从氯化铵水溶液中沉淀回收钼的研究

Masakazu Niinae, Tasuma Suzuki, A. Fuji, Nanae Matsunaga, J. Shibata
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引用次数: 3

摘要

催化剂广泛应用于石油炼制和化学工业。加氢脱硫(HDS)催化剂约占全球催化剂总消费量的三分之一。废HDS催化剂在氧化铝载体上含有钼、钒、镍和钴等稀有金属。在二次资源中,废HDS催化剂被认为是回收这些金属最重要的催化剂,因为它们不仅数量大、经济价值高,而且处理后还会引起环境问题。在大多数情况下,用湿法-变态反应法处理催化剂,如碱浸和酸浸,焙烧作为预处理步骤。在碱浸过程中,大部分钼和钒选择性地浸出于铝、镍和钴之上。采用溶剂萃取和沉淀汽提两阶段工艺从钼中分离钒。在pH约为4的条件下,用三正辛胺(TOA)同时提取钼和钒,然后用铵盐溶液剥离钼和钒。汽提过程中,单钒在pH > 8时以十水十氰酸四铵二钠铵盐的形式析出。本研究采用沉淀法从氯化铵水溶液中回收钼。钼与氯化铵在pH低于4时可析出为五水八钼酸四铵,且析出的pH区随温度的升高而增大。并对氯化钡和氯化钙对钼的沉淀进行了研究。
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A Study on Precipitation Recovery of Molybdenum from Aqueous Solutions of Ammonium Chloride
Catalysts are widely used in petroleum refining and chemical industries. Hydrodesulphurization (HDS) catalysts account for about one third of the total worldwide catalyst consumption. Spent HDS catalysts contain rare metals such as molybdenum, vanadium, nickel and cobalt on an alumina carrier. Among secondary resources, spent HDS catalysts are regarded the most important catalysts for recycling these metals due to not only their large amounts and economic values, but also the environmental concerns if disposed off. In most cases, spent catalysts are treated with hydromet- allurgical leaching processes such as caustic leaching and acid leaching with roasting as a pre-treatment step. In the alkaline leaching processes, most of the molybdenum and vanadium are selectively leached over aluminum, nickel and cobalt. Vanadium can be separated from molybdenum with a two stage process based on solvent extraction and precipitation stripping. Molybdenum and vanadium are simultaneously extracted with tri-n-octylamine (TOA) at around pH 4 followed by stripping of molybdenum and vanadium with ammonium salt solutions. In the stripping process, vanadium alone is precipitated as ammonium salts of tetraammonium disodium decavanadate decahydrate at pH > 8. In the present study, precipitation method was carried out to recovery of molybdenum from aqueous solutions of ammonium chloride. Molybdenum could be precipitated as tetraammonium octamolybdate pentahydrate with ammo- nium chloride at the pH below 4 and the pH region of precipitation increased with increase of temperature. And also, the precipitation of molybdenum with barium chloride and calcium chloride was also investigated.
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