WO2007071108A1

WO2007071108A1 - Process of produceing superfine cobalt powder with circulation technology and its apparatus

Info

Publication number: WO2007071108A1
Application number: PCT/CN2005/002265
Authority: WO
Inventors: Kaihua Xu
Original assignee: Shenzhen Gem High-Tech Joint-Stock Co., Ltd.; Jingmen Gem New Material Co., Ltd.
Priority date: 2005-12-21
Filing date: 2005-12-21
Publication date: 2007-06-28

Abstract

A process of producing superfine cobalt powder with circulation technology is provided, which synthesizes Co-compound precursor by means of twice extracting and atomization hydrolyzing, then the Co-compound precursor is subjected to explosion and thermal reduction at sectional temperatures to effectively obtain 0.1-2µm superfine cobalt powder from waste material containing cobalt. The said production process uses spent batteries as start material, and emits no waste water or exhaust gas during the process. The spheric or like-spheric and fiberous cobalt powder obtained by the said process is suitable for the manufacture of power battery and high performance powder metallurgy articles and helpful to increase the quality and service life of products. The cobalt powder produced by present invention has uniform particle distribution, good product consistence, adjustable particle shape, size or apparent density, low carbon content and good product quality. The apparatus used for said process is also provided in the present invention, which has simple structure and lowered cost.

Description

循环枝太生产超细钴粉的制造方法与设备技术领域 Method and device for manufacturing ultra-fine cobalt powder

本发明提供一种钴粉的制造方法，尤其是一种循环技术生产超细钴粉的制造方法；本发明进一步的目的在于提供上述制造方法所用的设备。 The present invention provides a method for producing cobalt powder, and more particularly to a method for producing ultrafine cobalt powder by a recycling technique; it is a further object of the present invention to provide an apparatus for the above manufacturing method.

背景技术 Background technique

金属钴粉是世界公认的战略金属材料，几十年来，一直是伦敦金属期货交易所的座上客。近五年来，由于金属钴粉在高能电池、硬质合金、军工等领域的大量使用，导致世界性的钴紧张。可以说，谁掌握钴的资源及其相关产品的制造技术，谁就掌握了化学能源、通讯、军工等众多关键工业领域的主动权。 Metallic cobalt powder is recognized as a strategic metal material in the world and has been a guest of the London Metal Futures Exchange for decades. In the past five years, due to the large-scale use of metallic cobalt powder in high-energy batteries, cemented carbide, military and other fields, the world's cobalt has been strained. It can be said that whoever masters the manufacturing technology of cobalt resources and related products, who has mastered the initiative in many key industrial fields such as chemical energy, communications, and military industry.

超细钴粉材料是本世纪新材料领域的先进代表之一。超细钴粉是用作高能电池、高强度硬质合金和军工器械生产的关键材料，被誉为现代工业味精。 Ultrafine cobalt powder material is one of the advanced representatives in the field of new materials in this century. Ultrafine cobalt powder is used as a key material in the production of high-energy batteries, high-strength cemented carbide and military equipment, and is known as modern industrial MSG.

锂离子电池含钴达 40%以上，镍氢电池含钴达 10%以上，因此，钴成为决定锂离子电池等新型化学能源成本的关键材料。 Lithium-ion batteries contain more than 40% cobalt, and nickel-hydrogen batteries contain more than 10% cobalt. Therefore, cobalt is a key material for determining the cost of new chemical energy sources such as lithium-ion batteries.

有资料显示，地球上的钴资源的储量有限，估计可供使用 60-70年。我国是贫钴国家，我国使用量的 80 %来源于南非，近年来，随着中国大量从南非进口钴的资源，南非政府已经开始限制，因此，如同石油一样，钴资源严重短缺。一年半来，钴价已经从 15万元 /吨狂涨到 35万元 /吨。 According to information, the reserves of cobalt resources on the earth are limited and are estimated to be available for 60-70 years. China is a cobalt-poor country. 80% of China's use comes from South Africa. In recent years, with the large amount of cobalt resources imported from South Africa, the South African government has begun to restrict. Therefore, like oil, there is a serious shortage of cobalt resources. In the past year and a half, the price of cobalt has risen from 150,000 yuan / ton to 350,000 yuan / ton.

现在各个国家都在进行循环技术利用二次资源的技术研发。中国的经济是以作为世界制造中心的高速发展的经济，中国不仅是世界钴的资源使用的转出口国，而且随着中国本土通讯业、汽车业的市场发展，业成为世界钴资源的实际市场使用大国。中国本土每年消耗的钴资源量在万吨以上，因此，发展循环技术，开发钴的二次资源的循环利用，对解决中国钴资源的贫乏问题和促进现代工业持续增长至关重要。 Nowadays, various countries are conducting technology research and development of recycling technology using secondary resources. China's economy is a fast-growing economy as a world manufacturing center. China is not only a transit country for the use of cobalt resources in the world, but with the development of China's domestic communications and automotive industries, the industry has become the real market for cobalt resources in the world. Use a big country. China's domestic consumption of cobalt resources is more than 10,000 tons per year. Therefore, the development of recycling technology and the recycling of secondary resources for the development of cobalt are crucial to solving the problem of poor cobalt resources in China and promoting the continued growth of modern industries.

中国正在成为世界高能电池和硬质合金的制造基地，至 2006年，中国锂离子电池、镍氢电池的生产总量将达到世界的 60%以上，顺应我国移动通讯和电动汽车产业的发展，每年用钴量已达 10000吨以上，每年增长速度达到 20% 以上，然而长期以来，这种超细钴粉只有比利时等少数国家生产，严重制约着我国高能电池和高强度硬质合金的发展，必须发展开发自主知识产权的低成本制造技术，以降低超细钴粉的成本，实现国产化。 China is becoming the world's manufacturing base for high-energy batteries and hard alloys. By 2006, the total production of lithium-ion batteries and nickel-hydrogen batteries in China will reach more than 60% of the world, in line with the development of China's mobile communication and electric vehicle industry. The amount of cobalt used has reached more than 10,000 tons, and the annual growth rate has reached more than 20%. However, for a long time, this ultra-fine cobalt powder has only been produced in a few countries such as Belgium, which seriously restricts the development of high-energy batteries and high-strength cemented carbides in China. Develop low-cost manufacturing technologies that develop independent intellectual property rights to reduce the cost of ultra-fine cobalt powder and achieve localization.

目前，现有技术中制造钴粉的方法有羰基法、电解法、还原法、雾化法等四大类方法。 At present, the methods for producing cobalt powder in the prior art include a carbonyl method, an electrolysis method, a reduction method, and an atomization method.

羰基法为传统方法，粒径可以达到 5-10 μ ιη以内，形貌为球状或链球状。该方法的优点是球状结构稳定，导电性和过充过放电性能好，可以良好用于动力镍氢电池的制造；缺点是含碳量高（0.2— 0.3%) ，会降低电池的容量且本生产方法致癌，是非环保方法，生产装备严格、投资大。 The carbonyl method is a conventional method, and the particle size can be within 5-10 μm, and the morphology is spherical or chain-like. The method has the advantages of stable spherical structure, good electrical conductivity and over-discharge and discharge performance, and can be well used for the manufacture of a power nickel-hydrogen battery; the disadvantage is that the carbon content is high (0.2-0.3%), which will reduce the capacity of the battery and The production method is carcinogenic, non-environmental, with strict production equipment and large investment.

电解法，其生成出来的钴粉为枝状粉末，用于粉末冶金工业。这种方法的缺点是能耗高、成本高、粒径粗（一般在 30 m左右），这种钴粉只能用于一般粉末冶金制品，不能用于电池和高强度粉末冶金制品。 In the electrolysis method, the cobalt powder produced is a dendritic powder and is used in the powder metallurgy industry. The disadvantages of this method are high energy consumption, high cost, and large particle size (generally around 30 m). This cobalt powder can only be used in general powder metallurgy products and cannot be used in batteries and high-strength powder metallurgy products.

雾化法有水雾化和气体雾化，本法同电解法一样，具有能耗高、成本高、粒径粗（一般在 30 u m左右）等缺点，工业价值不大。 The atomization method has water atomization and gas atomization. This method has the same disadvantages as the electrolysis method, such as high energy consumption, high cost, and large particle size (generally around 30 u m), and the industrial value is not large.

还原法包括液相还原法和高温固相还原法，液相还原法正在发展之中，以草酸钴为物料的高温还原法是目前钴粉生产的主要方法，以比利时五矿公司等公司为代表，已经形成规模，占钴粉生产量的 90%以上。但现有的这类钴粉形状为不规则形状，在工艺上还没有一套可以很好地控制产品的粒度以及颗粒大小、且可以稳定地批量生产的方法，在其使用设备上也存在很多问题需要解决。发明内容 The reduction method includes liquid phase reduction method and high temperature solid phase reduction method, liquid phase reduction method is developing, and high temperature reduction method using cobalt oxalate as material is the main method of current cobalt powder production, represented by companies such as Belgian Minmetals Corporation. , has formed a scale, accounting for more than 90% of the production of cobalt powder. But the existing cobalt powder of this type The shape is irregular, and there is no set of methods for controlling the particle size and particle size of the product well, and it can be stably mass-produced in the process. There are also many problems to be solved in the equipment for use. Summary of the invention

本发明的目的在于改进现有技术中的不足，提供一种采用二次资源、制造工艺简单、环保、投资少、适于工业化生产的循环技术生产超细钴粉的制造方法； The object of the present invention is to improve the deficiencies in the prior art, and to provide a manufacturing method for producing ultrafine cobalt powder by using a recycling technique with secondary resources, simple manufacturing process, environmental protection, low investment, and suitable for industrial production;

本发明进一步的目的在于提供一种使用上述方法的设备。 It is a further object of the present invention to provide an apparatus using the above method.

本发明的目的是这样实现的- 本发明提供的循环技术生产超细钴粉的制造方法是，采用二次含钴原料 (亦可称为含钴废料），经溶解、提纯、雾化水解沉淀和还原过程制成费氏粒径为 0.1-2.0微米、氧含量 <0.6%、碳含量 <0.05%、硫含量 <0.05 %的超细钴粉。 The object of the present invention is achieved by the method of the present invention for producing a superfine cobalt powder by using a secondary cobalt-containing raw material (also referred to as cobalt-containing waste), which is dissolved, purified, atomized and hydrolyzed. And the reduction process is made into an ultrafine cobalt powder having a particle diameter of 0.1 to 2.0 μm, an oxygen content of <0.6%, a carbon content of <0.05%, and a sulfur content of <0.05%.

所述溶解过程是使所述二次含钴废料中的钴溶解在盐酸或硫酸中的过程，在此过程中所述废料中的其它物质的一部分也溶解在其中，由此形成粗钴盐溶液； The dissolution process is a process of dissolving cobalt in the secondary cobalt-containing waste in hydrochloric acid or sulfuric acid, in which a part of other substances in the waste are also dissolved therein, thereby forming a crude cobalt salt solution. ;

所述提纯即为通过萃取剂含 P204 5— 50%+磺化煤油 95-50 % (体积比.）的混合液对所述粗钴盐溶液进行一次萃取和用萃取剂含 P507 10-50%+磺化煤油 95-50% (体积比.）的混合液对一次萃取得到的萃余相进行二次萃取得到钴含量高于所述粗钴盐溶液的精制氯化钴溶液或硫酸钴溶液；或者 The purification is carried out by extracting the crude cobalt salt solution once by using a mixture of P204 5-50%+sulfonated kerosene 95-50% (volume ratio) and containing P507 10-50% with the extractant. + sulfonated kerosene 95-50% (volume ratio.) of the mixture is subjected to secondary extraction of the raffinate phase obtained by one extraction to obtain a purified cobalt chloride solution or a cobalt sulfate solution having a cobalt content higher than the crude cobalt salt solution; Or

所述提纯过程为一个化学沉淀过程，根据所述粗钴盐溶液中一种或几种杂质的种类和沉淀特性选择沉淀剂加入所述粗钴盐溶液中，并调整溶液 pH值，使得所述杂质沉淀而被滤除，制成精制氯化钴或硫酸钴溶液；或者 The purification process is a chemical precipitation process, selecting a precipitant to be added to the crude cobalt salt solution according to the kind and precipitation characteristics of one or more impurities in the crude cobalt salt solution, and adjusting the pH value of the solution, so that the The impurities are precipitated and filtered to prepare a purified cobalt chloride or cobalt sulfate solution; or

所述提纯过程也可以是一个电化学沉积过程，根据所述粗钴盐溶液中一种或几种杂质的种类和沉积电位特性，选择适合的电流密度，以石墨为阳极，以钛板为阴极，以所述粗钴盐溶液为电解液进行电解，使杂质在阴极上析出而除去，制成精制氯化钴或硫酸钴溶液。 The purification process may also be an electrochemical deposition process, selecting a suitable current density according to the type and deposition potential characteristics of one or more impurities in the crude cobalt salt solution, using graphite as the anode and titanium plate as the cathode. The crude cobalt salt solution is electrolyzed as an electrolytic solution, and impurities are deposited on the cathode to be removed, thereby preparing a purified cobalt chloride or cobalt sulfate solution.

所述雾化水解即为在所述精制氯化钴或硫酸钴溶液中加入沉淀剂草酸、氢氧化钠和氨水中的一种或几种，几种原料以喷雾方式投料，进行搅拌，控制溶液的 pH得到草酸钴，或碳酸钴，或氢氧化钴或氢氧化钴和草酸钴混合的复合钴盐； The atomization hydrolysis is one or several kinds of precipitating agent oxalic acid, sodium hydroxide and ammonia water added to the refined cobalt chloride or cobalt sulfate solution, and several raw materials are sprayed, stirred, and the solution is controlled. a pH of cobalt oxide, or cobalt carbonate, or a composite cobalt salt of cobalt hydroxide or cobalt hydroxide and cobalt oxalate;

^述还原过程是将所述前驱体置于还原性气体中在 200-700Ό加热 1-8小时制成纤维状或类纤维状或球状或类球状超细钴粉。 The reduction process is carried out by placing the precursor in a reducing gas at 200-700 Torr for 1-8 hours to form a fibrous or fibrillar-like or spherical or spheroidal ultrafine cobalt powder.

本发明所述的二次含钴废料是其中钴含量为 0.1-55 %或以上，另外含有 Ni、 Fe、 Cd、 Cu、 Pb、 Mg、 Ca、 Cr、 Zr、 Si、 Zn、 Li、 Mn、 Fe、 Al中的一种或几种杂质的二次废料；具体的，其可以是： The secondary cobalt-containing waste according to the present invention has a cobalt content of 0.1-55 % or more, and further contains Ni, Fe, Cd, Cu, Pb, Mg, Ca, Cr, Zr, Si, Zn, Li, Mn, a secondary waste of one or more of Fe, Al; specifically, it may be:

1、废镍氢 /镍镉电池及其生产过程中的废料、边料，这类废料中含钴为 0.01-15%不等; 其它成份为 Ni、 Fe、 Cd、 Zn等， Ni: 5-70%, Fe: 0.01-10%。 Cd: 0.01-10%, Zn: 0.01-10% 1. Scrap nickel-hydrogen/nickel-cadmium batteries and scraps and trimming materials in the production process, such wastes contain 0.01-15% cobalt; other components are Ni, Fe, Cd, Zn, etc., Ni: 5- 70%, Fe: 0.01-10%. Cd: 0.01-10%, Zn: 0.01-10%

2、废锂离子电池及其生产过程中的废料、边料，这类废料中，含 Co为 5-60%, 其它成份为 Ni、 Li、石墨、 Mn等， Ni: 0.1-50%, Li: 1-20%。石墨： 1-30%, Mn: 0.1-50% 2. Waste lithium ion battery and waste material and edge material in the production process, such waste contains 5-60% Co, other components are Ni, Li, graphite, Mn, etc., Ni: 0.1-50%, Li : 1-20%. Graphite: 1-30%, Mn: 0.1-50%

3、废硬质合金产品及废硬质合金行业产生的废料，这类废料中含 Co: 1-30%, Ni: 0.1-10% 3. Scraps from waste carbide products and waste carbide industry, including Co: 1-30%, Ni: 0.1-10%

4、废人造金刚石产品及人造金刚石行业中的废料、边料和废触媒等，这类废料中含 Co: 1-10%, Ni: 1-40%, Mn: 1-30%, 微量 Fe、 Al、 Cu、 Mg、 Ca、 Gr等。 4. Scrap, trim and waste catalyst in waste synthetic diamond products and synthetic diamond industry, such as Co: 1-10%, Ni: 1-40%, Mn: 1-30%, trace Fe, Al, Cu, Mg, Ca, Gr et al.

5、化工行业及汽车行业的催化剂，这类废料中含 Co: 1-50%, 其余为 Ni、 Al、 Si等。在所述溶解过程中，加入盐酸或硫酸，其浓度重量百分数为：盐酸 5— 37 % , 硫酸 10— 98 %，加入量为所述废料重量之化学当量的 100%-200%，或以所述废料中所有金属总量来计算，为化学当量的 1.1-3.0倍，使之溶解，废料中的钴形成可溶性的氯化钴 ( ₀( 1₂或硫酸钴 CoS0_{4 ;} 废料中的其它可溶成分也溶解在盐酸或硫酸中形成可溶性氯化物或硫酸盐，由此形成粗氯化钴 0^1₂或硫酸钴 CoS0₄溶液；或是： 5. Catalysts for the chemical industry and the automotive industry. These wastes contain Co: 1-50%, and the rest are Ni, Al, Si, etc. In the dissolution process, hydrochloric acid or sulfuric acid is added, and the concentration percentage by weight is: 5 - 37 % of hydrochloric acid, 10 - 98 % of sulfuric acid, and the amount is 100% - 200% of the chemical equivalent of the weight of the waste, or Calculate the total amount of all metals in the waste, which is 1.1-3.0 times the chemical equivalent, so that it dissolves, and the cobalt in the waste forms soluble cobalt chloride ( ₀ (1 ₂ or cobalt sulfate CoS0 _{4 ;} other soluble in the waste) The component is also dissolved in hydrochloric acid or sulfuric acid to form a soluble chloride or sulfate, thereby forming a crude cobalt chloride 0^1 ₂ or a cobalt sulfate CoS0 ₄ solution; or:

在所述溶解过程中，以所述二次废料为阳极，以耐腐蚀性导电材料为阴极，以硫酸或盐酸为电解液，接通直流电，根据所述二次废料中钴和杂质的种类调整电解的电压和电流强度，使钴优先溶解在所述电解液中，废料中的其它可溶成分也部分的溶解在该电解液中，由此形成粗氯化钴或硫酸钴溶液。 In the dissolving process, the secondary waste is used as an anode, the corrosion-resistant conductive material is used as a cathode, sulfuric acid or hydrochloric acid is used as an electrolyte, and direct current is turned on, and the cobalt and impurities are adjusted according to the type of the secondary waste. The voltage and current intensity of the electrolysis preferentially dissolve cobalt in the electrolyte, and other soluble components in the scrap are also partially dissolved in the electrolyte, thereby forming a crude cobalt chloride or cobalt sulfate solution.

