦中回收金屬的方法，其中，該混合物較佳可以於1550℃以上的溫度下進行該初煉反應至少2小時。如此，可以提升氧化鈣與該鎳鋁精礦中的鋁形成鋁酸鈣的效率，可以有效地去除該鎳鋁精礦中的鋁，進而降低該重項中的鋁含量。 In the method for recovering metal from nickel-aluminum concentrate of the present invention, the mixture can preferably be subjected to the primary refining reaction at a temperature above 1550° C. for at least 2 hours. In this way, the efficiency of forming calcium aluminate between calcium oxide and aluminum in the nickel-aluminum concentrate can be improved, and the aluminum in the nickel-aluminum concentrate can be effectively removed, thereby reducing the aluminum content in the heavy item.
本發明的自鎳鋁精礦中回收金屬的方法，其中，該第一重項較佳可以於1550℃以上的溫度下進行該精煉反應至少2小時。如此，可以提升該重項中的釩與磷的氧化效率，進而可以有效地形成該釩磷精礦，而可以降低所獲得的鎳鉬鐵合金中的釩、磷含量。 In the method for recovering metals from nickel-aluminum concentrates of the present invention, the first heavy item preferably can carry out the refining reaction at a temperature above 1550° C. for at least 2 hours. In this way, the oxidation efficiency of vanadium and phosphorus in the heavy item can be improved, and the vanadium-phosphorus concentrate can be formed effectively, and the content of vanadium and phosphorus in the obtained nickel-molybdenum-iron alloy can be reduced.
〔本發明〕 〔this invention〕
S1:混料步驟 S1: mixing step
S2:初煉步驟 S2: Initial refining step
S3:精煉步驟 S3: Refining step
〔第1圖〕本發明的自鎳鋁精礦中回收金屬的方法之一實施例的流程圖。 [FIG. 1] A flow chart of one embodiment of the method for recovering metals from nickel-aluminum concentrates 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，作詳細說明如下： 本發明所述之「鎳鋁精礦」除包含鎳(nickel，Ni)及鋁(aluminum，Al)之外，尚可以包含釩(vanadium，V)及鉬(molybdenum，Mo)等有價金屬，且該鎳鋁精礦中亦含有一定含量的磷(phosphorus，P)。舉例而言，該鎳鋁精礦大致可以包含以重量百分比計約為3~8%的鎳、30~45%的鋁、0.1~1%的釩、0.1~1%的鉬、0.1~1%的磷，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-mentioned and other objects, features and advantages of the present invention more obvious and easy to understand, the preferred embodiments of the present invention are exemplified below, and are described in detail as follows in conjunction with the accompanying drawings: In addition to nickel (nickel, Ni) and aluminum (aluminum, Al), the "nickel-aluminum concentrate" described in the present invention may also contain valuable metals such as vanadium (V) and molybdenum (molybdenum, Mo), and The nickel-aluminum concentrate also contains a certain content of phosphorus (phosphorus, P). For example, the nickel-aluminum concentrate may roughly contain about 3-8% nickel, 30-45% aluminum, 0.1-1% vanadium, 0.1-1% molybdenum, 0.1-1% by weight It is 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，本發明的自鎳鋁精礦中回收金屬的方法之一實施例可以包含：一混料步驟S1、一初煉步驟(smelting step)S2及一精煉步驟(refining step)S3，以自該鎳鋁精礦中分離出具有經濟價值的一鎳鉬鐵合金。 Referring to FIG. 1, an embodiment of the method for recovering metals from nickel-aluminum concentrate of the present invention may include: a mixing step S1, a smelting step S2 and a refining step ) S3, to separate a nickel-molybdenum-iron alloy with economic value from the nickel-aluminum concentrate.
