TWI401213B - Process to recover valuable metals resource from nickel-cobalt residue of spent hydrodesulfurization (hds) catalyst - Google Patents
Process to recover valuable metals resource from nickel-cobalt residue of spent hydrodesulfurization (hds) catalyst Download PDFInfo
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本發明主要係關於一種廢加氫脫硫觸媒中鎳鈷精礦資源化回收方法，尤指一種由鎳鈷精礦中回收鎳與鈷之資源回收方法。The invention relates to a method for recycling nickel-cobalt concentrate in waste hydrodesulfurization catalyst, in particular to a method for recovering nickel and cobalt from nickel-cobalt concentrate.
國內處理廢加氫脫硫觸媒(Co-Mo-Ni/Al2
O3
廢觸媒，HDS廢觸媒)資源化廠，對於廢觸媒資源化回收製程，產生鎳鈷精礦(含鎳廢觸媒)(藍泥Blue Sludge(BS))，每年需處理量估計約15,000噸，由於國內廠家現行技術及設備不易處理，無針對含鎳廢觸媒資源化回收流程，因此目前對於含鎳廢觸媒均採安定化固化掩埋方式處理或轉運為提煉鎳之原料。不僅業者浪費委託處理費用、且無法回收有限的金屬資源，並將金屬資源留置國內再利用，此外對於土地狹隘的台灣，廢棄物處理的合法場地日益不易取得，因此鎳鈷精礦資源化回收技術已是刻不容緩的問題。
國內隨經濟迅速成長，能源需求日益頻繁，其中燃料油為工業與車輛必須使用燃料，使用量也與日俱增。汽機車燃料油在經過燃燒後所排放硫氧化物造成空氣污染問題也日益嚴重，故如何降低燃燒時所產生硫氧化物，為國內煉油廠與環保單位需努力的課題，在各先進國家如美國與加拿大已規範柴油硫含量由原先500ppm降為15ppm，並已於2006年6月實施。鉬一鈷觸媒定義為石油工業上加氫脫硫(hydrodesulfurization，HDS)所用之主要觸媒(catalyst)，製造乃以氧化鋁(Al2
O3
)膠體成型，經烘乾、煆燒成具高孔隙率之高表面積載體，再浸泡(impregnation)於含鉬酸銨與硝酸鈷混合溶液中，經烘乾、煆燒、再浸漬，如此重覆數次，再經一硫化處理而成。中油與台塑公司在脫硫過程中所使用觸媒類型包括鈷鉬、鎳鉬、鈷鉬鎳、鈷鉬釩鎳等，以鋁或矽為主要載體，於加氫脫硫過程中，會吸附硫、碳、釩((V)、鐵、鉬(Mo)、鎳(Ni)、鈷(Co)及其他微量元素，觸媒在長期使用後（6～24個月），由於重油中含有金屬雜質以及硫份，將會在觸媒表面造成金屬硫化物（主要是V3
S4
、NiS、Ni3
S2
）的沉積與積碳，所產生物理破壞、阻塞與毒化現象，使觸媒失去活性降低催化功能，需週期性排出而作廢。
一般而言加氫脫硫廢觸媒(spent HDS catalyst)中含有鈷、鎳、鉬、釩等有價金屬量頗高，視為資源加以回收處理，業者回收方式一般為鹼焙燒、浸漬、純化，浸漬後固液分離產生之殘渣即為鎳鈷精礦(含鎳廢觸媒，俗稱藍泥Blue Sludge(BS))，目前廢觸媒資源化回收處理現況與鎳鈷精礦(藍泥)(含鎳廢觸媒)形成之處理流程如第一圖所示。
本處理技術將鎳鈷精礦中之有價金屬資源化回收鎳、鈷金屬資源。由於鎳金屬用途廣泛，大至發電廠組件，小至日常所用之硬幣，均可見其蹤跡。鈷金屬可作為永久磁鐵、高速鋼、超硬工具、耐熱耐磨合金等，化合物則為塗料、色料、催化劑、化學品、電鍍、電池材料、釉藥以及觸媒原料等多方面。
回收氧化鋁載體應用廣於各方面，包括研磨、耐火材料、觸媒載體、複合材料、陶金與IC基板等產業。相關國內外廢加氫脫硫觸媒之資源化先前技術包含以下幾項：
1.中華民國新型專利第263795號揭露一種廢觸媒與混合的陶瓷圓球介質分選之裝置，藉以富集廢觸媒。惟該廢觸媒與混合的陶瓷圓球介質分選之裝置，其標的與揭露之方法與本案關係較無牽涉，僅為提供檢索歷程。
2.中華民國發明專利證第I295691號揭露一種廢脫硝觸媒之資源再生方法，利用加鹼(Na2
CO3
)800℃高溫焙燒，經由浸漬與溶媒萃取處理流程回收釩與鎢有價金屬的方法。惟該方法所回收之有價金屬與本案目的性關係較無牽涉，僅為提供檢索歷程。
3.美國專利證第4,670,229號揭示一種回收廢觸媒中有價金屬與氧化鋁之流程，將廢加氫脫硫觸媒利用濕式方法，添加NaOH(氫氧化鈉)/NaAlO2
(鋁酸鈉)，控制操作條件為提供氧以及至少200℃高溫，回收釩與鉬，至於產生的鎳與鈷再利用硫酸浸漬回收，此回收方式之缺點為(1)與目前世界上大部分採用加鹼(Na2
CO3
)800℃高溫焙燒處理廢加氫脫硫觸媒之流程不同(目前國內三家廢觸媒回收業者均採此方法回收釩與鉬)，因此此美國專利方法產生的殘渣推測為氧化鎳NiO與氧化鈷CoO，並非本方法加鹼焙燒後產生的NiAl2
O4
、NiFe2
O4
與CoAl2
O4
之難破壞的尖晶石結晶構造。(2)與本發明方法比較相對耗能(200℃與提供氧)與產生二氧化碳(CO2
)。
4.美國專利證第5,445,728號揭示一種回收以氧化鋁為基底的廢觸媒方法，採用高溫乾式處理，控制氣氛(焙燒溫度、時間與氧分壓氣氛)，此方法缺點為相對耗能與大量的碳排放。
5.美國專利證第4,657,745號揭示一種以氧化鋁為基底廢加氫脫硫觸媒回收方法，利用壓力釜(Autoclave)添加98%濃硫酸、硫化氫與水控制氣氛(溫度、氧氣與壓力)，之後再經由水洗與陽離子交換樹脂回收鎳鈷濾液，此方法缺點為相對高溫、高壓操作危險之疑慮與耗能。
6.網路上查詢美國Gulf化學公司已商業化運轉之廢觸媒資源化回收處理流程圖，針對回收釩(V2
O5
)、鉬(MoO3
)後的鎳、鈷殘渣，則是利用電弧爐加入焦炭(coke)高溫形成鎳鈷合金處理，此方法缺點相對耗能與大量的碳排放。且利用電弧爐添加焦炭(coke)高溫冶煉作為鎳鈷合金材料、顏料、塗料之應用，但缺點高溫冶煉耗能、大量碳排放以及顏料與塗料之色度不均不易掌控。
綜合以上各回收方法與設備，除與本案較無關聯之外，有回收有價金屬之目的性與本案較無牽涉，亦有存在前揭所在之問題而不理想，而依據文獻與理論不易利用傳統乾式的焙燒處理與傳統濕式的酸浸漬溶出鎳、鈷目的金屬之處理流程，達到有價金屬回收目的與需求。從而目前現況大多運至冶煉廠提煉為鎳原料或採安定化掩埋處理，不但有污染環境之疑慮、高溫冶煉耗能且無法回收其中的有價金屬資源(鎳與鈷)。Domestic treatment of waste hydrodesulfurization catalyst (Co-Mo-Ni/Al 2 O 3 waste catalyst, HDS waste catalyst) resource chemical plant, for the waste catalyst recycling process, producing nickel-cobalt concentrate (including nickel Waste Catalyst (Blue Sludge (BS)), the annual processing capacity is estimated to be about 15,000 tons. Because the current technology and equipment of domestic manufacturers are not easy to handle, there is no recycling process for nickel-containing waste catalysts. The waste catalysts are treated by a stable solidification and landfill method or transported as raw materials for refining nickel. Not only the industry wastes commissioned processing costs, but also cannot recover limited metal resources, and retains metal resources for domestic reuse. In addition, for Taiwan, where land is narrow, the legal site for waste disposal is increasingly difficult to obtain, so nickel-cobalt concentrate resource recycling technology It is an urgent issue.