所述提纯是萃取过程时，其为通过萃取剂含 P204 5— 50%+磺化煤油 95-50 % (体积比.）的混合液对所述粗钴盐溶液进行一次萃取和用萃取剂含 P507 10-50%+磺化煤油 95-50 % (体积比.) 的混合液对一次萃取得到的萃余相进行二次萃取得到钴含量高于所述粗钴盐溶液的精制氯化钴溶液或硫酸钴溶液；所述雾化水解即为在所述精制氯化钴或硫酸钴溶液中加入沉淀剂草酸、氢氧化钠和氨水中的一种或几种，几种原料以喷雾方式投料，进行搅拌，控制溶液的 pH得到草酸钴，或碳酸钴，或氢氧化钴或氢氧化钴和草酸钴混合的复合钴盐前驱体； When the purification process is an extraction process, the crude cobalt salt solution is extracted once and extracted with an extractant by a mixture containing P204 5-50%+sulfonated kerosene 95-50% (volume ratio). P507 10-50%+ sulfonated kerosene 95-50% (volume ratio) mixture is subjected to secondary extraction of the raffinate phase obtained by one extraction to obtain a purified cobalt chloride solution having a cobalt content higher than that of the crude cobalt salt solution. Or a cobalt sulphate solution; the atomized hydrolysis is one or more of adding a precipitating agent of oxalic acid, sodium hydroxide and ammonia in the refined cobalt chloride or cobalt sulfate solution, and several raw materials are sprayed by spraying. Stirring, controlling the pH of the solution to obtain cobalt oxalate, or cobalt carbonate, or a composite cobalt salt precursor of cobalt hydroxide or cobalt hydroxide and cobalt oxalate;

所述还原过程是将所述前驱体置于还原性气体中在 200-700°C加热 1-8小时制成纤维状或类纤维状或球状或类球状超细钴粉。当含镍的粗钴盐溶液中的其它金属杂质量较大时，'可以在所述溶钴和提纯工序之间设有一个除杂过程，以减轻后面萃取提纯工序的除杂压力。 The reduction process is carried out by placing the precursor in a reducing gas at 200 to 700 ° C for 1 to 8 hours to form a fibrous or fibrillar-like or spherical or spheroidal ultrafine cobalt powder. When the mass of the other metal in the nickel-containing crude cobalt salt solution is large, a dedusting process may be provided between the cobalt-dissolving process and the purification process to reduce the dedusting pressure of the subsequent extraction and purification process.

所述除杂过程是可以是一个化学沉淀过程，根据所述粗钴盐溶液中一种或几种杂质的种类和沉淀特性选择沉淀剂加入所述粗钴盐溶液中，并调整溶液 pH值，使得所述杂质沉淀而被滤除；或者 The impurity removing process may be a chemical precipitation process, selecting a precipitant to be added to the crude cobalt salt solution according to the kind and precipitation characteristics of the one or more impurities in the crude cobalt salt solution, and adjusting the pH value of the solution. Allowing the impurities to precipitate and being filtered out; or

所述除杂过程也可以是一个电化学沉积过程，根据所述粗钴盐溶液中一种或几种杂质的种类和沉积电位特性，选择适合的电流密度，以石墨为阳极，以钛板为阴极，以所述粗钴盐溶液为电解液进行电解，使杂质在阴极上析出而除去。在所述萃取过程中， The impurity removing process may also be an electrochemical deposition process, selecting a suitable current density according to the kind and deposition potential characteristics of one or more impurities in the crude cobalt salt solution, using graphite as an anode and titanium plate as The cathode is electrolyzed by using the crude cobalt salt solution as an electrolytic solution, and impurities are deposited on the cathode to be removed. During the extraction process,

( 1 ) 在所述一次萃取中，萃取剂为含 P204+磺化煤油的混合液与所述溶解过程中得到的粗钴盐溶液以 P204的流量为 2-15 1/min, 皂化用碱的流量为 75-190mol/min，使皂化率为 60-65 %，粗硫酸钴液或氯化钴的流量为 2-15 l/min、在 pH为 2-4、温度为 10-40Ό的调节下混合、分层，获得含钴量高于所述粗钴盐溶液的萃余相，制成半精制钴盐溶液； (1) In the primary extraction, the extractant is a mixture of P204+sulfonated kerosene and a crude cobalt salt solution obtained during the dissolution process, and the flow rate of P204 is 2-15 1/min, and the flow rate of the alkali for saponification 75-190mol/min, the saponification rate is 60-65%, the flow rate of crude cobalt sulfate or cobalt chloride is 2-15 l/min, and the mixture is adjusted under the condition of pH 2-4 and temperature 10-40 Ό. And stratifying, obtaining a raffinate phase having a cobalt content higher than the crude cobalt salt solution, and preparing a semi-refined cobalt salt solution;

( 2) 在所述二次萃取中，萃取剂含 P507+磺化煤油的混合液与所述溶解过程中得到的粗钴盐溶液以硫酸钴溶液流量为 0.8-15 1/min, P507二次萃取剂流量为 2-20 1/min, 皂化用碱流量为 200-1000ml/min，使皂化率为 20-50%的混合比例、在温度为 10-40°C的调节下混合、分层；留下萃取相，该萃取相与浓度为 0.1-0.8mol/L的硫酸或盐酸以 1-4 1/分比例、在温度为 10-40°C的调节下混合、分层，取反萃液成为精制氯化钴或硫酸钴溶液。 (2) In the secondary extraction, the extractant contains a mixture of P507+sulfonated kerosene and the crude cobalt salt solution obtained in the dissolution process with a flow rate of cobalt sulfate solution of 0.8-15 1 / min, P507 secondary extraction The flow rate of the agent is 2-20 1/min, the flow rate of the alkali for saponification is 200-1000 ml/min, and the saponification rate is 20-50%. Mixing and stratifying at a temperature of 10-40 ° C; leaving an extract phase with a concentration of 0.1-0.8 mol/L of sulfuric acid or hydrochloric acid at a ratio of 1-4 1 /min, The mixture is mixed and layered under the adjustment of a temperature of 10 to 40 ° C, and the stripping solution is taken to be a purified cobalt chloride or cobalt sulfate solution.

本发明的循环技术生产超细钴粉的制造方法：对于不含镍，只含 Cu/Fe/Pb/Mg/Ca等杂质的粗钴盐溶液，可以如上所述地用电化学或化学沉淀方法选择的除去的杂质，即将上述的通过萃取剂进行的二次萃取替换成其它的电化学或化学沉淀方法过程。所述雾化水解过程可以为： The method for producing ultrafine cobalt powder by the recycling technique of the present invention: For a crude cobalt salt solution containing no nickel and containing only impurities such as Cu/Fe/Pb/Mg/Ca, it can be electrochemically or chemically precipitated as described above. The selected removed impurities, i.e., the secondary extraction by the extractant described above, is replaced by another electrochemical or chemical precipitation process. The atomization hydrolysis process can be:

将所述精制氯化钴或硫酸钴溶液调整其浓度为 50-140g/L和制备成浓度为 100-300g/L、 pH为 3.0-5.5 (最佳为 4.0-4.5 ) 的沉淀剂——草酸铵溶液以雾状喷射到反应釜中，混合搅拌，反应时温度在 45-70°C间，反应时流量为： 30-100IJ 分，反应时间为 2分 -60分钟，最佳为 22— 25分钟；反应终点 pH值： 1.0-2.8，最佳为 1.7-1.9; 然后分离出前驱体草酸钴晶体；或为： The purified cobalt chloride or cobalt sulfate solution is adjusted to have a concentration of 50-140 g/L and a precipitant prepared to a concentration of 100-300 g/L and a pH of 3.0-5.5 (optimally 4.0-4.5) - oxalic acid The ammonium solution is sprayed into the reaction vessel in a mist form, mixed and stirred, and the reaction temperature is between 45-70 ° C, the flow rate during the reaction is: 30-100 IJ minutes, the reaction time is 2 minutes - 60 minutes, and the optimum is 22-25 Minute; reaction end point pH: 1.0-2.8, optimally 1.7-1.9; and then separate the precursor cobalt oxalate crystal; or:

将所述精制氯化钴或硫酸钴溶液调整其浓度为 50-140g/l和制备成浓度为 50-300g/L 的碳铵溶液以雾状喷射到反应釜中，所述精制氯化钴或硫酸钴溶液控制加入量为 50L〜300L/hr， pH值: 7.0-10, 最佳 7.5-9.0，碳酸铵按 Co⁺²计量的 1.1〜2.0倍加入，并通过调节碳酸铵的加入速度来稳定 pH值，混合搅拌，平均反应时间： 1一 10小时，反应温度： 50-70°C，，然后分离出前驱体球状或类球状碳酸钴晶体；或为： The purified cobalt chloride or cobalt sulfate solution is adjusted to have a concentration of 50-140 g/l and a solution prepared to a concentration of 50-300 g/L is sprayed into the reaction vessel in a mist, the refined cobalt chloride or The cobalt sulfate solution is controlled to be added in an amount of 50 L to 300 L/hr, pH: 7.0-10, optimally 7.5-9.0, and ammonium carbonate is added in an amount of 1.1 to 2.0 times measured by Co ^{+ 2} and stabilized by adjusting the rate of addition of ammonium carbonate. pH value, mixing and stirring, average reaction time: 1 to 10 hours, reaction temperature: 50-70 ° C, and then separating the precursor spherical or spheroidal cobalt carbonate crystal; or:

将所述精制氯化钴或硫酸钴溶液调整浓度为 50-140g/l 和制备成浓度为 15-35 % (重量百分比）的 NaOH溶液以雾状喷射到反应釜中，混合搅拌，同时加入 10— 30 % (重量百分比？）浓度的 NH₃溶液或通入纯度为 98 % (重量百分比）以上的 >«1₃气，其加入量以溶液中游离 Co²⁺浓度为度量，控制 NH₃ 加入量使游离 Co²⁺浓度为 0.5— 200毫克 /1，反应液的 pH为 7-14， Co²⁺液的加料速度为 50-300L/hr, NaOH溶液的加料速度由控制的 pH来匹配，反应温度为 40-70°C，搅拌速度为 70-250转 /分，控制结晶晶体的平均粒径为 2-15微米；平均反应时间为 2-50小时，制成球状或类球状前驱体氢氧化钴晶体；或为- 所述精制氯化钴或硫酸钴溶液调整浓度为 20-100g/L，沉淀剂为浓度为 0.1-3.0mol/L 的草酸铵与比重 d= 0.5-0.95 的 ΝΗ₃ · H₂O和重量百分比浓度为 10-35 %的 NaOH两个中的任意一种或两种的混合物，以雾状喷射到反应釜中，混合搅拌， Co²⁺液的加料速度为 30-300L/hr，反应液的 pH为 7-12，最佳值为 7.5-9.5，反应温度为 50-75 °C，最佳值为 60-70°C，通过调节 ΝΗ₃ · H₂O和 /或 NaOH的加入量来保持 pH稳定，反应中保持温度、加料速度稳定，加料速度同样通过用定量泵加料方式维持恒定；平均反应时间为 5-1200分钟，最佳值为 20-40分钟，通过控制各反应条件生成纤维状或类纤维状的草酸钴和氢氧化钴混合的复合钴盐。为了改善复杂钴盐的分散性能,可以加入 0.01-0.5% (重量百分比）的 PVP高分子表面活性剂.。具体的，制备草酸钴的水解方法可以是： The purified cobalt chloride or cobalt sulfate solution is adjusted to a concentration of 50-140 g / l and a NaOH solution prepared to a concentration of 15 - 35 % by weight is sprayed into the reaction vessel in a mist, mixed and stirred, and simultaneously added 10 — 30% (% by weight?) Concentration of NH ₃ solution or >«1 ₃ gas with a purity of 98% (by weight) or more, measured in the amount of free Co ²⁺ in the solution, controlled by NH ₃ addition The amount of free Co ²⁺ is 0.5-200 mg / 1, the pH of the reaction solution is 7-14, the feed rate of Co ²⁺ solution is 50-300 L / hr, and the feed rate of the NaOH solution is matched by the controlled pH. The reaction temperature is 40-70 ° C, the stirring speed is 70-250 rpm, the average crystal grain size of the control crystal is 2-15 microns; the average reaction time is 2-50 hours, and the spherical or spheroidal precursor hydrogen is prepared. Cobalt oxide crystal; or - the refined cobalt chloride or cobalt sulfate solution is adjusted to a concentration of 20-100 g / L, the precipitant is a concentration of 0.1-3.0 mol / L of ammonium oxalate and the specific gravity d = 0.5-0.95 ΝΗ ₃ · H ₂ O and the percentage concentration by weight of a mixture of any one or both of two 10-35% NaOH in order to fog Injected into the reactor, mixing, liquid feed rate of Co ²⁺ 30-300L / hr, pH of the reaction solution is 7-12, the optimum value of 7.5 to 9.5, the reaction temperature is 50-75 ° C, most The preferred value is 60-70 ° C, the pH is kept stable by adjusting the amount of ΝΗ ₃ · H ₂ O and/or NaOH added, the temperature is maintained during the reaction, the feeding rate is stable, and the feeding rate is also maintained constant by the dosing with a metering pump; The average reaction time is 5 to 1200 minutes, and the optimum value is 20 to 40 minutes. A composite cobalt salt in which fibrous or fibrillar cobalt oxalate and cobalt hydroxide are mixed is produced by controlling each reaction condition. In order to improve the dispersibility of the complex cobalt salt, 0.01 to 0.5% by weight of a PVP polymeric surfactant may be added. Specifically, the hydrolysis method for preparing cobalt oxalate may be:

a、制备草酸铵溶液： a, preparation of ammonium oxalate solution:

将草酸用温水（水温在 45— 65°C )溶解，并对其进行过滤，除去溶液中的固体杂质，再在草酸溶液中通入液氨，配制成 pH为 4.1-4.5，浓度为 130-150g/L 的草酸铵溶液。 b、制备钴氧化物前驱体草酸钴结晶： The oxalic acid is dissolved in warm water (water temperature at 45-65 ° C), and filtered to remove solid impurities in the solution, and then liquid ammonia is introduced into the oxalic acid solution to prepare a pH of 4.1-4.5, and the concentration is 130- 150 g/L ammonium oxalate solution. b. Preparation of cobalt oxide precursor precursor cobalt oxalate crystal:

将精制氯化钴或硫酸钴溶液调整其浓度为 50-140g/L 和制备成浓度为 130-150g/L 的草酸铵溶液以雾状喷射到反应釜中，混合搅拌，反应时温度在 50- 52°C间，反应时流量为： 35- 45L/分，反应时间为 5分 -7分，反应终点 pH 值： 1. 6-1. 8; 然后分离出晶体； The purified cobalt chloride or cobalt sulfate solution is adjusted to have a concentration of 50-140 g/L and an ammonium oxalate solution prepared to a concentration of 130-150 g/L is sprayed into the reaction vessel in a mist form, and stirred and stirred at a temperature of 50- Between 52 ° C, the flow rate during the reaction is: 35-45 L / min, the reaction time is 5 minutes - 7 minutes, the reaction end point pH: 1. 6-1. 8; and then the crystal is separated;

制备碳酸钴的水解方法可以是- a、制备碳酸铵溶液- 将碳酸氢铵用温水（水温 45— 65°C )溶解，并对其溶液进行过滤，除去溶液中固体杂质，配制成碳铵的浓度为 50— 300g/L，最好为 200-230 g/L The hydrolysis method for preparing cobalt carbonate may be - a, preparing ammonium carbonate solution - dissolving ammonium hydrogencarbonate in warm water (water temperature 45-65 ° C), and filtering the solution to remove solid impurities in the solution to prepare ammonium bicarbonate. Concentration 50-300g/L, preferably 200-230 g/L

b、将精制氯化钴或硫酸钴溶液调整其浓度为 50-140g/l，最好为 lOOg/1和浓度为 100- 300g/L的碳铵溶液以雾状喷射到反应釜中， Co液控制加入量为 50L〜 300L/hr, 碳酸铵按 Co+²计量的 1.1〜2. 0倍加入， pH值： 7. 5-8. 5，稳定 Co 液控制加入量，根据 pH值来调整碳酸铵的加入量，使 pH值稳定；混合搅拌，搅拌速度： 85- 150转 /min，平均反应时间： 1— 10小时，反应温度： 50- 60°C ; 通过上述雾化水解，可以制成草酸钴或碳酸钴晶体。其中如果钴液为氯化钴溶液，则可以生成纤维状或针状或类纤维状或类针状草酸钴或碳酸钴晶体，如果钴液为硫酸钴溶液，则可以生成球状或类球状碳酸钴或草酸钴晶体，通过上述条件的水解结晶，产生的晶体的晶粒都会是符合要求的，这样，在后面的工序中制成的钴粉的粒度的指标也就能够满足要求。 b. The purified cobalt chloride or cobalt sulfate solution is adjusted to have a concentration of 50-140 g/l, preferably 100 g/1 and a concentration of 100-300 g/L of ammonium bicarbonate solution sprayed into the reaction vessel in a mist, Co liquid The amount of controlled addition is 50L~300L/hr, and the ammonium carbonate is 1.1~ ² . 0 times added by Co+ ² , pH value: 7. 5-8. 5, the stable Co liquid is controlled to increase the amount, and the ammonium carbonate is adjusted according to the pH value. The amount of addition, the pH is stabilized; mixing and stirring, stirring speed: 85-150 rev / min, average reaction time: 1 - 10 hours, reaction temperature: 50-60 ° C; oxalic acid can be prepared by the above-mentioned atomization hydrolysis Cobalt or cobalt carbonate crystals. If the cobalt solution is a cobalt chloride solution, a fibrous or needle-like or fibrillar-like or needle-like cobalt oxalate or cobalt carbonate crystal can be formed. If the cobalt solution is a cobalt sulfate solution, spherical or spheroidal cobalt carbonate can be formed. Or cobalt oxalate crystals, by the hydrolysis crystallization of the above conditions, the crystal grains of the crystals produced are satisfactory, so that the particle size index of the cobalt powder produced in the subsequent process can satisfy the requirements.