詳而言之，於該混料步驟S1中，係混合該鎳鋁精礦與氧化鈣(calcium oxide，CaO)、碳(carbon，C)及純鐵(pure iron，鐵含量達99.8% 以上的鐵合金)等輔料(adjuvant)，以得一混合物。舉例而言，每公斤的鎳鋁精礦可以混合100~600克的氧化鈣、10~100克的碳及50~200克的純鐵。較佳地，每公斤的鎳鋁精礦可以混合至少300克的氧化鈣、至少50克的碳及100克的純鐵，如此可以降低最終獲得的鎳鉬鐵合金中的鋁含量。 Specifically, in the mixing step S1 , the nickel-aluminum concentrate is mixed with calcium oxide (CaO), carbon (C) and pure iron (the iron content reaches 99.8%). The above iron alloys) and other adjuvant materials (adjuvant) to obtain a mixture. For example, 100-600 grams of calcium oxide, 10-100 grams of carbon and 50-200 grams of pure iron can be mixed with each kilogram of nickel-aluminum concentrate. Preferably, at least 300 grams of calcium oxide, at least 50 grams of carbon and 100 grams of pure iron can be mixed with each kilogram of nickel-aluminum concentrate, so that the aluminum content in the final nickel-molybdenum-iron alloy can be reduced.
接著，於該初煉步驟S2中，工者可以將該混合物置入一電弧爐(electric arc furnace，EAF)的一反應室中，以於一大氣環境(atmosphere environment)中進行一初煉反應(即，於該電弧爐的反應室中，以體積百分比計，氧氣約佔所有氣體的20%)，使氧化鈣得以與該鎳鋁精礦中的鋁於高溫下進行反應而形成鋁酸鈣〔calcium aluminate，係鋁酸三鈣(3CaO‧Al2O3)、七鋁酸十二鈣(12CaO‧7Al2O3)、偏鋁酸鈣(CaO‧Al2O3)、二鋁酸鈣(CaO‧2Al2O3、六鋁酸鈣(CaO‧6Al2O3)、鋁酸二鈣(2CaO‧Al2O3)、三鋁酸五鈣(5CaO‧3Al2O3)及三鋁酸四鈣(4CaO‧3Al2O3)等化合物的統稱，且其中以鋁酸三鈣為該初煉反應所產生的鋁酸鈣中的主要成分〕，該混合物中的其餘成分(至少包含鎳、釩、鉬、磷及鐵)則由於其比重(specific gravity，約為6~10)大於鋁酸鈣的比重(約為3)，使鋁酸鈣會漂浮於該混合物中的其餘成分的上方，因此為便於說明，將此處所得的鋁酸鈣稱為〝第一輕項〞，且該混合物中的其餘成分則稱為〝第一重項〞。舉例而言，該初煉步驟S2可以於1450~1850℃之溫度下進行，且其反應時間可以為1~4小時。較佳地，該初煉步驟S2可以於1550℃以上的溫度下進行，且其反應時間可以為至少2小時，如此可以提升氧化鈣與該鎳鋁精礦中的鋁形成鋁酸鈣的效率，進而可以有效地去除該鎳鋁精礦中的鋁。 Next, in the primary refining step S2, the worker can put the mixture into a reaction chamber of an electric arc furnace (EAF) to perform a primary refining reaction in an atmosphere environment ( That is, in the reaction chamber of the electric arc furnace, in terms of volume percentage, oxygen accounts for about 20% of all gases), so that calcium oxide can react with the aluminum in the nickel-aluminum concentrate at high temperature to form calcium aluminate [ calcium aluminate, which is tricalcium aluminate (3CaO·Al 2 O 3 ), dodecacalcium heptaaluminate (12CaO·7Al 2 O 3 ), calcium metaaluminate (CaO·Al 2 O 3 ), calcium dialuminate ( CaO·2Al 2 O 3 , calcium hexaaluminate (CaO·6Al 2 O 3 ), dicalcium aluminate (2CaO·Al 2 O 3 ), pentacalcium trialuminate (5CaO·3Al 2 O 3 ) and trialuminate The general term for compounds such as tetracalcium (4CaO·3Al 2 O 3 ), among which tricalcium aluminate is the main component in the calcium aluminate produced by the primary refining reaction], the remaining components in the mixture (including at least nickel, Vanadium, molybdenum, phosphorus and iron), because their specific gravity (about 6~10) is greater than that of calcium aluminate (about 3), calcium aluminate will float above the rest of the components in the mixture, Therefore, for the convenience of description, the calcium aluminate obtained here is called the "first light item", and the rest of the components in the mixture are called the "first heavy item". For example, the preliminary refining step S2 can be performed in Carry out under the temperature of 1450～1850 ℃, and its reaction time can be 1～4 hour.Preferably, this preliminary refining step S2 can be carried out at the temperature above 1550 ℃, and its reaction time can be at least 2 hours, so The efficiency of calcium aluminate formation between calcium oxide and aluminum in the nickel-aluminum concentrate can be improved, and aluminum in the nickel-aluminum concentrate can be effectively removed.