With the rapid growth of the economy in the country, energy demand is becoming more frequent. Among them, fuel oil must use fuel for industry and vehicles, and the amount of use is increasing. The problem of air pollution caused by the emission of sulfur oxides from automobile fuel oil after combustion is also becoming more and more serious. Therefore, how to reduce the sulfur oxides generated during combustion is a problem that domestic refineries and environmental protection units need to work on in advanced countries such as the United States. With Canada, the diesel sulfur content has been reduced from the original 500ppm to 15ppm and was implemented in June 2006. Molybdenum-cobalt catalyst is defined as the main catalyst used in hydrodesulfurization (HDS) in the petroleum industry. It is made of alumina (Al 2 O 3 ) colloid, dried and simmered. The high-porosity high surface area carrier is impregnation in a mixed solution containing ammonium molybdate and cobalt nitrate, dried, simmered, and immersed, so as to be repeated several times, and then subjected to a vulcanization treatment. The types of catalysts used by CNPC and Formosa Plastics in the desulfurization process include cobalt molybdenum, nickel molybdenum, cobalt molybdenum nickel, cobalt molybdenum vanadium nickel, etc., with aluminum or antimony as the main carrier, which will adsorb during the hydrodesulfurization process. Sulfur, carbon, vanadium ((V), iron, molybdenum (Mo), nickel (Ni), cobalt (Co) and other trace elements, after long-term use of the catalyst (6 to 24 months), due to heavy metals Impurities and sulfur will cause deposition and carbon deposition of metal sulfides (mainly V 3 S 4 , NiS, Ni 3 S 2 ) on the surface of the catalyst, causing physical damage, blockage and poisoning, and the catalyst will be lost. The activity reduces the catalytic function and needs to be periodically discharged to be discarded.
In general, the spent HDS catalyst contains cobalt, nickel, molybdenum, vanadium and other valuable metals, which are considered as resources for recycling. The recovery methods are generally alkali roasting, impregnation, and purification. The residue produced by solid-liquid separation after impregnation is nickel-cobalt concentrate (containing nickel waste catalyst, commonly known as Blue Sludge (BS)). At present, the current situation of waste catalyst recycling and nickel-cobalt concentrate (blue mud) The process flow for forming a nickel-containing waste catalyst is as shown in the first figure.
The treatment technology recycles valuable metals in nickel-cobalt concentrate to recover nickel and cobalt metal resources. Nickel metal is widely used, ranging from power plant components to coins used in everyday use. Cobalt metal can be used as permanent magnet, high speed steel, super hard tool, heat resistant wear resistant alloy, etc. Compounds are coatings, pigments, catalysts, chemicals, electroplating, battery materials, glazes and catalyst materials.