制备前驱体氢氧化钴晶体的具体方法可以是： A specific method for preparing the precursor cobalt hydroxide crystals may be:

将所述精制氯化钴或硫酸钴溶液调整浓度为 120g/l和制备成浓度为 25 % 的 NaOH溶液以雾状喷射到反应釜中，混合搅拌，同时通入纯度为 98 %以上的 NH₃气，调节 NH₃加入量使游离 Co²⁺浓度为 10— 15毫克 /1，反应液的 pH为 9.8- 10.5 , Co²⁺液的加料速度为 160L/hr， NaOH溶液的加料速度由控制的 pH 来匹配，以定量泵实现加料，恒定 Co²⁺液的加料速度，调节 NaOH溶液的加料速度使 pH为 9.8— 10.5 ; 反应温度为 60°C，搅拌速度为 130— 140转 /分，控制结晶晶体的平均粒径为 5-8微米；平均反应时间为 5-8小时，制成前驱体氢氧化钴晶体；制备前驱体氢氧化钴和草酸钴的混合晶体的具体方法可以是： The purified cobalt chloride or cobalt sulfate solution is adjusted to have a concentration of 120 g/l and a NaOH solution prepared to a concentration of 25% is sprayed into the reaction vessel in a mist form, mixed and stirred, and simultaneously passed into the NH _{3 having a} purity of 98% or more. Gas, adjust the amount of NH ₃ added so that the free Co ²⁺ concentration is 10-15 mg / 1, the pH of the reaction solution is 9.8 - 10.5, the feed rate of Co ²⁺ solution is 160 L / hr, the feed rate of NaOH solution is controlled by The pH is matched, the dosing pump is used to feed, the constant Co ²⁺ liquid feeding rate is adjusted, the feeding speed of the NaOH solution is adjusted to make the pH 9.8-10.5; the reaction temperature is 60 ° C, the stirring speed is 130-140 rpm, control The average crystal grain size of the crystal crystal is 5-8 micrometers; the average reaction time is 5-8 hours, and the precursor cobalt hydroxide crystal is prepared; the specific method for preparing the mixed crystal of the precursor cobalt hydroxide and cobalt oxalate may be:

将精制氯化钴或硫酸钴溶液调整浓度为 20-100g/L最佳为 30-50g/L，沉淀剂为浓度为 0.1-3.0mol/L的草酸铵与比重 d=0.5-0.95的 ΝΗ₃ ·Η₂0和重量百分比浓度为 10-35 %的 NaOH两个中的任意一种或两种的混合物，以雾状喷射到反应釜中，混合搅拌， Co²⁺液的加料速度为 30-200L/hr，反应液的 pH为 7-12，最佳值为 8-9，反应温度为 50-75°C，最佳值为 60-70°C，通过 ΝΗ₃ ·'Η₂Ο和 / 或 NaOH的加入量同时保持 pH稳定，反应中保持温度、加料速度稳定，加料速度同样通过用定量泵加料方式维持恒定；平均反应时间为 5-60分钟，最佳值为 20-40分钟，通过各反应条件控制生成纤维状或类纤维状的草酸钴和氢氧化钴混合的复杂钴盐。所述还原过程的最佳方案为***热还原，其分预还原、还原和冷却三个阶段： The refined cobalt chloride or cobalt sulfate solution is adjusted to a concentration of 20-100 g/L, preferably 30-50 g/L, and the precipitating agent is ammonium oxalate having a concentration of 0.1-3.0 mol/L and ΝΗ ₃ having a specific gravity d=0.5-0.95. · Η ₂₀ and a mixture of 5% or 5% by weight of NaOH, either in a mixture or two, sprayed into the reactor in a mist, mixed and stirred, and the feed rate of Co ²⁺ is 30- 200L / hr, the pH of the reaction solution is 7-12, the optimum value is 8-9, the reaction temperature is 50-75 ° C, the optimum value is 60-70 ° C, by ΝΗ ₃ · 'Η ₂ Ο and / Or the addition amount of NaOH is kept at the same time, the pH is kept stable, the temperature is maintained during the reaction, the feeding rate is stable, and the feeding rate is also maintained constant by the dosing method by the metering pump; the average reaction time is 5-60 minutes, and the optimum value is 20-40 minutes. Each reaction condition controls the formation of a complex cobalt salt in which a fibrous or fibrillar-like cobalt oxalate and cobalt hydroxide are mixed. The best solution for the reduction process is blasting thermal reduction, which is divided into three stages of pre-reduction, reduction and cooling:

( 1 ) 预还原： (1) Pre-reduction:

将所述前驱体在还原气体保护性气体>½或 CO₂的保护气氛中，温度为 200 " 500°C , 还原 1-5 小时，在该还原阶段使晶体脱水和进行预还原，草酸钴或碳酸钴晶体裂解释放二氧化碳和一氧化碳的混合气体，具有还原性质，使草酸钴或碳酸钴晶体中的二氧化碳溢出，其可以使晶体堆变得疏松，即进行所谓的 ***； The precursor is in a protective atmosphere of reducing gas protective gas > 1⁄2 or CO ₂ at a temperature of 200 "500 ° C, reduction for 1-5 hours, in this reduction stage, the crystal is dehydrated and pre-reduced, and the crystal of cobalt oxalate or cobalt carbonate crystallizes to release a mixed gas of carbon dioxide and carbon monoxide, which has reducing properties, making cobalt oxalate or cobalt carbonate crystals Carbon dioxide overflow, which can make the crystal pile loose, that is, so-called blasting;

(2 ) 还原： (2) Restore:

将预还原后的晶体在 400-650Ό还原 1-10小时，还原过程在氢气和氮气形成还原气氛中进行，氢气和氮气的体积比为 3： 1，还原气体的通入量决定于前驱体的量，其比例关系以其中的氢气满足还原反应为准； The pre-reduced crystal is reduced at 400-650 Torr for 1-10 hours, and the reduction process is carried out in a reducing atmosphere of hydrogen and nitrogen. The volume ratio of hydrogen to nitrogen is 3: 1. The amount of reducing gas introduced is determined by the precursor. Quantity, the proportional relationship is based on which the hydrogen meets the reduction reaction;

( 3 )冷却 (3) cooling

在 N₂ 或 CO₂ ^保护气氛中将晶体冷却、惰化至室温，即可制成粒径在 0.1〜2.0 μ m的纤维状或球状或类球状超细钴粉。所述还原阶段又可分成多个升温阶段：前低温段、高温段，前低温段比高温段的温度低 30— 50°C：。所述冷却阶段可分成若干个温降阶梯，每个阶梯的温差在 40— 80°C。具体的***热还原制备超细钴粉可以是如下： The crystals are cooled and inerted to room temperature in a N ₂ or CO ₂ ^ protective atmosphere to obtain a fibrous or spherical or spheroidal ultrafine cobalt powder having a particle diameter of 0.1 to 2.0 μm. The reduction stage can be further divided into a plurality of temperature rising stages: a front low temperature section and a high temperature section, and the front low temperature section is 30-50 degrees lower than the temperature of the high temperature section: The cooling stage can be divided into several steps of temperature drop, and the temperature difference of each step is 40-80 °C. The specific blasting thermal reduction preparation of ultrafine cobalt powder can be as follows:

( 1 ) 预还原： (1) Pre-reduction:

将制出的草酸钴或碳酸钴晶体在还原气体 N₂或 C0₂的保护气氛中加热，温度为 200— 400°C还原 1-3小时，在该还原阶段使晶体脱水和进行预还原，使草酸钴或碳酸钴晶体中的二氧化碳溢出，其可以使晶体堆变得疏松，即进行所谓的***； The prepared cobalt oxalate or cobalt carbonate crystal is heated in a protective atmosphere of reducing gas N ₂ or CO ₂ at a temperature of 200-400 ° C for 1-3 hours, in which the crystal is dehydrated and pre-reduced, so that The carbon dioxide in the crystals of cobalt oxalate or cobalt carbonate overflows, which can make the crystal pile loose, that is, so-called blasting;

( 2 ) 还原： ( 2 ) Restore:

将预还原后的晶体在 400-650°C还原 1-6小时，还原过程在氢气和氮气形成还原气氛中进行，氢气和氮气的体积比为 3： 1,在实际的应用中可以方便地将液氨分解得到还原气体： 2NH3— 3H2+N2, 这样，既方便地得到了还原所需的氢气，也加入了具有保护作用的氮气，比起使用氢气方便、安全且价廉，具有较好的工业实用性。还原气体的通入量决定于前驱体的量，其比例关系以其中的氢气满足还原反应为宜。 ' The pre-reduced crystal is reduced at 400-650 ° C for 1-6 hours, and the reduction process is carried out in a reducing atmosphere of hydrogen and nitrogen. The volume ratio of hydrogen to nitrogen is 3:1, which can be conveniently used in practical applications. The liquid ammonia is decomposed to obtain a reducing gas: 2NH3—3H2+N2. Thus, the hydrogen required for reduction is conveniently obtained, and the protective nitrogen is also added, which is convenient, safer and cheaper than using hydrogen, and has better performance. Industrial applicability. The amount of the reducing gas to be introduced is determined by the amount of the precursor, and the proportional relationship is preferably such that the hydrogen therein satisfies the reduction reaction. '

对经过预还原阶段的所谓 "***"过程后的晶体进行还原，与还原气体接触，疏松的粉末可以与还原气体更充分的接触，因此，分段加热在制备本超细钴粉中有利于粉末疏松，松比低，且利于还原反应的进行，还可以缩短反应时间，提高生产效率，并使设备结构变得紧凑，减少占地面积。 The crystal after the so-called "blasting" process in the pre-reduction stage is reduced, and the contact with the reducing gas, the loose powder can be more fully contacted with the reducing gas, therefore, the segment heating is beneficial to the powder in the preparation of the ultra-fine cobalt powder. Loose, low pine ratio, and favorable for the reduction reaction, can also shorten the reaction time, improve production efficiency, and make the structure of the device compact and reduce the floor space.

还原阶段又可以分成多个升温阶段：前低温段、高温段，前低温段比高温段的温度可以是低 30— 5(TC，例如，前低温段为 460°C，在其中保温 40分钟，再升温到高温段 500Ό，保温 40分钟，这样可以是加热均匀； The reduction stage can be further divided into a plurality of heating stages: the front low temperature section and the high temperature section, and the temperature of the front low temperature section can be lower than the high temperature section by 30-5 (TC, for example, the former low temperature section is 460 ° C, and the temperature is kept therein for 40 minutes. Then heat up to 500 ° in the high temperature section and keep it for 40 minutes, which can be heated evenly;

( 3 ) 冷却 (3) cooling

在 Ν₂或 C0₂的保护气氛中将晶体冷却、惰化至室温，即可制成粒径在 0.1〜 2 m的纤维状或球状超细钴粉。 The crystal is cooled or inerted to room temperature in a protective atmosphere of Ν ₂ or C0 ₂ to obtain a fibrous or spherical ultrafine cobalt powder having a particle diameter of 0.1 to 2 m.

后冷却阶段还可以分成若干个温降阶梯，每个阶梯的温差可以在 100— 150 。C，如降温到 460°C保温 20分钟，继续降温到 300 °C保温 20分钟，最后自然冷却到室温。多段降温可以降低晶体的冷却速度，避免晶体结块和降低晶体的性能。 The post-cooling phase can also be divided into several steps of temperature drop, and the temperature difference of each step can be between 100 and 150. C, if it is cooled to 460 ° C for 20 minutes, continue to cool down to 300 ° C for 20 minutes, and finally naturally cool to room temperature. Multi-stage cooling can reduce the cooling rate of the crystal, avoid crystal agglomeration and reduce the performance of the crystal.

在上述还原过程中，如果加热温度太低，还原不彻底，晶体中的氧含量高， 65 如果温度太高，则粒径长大，比重过大。 In the above reduction process, if the heating temperature is too low, the reduction is not complete, and the oxygen content in the crystal is high, 65 If the temperature is too high, the particle size will grow and the specific gravity will be too large.

在预冷却和还原阶段使用的保护性气体最好为二氧化碳，因为其比空气重，保护效果比氮气好。本发明提供的循环技术生产超细钴粉的制造设备包括溶解设备、提纯设备、雾化水解反应器和还原设备，所述溶解设备为带有加热装置的反应器或带有加热装置及电解装置的反应器，所述提纯装置为萃取箱或带有加热装置及电解装置的反应器、所述还原设备为液压和机械传动的多段推舟。 The protective gas used in the pre-cooling and reduction stages is preferably carbon dioxide because it is heavier than air and has a better protection than nitrogen. The recycling apparatus for producing ultrafine cobalt powder provided by the present invention comprises a dissolving device, a purifying device, a atomization hydrolysis reactor and a reducing device, and the dissolving device is a reactor with a heating device or a heating device and an electrolyzing device In the reactor, the purification device is an extraction tank or a reactor with a heating device and an electrolysis device, and the reduction device is a multi-stage push boat that is hydraulically and mechanically driven.

所述萃取箱最好是逆流箱式萃取器。 The extraction tank is preferably a countercurrent tank extractor.

所述多段式推舟，包括三个通道壳体，其间通过输送管路相连接构成一个狭长的通道，在该通道的两端设有进口和出口，所述三个壳体从入口到出口顺序形成三个区域：为预还原区域、还原区域和冷却区域，所述推舟各区域通过不锈钢挂帘隔开或者设置自动控制的炉门或闸板，以限制各区的气体互相流动；该挂帘设在各区域之间的连接管路内和出口上，所述挂帘的上端与管壁铰接连接，其下端为自由端，各区域连接在一起，在推舟内形成一个可通过各个腔室的管状通道，在该管状通道中彼此相接触地设有若干个物料舟，在推舟的进口处设有可将物料舟推入所述管状通道中的物料舟推进装置，在所述在各个烧结腔室中设有加热装置和温度检测及调节装置，用以给各个腔室提供所需的温度；在所述各个腔室中还设有一个或多个进气口和排气口；所述冷却腔室中设有冷去 [3装置 The multi-stage push boat comprises three channel shells connected by a conveying pipeline to form an elongated passage, and an inlet and an outlet are arranged at both ends of the passage, and the three shells are arranged from the inlet to the outlet. Forming three regions: a pre-reduction zone, a reduction zone and a cooling zone, the zones of the push boat are separated by a stainless steel curtain or an automatically controlled furnace door or shutter is provided to restrict the mutual flow of gases in the zones; The upper end of the curtain is hingedly connected to the tube wall, and the lower end is a free end, and the regions are connected together to form a chamber through the chamber. a tubular passage in which a plurality of material boats are placed in contact with each other, and at the inlet of the push boat is provided a material boat propulsion device capable of pushing the material boat into the tubular passage, a heating device and a temperature detecting and regulating device are provided in the sintering chamber for providing the required temperature to each chamber; and one or more air inlets are also provided in each of the chambers And the exhaust port; the cooling chamber is provided with a cold [3 device

在各区域机壳的顶部设有进气口和排气口，在所述预还原区域和还原区域中，所述进气口和排气口设在该区域的两端且进出气口与推舟的行进方向相反；在每个区域中又通过隔板分隔成若干分段空间，该隔板在其下方设有通道孔使各分段空间连通令所述推舟通过；在预还原区域和还原区域中的分别设有若干个分段空间，在各分段空间中分别设置加热器以在不同分段空间形成不同的温度，在冷却区域也设有若干个分段空间，在各分段空间中分别设有冷却器；在冷却区域的前面几个分段空间中的中部机壳顶部设有进气口，在最后一个分段空间中部机壳顶部设有排气口。 An air inlet and an exhaust port are provided at the top of each regional cabinet, and in the pre-reduction area and the reduction area, the air inlet and the exhaust port are disposed at both ends of the area, and the air inlet and outlet are pushed and pushed The direction of travel is reversed; in each area, it is divided into a plurality of segmented spaces by a partition plate, and the partition plate is provided with a passage hole below the space for connecting the segments to pass the push boat; in the pre-reduction area and the reduction There are several segment spaces in the area, heaters are respectively arranged in each segment space to form different temperatures in different segment spaces, and several segment spaces are also arranged in the cooling region, in each segment space A cooler is respectively arranged in the middle; a gas inlet is arranged at the top of the middle casing in the first segment space of the cooling zone, and an exhaust port is arranged at the top of the middle casing of the last segment space.