值得注意的是，於該初煉步驟S2中，針對1公斤的鎳鋁精礦，係可以使用反應室體積為12,000cm3的電弧爐，並且由於混合10~100克的碳，在進行該初煉反應的1~4小時中，該鎳鋁精礦中包含鎳、釩、鉬等元素 的化合物〔例如，NiO、Ni2O3等鎳氧化物(nickel oxide)、VO、V2O3、VO2及V2O5等釩氧化物(vanadium oxide)及MoO2、MoO3等鉬氧化物(molybdenum oxide)〕可以被碳還原形成鎳、釩、鉬等金屬，如此經還原形成的鎳、釩、鉬等金屬可以與鐵共同形成該第一重項，而與該第一輕項分離。 It is worth noting that, in the preliminary refining step S2, for 1 kg of nickel-aluminum concentrate, an electric arc furnace with a reaction chamber volume of 12,000 cm 3 can be used, and since 10-100 grams of carbon is mixed, the preliminary During 1 to 4 hours of the refining reaction, the nickel-aluminum concentrate contains compounds of elements such as nickel, vanadium, and molybdenum (for example, nickel oxides such as NiO, Ni 2 O 3 , VO, V 2 O 3 , Vanadium oxides such as VO 2 and V 2 O 5 and molybdenum oxides such as MoO 2 and MoO 3 can be reduced by carbon to form metals such as nickel, vanadium, and molybdenum. Metals such as vanadium and molybdenum can form the first heavy item together with iron and separate from the first light item.
又，於該精煉步驟S3中，工者可以於收集該第一重項後，將該第一重項置入一精煉爐(finery forge)的一反應室中，並且對該精煉爐通入氧氣，在該精煉爐的反應室充滿氧氣之後，使該第一重項可以於一富氧環境(oxygen-rich environment)中進行一精煉反應(即，於該精煉爐的反應室中，以體積百分比計，氧氣約佔所有氣體的100%)，該第一重項中的釩與磷即可以被氧化而形成比重較小的釩氧化物(vanadium oxide，如VO、V2O3、VO2及V2O5等)及磷氧化物(phosphorus oxide，如P2O3、P2O5及P2O4等)，而漂浮於該第一重項中的其餘成分(至少包含鎳、鉬及鐵)的上方，因此為便於說明，將包含比重較小的釩氧化物及磷氧化物的混合物稱為〝第二輕項〞(比重約為3~4)，且前述之至少包含鎳、鉬及鐵的第一重項中的其餘成分則稱為〝第二重項〞(比重約為5~7)，該第二輕項可以進一步以釩磷精礦的形式分離，而該第二重項則且能夠以該鎳鉬鐵合金的形式進行回收。舉例而言，該精煉步驟S3可以於1450~1850℃之溫度下進行，且其反應時間可以為1~4小時。較佳地，該精煉步驟S3可以於1550℃以上的溫度下進行，且其反應時間可以為至少2小時，如此可以提升該第一重項中的釩與磷的氧化效率，進而可以有效地形成該第二輕項，進而與該第二重項分離，而可以獲得釩、磷含量較低的鎳鉬鐵合金。 Moreover, in the refining step S3, the worker can put the first heavy item into a reaction chamber of a finery forge after collecting the first heavy item, and supply oxygen to the refining forge , after the reaction chamber of the refining furnace is filled with oxygen, so that the first heavy item can carry out a refining reaction in an oxygen-rich environment (ie, in the reaction chamber of the refining furnace, by volume percentage In total, oxygen accounts for about 100% of all gases), and the vanadium and phosphorus in the first heavy item can be oxidized to form vanadium oxides (vanadium oxides, such as VO, V 2 O 3 , VO 2 and V 2 O 5 , etc.) and phosphorus oxides (such as P 2 O 3 , P 2 O 5 and P 2 O 4 , etc.), and the rest of the components floating in the first item (including at least nickel, molybdenum, etc.) and iron), so for the convenience of description, the mixture containing the vanadium oxide and phosphorus oxide with a smaller specific gravity is called the "second light item" (the specific gravity is about 3~4), and the aforementioned one contains at least nickel, The rest of the first heavy item of molybdenum and iron is called the "second heavy item" (specific gravity is about 5~7). The second light item can be further separated in the form of vanadium-phosphorus concentrate, and the second The most important thing is that it can be recycled in the form of this nickel-molybdenum-iron alloy. For example, the refining step S3 can be performed at a temperature of 1450-1850° C., and the reaction time can be 1-4 hours. Preferably, the refining step S3 can be carried out at a temperature above 1550 ° C, and the reaction time can be at least 2 hours, so that the oxidation efficiency of vanadium and phosphorus in the first heavy item can be improved, and then can effectively form The second light item is further separated from the second heavy item to obtain a nickel-molybdenum-iron alloy with lower content of vanadium and phosphorus.