The recovery of alumina carriers is widely used in various fields, including grinding, refractory materials, catalyst carriers, composite materials, pottery and IC substrates. The related technologies for the recycling of waste hydrogenation desulfurization catalysts at home and abroad include the following:
1. The Republic of China New Patent No. 263795 discloses a device for sorting waste catalysts and mixed ceramic sphere media to enrich waste catalysts. However, the apparatus for sorting and exposing the waste catalyst and the mixed ceramic ball medium has no relationship with the method of the subject and the disclosure, and only provides a search process.
2. Republic of China Invention Patent No. I295691 discloses a resource regeneration method for waste denitrification catalyst, which utilizes alkali (Na 2 CO 3 ) 800 ° C high temperature roasting to recover vanadium and tungsten valuable metals through impregnation and solvent extraction processes. method. However, the valuable metals recovered by this method are less involved in the purpose of the case, and only provide a search history.
3. U.S. Patent No. 4,670,229 discloses a process for recovering valuable metals and alumina from waste catalysts. The waste hydrodesulfurization catalyst is wetted by adding NaOH (sodium hydroxide) / NaAlO 2 (sodium aluminate). The operating conditions are controlled to provide oxygen and a high temperature of at least 200 ° C to recover vanadium and molybdenum, and the resulting nickel and cobalt are reused by sulfuric acid impregnation recovery. The disadvantages of this recovery method are (1) and the current use of alkali in most of the world ( Na 2 CO 3 ) 800 ° C high temperature roasting process of waste hydrodesulfurization catalyst is different (currently three domestic waste catalyst recycling companies use this method to recover vanadium and molybdenum), so the residue produced by this US patent method is presumed to be oxidation Nickel NiO and cobalt oxide CoO are not the spinel crystal structures of NiAl 2 O 4 , NiFe 2 O 4 and CoAl 2 O 4 which are produced by the calcination of the base. (2) Relative energy consumption (200 ° C and oxygen supply) and carbon dioxide production (CO 2 ) are compared with the method of the present invention.
4. U.S. Patent No. 5,445,728 discloses a waste catalyst process for recovering alumina based on high temperature dry treatment to control the atmosphere (baking temperature, time and oxygen partial pressure atmosphere). The disadvantage of this method is relative energy consumption and mass. Carbon emissions.
5. U.S. Patent No. 4,657,745 discloses an aluminum-based waste hydrodesulfurization catalyst recovery method using an autoclave to add 98% concentrated sulfuric acid, hydrogen sulfide and water to control the atmosphere (temperature, oxygen and pressure). Then, the nickel-cobalt filtrate is recovered by washing with water and cation exchange resin. The disadvantage of this method is the concern and energy consumption of relatively high temperature and high pressure operation.
6. On the Internet, query the recycling process of waste catalyst recycling in the commercial operation of Gulf Chemical Company of the United States. For the recovery of nickel and cobalt residues after vanadium (V 2 O 5 ) and molybdenum (MoO 3 ), the arc is utilized. The furnace is heated to coke (Coke) to form a nickel-cobalt alloy. This method has the disadvantage of relatively energy consumption and a large amount of carbon emissions. Moreover, the use of electric arc furnace to add coke (high temperature smelting) as a nickel-cobalt alloy material, pigment, coating application, but the disadvantages of high-temperature smelting energy consumption, a large amount of carbon emissions and pigment and coating chromaticity unevenness is not easy to control.
In addition to the above-mentioned various recovery methods and equipment, apart from being less relevant to the case, the purpose of recovering valuable metals is less involved in this case, and there are problems in the previous disclosure, but it is not easy to use the tradition based on literature and theory. The dry calcination treatment and the traditional wet acid leaching process for the dissolution of nickel and cobalt target metals achieve the purpose and demand for valuable metal recovery. Therefore, most of the current conditions are sent to the smelting plant for refining to nickel raw materials or mining and burial treatment. Not only do they have environmental concerns, high-temperature smelting energy consumption, and the inability to recover valuable metal resources (nickel and cobalt).
有鑑於先前技術之問題，本發明人研發將廢加氫脫硫觸媒中鎳鈷精礦(含鎳廢觸媒，俗稱藍泥Blue Sludge(BS))資源化回收方法，以濕式冶金技術為基礎，採逆流方式回收鈷、鎳有價金屬，不僅沒有乾式焙燒高耗能與二氧化碳排放缺點，利用自身放熱反應更能響應世界節能減碳新趨勢新穎性之創新技術。此外，協助業者節省委託處理費用、回收有限的金屬資源，並將鎳鈷金屬資源留置國內再利用。創造鎳鈷精礦(含鎳廢觸媒，俗稱藍泥Blue Sludge(BS))回收有價金屬再利用價值，達到鎳鈷精礦資源化最大經濟價值與誘因。
為達此一目的，本發明設計一種廢加氫脫硫觸媒中鎳鈷精礦資源化回收方法，該鎳鈷精礦包括以鋁為載體之鋁成分，其步驟至少包括為：
(1)鎳鈷精礦烘乾、研磨與過篩：
將鎳鈷精礦經烘乾、研磨並且過篩在符合ASTM篩號#30~ #70區間的粒徑範圍取得過篩物；
(2)氧化反應：
將(1)步驟之過篩物置於一反應槽：在反應槽中添加強氧化劑，令鎳鈷精礦重量與強氧化劑體積比例為，於每1公升之強氧化劑，少於或等於1公斤之鎳鈷精礦，並攪拌，反應時間至少30分鐘；
(3)加酸反應：待(2)步驟攪拌後，再添加強酸酸液於反應槽中，令鎳鈷精礦重量與該強酸酸液體積比例為，於每1公升之強酸酸液，少於或等於1公斤之鎳鈷精礦；持續攪拌，反應時間至少30分鐘；
(4)逆向噴水反應：於(3)步驟攪拌後，徐緩噴水於反應槽中，令鎳鈷精礦重量與該水體積比例為，於每1公升之水，少於或等於1公斤之鎳鈷精礦；持續攪拌，反應時間至少30分鐘；