所述雾化水解反应器包括一个反应罐，其上包括加热装置、搅拌装置和进料装置，所述进料装置包括若干进料喷管，其中一些进料喷管的喷嘴设于反应罐罐体的上部，另一些进料哦喷管的喷嘴设于反应罐罐体的中部或下部；本发明提供的循环技术生产超细钴粉的制造方法通过有效的溶出钴的工艺、将钴和杂质分离的提纯工艺如化学沉淀、电化学沉淀和二次萃取工艺以及通过雾化水解工艺及其特定的工艺条件和***还原法可以从含钴的各种废料中高效制成超细钴粉。 The atomization hydrolysis reactor comprises a reaction tank comprising a heating device, a stirring device and a feeding device, the feeding device comprising a plurality of feeding nozzles, wherein some nozzles of the feeding nozzle are arranged in the reaction tank The upper part of the body, the other nozzles of the nozzle are arranged in the middle or the lower part of the reaction tank body; The recycling technology provided by the invention provides a method for producing ultrafine cobalt powder by effectively dissolving cobalt, cobalt and impurities Separate purification processes such as chemical precipitation, electrochemical precipitation, and secondary extraction processes, as well as ultra-fine cobalt powders can be efficiently produced from various cobalt-containing wastes by atomization hydrolysis processes and their specific process conditions and blasting reduction processes.

本发明的核心是二次含钴废料的除杂提纯技术、雾化水解沉积合成钴化合物前驱体，然后在多段温度下进行***热还原生成超细钴粉。 The core of the invention is a depurcation and purification technology of secondary cobalt-containing waste, a precursor of hydrolyzed deposition of a synthetic cobalt compound, and then blasting thermal reduction at a plurality of temperatures to form ultrafine cobalt powder.

雾化水解沉积的采用，可以根本性消除胶体物质沉积，维持稳定的结晶生长环境，因而，可以合成具有特定形状和粒径的晶体。本发明通过加压喷雾的方式和稳定 pH工艺来实施雾化水解沉积，合成的氧化物前驱体在特定形状下, 均匀分布，由此在多段温度下进行***热还原生成特定形状超细钴粉，以满足电池和粉末冶金不同行业对产品的不同需求。 The use of atomized hydrolysis deposition can fundamentally eliminate the deposition of colloidal substances and maintain a stable crystal growth environment, and thus, crystals having a specific shape and particle diameter can be synthesized. The invention implements atomized hydrolysis deposition by means of pressurized spraying and a stable pH process, and the synthesized oxide precursor is uniformly distributed under a specific shape, thereby performing blasting thermal reduction at a plurality of stages to form ultrafine cobalt powder of a specific shape. To meet the different needs of different products in different industries of battery and powder metallurgy.

本方法可以制备不同粒径和形状的产品。本发明特殊的溶钴和提纯工艺组合，使得本工艺可以适合于多种组成、含量不同的各种含钴二次废料的回收处理。 The method can produce products of different particle sizes and shapes. The special combination of the dissolved cobalt and the purification process of the invention makes the process suitable for the recovery treatment of various cobalt-containing secondary wastes having different compositions and contents.

本发明提供的采用雾化水解法和控制气氛分解法等独特技术生产超细钴粉材料，是一种环境友好的方法，可以生产球状和针状两种超细钴粉，具有成本低、粒径细、松比合理的特点，可以用于动力电池和高性能粉末冶金制品的制造。当控制生成球状 /类球状时，粒径： 0.1〜1.5 μ πι，松比： 0.3〜； L0g/cm3，分布均匀、产品一致性好，可用于动力电池，明显提高电池的导电性、大电流充放电性能，延长电池循环寿命；当控制成针状时，横向轴径 0.1〜0.5 μ ιη，纵向轴长 0.5〜10 u m，用作粉末冶金切屑刀具、硬质合金等超硬材料的骨架，提高这些粉末冶金制品的硬度与耐磨性能，从而达到全面取代现有钴粉，再有，本发明的方法制备的钴粉的含碳量低，产品质量好，成本低，具有十分优异的价格性能比。本方法可以很好地控制产品的粒度以及颗粒大小、且可以稳定地批量生产超细球状和纤维状钴粉。本发明提供的制作设备可以为上述方法提供可靠的保证，同时该设备结构简单，制造成本低。 The invention provides an ultra-fine cobalt powder material by using a unique technology such as atomization hydrolysis method and controlled atmosphere decomposition method, which is an environmentally friendly method, and can produce two kinds of ultrafine cobalt powders, which are spherical and needle-shaped, and have low cost and grain. The characteristics of fine diameter and loose ratio can be used for the manufacture of power batteries and high-performance powder metallurgy products. When the control generates a spherical/spherical shape, the particle size: 0.1~1.5 μ πι, loose ratio: 0.3~; L0g/cm3, uniform distribution, good product consistency, can be used for power batteries, significantly improve the conductivity and high current of the battery Charge and discharge performance, prolong battery cycle life; When controlled into needle shape, the transverse shaft diameter is 0.1~0.5 μ ιη, and the longitudinal axis length is 0.5~10 um. It is used as the skeleton of superhard materials such as powder metallurgy chip cutters and hard alloys. The hardness and wear resistance of these powder metallurgical products are improved to completely replace the existing cobalt powder. Further, the cobalt powder prepared by the method of the invention has low carbon content, good product quality, low cost and excellent price. Performance ratio. The method can well control the particle size and particle size of the product, and can stably produce ultrafine spherical and fibrous cobalt powder in batches. The manufacturing device provided by the invention can provide a reliable guarantee for the above method, and the device has the advantages of simple structure and low manufacturing cost.

附图说明 DRAWINGS

下面结合附图对本发明作进一步说明。 The invention will now be further described with reference to the accompanying drawings.

图 1为本发明的用于制备制造动力电池的超细钴粉的工艺流程图；图 2为用硬质合金废料通过电解溶解得到粗钴盐溶液并制备超细钴粉的工艺流程图； 1 is a flow chart of a process for preparing an ultrafine cobalt powder for manufacturing a power battery according to the present invention; and FIG. 2 is a process flow chart for obtaining a crude cobalt salt solution by electrolytic solution of a cemented carbide scrap and preparing an ultrafine cobalt powder;

图 3为***还原炉的结构示意图。 Figure 3 is a schematic view showing the structure of the blasting reduction furnace.

具体实施方式 detailed description

实施例 1 : Example 1

本实施例的循环技术生产超细球状的制造方法的工艺流程图见图 1。在本实施例中所使用的废料（二次粗钴料）为： The process flow of the manufacturing method of the ultra-fine spherical shape by the recycling technique of this embodiment is shown in Fig. 1. The waste (secondary coarse cobalt) used in this embodiment is:

1、废镍氢 /镍镉电池及其生产过程中的废料、边料，这类废料中含钴为 1.0-15%不等; 其它成份为 Ni、 Fe、 Cd、 Zn等， Ni: 10-60%, Fe: 1-10%。 Cd: 0.1-10%, Zn: 0.1-10% 1. Scrap nickel-hydrogen/nickel-cadmium batteries and scraps and trimmings in the production process, such wastes contain 1.0-15% cobalt; other components are Ni, Fe, Cd, Zn, etc., Ni: 10- 60%, Fe: 1-10%. Cd: 0.1-10%, Zn: 0.1-10%

2、废锂离子电池及其生产过程中的废料、边料，这类废料中，含 Co为 5-50%, 其它成份为 Ni、 Li、石墨、 Mn等， Ni: 1-20%, Li: 1-20%。石墨： 1-30%, Mn: 1-30% 2. Waste lithium ion battery and waste material and edge material in the production process. The waste contains 5-50% Co, other components are Ni, Li, graphite, Mn, etc., Ni: 1-20%, Li : 1-20%. Graphite: 1-30%, Mn: 1-30%

步骤 1 : 溶解 Step 1: Dissolve

在所述二次含钴废料或钴渣中加入硫酸或盐酸，其浓度为：硫酸 10— 98 %或盐酸 5— 37 % (重量百分数），硫酸或盐酸加入量以废料中所有金属总量来计算，化学当量 100%-200%，使废料溶解，废料中的钴形成可溶性的硫酸钴 CoSO₄; 废料中的其他成分也溶解在硫酸中形成硫酸盐，由此形成粗硫酸钴 CoS0₄溶液或粗氯化钴 CoCl₂溶液； Adding sulfuric acid or hydrochloric acid to the secondary cobalt-containing scrap or cobalt slag at a concentration of 10-98% sulfuric acid or 5-17% by weight of hydrochloric acid, and the amount of sulfuric acid or hydrochloric acid added is the total amount of all metals in the scrap. Calculate, chemical equivalent 100%-200%, so that the waste dissolves, the cobalt in the waste forms soluble cobalt sulfate CoSO ₄ ; other components in the waste are also dissolved in sulfuric acid to form sulfate, thereby forming a crude cobalt sulfate CoS0 ₄ solution or Crude cobalt chloride CoCl ₂ solution;

步骤 2: 提纯 Step 2: Purification

将步骤 1 获得的粗硫酸钴或粗氯化钴溶液在进入萃取前进行化学预除杂：以 CoSO₄溶液除杂为例： The crude cobalt sulfate or crude cobalt chloride solution obtained in step 1 is subjected to chemical pre-decontamination before entering the extraction: taking CoSO ₄ solution for impurity removal as an example:

1、 Ca/Mg脱除：将 CoS0₄溶液进行 Ca/Mg脱除，以达到溶液中的 1. Removal of Ca/Mg: The CoS0 ₄ solution is removed by Ca/Mg to reach the solution.

[Ca²⁺]<lg/l, [Mg²⁺]<2g/l。 [Ca ²⁺ ]<lg/l, [Mg ²⁺ ]<2g/l.

操作如下： The operation is as follows:

配制氟化钠溶液：配制 20%的 NaF溶液，在 1M³的容器中，加入纯水 800L，加入 NaF200Kg，搅拌溶解；调 pH: 将待除 Ca/Mg的 CoSO4溶液泵入除 Ca/Mg槽，加到体积的 70%，调 pH 5—5.5； Prepare sodium fluoride solution: prepare 20% NaF solution, add 800L of pure water in a 1M ³ container, add NaF200Kg, stir and dissolve; Adjust pH: pump the Ca/Mg CoSO4 solution into the Ca/Mg tank, add 70% of the volume, adjust the pH 5-5.5;

升温：在保温状态下，升温至 90-100°C ; Heating: In the state of heat preservation, the temperature is raised to 90-100 ° C;

反应沉 Ca Mg: 先按 CoS04溶液中 Ca/Mg的含量，计算好理论 NaF溶液的加入量，实际过量 100%--150%，在搅拌状态下， 60分钟内慢慢加入配制好 NaF溶液，维持 90°C— 100°C，加完料后，搅拌 30— 60分钟，取样分析 Ca/Mg。 Reaction precipitation Ca Mg: Firstly, according to the content of Ca/Mg in CoS04 solution, the theoretical NaF solution is calculated. The actual excess is 100%--150%. Under stirring, slowly add NaF solution in 60 minutes. Maintain 90 ° C - 100 ° C, add the material, stir for 30-60 minutes, sample and analyze Ca / Mg.

过滤：趁热过滤，滤液存入中间槽冷却，视过滤情况，采取一次或多次过滤。 Filtration: Filter while hot, store the filtrate in the middle tank for cooling, and take one or more filtrations depending on the filtration.

1、净化除 Fe 1, purification and removal of Fe

对上述含铁的 CoSO₄的溶液进行净化除 Fe，以达到萃取的要求： [Fe3+]<400mg/l Purification of the above iron-containing CoSO ₄ solution in addition to Fe to achieve the extraction requirements: [Fe3+]<400mg/l

操作如下： The operation is as follows:

备料：待理的 CoSO₄溶液必须是经过滤的清亮溶液，以泵抽入除 Fe槽加到反应槽的 70%。 Preparation: The treated CoSO ₄ solution must be a filtered clear solution that is pumped into the removal tank to remove 70% of the reaction tank.

准备 CoC0₃干粉 Prepare CoC0 ₃ dry powder

加入氧化剂：加入氧化剂 H₂0₂，按除铁理论用量的 1.2— 2倍加入，反应时间 1小时。 Adding oxidizing agent: Adding oxidizing agent H ₂ 0 ₂ , adding 1.2-2 times of the theoretical amount of iron removal, the reaction time is 1 hour.

升温，调 pH: 升温至 70— 80°C，加入准备好的 CoCO₃干粉，在 4小时内分多次撒入干粉，每次 3— 5Kg，直到 PH=3.8— 4.5; Raise the temperature, adjust the pH: heat up to 70-80 ° C, add the prepared CoCO ₃ dry powder, sprinkle the dry powder several times in 4 hours, each time 3 - 5Kg, until PH = 3.8 - 4.5;

搅拌反应：搅拌反应 1一 2小时，取样分析，趁热过滤，滤液存入中间槽冷却，视过滤情况，采取一次或多次过滤。 Stirring reaction: Stir the reaction for 1 to 2 hours, sample and analyze, filter while hot, store the filtrate in the middle tank, and filter one or more times depending on the filtration.

3、除铜、铅、镉 3, in addition to copper, lead, cadmium

对 COS0₄含铜、铅、镉、超标的溶液进行净化除铜、铅、镉,以达到萃取要求： [Cu] <10g/l, [Pb]<10mg/1， [Cd]<2g/1; Purify copper, lead, cadmium and super-standard solutions of COS0 ₄ to remove copper, lead and cadmium to achieve extraction requirements: [Cu] <10g/l, [Pb]<10mg/1, [Cd]<2g/1 ;

配制硫化钠溶液：配制 100— 120g/.l的硫化钠溶液，将粗硫酸钴或硫酸镍溶液加温至 65— 75°C，用 Na₂C0₃溶液将 pH调至 2— 2.2，在搅拌状态下慢慢加入 N S溶液，加入量为溶液中含铜、铅、镉总量化学当量的 1.5倍，搅拌反应 1一 2hr，反应终点 pH为 2.2，过滤。 Prepare sodium sulfide solution: Prepare 100-120g/.l sodium sulfide solution, warm crude cobalt sulfate or nickel sulfate solution to 65-75 °C, adjust the pH to 2-2.2 with Na ₂ C0 ₃ solution, stir The NS solution was slowly added in an amount of 1.5 times the chemical equivalent of total copper, lead and cadmium in the solution, and the reaction was stirred for 1 to 2 hr, and the pH of the reaction was 2.2, and filtered.

当然，在 [Ca²⁺]<lg/l， [Mg²⁺]<2g/l , [Cu] <10g/l , [Pb]<10mg/l₅[Cd]<2g/l [Fe3+]<400mg/l时，可以省去以上化学预除杂过程。 Of course, in [Ca ²⁺ ]<lg/l, [Mg ²⁺ ]<2g/l , [Cu] <10g/l , [Pb]<10mg/l ₅ [Cd]<2g/l [Fe3+]< At 400 mg/l, the above chemical pre-separation process can be omitted.

4、二次萃取，获得纯净的硫酸钴溶液；在萃取过程中，通过二次萃取可除去溶液中的微量 Fe、 Cd、 Zn、 Li、 Mn。并实现 Ni和 Co的分离。 4. Secondary extraction to obtain a pure cobalt sulfate solution; during the extraction process, trace amounts of Fe, Cd, Zn, Li, and Mn in the solution can be removed by secondary extraction. And the separation of Ni and Co is realized.

具体的是： Specifically:

( 1 ) 在粗硫酸钴溶液中加入硫酸调酸，调节溶液的 pH值为 2-4备用； (1) adding sulfuric acid to the crude cobalt sulfate solution to adjust the pH of the solution to 2-4;

(2) 配制萃取剂（液）、洗酸和反萃取剂（液） (2) Preparation of extractant (liquid), acid washing and stripping agent (liquid)

一次萃取剂（液）为含 P204 10%和磺化煤油 90% (体积比）的混合液； P204为 [二一（2-乙基己基）磷酸] (国外称为 D2EHPA) ； The primary extractant (liquid) is a mixture containing 10% of P204 and 90% by volume of sulfonated kerosene; P204 is [di(2-ethylhexyl)phosphoric acid] (known abroad as D2EHPA);

二次萃取剂（液）为含 P50720%+磺化煤油 80% (体积比）的混合液； P507[2- 乙基己基磷酸 *单（2-乙基己基）酯] (国外称为 PC88A) ； The secondary extractant (liquid) is a mixture containing P50720%+sulfonated kerosene 80% by volume; P507[2-ethylhexylphosphoric acid*mono(2-ethylhexyl)ester] (known abroad as PC88A) ;

反萃取剂（液）为含硫酸或盐酸 1.0-1.5mol/L的纯水溶液，本实施例中为含硫酸 1.3mol/L的纯水溶液； The stripping agent (liquid) is a pure aqueous solution containing sulfuric acid or hydrochloric acid 1.0-1.5 mol/L, in this embodiment, a pure aqueous solution containing sulfuric acid 1.3 mol/L;

洗酸 1 为含硫酸或盐酸 0.30-1.0mol/L 的溶液，本实施例中为含硫酸 0.45mol/L的纯水溶液； Washing acid 1 is a solution containing sulfuric acid or hydrochloric acid of 0.30-1.0 mol/L, in this embodiment, a pure aqueous solution containing sulfuric acid 0.45 mol/L;

洗酸 2 为含硫酸或盐酸 0.10-0.8mol/L 的溶液；本实施例中为含硫酸 0.2mol/L的纯水溶液； The acid washing 2 is a solution containing sulfuric acid or hydrochloric acid of 0.10-0.8 mol/L; in this embodiment, sulfuric acid is contained. 0.2 mol/L of pure aqueous solution;

皂化用碱为 2-10mol/L的氢氧化钠溶液；本实施例中为 5.5mol/L的氢氧化钠溶液； The saponification base is a 2-10 mol/L sodium hydroxide solution; in this embodiment, a 5.5 mol/L sodium hydroxide solution;

( 3 ) 萃取：一次萃取和二次萃取是两个连续的操作过程，每个萃取过程在相互连通的若干个萃取箱中进行。 (3) Extraction: Primary extraction and secondary extraction are two consecutive operations, each of which is carried out in several extraction tanks that are connected to each other.