值得注意的是，於該精煉步驟S3中，針對1公斤的第一重項，係可以使用反應室體積為12,000cm3的精煉爐，並且由於釩氧化物及磷氧化物的形成會持續消耗掉該精煉爐的反應室中的氧氣，在進行該精煉反應的1 ~4小時中，持續以2~3L/分鐘的流速將氧氣(純度為99.8%以上)導入該精煉爐的反應室，而使該精煉爐的反應室可以維持該富氧環境的狀態，惟工者可以依據該反應室中氧氣的消耗速度、該反應室的體積大小等因素，自行調整導入該反應室的氧氣的流速，僅需確保該反應室中的氧氣含量即可，此為本發明所屬技術領域中具有通常知識者可以理解，於此不加以贅述。 It is worth noting that, in the refining step S3, for the first weight of 1 kg, a refining furnace with a reaction chamber volume of 12,000 cm 3 can be used, and due to the formation of vanadium oxides and phosphorus oxides, it will continue to be consumed The oxygen in the reaction chamber of the refining furnace is continuously introduced into the reaction chamber of the refining furnace at a flow rate of 2 to 3 L/min at a flow rate of 2 to 3 L/min for 1 to 4 hours, so that The reaction chamber of the refining furnace can maintain the state of the oxygen-enriched environment, but the worker can adjust the flow rate of the oxygen introduced into the reaction chamber according to factors such as the consumption rate of oxygen in the reaction chamber and the volume of the reaction chamber. It is only necessary to ensure the oxygen content in the reaction chamber, which can be understood by those with ordinary knowledge in the technical field to which the present invention pertains, and will not be repeated here.
為證實依本實施例之自鎳鋁精礦中回收金屬的方法確實可以自該鎳鋁精礦中回收金屬，遂取包含以重量百分比計為5.0%的鎳、30.1%的鋁、0.5%的釩、0.5%的鉬、0.2%的磷，且其餘比例為不可避免之雜質的鎳鋁精礦，並進行以下試驗： In order to confirm that the method for recovering metals from nickel-aluminum concentrates according to the present embodiment can indeed recover metals from the nickel-aluminum concentrates, samples containing 5.0% nickel, 30.1% aluminum, 0.5% by weight of Vanadium, 0.5% molybdenum, 0.2% phosphorus, and nickel-aluminum concentrate with the remaining proportions as unavoidable impurities, and the following tests are carried out:
(A)氧化鈣添加量的調整 (A) Adjustment of calcium oxide addition amount
本試驗係取1,000克的鎳鋁精礦，混合如第1表所示之重量的氧化鈣、50克的碳及100克的純鐵之後，於1550℃的溫度下進行該初煉反應2小時，在移除該第一輕項(鋁酸鈣)之後，分析所獲得的第一重項中各化學元素的殘留率。 In this test, 1,000 grams of nickel-aluminum concentrate was mixed with calcium oxide, 50 grams of carbon and 100 grams of pure iron in the weight shown in Table 1, and the primary smelting reaction was carried out at a temperature of 1550°C for 2 hours. , after removing the first light term (calcium aluminate), analyze the residual rate of each chemical element in the obtained first heavy term.
請參照第1表所示，在該初煉步驟S2之後，第A1~A6組的第一重項中的鋁的去除率均可以達90%以上，使鋁的殘留率均不足10%，而在氧化鈣的添加量為300克以上時(即，第A3~A6組)，該第一重項中的鋁的去除率更可以達95%以上，使鋁的殘留率均不足5%。 Please refer to Table 1. After the initial refining step S2, the removal rate of aluminum in the first heavy item of Groups A1 to A6 can all reach more than 90%, so that the residual rate of aluminum is less than 10%, and When the addition amount of calcium oxide is more than 300 grams (ie, groups A3 to A6), the removal rate of aluminum in the first heavy item can reach more than 95%, so that the residual rate of aluminum is less than 5%.