(5)反應完成後進行固液分離：
固相冷卻後形成硫酸鋁副產物，液相之鎳鈷濾液則進行溶媒萃取分離純化程序；
(6)溶媒萃取(Solvent Extraction)分離純化程序：鎳鈷濾液添加濃度至少為濃度20%的二烷基膦酸(CYANEX272)為萃取劑，進行溶媒萃取分離純化回收鎳與鈷，利用硫酸進行反萃取(Stripping)，調整pH為3.0～5.0，形成硫酸鎳溶液，至於鈷回收，則利用濃度至少4M的硫酸調整pH為0～1。
本發明主要在於將鎳鈷精礦(藍泥Blue Sludge(BS))研磨成粉狀，採用濕式冶金逆流、反向方式處理，該稱「逆流」或稱「反向」，係指與傳統上之強酸液(尤其是硫酸)與水配置過程中，以強酸液加入水中之操作手法呈相反，即本發明係以水加入強酸液中。惟，本發明以徐緩並控制入水，避免其大量放熱之危險。從而，本發明突破傳統濕法冶金酸浸漬金屬回收率偏低方式，使用強酸液與強氧化劑及水，能有效破壞鎳鈷精礦尖晶石結構，並利用強酸液(尤其是硫酸)與水配置過程中，自身放熱反應來促進反應進行，不僅大幅節能，更可使鈷回收率達到85%，鎳回收率更達到95%。且本發明以濕式冶金技術為基礎回收鈷、鎳，不僅沒有乾式焙燒二氧化碳排放缺點，利用自身放熱反應更能響應世界節能減碳趨勢。In view of the problems of the prior art, the inventors have developed a method for recycling nickel-cobalt concentrate (a nickel-containing waste catalyst, commonly known as Blue Sludge (BS)) in a waste hydrodesulfurization catalyst, using wet metallurgy technology. On the basis of this, the reverse-flow method is used to recover cobalt and nickel valuable metals. It not only has no disadvantages of dry calcination, high energy consumption and carbon dioxide emissions, but also uses its own exothermic reaction to respond to the novelty of the new trend of energy saving and carbon reduction in the world. In addition, it helps the operator to save commissioned processing costs, recover limited metal resources, and retain nickel-cobalt metal resources for domestic reuse. The creation of nickel-cobalt concentrate (containing nickel waste catalyst, commonly known as Blue Sludge (BS)) to recover the valuable value of valuable metals, to achieve the maximum economic value and incentives for the recycling of nickel-cobalt concentrate.
To achieve the above objective, the present invention provides a method for recycling nickel-cobalt concentrate in a waste hydrodesulfurization catalyst, the nickel-cobalt concentrate comprising an aluminum component based on aluminum, the steps of which include at least:
(1) Drying, grinding and sieving of nickel-cobalt concentrate:
The nickel-cobalt concentrate is dried, ground and sieved to obtain a sieve in a particle size range conforming to the ASTM sieve number #30 to #70;
(2) Oxidation reaction:
The sieve of the step (1) is placed in a reaction tank: a strong oxidant is added to the reaction tank, and the ratio of the weight of the nickel-cobalt concentrate to the volume of the strong oxidant is, and the oxidant per 1 liter is less than or equal to 1 kg. Nickel-cobalt concentrate, and stirred, the reaction time is at least 30 minutes;
(3) Adding acid reaction: After the step (2) is stirred, a strong acid acid solution is added to the reaction tank, so that the weight ratio of the nickel-cobalt concentrate to the strong acid acid solution is less than 1 liter of strong acid acid solution. At or equal to 1 kg of nickel-cobalt concentrate; continuous stirring, reaction time of at least 30 minutes;
(4) Reverse water spray reaction: After stirring in step (3), slowly spray water in the reaction tank so that the weight ratio of nickel-cobalt concentrate to the water volume is less than or equal to 1 kg of nickel per 1 liter of water. Cobalt concentrate; continuous stirring, reaction time of at least 30 minutes;
(5) Solid-liquid separation after completion of the reaction:
After the solid phase is cooled, a by-product of aluminum sulfate is formed, and the nickel-cobalt filtrate in the liquid phase is subjected to a solvent extraction separation and purification procedure;
(6) Solvent Extraction separation and purification procedure: nickel-cobalt filtrate is added with a concentration of at least 20% dialkylphosphonic acid (CYANEX272) as an extractant, and solvent extraction, purification and recovery of nickel and cobalt, using sulfuric acid for reverse Stripping, adjusting the pH to 3.0-5.0 to form a nickel sulfate solution, and for cobalt recovery, adjusting the pH to 0 to 1 with sulfuric acid having a concentration of at least 4M.
The invention mainly consists in grinding a nickel-silica concentrate (Blue Sludge (BS)) into a powder form, and adopts a wet metallurgy countercurrent or reverse manner treatment. The term "countercurrent" or "reverse" refers to the tradition. In the process of disposing a strong acid solution (especially sulfuric acid) and water, the operation of adding a strong acid solution to water is reversed, that is, the present invention is added with water into a strong acid solution. However, the present invention slows down and controls the ingress of water to avoid the risk of a large amount of heat release. Therefore, the invention breaks through the low recovery mode of the traditional hydrometallurgical acid impregnated metal, and the strong acid liquid and the strong oxidant and water can effectively destroy the structure of the nickel-cobalt concentrate spinel, and utilize the strong acid liquid (especially sulfuric acid) and water. During the configuration process, the self-heating reaction promotes the reaction, which not only saves a lot of energy, but also achieves a cobalt recovery rate of 85% and a nickel recovery rate of 95%. Moreover, the invention recovers cobalt and nickel based on the wet metallurgy technology, and has the disadvantages of not only the dry roasting carbon dioxide emission, but also the self-heating reaction to respond to the world energy saving and carbon reduction trend.