一次萃取 (分馏萃取)： One extraction (fractional extraction):

A、萃取除杂： A, extraction and impurity removal:

将在（1 ) 中经过调酸的粗硫酸钴、（2) 中制备的一次萃取剂以及皂化用碱通入萃取器中，其中，一次萃取剂 P204的流量为 2-151/min，皂化用碱的流量为 50-190mol/min 使皂化率为 60-65 %，粗硫酸钴液或氯化钴的流量为 2-151/min, 充分搅拌，静止分层，在常温进行一次萃取，引出的萃余相作为半精制硫酸钴或氯化钴溶液备用，杂质进入负载有机相，并进入下一级洗涤段。 Cobalt crude cobalt sulfate in (1), primary extractant prepared in (2), and saponification alkali are introduced into the extractor, wherein the flow rate of the primary extractant P204 is 2-151/min, for saponification The flow rate of the base is 50-190 mol/min, the saponification rate is 60-65%, the flow rate of the crude cobalt sulfate solution or cobalt chloride is 2-151/min, fully stirred, statically layered, and once extracted at room temperature, the extraction is carried out. The raffinate phase is reserved as a semi-refined cobalt sulphate or cobalt chloride solution, and the impurities enter the supported organic phase and enter the next stage of the scrubbing section.

B、洗钴： B. Washing cobalt:

将负载有机相通入洗涤段，将（2) 中配制的洗酸 1以 50-150ml/min的流量加入萃取器中，充分搅拌，静止分层，洗涤负载有机相，从萃取剂中进一步提取出剩余的钴，与 A步骤中的萃余相即半精制硫酸钴或氯化钴溶液合并备用，该过程可对萃取相残存的钴离子进一步回收； The loaded organic phase is passed to the washing section, and the washing acid 1 prepared in (2) is added to the extractor at a flow rate of 50-150 ml/min, stirred thoroughly, statically layered, the organic phase is washed, and the extractant is further extracted. The remaining cobalt is combined with the raffinate phase in the A step, that is, the semi-refined cobalt sulfate or cobalt chloride solution, and the process can further recover the cobalt ions remaining in the extracted phase;

C、反萃杂质： C, stripping impurities:

负载有机相进入反萃段，同时通入（2) 中配制的反萃取剂，反萃取液的流量为 100-500ml/min，充分搅拌，静止分相，引出再生的萃取剂，循环使用，含杂质的反萃液进入污水处理***； The organic phase is loaded into the stripping section, and the stripping agent prepared in (2) is introduced. The flow rate of the stripping solution is 100-500 ml/min, fully stirred, static phase separation, and the regenerated extractant is taken out, recycled, including The stripping solution of impurities enters the sewage treatment system;

在本一次萃取中，可除去粗 CoS0₄或 CoCl₂中的大部分杂质元素： Fe、 Cu、 Zn、 i、 Cr、 Cd、 Ca、等。本实施例中，可除去粗 CoS0₄中的大部分杂质元素： Fe、 Cd、 Zn、 Ca、 Li、 Mn。 In this extraction, most of the impurity elements in the crude CoS0 ₄ or CoCl ₂ can be removed: Fe, Cu, Zn, i, Cr, Cd, Ca, and the like. In this embodiment, most of the impurity elements in the crude CoS0 ₄ can be removed: Fe, Cd, Zn, Ca, Li, Mn.

在萃取中使用逆流箱式萃取器，粗硫酸钴溶液流量视萃取器生产能力和杂质含量而定，上面只是就一种具体的工艺提出的一种工艺参数。 A countercurrent box extractor is used in the extraction. The flow rate of the crude cobalt sulfate solution depends on the capacity of the extractor and the amount of impurities. The above is only one process parameter proposed for a specific process.

二次萃取： Secondary extraction:

A、萃取钴： A, extraction of cobalt:

将在一次萃取中获得的半精制硫酸钴溶液、 (2 )中配制的二次萃取剂以及皂化用碱通入萃取器中，其中硫酸钴溶液流量为 0.8-15 1/min,二次萃取剂流量为 2-20 1/min，皂化用碱流量为 200-1000ml/min，使皂化率为 20-40% , 充分搅拌，静止分层，在常温进行二次萃取，钴进入负载有机相；引出萃余液，根据镍含量另行处理。 The semi-refined cobalt sulfate solution obtained in one extraction, the secondary extractant prepared in (2), and the alkali for saponification are introduced into the extractor, wherein the flow rate of the cobalt sulfate solution is 0.8-15 1 /min, and the secondary extractant The flow rate is 2-20 1/min, the flow rate of alkali for saponification is 200-1000 ml/min, the saponification rate is 20-40%, fully stirred, static layering, secondary extraction at normal temperature, cobalt enters the loaded organic phase; The raffinate is treated separately according to the nickel content.

B、洗杂质： B, wash impurities:

将二次萃取的负载有机相和（2 ) 中配制的洗酸 2通入洗涤段，洗酸 2流量为 0.1-3.01/min，充分搅拌，静止分相，负载有机相进入下一级反萃段，洗涤同 A步骤中的萃余液合并，在萃余液中还存在一些镍元素； The second extraction of the supported organic phase and the washing acid 2 prepared in (2) are passed to the washing section, the acid washing 2 flow rate is 0.1-3.01/min, the mixture is fully stirred, the stationary phase is separated, and the organic phase is loaded into the next stage. In the section, the washing is combined with the raffinate in the step A, and some nickel elements are present in the raffinate;

C、反萃钴： C, counter-cobalt:

负载有机相进入下一级反萃段，同时通入（2 ) 中配制的反萃取剂，反萃取剂流量为 100-200mgl/min，充分搅拌，静止分相，引出再生的萃取剂，循环使用，反萃液为精制钴液。 The organic phase is loaded into the next-stage stripping section, and the stripping agent prepared in (2) is introduced. The stripping agent flow rate is 100-200 mgl/min, fully stirred, static phase separation, and the regenerated extractant is taken out, and recycled. The stripping solution is a refined cobalt solution.

在本二次萃取中可除去己除杂质的半精制氯化钴或硫酸钴溶液中的钠、镍、镁等。 In the second extraction, sodium, nickel, magnesium, or the like in the semi-refined cobalt chloride or cobalt sulfate solution from which impurities have been removed can be removed.

在本实施例中，二次萃取中可除去半精制硫酸钴溶液中的钠和少量的镍制成精制硫酸钴溶液； In this embodiment, the sodium in the semi-refined cobalt sulfate solution and a small amount of nickel can be removed in the secondary extraction. Into a refined cobalt sulfate solution;

在所述的二次萃取中 A和 B步骤中引出的所述萃余液和洗液中还存在一些镍元素，对其迸行处理 .· In the secondary extraction, some of the nickel elements are present in the raffinate and the washing liquid extracted in the steps A and B, and are treated in the same manner.

将所述含镍溶液根据镍含量分别处理，以回收镍，含镍浓度低可排入污水 ***回收镍，含镍浓度高，可用化学沉淀法或萃取法回收镍。 The nickel-containing solution is separately treated according to the nickel content to recover nickel. The nickel-containing concentration is low and can be discharged into the sewage system to recover nickel. The nickel-containing concentration is high, and nickel can be recovered by chemical precipitation or extraction.

同样的，在本二次萃取中使用逆流箱式萃取器，本实施例使用箱式萃取器，其中硫酸钴溶液的流量视萃取器生产能力和杂质含量而定。 Similarly, in the present secondary extraction, a countercurrent box type extractor is used. In this embodiment, a box type extractor is used, wherein the flow rate of the cobalt sulfate solution depends on the productivity of the extractor and the impurity content.

皂化用碱是为平衡萃取过程中产生的酸（H+) 而进行的预中和作用；在所述二次萃取过程中，按照操作规程的要求配制好萃取剂，粗钴液（料液），洗钴液（洗酸）、反萃液（反酸），皂化用碱，按设定的流量进行萃取除杂、洗钴、反萃杂质三段操作。萃取除杂是将粗钴液中的杂质萃取进入萃取剂而钴则留在料液（萃余液）中，从而实现钴和杂质的分离；萃杂后的萃取剂在洗钴段被洗酸洗涤，使萃取剂中部分夹带的钴洗脱进入萃余液，而杂质不被洗脱，以提高 Co的回收率；反萃段，则是将萃取剂萃取的杂质被反萃液（反酸）反萃下来，进入反萃液中，外排进入污水处理***，萃取剂得到再生，进入下一个萃取操作循环，过程是连续进行的。 The saponification base is a pre-neutralization effect for balancing the acid (H+) generated during the extraction process; in the secondary extraction process, the extractant is prepared according to the requirements of the operation procedure, the crude cobalt solution (liquid solution), Washing cobalt solution (washing acid), stripping solution (reverse acid), alkali for saponification, three-stage operation of extracting and removing impurities, washing cobalt and stripping impurities according to the set flow rate. The extraction impurity is extracted from the impurities in the crude cobalt solution into the extractant and the cobalt is left in the feed liquid (raffinate) to separate the cobalt and the impurities; the extractant after the extraction is washed in the cobalt-washing section. Washing, the partially entrained cobalt in the extractant is eluted into the raffinate, and the impurities are not eluted to increase the recovery of Co; in the stripping section, the impurities extracted by the extractant are stripped (reacid) After stripping, it enters the stripping solution, and the effluent enters the sewage treatment system, and the extractant is regenerated and proceeds to the next extraction operation cycle, and the process is continuous.

步骤 3 : 雾化水解制取氧化物前驱体一碳酸钴晶体 Step 3: Atomization hydrolysis to prepare an oxide precursor, cobalt carbonate crystal

a、制备钴氧化物前驱体碳酸钴结晶： a, preparation of cobalt oxide precursor cobalt carbonate crystal:

将碳酸氢铵用温水（水温 = 45- 5(TC ) 溶解，并对其溶液进行过滤，除去溶液中固体杂质，配制成碳铵的浓度为 225g/L土 5的溶液。 Ammonium bicarbonate was dissolved in warm water (water temperature = 45 - 5 (TC), and the solution was filtered to remove solid impurities in the solution to prepare a solution having a concentration of ammonium bicarbonate of 225 g/L of soil 5.

将精制硫酸钴溶液调整其浓度为 85g/L和浓度为 225g/L的碳铵溶液以雾状喷射到反应釜中，硫酸钴溶液控制加入量为 200L〜250L/hr，碳酸铵按 Co+²计量的 1.5〜2. 0倍加入，混合搅拌，搅拌速度： 120r/min，反应温度： 55- 60°C , 反应 pH值： 7. 5 ±0. 1，反应过程中，维持 pH的稳定，当 D50=8- 15um时，分离出晶体；反应方式：对冲，即在反应器中的上部和下部分设两个进料喷嘴，上面一个喷嘴喷口向下，下面一个喷嘴喷口向上喷出物料。最好是钴液喷嘴在上，碳酸氢铵喷嘴在下。 The refined ammonium sulfate solution was adjusted to a concentration of 85 g/L and a concentration of 225 g/L of ammonium bicarbonate solution was sprayed into the reaction vessel in a mist form. The cobalt sulfate solution was controlled to be added in an amount of 200 L to 250 L/hr, and ammonium carbonate was measured by Co + ² 1.5~2. 0 times addition, mixing and stirring, stirring speed: 120r/min, reaction temperature: 55-60°C, reaction pH: 7. 5 ±0. 1, during the reaction, maintain pH stability, when When D50=8-15um, the crystal is separated; Reaction mode: Hedging, that is, two feeding nozzles are arranged in the upper part and the lower part of the reactor, one nozzle nozzle is downward, and the lower nozzle nozzle is sprayed upward. Preferably, the cobalt liquid nozzle is on and the ammonium bicarbonate nozzle is below.

通过上述雾化水解，可以制成球状碳酸钴晶体。 By the above-described atomization hydrolysis, spherical cobalt carbonate crystals can be produced.

所述雾化水解反应器包括一个反应罐，其上包括加热装置、搅拌装置和进料装置，所述进料装置包括若干进料喷管，最好是其中一些进料喷管的喷嘴设于反应罐罐体的上部，另一些进料喷管的喷嘴设于反应罐罐体的下部； The atomization hydrolysis reactor comprises a reaction tank comprising a heating device, a stirring device and a feeding device, the feeding device comprising a plurality of feed nozzles, preferably some of the nozzles of the feed nozzles are provided The upper part of the reaction tank body, and the nozzles of the other feed nozzles are arranged at the lower part of the reaction tank body;

在所述雾化水解过程中，所述反应物的投料为对冲方式，即在反应器中的上部和下部分设都设有进料喷嘴，上面一个喷嘴喷口向下，下面一个喷嘴喷口向上喷出物料。所述钴液从在上的喷嘴向下喷出，所述沉淀剂从在下的喷嘴向上喷出。 In the atomization hydrolysis process, the reactant is charged in a hedging manner, that is, a feed nozzle is provided in both the upper portion and the lower portion of the reactor, and one nozzle nozzle is downward and a nozzle nozzle is sprayed upward. Material. The cobalt liquid is ejected downward from the upper nozzle, and the precipitant is ejected upward from the lower nozzle.

在反应器中，很纯的所述钴液与其它反应物通过反冲方式加入反应器进行雾化水解形成结晶一一钴氧化物前驱体。然后，将该前驱体进行干燥备用。 In the reactor, the very pure cobalt liquid and other reactants are fed back into the reactor by back-flushing to form a crystalline one-cobalt oxide precursor. Then, the precursor is dried for use.

步骤 4: ***热还原制备球状超细钴粉 Step 4: Preparation of spherical ultrafine cobalt powder by blasting thermal reduction

分预还原、还原和冷却三个阶段： There are three stages of pre-reduction, reduction and cooling:

( 1 ) 预还原- 将步骤 3制出的碳酸钴晶体投入液压多段推舟还原炉 1 (如图 4所示）的入口中，还原炉 1包括三个通道壳体，其间通过输送管路相连接构成一个狭长的通道，在该通道的两端设有进口和出口，在该通道中设有若干用于盛放前驱体的物料盒一一推舟。所述三个壳体从入口到出口顺序形成三个区域：为预还原区域 11、还原区域 12和冷却区域 13，各区域通过不锈钢挂帘 2隔开，该挂帘设在各区域之间的连接管路内和出口上，所述挂帘 2的上端与管壁铰接连接，其下端为自由端，推舟在设于通道进口端外面的电动推杆推动下依次进入通道内，随着后面推舟的推入，使前面的推舟被推动前行。在各区域的机壳的顶部设有进气口和排气口，在所述预还原区域和还原区域中，所述迸气口和排气口设在该区域的两端且进出气口与推舟的行进方向相反；在每个区域中又通过隔板分隔成若干分段空间，该隔板在其下方设有通道孔使各分段空间连通令所述推舟通过；在预还原区域 11和还原区域 12中的分别设有 4个和 6个分段空间，在各分段空间中分别设置加热器以在不同分段空间形成不同的温度，在冷却区域液设有 3个分段空间，在各分段空间中分别设有冷却器；在冷却区域的前面几个分段空间中的中部机壳顶部设有进气口，在最后一个分段空间中部即可顶部设有排气口。 (1) Pre-reduction - The cobalt carbonate crystal produced in the step 3 is introduced into the inlet of the hydraulic multi-stage push boat reduction furnace 1 (shown in Fig. 4), and the reduction furnace 1 includes three passage casings through which the conveying line is passed. The connection constitutes an elongated passage, and an inlet and an outlet are provided at both ends of the passage, and a plurality of material boxes for holding the precursor are provided in the passage. The three housings form three zones sequentially from the inlet to the outlet: for prepayment The original area 11, the reduction area 12 and the cooling area 13, each area is separated by a stainless steel curtain 2, which is disposed in the connecting line between the respective areas and the outlet, the upper end of the hanging curtain 2 and the wall The hinged connection has a lower end with a free end, and the push boat is sequentially pushed into the channel under the push of the electric push rod disposed outside the inlet end of the passage. With the push of the push boat behind, the front push boat is pushed forward. An air inlet and an exhaust port are provided at a top of the casing of each area, and in the pre-reduction area and the reduction area, the helium port and the exhaust port are disposed at both ends of the area, and the inlet and outlet ports and the push boat are The direction of travel is reversed; in each area, it is divided into a plurality of segment spaces by a partition plate, and the partition plate is provided with a passage hole below the space for connecting the segments to pass the push boat; in the pre-reduction region 11 and There are 4 and 6 segment spaces in the reduction region 12, respectively, heaters are arranged in each segment space to form different temperatures in different segment spaces, and three segment spaces are provided in the cooling region liquid. Coolers are respectively arranged in each segment space; an air inlet is arranged at the top of the middle casing in the first segment space of the cooling zone, and an exhaust port is provided at the top in the middle of the last segment space.

在预还原区域 11中通入保护性气体 C0₂，在该保护气氛中加热碳酸钴晶体，加热温度为 200— 400Ό , 加热时间 30rain，然后再保温 1小时，在该还原阶段使晶体脱水和进行预还原，使碳酸钴晶体中的二氧化碳溢出，其可以使晶体堆变得疏松，即进行所谓的***； A protective gas C0 _{2 is introduced} into the pre-reduction zone 11, and the cobalt carbonate crystal is heated in the protective atmosphere at a heating temperature of 200-400 Torr, a heating time of 30 min, and then further incubated for 1 hour, in which the crystal is dehydrated and subjected to a reduction. Pre-reduction, causing carbon dioxide in the cobalt carbonate crystal to overflow, which can make the crystal pile loose, that is, so-called blasting;

(2 ) 还原： (2) Restore:

预还原后的晶体在推舟中继续前行，进入还原区域 12，在 4个分隔空间内依次通过，第一个空间为低温区，后面的 3个空间为高温区，其又分成前低温区、高温区和后低温区，低温区温度 300- 400°C，高温区温度为 400-550°C , 前低温段和后低温段的温度比高温段的温度低 30— 50°C。在各空间物料停留的时间为 10- 60min。这样的加热方式可以使晶体颗粒在受热较均匀后再继续升温到高温段进行还原。还原过程在氢气和氮气形成还原气氛中进行，氢气和氮气的体积比为 3： 1，将液氨分解得到还原气体： 2NH₃→ 3¾+N₂。 The pre-reduced crystal continues to advance in the push boat, enters the reduction zone 12, passes sequentially in four compartments, the first space is a low temperature zone, and the latter three spaces are high temperature zones, which are further divided into a pre-low temperature zone. , high temperature zone and post low temperature zone, low temperature zone temperature 300-400 °C, high temperature zone temperature of 400-550 °C, the temperature of the former low temperature section and the post low temperature section is 30-50 °C lower than the temperature of the high temperature section. The time spent in each space material is 10-60 min. Such a heating method can make the crystal particles continue to be heated to a high temperature section for reduction after being heated more uniformly. The reduction process is carried out in a reducing atmosphere in which hydrogen and nitrogen are formed. The volume ratio of hydrogen to nitrogen is 3:1, and the liquid ammonia is decomposed to obtain a reducing gas: 2NH ₃ → 33⁄4+N ₂ .