(B)碳添加量的調整 (B) Adjustment of carbon addition amount
本試驗係取1,000克的鎳鋁精礦，混合300克的氧化鈣、如第2表所示之重量的碳及100克的純鐵之後，於1550℃的溫度下進行該初煉反應2小時，在移除該第一輕項(鋁酸鈣)之後，分析所獲得的第一重項中各化學元素的殘留率。 In this test, 1,000 grams of nickel-aluminum concentrate was taken, mixed with 300 grams of calcium oxide, carbon as shown in Table 2, and 100 grams of pure iron, and the primary refining reaction was carried out at a temperature of 1550°C for 2 hours. , after removing the first light term (calcium aluminate), analyze the residual rate of each chemical element in the obtained first heavy term.
請參照第2表所示，在該初煉步驟S2之後，第B1~B5組的第一重項中的鋁的去除率均可以達90%以上，使鋁的殘留率均不足10%，而在碳的添加量為50克以上時(即，第B2~B5組)，該第一重項中的鋁的去除率更可以達95%以上，使鋁的殘留率均不足5%。 Please refer to Table 2, after the preliminary refining step S2, the removal rate of aluminum in the first heavy item of Groups B1 to B5 can all reach more than 90%, so that the residual rate of aluminum is less than 10%, and When the amount of carbon added is more than 50 grams (ie, Groups B2 to B5), the removal rate of aluminum in the first heavy item can reach more than 95%, so that the residual rate of aluminum is less than 5%.
(C)純鐵添加量的調整 (C) Adjustment of the amount of pure iron added
本試驗係取1,000克的鎳鋁精礦，混合300克的氧化鈣、50克的碳及如第3表所示之重量的純鐵之後，於1550℃的溫度下進行該初煉反應2小時，在移除該第一輕項(鋁酸鈣)之後，分析所獲得的第一重項中各化學元素的殘留率。 In this test, 1,000 grams of nickel-aluminum concentrate was taken, mixed with 300 grams of calcium oxide, 50 grams of carbon and pure iron in the weight shown in Table 3, and the primary refining reaction was carried out at a temperature of 1550 °C for 2 hours , after removing the first light term (calcium aluminate), analyze the residual rate of each chemical element in the obtained first heavy term.
請參照第3表所示，在該初煉步驟S2之後，第C1~C5組的第一重項中的鋁的殘留率去除率均可以達90%以上，使鋁的均不足10%，而在純鐵的添加量為100克以上時(即，第C2~C5組)，該第一重項中的鋁的去除率更可以達95%以上，使鋁的殘留率均不足5%。 Please refer to Table 3, after the primary refining step S2, the removal rate of the residual aluminum in the first heavy item of the groups C1 to C5 can all reach more than 90%, so that the aluminum content is less than 10%, and When the amount of pure iron added is more than 100 grams (ie, groups C2 to C5), the removal rate of aluminum in the first heavy item can reach more than 95%, so that the residual rate of aluminum is less than 5%.
(D)初煉溫度的調整 (D) Adjustment of primary refining temperature
本試驗係取1,000克的鎳鋁精礦，混合300克的氧化鈣、50克的碳及100克的純鐵之後，於如第4表所示的溫度下進行該初煉反應2小時，在移除該第一輕項(鋁酸鈣)之後，分析所獲得的第一重項中各化學元素的殘留率。 In this experiment, 1,000 grams of nickel-aluminum concentrate was taken, mixed with 300 grams of calcium oxide, 50 grams of carbon and 100 grams of pure iron, and the primary refining reaction was carried out at the temperature shown in Table 4 for 2 hours. After removing the first light term (calcium aluminate), the obtained first heavy term was analyzed for the residual rate of each chemical element.