以下配合圖式之輔助，說明本發明之內容、特色與實施例，俾使貴審查委員更進一步瞭解。
首先，請配合參閱第三圖所示，本發明之實施步驟為：
(1)鎳鈷精礦烘乾、研磨與過篩：
將鎳鈷精礦經烘乾、研磨並且過篩在符合ASTM篩號#30~ #70區間的粒徑範圍取得過篩物；在研磨過程與過篩過程中所使用的破碎研磨機具可以為顎碎機、碎礦機、搗礦機、研磨機、轉磨機或磨礦機。至於過篩機具則可以為震動搖篩機、搖動篩、定篩、轉篩或標準篩進行。
(2)氧化反應：
將(1)步驟之過篩物置於一反應槽：在反應槽中添加強氧化劑，令鎳鈷精礦重量與強氧化劑體積比例為，於每1公升之強氧化劑，少於或等於1公斤之鎳鈷精礦，並攪拌，反應時間至少30分鐘；該強氧化劑可以為過氧化氫(Hydrogen Peroxide，H2
O2
)、過硫酸鈉(Sodium Persulfate，Na2
S2
O8
)、高錳酸鉀(Potassium Permanganate，KMnO4
)、重鉻酸鉀(Potassium Dichromate，K2
Cr2
O7
)或硝酸(Nitric Acid，HNO3
)。
(3)加酸反應：待(2)步驟攪拌後，再添加強酸酸液於反應槽中，令鎳鈷精礦重量與該強酸酸液體積比例為，於每1公升之強酸酸液，少於或等於1公斤之鎳鈷精礦；持續攪拌，反應時間至少30分鐘。
(4)逆向噴水反應：於(3)步驟攪拌後，徐緩噴水於反應槽中，其中步驟(4)逆向噴水反應中所添加的噴水可以為回收製程中之循環水、熱水、淨化水。令鎳鈷精礦重量與該水體積比例為，於每1公升之水，少於或等於1公斤之鎳鈷精礦；持續攪拌，反應時間至少30分鐘。
(5)反應完成後進行固液分離：
固相冷卻後形成硫酸鋁副產物，液相之鎳鈷濾液則進行溶媒萃取分離純化程序。
(6)溶媒萃取(Solvent Extraction)分離純化程序：鎳鈷濾液添加濃度至少為濃度20%的二烷基膦酸(CYANEX272)為萃取劑，進行溶媒萃取分離純化回收鎳與鈷，利用硫酸進行反萃取(Stripping)，調整pH為3.0～5.0，形成硫酸鎳溶液，至於鈷回收，則利用濃度至少4M的硫酸調整pH為0～1。
本發明將鎳鈷精礦研磨成粉狀，採用濕式冶金方式，噴水於酸液(尤其硫酸)浸漬液中之逆流方式，可以突破傳統酸浸漬回收率不高方式之問題，而利用強酸加氧化劑及噴水，有效破壞尖晶石結構，以自身放熱反應促進反應進行，加上後段的溶媒萃取純化反應，因此本發明之資源化處理流程，不僅可以節能，更能夠使鈷回收率達到85%以上，鎳回收率達到95%以上。
更重要者，以本發明此種濕式冶金技術為基礎回收鈷、鎳，不僅沒有乾式焙燒高耗能與二氧化碳排放缺點，利用自身放熱反應更能響應世界節能減碳新趨勢新穎性之創新技術，在產業上達到回收有限的金屬資源，節省委託處理費用，更能響應世界節能減碳新趨勢新穎性之創新技術，達到鎳鈷精礦資源化最大經濟價值與誘因。
至於本發明之實際操作過程與結果如下：
取業者將回收廢加氫脫硫觸媒(HDS)中釩、鉬後，殘留固體殘渣(鎳鈷精礦，含鎳廢觸媒，俗稱藍泥Blue Sludge(BS))樣品之pH分析結果如表1所示，由於經鹼焙燒處理為鹼性產物-鎳鈷精礦。其三成分如表2所示，其XRD分析結果如第二圖所示，其ICP-OES全量基本分析結果如表3所示；
表1. 鎳鈷精礦樣品之pH基本分析結果
分析過程為環保署公告NIEA R208.03C－廢棄物氫離子濃度指數(pH)測定方法。
表2. 鎳鈷精礦樣品之三成份基本分析結果
表3. 鎳鈷精礦樣品之ICP-OES全量基本分析結果
包括鎳鈷精礦(含鎳廢觸媒，俗稱藍泥Blue Sludge(BS))經烘乾研磨在符合ASTM之篩號#30~ 篩號#70區間的粒徑範圍，之後在添加1.強氧化劑H2
O2
+2.濃硫酸H2
SO4
+3.噴水H2
O，操作條件為添加雙氧水之固液比(50g的藍泥/100ml的雙氧水=1/2)與反應時間(30 min)，攪拌均勻後再添加濃硫酸同樣固液比維持(50g的藍泥/100ml的98%濃硫酸=1/2)與反應時間(30 min)，攪拌均勻後，之後再滴加熱水之同樣維持固液比(50g的藍泥/100ml的熱水=1/2)與反應時間(30 min)，實驗完成後，進行固液分離，固相冷卻後形成硫酸鋁副產物。液相則進行溶媒萃取分離純化程序，添加濃度為20%的萃取劑Cyanex272，實驗操作條件為調整O/A油水比為1/1、操作溫度為40℃、轉速為1,200rpm、接觸時間為30分鐘、pH為6.0，進行溶媒萃取分離純化回收鎳與鈷，利用硫酸進行反萃，調整pH為4.0，形成硫酸鎳溶液，鎳的回收率約達95%，至於鈷的回收，則利用濃度4M的硫酸調整pH為0.2，鈷的回收率約為85%，本發明之含鎳廢觸媒資源化濕式回收處理實施步驟流程圖如第三圖所示，處理後之質量平衡圖如第四圖所示。
經由上述說明可知，本發明具有以下各項優點：
一、依據本發明方法，突破傳統利用乾式高溫冶煉回收鎳鈷精礦，不僅節能與無二氧化碳排放，更能響應世界節能減碳新趨勢新技術。且改進傳統濕法冶金浸漬率偏低的回收率，採用逆流方式能有效破壞其尖晶石結構，以自身放熱反應來促進反應的進行，加上後段的溶媒萃取純化反應，此資源化處理流程不僅節能，更可使鈷回收率達到85%以上，鎳回收率達到95%以上。
二、本發明不僅大幅節省業者委託處理費用與有效解決國內掩埋場不易取得之窘竟，且回收有限的金屬資源，並將有價的金屬資源留置國內再利用。
三、本發明不需改變現有業者之回收處理流程，且相較於乾式冶煉回收設施，採濕式回收鎳鈷，產生更大經濟效益與誘因。四、本發明所提供之資源化回收方法可應用於各種具尖晶石構造之廢棄物(如煉鋼煙塵、煉銅煙塵、焚化飛灰等)資源化方面。
綜上所述，本發明誠已符合發明專利申請要件，爰依法提出發明專利之申請，懇請惠予審查，並早日賜準專利，實感德澤。The contents, features and embodiments of the present invention will be described with reference to the accompanying drawings, which will enable the reviewing committee to further understand.
First, please refer to the third figure, the implementation steps of the present invention are:
(1) Drying, grinding and sieving of nickel-cobalt concentrate:
The nickel-cobalt concentrate is dried, ground and sieved to obtain a sieve in a particle size range conforming to the ASTM sieve number #30 to #70; the crushing and grinding machine used in the grinding process and the screening process may be 颚Shredders, crushers, boring mills, grinders, turning mills or grinding machines. As for the sifting machine, it can be carried out for a vibrating shaker, a shaker screen, a sieve, a sieve or a standard sieve.
(2) Oxidation reaction:
The sieve of the step (1) is placed in a reaction tank: a strong oxidant is added to the reaction tank, and the ratio of the weight of the nickel-cobalt concentrate to the volume of the strong oxidant is, and the oxidant per 1 liter is less than or equal to 1 kg. Nickel-cobalt concentrate, stirred and reacted for at least 30 minutes; the strong oxidant may be hydrogen peroxide (H 2 O 2 ), sodium persulfate (Na 2 S 2 O 8 ), permanganic acid Potassium (Potassium Permanganate, KMnO 4 ), Potassium Dichromate (K 2 Cr 2 O 7 ) or Nitric Acid (HNO 3 ).
(3) Adding acid reaction: After the step (2) is stirred, a strong acid acid solution is added to the reaction tank, so that the weight ratio of the nickel-cobalt concentrate to the strong acid acid liquid is, in the strong acid liquid per 1 liter, less At or equal to 1 kg of nickel-cobalt concentrate; continuous stirring, the reaction time is at least 30 minutes.
(4) Reverse water spray reaction: After stirring in the step (3), the spray water is slowly sprayed in the reaction tank, wherein the spray water added in the reverse spray water reaction in the step (4) may be circulating water, hot water and purified water in the recovery process. The ratio of the weight of the nickel-cobalt concentrate to the volume of the water is, for every 1 liter of water, less than or equal to 1 kilogram of nickel-cobalt concentrate; continuous stirring, the reaction time is at least 30 minutes.
(5) Solid-liquid separation after completion of the reaction:
After the solid phase is cooled, a by-product of aluminum sulfate is formed, and the nickel-cobalt filtrate in the liquid phase is subjected to a solvent extraction separation and purification procedure.
(6) Solvent Extraction separation and purification procedure: nickel-cobalt filtrate is added with a concentration of at least 20% dialkylphosphonic acid (CYANEX272) as an extractant, and solvent extraction, purification and recovery of nickel and cobalt, using sulfuric acid for reverse Stripping, adjusting the pH to 3.0-5.0 to form a nickel sulfate solution, and for cobalt recovery, adjusting the pH to 0 to 1 with sulfuric acid having a concentration of at least 4M.
The invention pulverizes the nickel-cobalt concentrate into a powder form, adopts a wet metallurgy method, and sprays water in a countercurrent manner in an acid liquid (especially sulfuric acid) impregnation liquid, which can break through the problem that the traditional acid impregnation recovery rate is not high, and utilizes strong acid addition. The oxidant and water spray effectively destroy the spinel structure, promote the reaction by its own exothermic reaction, and add the solvent extraction and purification reaction in the latter stage. Therefore, the resource treatment process of the present invention can not only save energy but also achieve a cobalt recovery rate of 85%. Above, the nickel recovery rate is over 95%.
More importantly, based on the wet metallurgy technology of the present invention, cobalt and nickel are recovered, and there is no shortage of dry calcination, high energy consumption and carbon dioxide emission, and the use of self-heating reaction can respond to the novelty of the world's new trend of energy saving and carbon reduction. In the industry, it can achieve the recovery of limited metal resources, save on commissioned processing costs, and respond to the world's innovative new technologies of energy saving and carbon reduction, and achieve the maximum economic value and incentives for the recycling of nickel-cobalt concentrates.