( 3) 冷却 (3) Cooling

还原后的物料进入冷却区域，在 C0₂的保护气氛中将晶体冷却、惰化至室温，即可制成粒径在 0.1〜2 μ ηι的球状超细钴粉。冷却区域分成 3个温降阶梯分隔空间，每个阶梯的温差可以在 40— 80°C，如降温到 460°C保温 40分钟，继续降温到 400Ό保温 40分钟，最后自然冷却到室温。多段降温可以降低晶体的冷却速度，避免晶体结块和降低晶体的性能。 The reduced material enters the cooling zone, and the crystal is cooled and inerted to room temperature in a protective atmosphere of C0 ₂ to prepare spherical ultrafine cobalt powder having a particle diameter of 0.1 to 2 μ η. The cooling zone is divided into three steps of temperature drop step separation. The temperature difference of each step can be 40-80 °C, such as cooling to 460 °C for 40 minutes, continue to cool down to 400 Ό for 40 minutes, and finally cool to room temperature. Multi-stage cooling can reduce the cooling rate of the crystal, avoid crystal agglomeration and reduce the performance of the crystal.

循环技术生产超细钴粉的制造设备包括溶解设备、提纯设备、雾化水解反应器和还原设备，所述溶解设备为带有加热装置的反应器或带有加热装置及电解装置的反应器，所述提纯装置为萃取箱或带有加热装置及电解装置的反应器、所述还原设备为如上所述的液压和机械传动的多段推舟。 The recycling apparatus for producing ultrafine cobalt powder includes a dissolution apparatus, a purification apparatus, an atomization hydrolysis reactor, and a reduction apparatus, and the dissolution apparatus is a reactor with a heating device or a reactor with a heating device and an electrolysis device. The purification device is an extraction tank or a reactor with a heating device and an electrolysis device, and the reduction device is a multi-stage push boat that is hydraulically and mechanically driven as described above.

所述萃取箱是逆流箱式萃取器。 The extraction tank is a countercurrent tank extractor.

实施例 2: Example 2:

本实施例提供循环技术生产超细球状的制造方法。在本实施例中所使用的废料为： This embodiment provides a manufacturing method for producing an ultra-fine spherical shape by a circulation technique. The waste used in this embodiment is:

1、金刚石行业中的废触媒，这类废料中含 Co: 1-10%, Ni: 10-40%, Mn: 10-50%, 微量 Fe、 A1等。 1. Waste catalyst in the diamond industry, such waste contains Co: 1-10%, Ni: 10-40%, Mn: 10-50%, trace Fe, A1, etc.

步骤 1 : 溶解 Step 1: Dissolve

在所述二次含钴废料或钴渣中加入盐酸，其浓度为 5— 30%，（重量百分数），加入量视原料不同而不同，为 100%-150% (重量百分比）（为废料按所有金属总量来计算化学当量)，使之溶解，废料中的钴形成可溶性的氯化钴 CoCl_2; 废料中的其他成分也溶解在盐酸中形成可溶性氯化物，由此形成粗氯化钴Hydrochloric acid is added to the secondary cobalt-containing scrap or cobalt slag at a concentration of 5-30%, (weight percent), and the amount added varies from 100% to 150% by weight (for waste) The total amount of all metals is calculated to dissolve the chemical equivalent), and the cobalt in the waste forms soluble cobalt chloride CoCl _{2 ;} The other components in the waste are also dissolved in hydrochloric acid to form soluble chloride, thereby forming coarse cobalt chloride.

CoCl₂溶液； CoCl ₂ solution;

由于本实施例中所用原料杂质较多，而突出的是 Mn的含量较高。为此，在萃取之前设置一个化学除杂的过程。 Since the raw material impurities used in the present embodiment are large, the content of Mn is high. To this end, a chemical cleaning process is set up prior to extraction.

步骤 2：化学提纯 Step 2: Chemical Purification

采^硫酸铵部分淀镍和硫酸铵、碳铵、氨水混合溶液沉錳两步沉淀的方法。 A method of two-step precipitation of ammonium sulphate and ammonium sulphate, ammonium sulphate, ammonium bicarbonate and ammonia mixed solution.

溶液中金属离子的浓度为： Ni为 50g/L， Co为 4g/L， Mn为 20g/L。对此溶液加硫酸铵（重量百分比 30%- 70%) ，硫酸铵的加入量为溶液中镍的物质的量的 1. 1倍，搅拌反应 20分钟，过滤，分析滤液成分；滤液中加入硫酸铵（重量百分比 30%- 70°/。）、碳铵（重量百分比 30%- 70%) 和氨水（10-30%) 的混合溶液，搅拌反应 30分钟，过滤，分析滤液中的金属镍、钴和锰浓度。反应溶液中总氨浓度控制在 4mol/L左右，反应终点 pH值通过调节硫酸铵和氨水的配比控制在 10左右。碳铵的用量为锰的物质的量的 0. 8倍。 The concentration of metal ions in the solution was: Ni was 50 g/L, Co was 4 g/L, and Mn was 20 g/L. To the solution, ammonium sulfate (30% - 70% by weight) is added, ammonium sulfate is added in an amount of 1.1 times the amount of nickel in the solution, the reaction is stirred for 20 minutes, filtered, and the filtrate component is analyzed; sulfuric acid is added to the filtrate. A mixed solution of ammonium (30%-70% by weight), ammonium bicarbonate (30%-70% by weight) and ammonia (10-30%), stirred for 30 minutes, filtered, and analyzed for metallic nickel in the filtrate. Cobalt and manganese concentrations. The total ammonia concentration in the reaction solution is controlled at about 4 mol/L, and the pH of the reaction end point is controlled to about 10 by adjusting the ratio of ammonium sulfate to ammonia. 8倍。 The amount of the amount of manganese is 0.8 times.

分析结果表 1 溶液种类及浓度金属沉淀率（％) 溶液初始浓度（g/L) 硫酸铵沉镍后浓度择性沉锰后浓度 Ni Co Mn 种类 Analysis Results Table 1 Solution Type and Concentration Metal Precipitation Rate (%) Solution Initial Concentration (g/L) Ammonium Sulfate After Nickel Concentration Selective Post-Mn Manganese Concentration Ni Co Mn Species

溶液 Ni50 Co4 Mn20 Ni20. 1 Co3. 5 Nill. 8 Co2 Mnl. 2 0. 87 5. 17 87 Solution Ni50 Co4 Mn20 Ni20. 1 Co3. 5 Nill. 8 Co2 Mnl. 2 0. 87 5. 17 87

Mnl9. 4 Mnl9. 4

从表 1的分析结果看，在溶液中第一步加入硫酸铵后，大部分的镍以硫酸镍铵复盐的形式从溶液中被沉淀下来，初步实现镍钴和锰的分离，其中有少量的钴和锰以吸附的形式被沉淀下来。第二步加入碳铵、氨水和硫酸铵的混合溶液，大量的锰被沉淀下来，而钴则留在溶液中，从而实现钴和锰的分离。 From the analysis results in Table 1, after the first step of adding ammonium sulfate in the solution, most of the nickel is precipitated from the solution in the form of a double-salt ammonium sulfate, and the separation of nickel-cobalt and manganese is initially achieved, among which a small amount The cobalt and manganese are precipitated in the form of adsorption. In the second step, a mixed solution of ammonium bicarbonate, ammonia water and ammonium sulfate is added, a large amount of manganese is precipitated, and cobalt is left in the solution, thereby achieving separation of cobalt and manganese.

镍、钴的回收率及锰的沉淀率为： . The recovery of nickel and cobalt and the precipitation rate of manganese:

镍的回收率 q _ni = 99. 13 % Nickel recovery rate q _ni = 99. 13 %

钴的回收率 η。。= 94. 83 % The recovery of cobalt is η. . = 94. 83 %

锰的沉淀率 D = 87 % Manganese precipitation rate D = 87 %

对于直接用化学沉淀法替代萃取法的提纯过程，与上述过程基本相同。关于电化学沉积过程的所述提纯过程是根据所述粗钴盐溶液中一种或几种杂质的种类和沉积电位特性，选择适合的电流密度，以石墨为阳极，以钛板为阴极，以所述粗钴盐溶液为电解液进行电解，使杂质在阴极上析出而除去，制成精制氯化钴或硫酸钴溶液；该技术可以用现有技术中的方法根据所含杂质的种类和含量确定相应参数进行，这为本领域技术人员所熟知，故此，在这里就不再赘述。 The purification process for directly replacing the extraction method by chemical precipitation is basically the same as the above process. The purification process for the electrochemical deposition process is based on the type and deposition potential characteristics of one or more impurities in the crude cobalt salt solution, and a suitable current density is selected, using graphite as the anode and titanium plate as the cathode. The crude cobalt salt solution is electrolyzed by an electrolytic solution, and impurities are precipitated on the cathode to be removed, thereby preparing a purified cobalt chloride or cobalt sulfate solution; the technique can be based on the type and content of impurities contained in the prior art. It is determined that the corresponding parameters are performed, which are well known to those skilled in the art, and therefore will not be described herein.

步骤 2: 萃取 Step 2: Extraction

将步骤 2经过化学提纯后的粗氯化钴溶液进行二次萃取,获得纯净的氯化钴溶液; 在萃取过程中，通过二次萃取可除去溶液中的 Ni、 Mn、 Fe、 A1等多种杂质元素。 The crude cobalt chloride solution after the chemical purification in step 2 is subjected to secondary extraction to obtain a pure cobalt chloride solution; in the extraction process, Ni, Mn, Fe, A1, etc. in the solution can be removed by secondary extraction. Impurity element.

具体的是 · Specifically,

( 1 ) 在粗氯化钴溶液中加入盐酸调酸，调节溶液的 pH值为 2-4备用； (1) adding hydrochloric acid to the crude cobalt chloride solution to adjust the pH of the solution to 2-4;

(2 ) 配制萃取剂（液）和反萃取剂（液）： (2) Preparation of extractant (liquid) and stripping agent (liquid):

一次萃取剂（液）为含 P204 8%和磺化煤油 92% (体积比.）的混合液；二次萃取剂（液）为含 P50725%+磧化煤油 75% (体积比）的混合液；反萃取剂（液）为含 HC11.2-1.5mol/L的纯水溶液；洗酸 1为含 HC10.35-1.0mol/L的溶液； The primary extractant (liquid) is a mixture containing P204 8% and sulfonated kerosene 92% (volume ratio); the secondary extractant (liquid) is a mixture containing P50725%+ sulphurized kerosene 75% by volume. The stripping agent (liquid) is a pure aqueous solution containing HC11.2-1.5mol/L; Washing acid 1 is a solution containing HC 10.35-1.0 mol/L;

洗酸 2为含硫酸 0.15-0.8mol/L的溶液； Washing acid 2 is a solution containing 0.15-0.8 mol/L of sulfuric acid;

皂化用碱为 3-8.5mol/L的氢氧化钠溶液； The saponification base is a 3-8.5 mol/L sodium hydroxide solution;

( 3 ) 萃取： (3) Extraction:

本实施例的两个萃取段所用设备与实施例 1相同，过程液基本相同。步骤 3 : 雾化水解制取氧化物前驱体一草酸钴钴晶体 The apparatus for the two extraction sections of this example was the same as that of Example 1, and the process liquids were substantially the same. Step 3: Atomization hydrolysis to prepare an oxide precursor, cobalt oxalate crystal

a、制备草酸铵溶液： a, preparation of ammonium oxalate solution:

将草酸铵用温水（水温在 45- 55Ό ) 溶解，并对其进行过滤，除去溶液中的固体杂质，再在草酸溶液中通入液氨，配制成 pH 为 4.3-4.5，浓度为 130-150g/L的草酸铵溶液。 Ammonium oxalate is dissolved in warm water (water temperature of 45-55 Ό), and filtered to remove solid impurities in the solution, and then liquid ammonia is introduced into the oxalic acid solution to prepare a pH of 4.3-4.5, and the concentration is 130-150 g. /L of ammonium oxalate solution.

b、制备钴氧化物前驱体草酸钴结晶： b. Preparation of cobalt oxide precursor precursor cobalt oxalate crystal:

将精制氯化钴溶液调整其浓度为 85 ±5g/L (温度为 25-28°C、pH为 0. 7±0. 1 ) 和制备成浓度为 139±2g/L (温度为 65-70°C )的草酸铵溶液以雾状喷射到反应釜中。混合搅拌，搅拌速度为 90-250转 /min, 反应时温度在 50- 52°C间，控制加料速度使反应时间为 2分- 5分，然后分离出晶体； The purified cobalt chloride solution was adjusted to a concentration of 85 ± 5 g / L (temperature of 25-28 ° C, pH of 0.7 ± 0.1) and prepared to a concentration of 139 ± 2 g / L (temperature of 65-70) The ammonium oxalate solution of °C) was sprayed into the reaction vessel in a mist. Mixing and stirring, the stirring speed is 90-250 rev / min, the reaction temperature is between 50-52 ° C, the feeding speed is controlled so that the reaction time is 2 minutes - 5 minutes, and then the crystal is separated;

或者： Or:

a、制备草酸铵溶液： a, preparation of ammonium oxalate solution:

^草酸用温水（水 ^在 45— 65°C )溶解，并对其进行过滤，除去溶液中的固体杂质，再在草酸溶液中通入液氨，配制成 pH为 4.1-4.5，浓度为 130-150g/L 的草酸铵溶液。 ' ^ Oxalic acid is dissolved in warm water (water ^ at 45-65 ° C), and filtered to remove solid impurities in the solution, and then liquid ammonia is introduced into the oxalic acid solution to prepare a pH of 4.1-4.5, a concentration of 130 -150 g/L ammonium oxalate solution. '

b、制备钴氧化物前驱体草酸钴结晶- 制备草酸钴结晶- 将精制氯化钴溶液调整其浓度为 50-140g/L和制备成浓度为 130-150g/L的草酸铵溶液以雾状喷射到反应釜中，混合搅拌，反应时温度在 50- 52Ό间，反应时流量为： 35- 45L/分，反应时间为 5 - 7分钟，反应终点 pH值： 1. 6-1. 8; 然后分离出晶体； ― b. Preparation of cobalt oxide precursor cobalt oxalate crystal - preparation of cobalt oxalate crystal - adjusting the concentration of cobalt chloride solution to a concentration of 50-140 g / L and preparing an ammonium oxalate solution having a concentration of 130-150 g / L to spray in a mist Into the reaction vessel, mixing and stirring, the reaction temperature is between 50 and 52 ,, the reaction flow rate is: 35-45 L / min, the reaction time is 5 - 7 minutes, the reaction end point pH: 1. 6-1. 8; Separating crystals; ―

通过上述雾化水解，可以制成针状草酸钴。 The needle-like cobalt oxalate can be produced by the above-described atomization hydrolysis.

步骤 4: ***热还原制备超细钴粉 Step 4: Preparation of ultrafine cobalt powder by blasting thermal reduction

将步骤 3制备的草酸钴晶体在如图 3所示的推舟中还原成超细钴粉，同样经过预加热、加热和冷却三个阶段进行。在预还原区域中通入保护性气体 C0₂，在该保护气氛中加热草酸钴晶体，加热温度为 250- 350°C，加热时间 40min，然后再保温 1小时，在该还原阶段使晶体脱氷和进行预还原，使草酸钴晶体中的二氧化碳溢出，其可以使晶体堆变得疏松，即进行所谓的***； The cobalt oxalate crystal prepared in the step 3 is reduced into ultrafine cobalt powder in a push boat as shown in FIG. 3, and is also subjected to three stages of preheating, heating and cooling. In the pre-reduction zone, a protective gas C0 _{2 is introduced} , and the cobalt oxalate crystal is heated in the protective atmosphere at a heating temperature of 250-350 ° C, a heating time of 40 min, and then further incubated for 1 hour, in which the crystal is de- iceed. And performing pre-reduction to cause carbon dioxide in the cobalt oxalate crystal to overflow, which can make the crystal pile loose, that is, so-called blasting;

( 2 ) 还原： ( 2 ) Restore:

预还原后的晶体在推舟中继续前行，进入还原区域，在 4个分隔空间内依次通过，低温区温度 400°C，高温区温度为 500- 550Ό , 前低温段和后低温段的温度比高温段的温度低 30— 50°C。在各空间物料停留的时间为 40- 60min。还原过程在氢气和氮气形成还原气氛中进行，氢气和氮气的体积比为 3： 1，将液氨分解得到还原气体： 2NH₃→ 3H₂+N₂。 The pre-reduced crystals continue to advance in the push boat, enter the reduction zone, pass sequentially in four compartments, the temperature in the low temperature zone is 400 ° C, the temperature in the high temperature zone is 500-550 Ό, the temperature of the front low temperature section and the post low temperature section It is 30-50 °C lower than the temperature in the high temperature section. The time spent in each space material is 40-60 min. The reduction process is carried out in a reducing atmosphere in which hydrogen and nitrogen are formed, and the volume ratio of hydrogen to nitrogen is 3:1, and liquid ammonia is decomposed to obtain a reducing gas: 2NH ₃ → 3H ₂ + N ₂ .