請參照第4表所示，在該初煉步驟S2之後，第D1~D5組的第一重項中的鋁的去除率均可以達90%以上，使鋁的殘留率均不足10%，而 在初煉溫度為1550℃以上時(即，第D2~D5組)，該第一重項中的鋁的去除率更可以達95%以上，使鋁的殘留率均不足5%。 Please refer to Table 4, after the preliminary refining step S2, the removal rate of aluminum in the first heavy item of groups D1 to D5 can all reach more than 90%, so that the residual rate of aluminum is less than 10%, and When the initial smelting temperature is above 1550°C (ie, groups D2 to D5), the removal rate of aluminum in the first heavy item can reach more than 95%, so that the residual rate of aluminum is less than 5%.
(E)初煉時間的調整 (E) Adjustment of the initial training time
本試驗係取1,000克的鎳鋁精礦，混合300克的氧化鈣、50克的碳及100克的純鐵之後，於1550℃的溫度下進行該初煉反應，反應時間係如第5表所示，在移除該第一輕項(鋁酸鈣)之後，分析所獲得的第一重項中各化學元素的殘留率。 In this experiment, 1,000 grams of nickel-aluminum concentrate was taken, mixed with 300 grams of calcium oxide, 50 grams of carbon and 100 grams of pure iron, and the primary refining reaction was carried out at a temperature of 1550 °C. The reaction time is shown in Table 5. As shown, after removing the first light term (calcium aluminate), the obtained first heavy term was analyzed for the residual rate of each chemical element.
請參照第5表所示，在該初煉步驟S2之後，第E1~E4組的第一重項中的鋁的去除率均可以達90%以上，使鋁的殘留率均不足10%，而在初煉時間為2小時以上時(即，第E2~E4組)，該第一重項中的鋁的去除率更可以達95%以上，使鋁的殘留率均不足5%。 Please refer to Table 5, after the preliminary refining step S2, the removal rate of aluminum in the first heavy item of the groups E1 to E4 can all reach more than 90%, so that the residual rate of aluminum is less than 10%, and When the initial smelting time is more than 2 hours (ie, Groups E2 to E4), the removal rate of aluminum in the first heavy item can reach more than 95%, so that the residual rate of aluminum is less than 5%.
(F)精煉溫度的調整 (F) Adjustment of refining temperature
本試驗係取1,000克的鎳鋁精礦，混合300克的氧化鈣、50克的碳及100克的純鐵之後，於1550℃的溫度下進行該初煉反應2小時，在移除該第一輕項(鋁酸鈣)之後，再將所獲得的第一重項於如第6表所示的溫度下進行該精煉反應2小時，並在移除該第二輕項(釩磷精礦)之後，分析 所獲得的第二重項中各化學元素的殘留率。 In this experiment, 1,000 grams of nickel-aluminum concentrate was taken, mixed with 300 grams of calcium oxide, 50 grams of carbon and 100 grams of pure iron, and the primary refining reaction was carried out at a temperature of 1550 ° C for 2 hours. After a light item (calcium aluminate), the first heavy item obtained is then subjected to the refining reaction at the temperature shown in Table 6 for 2 hours, and the second light item (vanadium phosphate concentrate) is removed after removing the second light item. ), after analyzing The residual ratio of each chemical element in the obtained second weight term.
請參照第6表所示，在該精煉步驟S3之後，第F1~F5組的第二重項中的釩、磷的去除率均可以達90%以上，使釩、磷的殘留率均不足10%，而在精煉溫度為1550℃以上時(即，第F2~F5組)，該第二重項中的釩、磷的去除率更可以達95%以上，使釩、磷的殘留率均不足5%。 Please refer to Table 6. After the refining step S3, the removal rates of vanadium and phosphorus in the second heavy item of Groups F1 to F5 can all reach more than 90%, so that the residual rates of vanadium and phosphorus are less than 10%. %, and when the refining temperature is above 1550 °C (ie, Groups F2 to F5), the removal rate of vanadium and phosphorus in the second heavy item can reach more than 95%, so that the residual rate of vanadium and phosphorus is insufficient. 5%.