As for the actual operation process and results of the present invention, the following are as follows:
After the recycler recovers the vanadium and molybdenum in the waste hydrodesulfurization catalyst (HDS), the pH analysis results of the residual solid residue (nickel-cobalt concentrate, nickel-containing waste catalyst, commonly known as Blue Sludge (BS)) As shown in Table 1, it was treated as a basic product-nickel-cobalt concentrate by alkali calcination. The three components are shown in Table 2, and the results of XRD analysis are shown in the second figure. The results of the basic analysis of ICP-OES total are shown in Table 3;
Table 1. Basic pH analysis results for nickel-cobalt concentrate samples
The analysis process is the EPA's announcement of NIEA R208.03C - Waste Hydrogen Ion Concentration Index (pH) determination method.
Table 2. Basic analysis results of three components of nickel-cobalt concentrate samples
Table 3. Basic analysis results of ICP-OES for nickel-cobalt concentrate samples
Including nickel-cobalt concentrate (containing nickel waste catalyst, commonly known as Blue Sludge (BS)) after drying and grinding in the particle size range in accordance with ASTM sieve #30~ sieve #70 interval, after adding 1. strong Oxidant H 2 O 2 +2. Concentrated sulfuric acid H 2 SO 4 +3. Water spray H 2 O, operating conditions are the solid-liquid ratio of adding hydrogen peroxide (50g of blue mud / 100ml of hydrogen peroxide = 1/2) and reaction time (30 Min), after mixing evenly, add concentrated sulfuric acid and maintain the same solid-liquid ratio (50g blue mud / 100ml 98% concentrated sulfuric acid = 1/2) and reaction time (30 min), stir evenly, then drip the heated water Also maintain the solid-liquid ratio (50g of blue mud / 100ml of hot water = 1/2) and reaction time (30 min), after the completion of the experiment, solid-liquid separation, solid phase cooling to form aluminum sulfate by-product. In the liquid phase, the solvent extraction and purification procedure was carried out, and the extractant Cyanex272 with a concentration of 20% was added. The experimental operating conditions were adjusted O/A oil-water ratio to 1/1, operating temperature was 40 ° C, rotation speed was 1,200 rpm, and contact time was 30. Minutes, pH 6.0, solvent extraction separation and purification of nickel and cobalt, stripping with sulfuric acid, adjusting the pH to 4.0, forming a nickel sulfate solution, the recovery of nickel is about 95%, as for the recovery of cobalt, the concentration of 4M The sulfuric acid adjusted pH is 0.2, and the recovery rate of cobalt is about 85%. The flow chart of the implementation steps of the nickel-containing waste catalyst resource-based wet recycling process of the present invention is shown in the third figure, and the mass balance diagram after treatment is as shown in the fourth figure. The figure shows.
As can be seen from the above description, the present invention has the following advantages:
First, according to the method of the present invention, the traditional use of dry high-temperature smelting to recover nickel-cobalt concentrate is not only energy-saving and carbon dioxide-free, but also more responsive to the world's new energy-saving and carbon-reduction technologies. Moreover, the recovery rate of the traditional hydrometallurgical impregnation rate is improved, and the counter-current method can effectively destroy the spinel structure, and the self-exothermic reaction is used to promote the reaction, and the solvent extraction and purification reaction in the latter stage is used. Not only energy saving, but also the cobalt recovery rate of more than 85%, nickel recovery rate of more than 95%.
Second, the invention not only greatly saves the commissioned processing fee of the operator and effectively solves the problem that the domestic landfill is difficult to obtain, but also recovers limited metal resources, and retains the valuable metal resources for domestic use.
Third, the present invention does not need to change the recycling process of the existing industry, and compared with the dry smelting and recycling facility, the wet recovery of nickel and cobalt produces greater economic benefits and incentives. 4. The resource recovery method provided by the invention can be applied to the resource utilization of various spinel-structured wastes (such as steelmaking soot, copper-smelting soot, incineration fly ash, etc.).
In summary, the invention has met the requirements of the invention patent application, and the application for the invention patent was filed according to law, and the application was granted for review, and the patent was granted as soon as possible.
第一圖為目前廢觸媒資源化回收處理現況與鎳鈷精礦(藍泥)(含鎳廢觸媒)形成之流程圖。
第二圖為本發明實做過程取鎳鈷精礦樣品XRD分析結果。
第三圖為本發明實施例之含鎳廢觸媒資源化濕式回收處理實施步驟流程圖。
第四圖為本發明實施例之含鎳廢觸媒資源化濕式回收處理結果質量平衡圖。The first picture shows the current situation of the current situation of waste catalyst recycling and the formation of nickel-cobalt concentrate (blue mud) (including nickel waste catalyst).
The second figure shows the results of XRD analysis of nickel-cobalt concentrate samples taken in the actual process of the present invention.
The third figure is a flow chart of the steps for implementing the wet recycling process of the nickel-containing waste catalyst in the embodiment of the present invention.
The fourth figure is a mass balance diagram of the results of the wet recycling process of the nickel-containing waste catalyst in the embodiment of the present invention.