( 3 ) 冷却 (3) cooling

还原后的物料进入冷却区域，在 C0₂的保护气氛中将晶体冷却、惰化至室温，即可制成粒径在 0.1〜2 μ πι的超细钴粉。冷却区域分成 3个温降阶梯分隔空间，每个阶梯的温差可以在 40— 80°C , 如降温到 460°C保温 40分钟，继续降温到 400Ό保温 40分钟，最后自然冷却到室温。实施例 3: The reduced material enters the cooling zone, and the crystal is cooled and inerted to room temperature in a protective atmosphere of C0 ₂ to prepare an ultrafine cobalt powder having a particle diameter of 0.1 to 2 μm. The cooling zone is divided into three steps of temperature drop step separation. The temperature difference of each step can be 40-80 °C, such as cooling to 460 °C for 40 minutes, continue to cool down to 400 Ό for 40 minutes, and finally cool to room temperature. Example 3:

本实施例中所使用的二次原料为硬质合金废料块，其工艺流程图见图 3所示，其溶解工序使用的是电解溶解法。 The secondary raw material used in this embodiment is a cemented carbide scrap, and the process flow chart is shown in Fig. 3, and the dissolution process uses electrolytic dissolution.

在一电解槽中注入浓度为 1. 5- 5克当量 /升盐酸溶液，在其中设置由聚氯乙稀孔板制成的阳极筐，在该筐中装入硬质合金废料块作为阳极。在电解槽中 ***导电板作为阴极，其可以是石墨板，最好采用钛金属板。该阴极和阳极连接直流电源。槽电压控制在 1. 5- 4. 0V，电流密度为 50- 300安培 /米 ²时，电解槽中的盐酸的浓度始终保持在 1. 5-5克当量 /升，当其在电解过程中浓度下降时，及时补充盐酸。 An electrolytic solution having a concentration of 1.5 - 5 gram equivalents per liter of hydrochloric acid was placed in an electrolytic cell, and an anode basket made of a polyvinyl chloride orifice plate was placed therein, and a cemented carbide scrap block was placed in the basket as an anode. A conductive plate is inserted as a cathode in the electrolytic cell, which may be a graphite plate, preferably a titanium metal plate. The cathode and anode are connected to a DC power source. 5-5公斤当量/升, When it is in the process of electrolysis, the concentration of hydrochloric acid in the electrolytic cell is always maintained at 1. 5-5 gram / liter, during the electrolysis process, when the current is in the range of 1.5 - 4. 0V, the current density is 50-300 amps / m ² When the concentration drops, hydrochloric acid is replenished in time.

硬质合金材料中含有较多的碳化钨，在从中电解溶钴中，碳化钨不溶解，可以回收，再加工成碳化钨粉末，重新用于硬质合金材料的制作。在电解过程中，硬质合金表面上会形成一层碳化钨壳，它会导致阳极钝化。因此，在电解过程中应及时进行去壳。可以通过将形成碳化钨壳的硬质合金置入球磨机中研磨去壳，定期人工振动盛在聚氯乙稀筐中的合金也有破壳的作用。 The cemented carbide material contains a large amount of tungsten carbide. In the electrolytically dissolved cobalt, the tungsten carbide is not dissolved, can be recovered, and is processed into tungsten carbide powder, which is reused for the production of the cemented carbide material. During the electrolysis process, a layer of tungsten carbide shell is formed on the surface of the cemented carbide, which causes the anode to be passivated. Therefore, the shelling should be carried out in time during the electrolysis process. The hard alloy which forms the tungsten carbide shell can be placed in a ball mill to be etched and shelled, and the alloy artificially vibrating in the polyvinyl chloride basket at regular intervals also has the function of breaking the shell.

当电解液中钴的浓度达到 70克 /升以上时，将其引出电解槽即为粗氯化钴盐溶液。重新注入新的盐酸溶液。电解溶液工序得到继续进行。接下来对于电解液的处理见图，且与实施例 1基本相同。实施例 4: When the concentration of cobalt in the electrolyte reaches 70 g / liter or more, it is taken out of the electrolytic cell to be a crude cobalt chloride salt solution. Re-inject the new hydrochloric acid solution. The electrolytic solution process is continued. Next, the treatment of the electrolyte is shown in the drawings, and is basically the same as in the first embodiment. Example 4:

本实施例中给出几种雾化水解制成前驱体的具体方法。其原料为如同前面实施例中制出的精制氯化钴或硫酸钴溶液。 In this embodiment, several specific methods for atomization hydrolysis to form a precursor are given. The raw material is a purified cobalt chloride or cobalt sulfate solution as prepared in the previous examples.

( 1 ) 雾化水解制前驱体草酸钴晶体 (1) atomization hydrolysis precursor precursor cobalt oxalate crystal

将所述精制氯化钴或硫酸钴溶液调整其浓度为 50-140g/L和制备成浓度为 100-300g/L、 pH为 4.3-4.5的草酸铵溶液以雾状喷射到反应釜中，混合搅拌，反应时温度在 45-70°C间，反应时流量为： 35-45L/分，'反应时间为 2分 -8分，反应终点 pH值： 1.6-1.8; 然后分离出前驱体草酸钴晶体。 The purified cobalt chloride or cobalt sulfate solution is adjusted to have a concentration of 50-140 g/L, and a ammonium oxalate solution prepared to a concentration of 100-300 g/L and a pH of 4.3-4.5 is sprayed into the reaction vessel in a mist form, and mixed. Stirring, the reaction temperature is between 45-70 ° C, the flow rate during the reaction is: 35-45 L / min, 'reaction time is 2 minutes - 8 minutes, the reaction end point pH: 1.6-1.8; then the precursor cobalt oxalate is separated Crystal.

( 2) 雾化水解制前驱体碳酸钴晶体 (2) Ammonia hydrolyzed precursor cobalt carbonate crystal

将所述精制氯化钴或硫酸钴溶液调整其浓度为 50-140g/l和制备成浓度为 100-300g/L的碳铵溶液以雾状喷射到反应釜中，所述精制氯化钴或硫酸钴溶液控制加入量为 80L〜300L/hr, 碳酸铵按 Co+²计量的 1.1〜2.0倍加入，混合搅拌，平均反应时间： 1一 5小时，反应温度： 50-70°C， pH值： 7.0-9，然后分离出前驱体碳酸钴晶体。 The purified cobalt chloride or cobalt sulfate solution is adjusted to have a concentration of 50-140 g/l and a solution prepared to a concentration of 100-300 g/L is sprayed into the reaction vessel in a mist, the refined cobalt chloride or The cobalt sulfate solution is controlled to be added in an amount of 80 L to 300 L/hr, and ammonium carbonate is added in an amount of 1.1 to 2.0 times measured by Co + ² , and the mixture is stirred. The average reaction time is 1 to 5 hours, the reaction temperature is 50-70 ° C, and the pH is: 7.0-9, then the precursor cobalt carbonate crystals were separated.

( 3 ) 雾化水解制前驱体氢氧化钴晶体 (3) Ammonia hydrolyzed precursor precursor cobalt hydroxide crystal

将所述精制氯化钴或硫酸钴溶液调整浓度为 50-140g/l 和制备成浓度为 15-35 %的 NaOH溶液以雾状喷射到反应釜中，混合搅拌，同时加入 98%浓度的 NH₃气，调节 NH₃加入量使游离 Co²⁺浓度为 0.5— 100毫克 /1, 最佳为 10-15 毫克 /1，反应液的 pH为 8-11，其最佳值为 9.8-10.5; 稳定 Co²⁺液的加料速度为 70-300L/hr 中的一个值，如 160L/hr，采用计量泵等定量加料装置实现定量加料。 NaOH溶液的加料速度与控制 pH来匹配，反应温度为 40-65°C，最佳值为 50-60°C ; 搅拌速度为 90-150转 /分，控制结晶晶体的平均粒径为 3-15微米，粒度的最佳值为 5-10微米；本反应可以是连续的，连续加料，连续排料，也可以是间歇的，即为一反应釜为一周期；无论是连续式还是间歇式反应，其平均反应时间为 2-50小时，最佳为 5-8小时。 (4)雾化水解制前驱体草酸钴和氢氧化钴混合的复杂钴盐 The purified cobalt chloride or cobalt sulfate solution is adjusted to a concentration of 50-140 g/l and a NaOH solution prepared to a concentration of 15-35 % is sprayed into the reaction vessel in a mist form, mixed and stirred, and 98% concentration of NH is added. ₃ gas, adjust the amount of NH ₃ added so that the concentration of free Co ²⁺ is 0.5-100 mg / 1, preferably 10-15 mg / 1, the pH of the reaction solution is 8-11, the optimum value is 9.8-10.5; The feed rate of the stabilized Co ²⁺ liquid is a value of 70-300 L/hr, such as 160 L/hr, and the dosing device such as a metering pump is used for the quantitative dosing. The feed rate of the NaOH solution is matched with the control pH. The reaction temperature is 40-65 ° C, the optimum value is 50-60 ° C; the stirring speed is 90-150 rpm, and the average crystal grain size of the control crystal is 3- 15 micron, the optimum particle size is 5-10 microns; the reaction can be continuous, continuous feeding, continuous discharge, or intermittent, that is, one cycle of a reactor; whether continuous or intermittent The reaction has an average reaction time of 2 to 50 hours, preferably 5 to 8 hours. (4) complex cobalt salt mixed with cobalt oxalate and cobalt hydroxide prepared by atomization hydrolysis

所述精制氯化钴或硫酸钴溶液调整浓度为 20-100_g/L最佳为 30-50g/L, 沉淀剂为浓度为 0.1-2.0mol/L的草酸铵与比重 d==0.5-0.95的 ΝΗ₃ ·Η₂0和重量百分比浓度为 10-35%的 NaOH两个中的任意一种或两种的混合物，以雾状喷射到反应釜中，混合搅拌， Co²⁺液的加料速度为 30-200L/hr，反应液的 pH为 7-12，最佳值为 8-9，反应温度为 50-75°C , 最佳值为 60-70°C，通过 ΝΗ₃ · H₂O和 / 或 NaOH的加入量同时保持 pH稳定，反应中保持温度、加料速度稳定，加料速度同样通过用定量泵加料方式维持恒定；平均反应时间为 5-60分钟，最佳值为 20-40分钟，通过各反应条件控制生成纤维状或类纤维状的草酸钴和氢氧化钴混合的复杂钴盐。工业实用性 The refined cobalt chloride or cobalt sulfate solution is adjusted to a concentration of 20-100 _g / L, preferably 30-50 _g / L, and the precipitant is a concentration of 0.1-2.0 mol / L of ammonium oxalate and the specific gravity d == 0.5-0.95 a mixture of ΝΗ ₃ · Η ₂ 0 and a concentration of 10-35% by weight of NaOH, or a mixture of the two, sprayed into the reaction vessel in a mist, mixed and stirred, the feed rate of the Co ²⁺ solution For 30-200 L/hr, the pH of the reaction solution is 7-12, the optimum value is 8-9, the reaction temperature is 50-75 ° C, and the optimum value is 60-70 ° C, passing ΝΗ ₃ · H ₂ O And / or NaOH added amount while maintaining the pH stability, the temperature is maintained during the reaction, the feed rate is stable, and the feed rate is also maintained constant by the dosing with a metering pump; the average reaction time is 5-60 minutes, and the optimum value is 20-40 minutes. A complex cobalt salt in which fibrous or fibrillar cobalt oxalate and cobalt hydroxide are mixed is controlled by each reaction condition. Industrial applicability

~~本循环技术生产超细钴粉的制造方法, 通过二次萃取除杂提纯、雾化水解沉积合成钴化合物前驱体，然后在多段温度下进行***热还原从含钴的废料中高效制成粒径在 0. 1〜2 μ πι的超细钴粉，用废旧电池等作为原料，在生产中无废水废气排放，对环境友好，通过本方法可以得到球状 /类球状和纤维状钴粉，适合于动力电池和高性能粉末冶金制品的制造，且有利于提高产品的质量和寿命。本方法制备的钴粉颗粒分布均匀，产品一致性好，颗粒的形状、粒径、松比可调，含碳量低，产品质量好。本发明提供的上述方法所用的设备，其结构简单，制造成本低，投资少。 ~~ The manufacturing method of ultra-fine cobalt powder by this cycle technology, the synthesis of cobalt compound precursor by secondary extraction, impurity purification, atomization hydrolysis deposition, and then blasting thermal reduction at multiple temperatures to efficiently make from cobalt-containing waste Ultrafine cobalt powder having a particle diameter of 0.1 to 2 μ πι, using waste batteries and the like as raw materials, without waste water and exhaust gas in production, is environmentally friendly, and spherical/spherical and fibrous cobalt powder can be obtained by the method. It is suitable for the manufacture of power batteries and high-performance powder metallurgy products, and is beneficial to improve the quality and life of products. The cobalt powder particles prepared by the method have uniform distribution, good product consistency, adjustable particle shape, particle size and looseness ratio, low carbon content and good product quality. The apparatus used in the above method provided by the present invention has a simple structure, low manufacturing cost, and low investment.

Claims

权利要求 Rights request

1、一种循环技术生产超细钴粉的制造方法，其特征在于：采用二次含钴废料，经溶解、提纯、雾化水解沉淀和还原过程制成费氏粒径为 0.1-2.0微米、氧含量 <0.6%、碳含量 <0.05%、硫含量 <0.05 %的超细钴粉。 1. A method for producing ultrafine cobalt powder by a recycling technique, characterized in that: using a secondary cobalt-containing waste material, a Fischer particle size of 0.1-2.0 micrometer is formed by dissolution, purification, atomization hydrolysis precipitation and reduction, Ultrafine cobalt powder having an oxygen content of <0.6%, a carbon content of <0.05%, and a sulfur content of <0.05%.

2、根据权利要求 1所述的循环技术生产超细钴粉的制造方法，其特征在于： 2. A method of producing ultrafine cobalt powder by the recycling technique according to claim 1, wherein:

所述二次含钴废料是其中钴含量为 0.5-55 %或以上，另外含有 Ni、Fe、 Cd、 Cu、 Pb、 Mg、 Ca、 Cr、 Zr、 Si、 Zn、 Li、 Mn、 Fe、 Al中的一种或几种杂质的二次废料； The secondary cobalt-containing waste material has a cobalt content of 0.5-55 % or more, and additionally contains Ni, Fe, Cd, Cu, Pb, Mg, Ca, Cr, Zr, Si, Zn, Li, Mn, Fe, Al. Secondary waste of one or more impurities in the process;

所述提纯即为通过萃取剂含 P204 5— 50%+磺化煤油 95-50%体积比的混合液对所述粗钴盐溶液进行一次萃取和用萃取剂含 P507 10-50%+磺化煤油 95-50 %体积比.的混合液对一次萃取得到的萃余相进行二次萃取得到钴含量高于所述粗钴盐溶液的精制氯化钴溶液或硫酸钴溶液；或者 The purification is carried out by extracting the crude cobalt salt solution once by using a mixture of P204 5-50%+sulfonated kerosene 95-50% by volume and containing P507 10-50%+sulfonation with an extractant. The mixture of 95-50% by volume of kerosene is subjected to secondary extraction of the raffinate phase obtained by one extraction to obtain a purified cobalt chloride solution or a cobalt sulfate solution having a cobalt content higher than the crude cobalt salt solution;

所述提纯过程是一个电化学沉积过程，根据所述粗钴盐溶液中一种或几种杂质的种类和沉积电位特性，选择适合的电流密度，以石墨为阳极，以钛板为阴极，以所述粗钴盐溶液为电解液进行电解，使杂质在阴极上析出而除去，制成精制氯化钴或硫酸钴溶液； The purification process is an electrochemical deposition process, according to the type and deposition potential characteristics of one or more impurities in the crude cobalt salt solution, selecting a suitable current density, using graphite as the anode and titanium plate as the cathode, The crude cobalt salt solution is electrolyzed by an electrolytic solution, and the impurities are precipitated on the cathode to be removed, thereby preparing a purified cobalt chloride or cobalt sulfate solution;

所述还原过程是将所述前驱体置于还原性气体中在 200-700Ό加热 1-8小时制成纤维状或类纤维状或球状或类球状超细钴粉。 The reduction process is carried out by placing the precursor in a reducing gas at 200 to 700 Torr for 1 to 8 hours to form a fibrous or fibrillar-like or spherical or spheroidal ultrafine cobalt powder.

3、根据权利要求 1或 2所述的循环技术生产超细钴粉的制造方法，其特征在于：在所述溶解过程中，加入盐酸或硫酸，其浓度重量百分数为：盐酸 5 -37% , 硫酸 10— 98 %，盐酸 5— 30%，硫酸 10_98 %，加入量为所述废料重量之化学当量的 100%-200%，或以所述废料中所有金属总量来计算，为化学当量的 1.1-3.0倍，使之溶解，废料中的钴形成可溶性的氯化钴 CoCl₂或硫酸钴 CoSO₄; 废料中的其它可溶成分也溶解在盐酸或硫酸中形成可溶性氯化物或硫酸盐，由此形成粗氯化钴 <：0 ₂或硫酸钴 CoS0₄溶液；或是： 3. The method for producing ultrafine cobalt powder according to the recycling technique according to claim 1 or 2, wherein: in the dissolving process, hydrochloric acid or sulfuric acid is added, and the concentration by weight is: 5-37% hydrochloric acid, 10-98% sulfuric acid, 5-30% hydrochloric acid, 10_98% sulfuric acid, added in an amount of 100%-200% of the stoichiometric weight of the waste, or calculated as the stoichiometric amount of all metals in the waste. 1.1-3.0 times, to dissolve, the cobalt in the waste forms soluble cobalt chloride CoCl ₂ or cobalt sulfate CoSO ₄ ; other soluble components in the waste are also dissolved in hydrochloric acid or sulfuric acid to form soluble chloride or sulfate, This forms a crude cobalt chloride <:0 ₂ or cobalt sulfate CoS0 ₄ solution; or:

在所述溶解过程中，以所述二次废料为阳极，以耐腐蚀性导电材料为阴极，以硫酸或盐酸为电解液，接通直流电，根据所述二次废料中钴和杂质的种类调整电解的电压和电流强度，使钴优先溶解在所述电解液中，废料中的其它可溶成分也部分的溶解在该电解液中，由此形成粗氯化钴或硫酸钴溶液。 In the dissolving process, the secondary waste is used as an anode, the corrosion-resistant conductive material is used as a cathode, and sulfuric acid or hydrochloric acid is used as an electrolyte to turn on direct current, according to the type of cobalt and impurities in the secondary waste. The voltage and current intensity of the electrolysis are such that cobalt is preferentially dissolved in the electrolyte, and other soluble components in the waste are partially dissolved in the electrolyte, thereby forming a crude cobalt chloride or cobalt sulfate solution.