(G)精煉時間的調整 (G) Adjustment of refining time
本試驗係取1,000克的鎳鋁精礦，混合300克的氧化鈣、50克的碳及100克的純鐵之後，於1550℃的溫度下進行該初煉反應2小時，在移除該第一輕項(鋁酸鈣)之後，再將所獲得的第一重項於1550℃的溫度下進行該精煉反應，反應時間係如第7表所示，並在移除該第二輕項(釩磷精礦)之後，分析所獲得的第二重項中各化學元素的殘留率。 In this experiment, 1,000 grams of nickel-aluminum concentrate was taken, mixed with 300 grams of calcium oxide, 50 grams of carbon and 100 grams of pure iron, and the primary refining reaction was carried out at a temperature of 1550 ° C for 2 hours. After a light item (calcium aluminate), the obtained first heavy item is then subjected to the refining reaction at a temperature of 1550° C. The reaction time is as shown in Table 7, and after removing the second light item ( After vanadium phosphate concentrate), the residual rate of each chemical element in the obtained second heavy term was analyzed.
請參照第7表所示，在該精煉步驟S3之後，第G1~G4組的第二重項中的釩、磷的去除率均可以達90%以上，使釩、磷的殘留率均不足10%，而在精煉時間為2小時以上時(即，第G2~G4組)，該第二重項中的釩、磷的去除率更可以達95%以上，使釩、磷的殘留率均不足5%。 Please refer to Table 7, after the refining step S3, the removal rate of vanadium and phosphorus in the second heavy item of Groups G1 to G4 can all reach more than 90%, so that the residual rate of vanadium and phosphorus is less than 10%. %, and when the refining time is more than 2 hours (that is, the G2~G4 group), the removal rate of vanadium and phosphorus in the second item can reach more than 95%, so that the residual rate of vanadium and phosphorus is insufficient. 5%.
綜上所述，本發明的自鎳鋁精礦中回收金屬的方法，藉由混合氧化鈣、碳及純鐵等輔料，使該鎳鋁精礦於該大氣環境中進行該初煉反應，而可以去除該鎳鋁精礦中的鋁，續於該富氧環境中進行該精煉反應，進而可以去除該鎳鋁精礦中的釩及磷，該鎳鋁精礦中僅存的鎳與鉬，則能夠與該輔料中的純鐵共同形成該鎳鉬鐵合金，該鎳鉬鐵合金後續可以作為煉鋼的原料(如可以用於形成抗腐蝕性佳、強度良好，且價格較高的316不鏽鋼)，為本發明之功效。 To sum up, the method for recovering metal from nickel-aluminum concentrate of the present invention, by mixing auxiliary materials such as calcium oxide, carbon and pure iron, makes the nickel-aluminum concentrate carry out the primary refining reaction in the atmospheric environment, and The aluminum in the nickel-aluminum concentrate can be removed, and the refining reaction is continued in the oxygen-rich environment, and then vanadium and phosphorus in the nickel-aluminum concentrate can be removed, and the only remaining nickel and molybdenum in the nickel-aluminum concentrate, Then it can form the nickel-molybdenum-iron alloy together with the pure iron in the auxiliary material, and the nickel-molybdenum-iron alloy can be used as a raw material for steelmaking (for example, it can be used to form 316 stainless steel with good corrosion resistance, good strength, and higher price), This is the effect of the present invention.
再且，本案藉由氧化鈣、鈣及純鐵等輔料的添加量，與該初煉反應、該精煉反應的溫度、時間等參數的調整，可以有效地去除該鎳鋁精礦中的鋁、釩及磷，可以達成提升所獲得的鎳鉬鐵合金的純度之功效。 Furthermore, in this case, the addition of calcium oxide, calcium, pure iron and other auxiliary materials, and the adjustment of parameters such as the temperature and time of the primary refining reaction and the refining reaction, can effectively remove aluminum, aluminum, aluminum, nickel and other minerals in the nickel-aluminum concentrate. Vanadium and phosphorus can achieve the effect of improving the purity of the obtained nickel-molybdenum-iron alloy.
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 the above-mentioned preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make various changes and modifications relative to the above-mentioned embodiments without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the patent application attached hereto.
S1:混料步驟 S1: mixing step
S2:初煉步驟 S2: Initial refining step
S3:精煉步驟 S3: Refining step
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| CN112210634A (en) * | 2020-09-11 | 2021-01-12 | 钢研晟华科技股份有限公司 | Method and device for preparing nickel-molybdenum-iron alloy from low-grade nickel-molybdenum ore |
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| CN112210634A (en) * | 2020-09-11 | 2021-01-12 | 钢研晟华科技股份有限公司 | Method and device for preparing nickel-molybdenum-iron alloy from low-grade nickel-molybdenum ore |
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