Claims (3)
(1)鎳鈷精礦烘乾、研磨與過篩：
將鎳鈷精礦經烘乾、研磨並且過篩在符合ASTM篩號#30~ #70區間的粒徑範圍取得過篩物；
(2)氧化反應：
將(1)步驟之過篩物置於一反應槽：在反應槽中添加強氧化劑，令鎳鈷精礦重量與強氧化劑體積比例為，於每1公升之強氧化劑，少於或等於1公斤鎳鈷精礦，並攪拌，反應時間至少30分鐘；
(3)加酸反應：
待(2)步驟攪拌後，再添加強酸酸液於反應槽中，令鎳鈷精礦重量與該強酸酸液體積比例為，於每1公升之強酸酸液，少於或等於1公斤之鎳鈷精礦；持續攪拌，反應時間至少30分鐘；
(4)逆向噴水反應：
於(3)步驟攪拌後，徐緩噴水於反應槽中，令鎳鈷精礦重量與該水體積比例為，於每1公升之水，少於或等於1公斤之鎳鈷精礦；持續攪拌，反應時間至少30分鐘；
(5)反應完成後進行固液分離：
固相冷卻後形成硫酸鋁副產物，液相之鎳鈷濾液則進行溶媒萃取分離純化程序；
(6)溶媒萃取(Solvent Extraction)分離純化程序：
鎳鈷濾液添加濃度至少為濃度20%的二烷基膦酸(CYANEX272)為萃取劑，進行溶媒萃取分離純化回收鎳與鈷，利用硫酸進行反萃取(Stripping)，調整pH為3.0～5.0，形成硫酸鎳溶液，至於鈷回收，則利用濃度至少4M的硫酸調整pH為0～1。A method for recycling nickel-cobalt concentrate in waste hydrodesulfurization catalyst, the nickel-cobalt concentrate comprising aluminum component supported by aluminum, the steps comprising at least:
(1) Drying, grinding and sieving of nickel-cobalt concentrate:
The nickel-cobalt concentrate is dried, ground and sieved to obtain a sieve in a particle size range conforming to the ASTM sieve number #30 to #70;
(2) Oxidation reaction:
The sieve of the step (1) is placed in a reaction tank: a strong oxidant is added to the reaction tank so that the weight ratio of the nickel-cobalt concentrate to the strong oxidant is, for every 1 liter of the strong oxidant, less than or equal to 1 kg of nickel. Cobalt concentrate, and stirred, the reaction time is at least 30 minutes;
(3) Adding acid reaction:
After the step (2) is stirred, a strong acid acid solution is added to the reaction tank, so that the weight ratio of the nickel-cobalt concentrate to the strong acid acid liquid is, in the strong acid liquid per 1 liter, less than or equal to 1 kg of nickel. Cobalt concentrate; continuous stirring, reaction time of at least 30 minutes;
(4) Reverse water spray reaction:
After stirring in step (3), slowly spray water into the reaction tank so that the weight ratio of the nickel-cobalt concentrate to the water volume is less than or equal to 1 kg of nickel-cobalt concentrate per 1 liter of water; continuous stirring, The reaction time is at least 30 minutes;
(5) Solid-liquid separation after completion of the reaction:
After the solid phase is cooled, a by-product of aluminum sulfate is formed, and the nickel-cobalt filtrate in the liquid phase is subjected to a solvent extraction separation and purification procedure;
(6) Solvent Extraction separation and purification procedures:
The nickel-cobalt filtrate is added with a concentration of at least 20% dialkylphosphonic acid (CYANEX272) as an extractant, and the solvent is extracted and purified to recover nickel and cobalt, and stripping is performed by using sulfuric acid to adjust the pH to 3.0-5.0. The nickel sulfate solution, as for cobalt recovery, is adjusted to a pH of 0 to 1 using sulfuric acid having a concentration of at least 4M.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5722119A (en) * | 1980-07-14 | 1982-02-05 | Mitsubishi Steel Mfg Co Ltd | Recovering process of value from waste catalyst for hydrogenation and desulfurization of petroleum |
| US4657745A (en) * | 1986-03-31 | 1987-04-14 | Chemical & Metal Industries, Inc. | Value recovery from spent alumina-base catalyst |
| US20010001650A1 (en) * | 1999-03-09 | 2001-05-24 | William P.C. Duyvesteyn | Recovery of nickel and cobalt from ore |
| US20040050212A1 (en) * | 2000-09-15 | 2004-03-18 | Cheng Chu Yong | Solvent extraction process for recovering nickel and cobalt from each solutions |
| TW200607867A (en) * | 2004-08-02 | 2006-03-01 | Skye Resources Inc | Method for nickel and cobalt recovery from laterite ores by combination of atmospheric and moderate pressure leaching |
| US20080131343A1 (en) * | 2006-09-14 | 2008-06-05 | Albemarle Netherlands B.V. | Process for recovering group vib metals from a catalyst |
-
2010
- 2010-02-02 TW TW99103076A patent/TWI401213B/en active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5722119A (en) * | 1980-07-14 | 1982-02-05 | Mitsubishi Steel Mfg Co Ltd | Recovering process of value from waste catalyst for hydrogenation and desulfurization of petroleum |
| US4657745A (en) * | 1986-03-31 | 1987-04-14 | Chemical & Metal Industries, Inc. | Value recovery from spent alumina-base catalyst |
| US20010001650A1 (en) * | 1999-03-09 | 2001-05-24 | William P.C. Duyvesteyn | Recovery of nickel and cobalt from ore |
| US20040050212A1 (en) * | 2000-09-15 | 2004-03-18 | Cheng Chu Yong | Solvent extraction process for recovering nickel and cobalt from each solutions |
| TW200607867A (en) * | 2004-08-02 | 2006-03-01 | Skye Resources Inc | Method for nickel and cobalt recovery from laterite ores by combination of atmospheric and moderate pressure leaching |
| US20080131343A1 (en) * | 2006-09-14 | 2008-06-05 | Albemarle Netherlands B.V. | Process for recovering group vib metals from a catalyst |
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| TW201127753A (en) | 2011-08-16 |
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