4、根据权利要求 2所述的循环技术生产超细钴粉的制造方法，其特征在于：所述提纯是萃取过程时，在所述萃取过程中， 4. The method for producing ultrafine cobalt powder according to the recycling technique according to claim 2, wherein: the purification is an extraction process, and during the extraction process,

( 1 ) 在所述一次萃取中，萃取剂为含 P204+磺化煤油的混合液与所述溶解过程中得到的粗钴盐溶液以 P204的流量为 2-15 1/min, 皂化用碱的流量为 75-190mol/min，使皂化率为 60-65%，粗硫酸钴液或氯化钴的流量为 2-15 l/min、在 pH为 2-4、温度为 10-40°C的调节下混合、分层，获得含钴量高于所述粗钴盐溶液的萃余相，制成半精制钴盐溶液； (1) In the primary extraction, the extractant is a mixture of P204+sulfonated kerosene and a crude cobalt salt solution obtained during the dissolution process, and the flow rate of P204 is 2-15 1/min, and the flow rate of the alkali for saponification 75-190mol/min, the saponification rate is 60-65%, the flow rate of crude cobalt sulfate or cobalt chloride is 2-15 l/min, the pH is 2-4, and the temperature is 10-40 °C. Mixing and layering, obtaining a raffinate phase containing a cobalt content higher than the crude cobalt salt solution, and preparing a semi-refined cobalt salt solution;

(2) 在所述二次萃取中，萃取剂含 P507+磺化煤油的混合液与所述溶解过程中得到的粗钴盐溶液以硫酸钴溶液流量为 0.8-15 1/min, P507二次萃取剂流量为 2-20 l/min，皂化用碱流量为 200-1000ml/min，使皂化率为 20-50%的混合比例、在温度为 10-40°C的调节下混合、分层；留下萃取相，该萃取相与浓度为 0.1-0.8mol/L的硫酸或盐酸以 1-4 1/分比例、在温度为 10-40Ό的调节下混合、分层，取反萃液成为精制氯化钴或硫酸钴溶液。 (2) In the secondary extraction, the extractant contains a mixture of P507+sulfonated kerosene and the crude cobalt salt solution obtained in the dissolution process with a flow rate of cobalt sulfate solution of 0.8-15 1/min, P507 secondary extraction The flow rate of the agent is 2-20 l/min, the flow rate of the alkali for saponification is 200-1000 ml/min, the mixing ratio of the saponification rate is 20-50%, and the mixture is mixed and layered under the adjustment of the temperature of 10-40 ° C; The extract phase is mixed with sulfuric acid or hydrochloric acid at a concentration of 0.1-0.8 mol/L at a ratio of 1-4 1 /min, and the mixture is stratified at a temperature of 10-40 Torr, and the stripping solution is taken to be a purified chlorine. Cobalt or cobalt sulfate solution.

5、根据权利要求 1或 2所述的循环技术生产超细钴粉的制造方法，其特征在于：所述雾化水解即为在所述精制氯化钴或硫酸钴溶液中加入沉淀剂草酸、氢氧化钠和氨水中的一种或几种，几种原料以喷雾方式投料，进行搅拌，控制溶液的 pH得到草酸钴，或碳酸钴，或氢氧化钴或氢氧化钴和草酸钴混合的复合钴盐前驱体。 The method for producing ultrafine cobalt powder according to the recycling technique according to claim 1 or 2, wherein: the atomization hydrolysis is to add a precipitant oxalic acid to the refined cobalt chloride or cobalt sulfate solution, One or several kinds of sodium hydroxide and ammonia water, several raw materials are sprayed, stirred, and the pH of the solution is controlled to obtain cobalt oxalate, or cobalt carbonate, or a composite of cobalt hydroxide or cobalt hydroxide and cobalt oxalate. Cobalt salt precursor.

6、根据权利要求 1或 2所述的循环技术生产超细钴粉的制造方法，其特征在于：在所述溶解和提纯工序之间设有一个除杂过程， A method of producing ultrafine cobalt powder by the recycling technique according to claim 1 or 2, wherein: a dedusting process is provided between said dissolving and purifying steps,

所述除杂过程是一个化学沉淀过程，根据所述粗钴盐溶液中一种或几种杂质的种类和沉淀特性选择沉淀剂加入所述粗钴盐溶液中，并调整溶液 pH值，使得所述杂质沉淀而被滤除；或者 The impurity removal process is a chemical precipitation process, and a precipitant is added to the crude cobalt salt solution according to the kind and precipitation characteristics of one or several impurities in the crude cobalt salt solution, and the pH value of the solution is adjusted, so that The impurities are precipitated and filtered; or

所述除杂过程是一个电化学沉积过程，根据所述粗钴盐溶液中一种或几种杂质的种类和沉积电位特性，选择适合的电流密度，以耐腐蚀性导电材料为阳极或阴极，或以石墨为阳极，以钛板为阴极，以所述粗钴盐溶液为电解液迸行电解，使杂质在阴极上析出而除去。 The impurity removal process is an electrochemical deposition process, and according to the type and deposition potential characteristics of one or more impurities in the crude cobalt salt solution, a suitable current density is selected, and the corrosion-resistant conductive material is used as an anode or a cathode. Or, graphite is used as an anode, a titanium plate is used as a cathode, and the crude cobalt salt solution is used as an electrolytic solution for electrolysis, and impurities are deposited on the cathode to be removed.

7、根据权利要求 4所述的循环技术生产超细钴粉的制造方法，其特征在于：所述萃取过程为： 7. The method for producing ultrafine cobalt powder according to the recycling technique of claim 4, wherein: the extraction process is:

( 1 )粗钴盐溶液调酸：在所述粗氯化钴加入盐酸或在所述硫酸钴溶液中加入硫酸，调节溶液的 pH值为 2-4备用； (1) adjusting the acid in the crude cobalt salt solution: adding hydrochloric acid to the crude cobalt chloride or adding sulfuric acid to the cobalt sulfate solution, adjusting the pH of the solution to 2-4;

(2) 配制萃取剂和反萃取剂 (2) Preparation of extractant and stripping agent

一次萃取剂为体积比是 P204 5— 20%+磺化煤油 95-80%的混合液；二次萃取剂为体积比是 P507 10-30%+磺化煤油 90-70%的混合液；反萃取剂为含硫酸或盐酸 1.0-5mol/L的纯水溶液； The primary extractant is a mixture of P204 5-20%+sulfonated kerosene 95-80%; the secondary extractant is a mixture of P507 10-30%+sulfonated kerosene 90-70%; The extracting agent is a pure aqueous solution containing sulfuric acid or hydrochloric acid of 1.0-5 mol/L;

洗酸 1为含硫酸或盐酸 0.30-0.8mol/L的纯水溶液； Washing acid 1 is a pure aqueous solution containing sulfuric acid or hydrochloric acid 0.30-0.8 mol/L;

洗酸 2为含硫酸或盐酸 0.10-0.8mol/L的纯水溶液；皂化用碱为 l-10mol/L的氢氧化钠溶液； Washing acid 2 is a pure aqueous solution containing 0.10-0.8 mol/L of sulfuric acid or hydrochloric acid; The saponification base is a l-10 mol/L sodium hydroxide solution;

( 3 ) 萃取： (3) Extraction:

一次萃取（分馏萃取）： One extraction (fractionation extraction):

a、萃取除杂： a, extraction and impurity removal:

将在（1 ) 中经过调酸的粗氯化钴或粗硫酸钴、（2 ) 中制备的一次萃取剂以及皂化用碱通入萃取器中，其中，一次萃取剂 P204的流量为 2-151/min，皂化用碱的流量为 50-300mol/min使皂化率为 60-65 % , 粗硫酸钴液或氯化钴的流量为 2-151/min，充分搅拌，静置、分相，在常温进行一次萃取，引出的萃余相作为半精制氯化钴或硫酸钴溶液备用，负载有机相进入下一级洗涤段； The crude cobalt chloride or crude cobalt sulfate in (1), the primary extractant prepared in (2), and the saponification base are introduced into the extractor, wherein the flow rate of the primary extractant P204 is 2-151. /min, the saponification base flow rate is 50-300mol/min to make the saponification rate 60-65%, the crude cobalt sulfate solution or cobalt chloride flow rate is 2-151/min, stir well, let stand, phase separation, The extraction is carried out at room temperature, and the extracted raffinate phase is used as a semi-refined cobalt chloride or cobalt sulfate solution, and the organic phase is loaded into the next-stage washing section;

b、洗钴： b. Washing cobalt:

将前一步骤中的所述萃取相以 2-15IJmin流量通入下一级洗涤段中，将 (2) 中配制的洗酸 1以 80-120ml/min的流量加入萃取器中，充分搅拌，静置 10-20min 分相，洗涤所述负载有机相，从萃取剂中进一步提取出剩余的钴，洗液与 a步骤中的萃余相即半精制氯化钴或硫酸钴溶液合并备用，该过程对萃取相残存的钴离子进一步回收； The extract phase in the previous step is introduced into the next-stage washing section at a flow rate of 2-15 IJmin, and the washing acid 1 prepared in (2) is added to the extractor at a flow rate of 80-120 ml/min, and thoroughly stirred. The mixture is allowed to stand for 10-20 min, the loaded organic phase is washed, and the remaining cobalt is further extracted from the extractant, and the washing liquid is combined with the raffinate phase in the step a, that is, the semi-refined cobalt chloride or cobalt sulfate solution, and the process is combined. Further recovering cobalt ions remaining in the extract phase;

c、反萃杂质： c, stripping impurities:

负载有机相以 2-15L/min流量进入下一级反萃段，同时通入（2 )中配制的反萃取剂，反萃取液的流量为 100-200ml/min，充分搅拌，静置分相，引出再生的萃取剂，循环使用，含杂质反萃液进入污水处理***； The loaded organic phase enters the next-stage stripping section at a flow rate of 2-15 L/min, and the stripping agent prepared in (2) is introduced. The flow rate of the stripping solution is 100-200 ml/min, fully stirred, and the phase separation is carried out. , extracting the regenerated extractant, recycling, and containing the impurity stripping solution into the sewage treatment system;

二次萃取 (分馏萃取)： Secondary extraction (fractionation extraction):

a、萃取钴： a, extraction of cobalt:

将在一次萃取中获得的半精制氯化钴或硫酸钴溶液、（2 ) 中配制的二次萃取剂 P507 以及皂化用碱通入萃取器中，其中硫酸'钴或氯化钴溶液流量为 0.8-4 1/min, 二次萃取剂流量为 5-20 I/min, 皂化用碱流量为 200-700ml/min，使皂化率为 35 % (20-40%) ，充分搅拌，静置 10-20min分相，在常温进行二次萃取，钴进入负载有机相;引出萃余相，根据含镍情况另行处理； The semi-refined cobalt chloride or cobalt sulfate solution obtained in one extraction, the secondary extractant P507 prepared in (2), and the saponification base are introduced into the extractor, wherein the flow rate of the sulfuric acid 'cobalt or cobalt chloride solution is 0.8. -4 1/min, the secondary extractant flow rate is 5-20 I/min, the saponification alkali flow rate is 200-700ml/min, the saponification rate is 35% (20-40%), fully stirred, and allowed to stand 10- 20min phase separation, secondary extraction at room temperature, cobalt into the loaded organic phase; extraction of the raffinate phase, according to the nickel content;

b、洗涤杂质： b, washing impurities:

将负载有机相以 5-20LAnin流量和（2 )中配制的洗酸 2通入下一级洗涤段，洗酸 2流量为 0.1-1.01/min，充分搅拌，静置 ( 10-20min)分相，负载有机相进入下一级反萃段，洗液同 a步骤中的萃余液合并； The loaded organic phase is passed to the next stage washing section with a flow rate of 5-20 LAnin and the washing acid 2 prepared in (2), the flow rate of the acid washing 2 is 0.1-1.01/min, fully stirred, and the phase separation is carried out (10-20 min). , the organic phase is loaded into the next-stage stripping section, and the washing liquid is combined with the raffinate in step a;

c、反萃提钴 c, counter extraction and cobalt extraction

负载有机相以 5-20L/min流量进入下一级反萃段，同时通入（2 ) 中配制的反萃取剂，反萃液流量为 100-200mL/min，充分搅拌，静置 10-20min，分相，引出再生的萃取剂，循环使用，含精制氯化钴或硫酸钴的反萃液做为成品使用。 The loaded organic phase enters the next-stage stripping section at a flow rate of 5-20 L/min, and the stripping agent prepared in (2) is introduced at the same time. The stripping solution flow rate is 100-200 mL/min, fully stirred, and allowed to stand for 10-20 min. , phase separation, extraction of regenerated extractant, recycling, use of refined cobalt chloride or cobalt sulfate stripping solution as a finished product.

8、根据权利要求 Ί所述的循环技术生产超细钴粉的方法，其特征在于：在所述的二次萃取中 a和 b步骤中引出的所述萃余液和洗液中还存在一些镍元素，对其进行处理： 8. The method for producing ultrafine cobalt powder according to the recycling technique according to claim ,, characterized in that: in said secondary extraction, a plurality of said raffinate and washing liquid are extracted from a and b steps. Nickel, treat it:

将所述含镍溶液根据镍含量分别处理，以回收镍，或含镍浓度低排入污水 ***回收镍，或含镍浓度高，用化学沉淀法或萃取法回收镍。 9、根据权利要求 5所述的循环技术生产超细钴粉的制造方法，其特征在于：所述雾化水解过程为： The nickel-containing solution is separately treated according to the nickel content to recover nickel, or the nickel-containing low concentration is discharged into the sewage system to recover nickel, or the nickel-containing concentration is high, and the nickel is recovered by chemical precipitation or extraction. 9. The method for producing ultrafine cobalt powder according to the recycling technique according to claim 5, wherein: the atomization hydrolysis process is:

将所述精制氯化钴或硫酸钴溶液调整其浓度为 50-140g/L和制备成浓度为 100-300g/L、 pH为 3.0-5.5或为 4.0-4.5的沉淀剂——草酸铵溶液以雾状喷射到反应釜中，混合搅拌，反应时温度在 45_:70°C间，反应时流量为： 30-100L/ 分，反应时间为 2分 -60分钟，或为 22— 25分钟；反应终点 pH值： 1.0-2.8，或为 1.7-1.The purified cobalt chloride or cobalt sulfate solution is adjusted to have a concentration of 50-140 g/L and a precipitant prepared as a concentration of 100-300 g/L, a pH of 3.0-5.5 or 4.0-4.5, an ammonium oxalate solution. mist injected into the reactor, mixed and stirred, the reaction temperature is at _45: between 70 ° C, the reaction flow: 30-100L / min, and the reaction time was 2 minutes to 60 minutes, or from 22-25 min; reaction Endpoint pH: 1.0-2.8, or 1.7-1.

9; 然后分离出前驱体草酸钴晶体；或为： 9; then separating the precursor cobalt oxalate crystal; or:

将所述精制氯化钴或硫酸钴溶液调整其浓度为 50-140g/l和制备成浓度为 50-300g/L 的碳铵溶液以雾状喷射到反应釜中，所述精制氯化钴或硫酸钴溶液控制加入量为 50L〜300L/hr， pH值: 7.0-10, 或为 7.5-9.0，碳酸铵按 Co⁺²计量的 1.1〜2.0倍加入，并通过调节碳酸铵的加入速度来稳定 pH值，混合搅拌，平均反应时间： 1一 10小时，反应温度： 50-70°C，然后分离出前驱体球状或类球状碳酸钴晶体；或为： The purified cobalt chloride or cobalt sulfate solution is adjusted to have a concentration of 50-140 g/l and a solution prepared to a concentration of 50-300 g/L is sprayed into the reaction vessel in a mist, the refined cobalt chloride or The cobalt sulfate solution is controlled to be added in an amount of 50 L to 300 L/hr, pH: 7.0-10, or 7.5-9.0, and ammonium carbonate is added in an amount of 1.1 to 2.0 times measured by Co ⁺² , and is stabilized by adjusting the rate of addition of ammonium carbonate. pH value, mixing and stirring, average reaction time: 1 to 10 hours, reaction temperature: 50-70 ° C, and then separating the precursor spherical or spheroidal cobalt carbonate crystal; or:

将所述精制氯化钴或硫酸钴溶液调整浓度为 50-140g/l和制备成重量百分比浓度为 15-35 %的 NaOH溶液以雾状喷射到反应釜中，混合搅拌，同时加入重量百分比 10— 30 %浓度的 NH₃溶液或通入纯度为重量百分比 98%以上的 NH₃气，其加入量以溶液中游离. Co²⁺浓度为度量，控制 NH₃加入量使游离 Co²⁺ 浓度为 0.5— 200毫克 /1，反应液的 pH为 7-14，Co²⁺液的加料速度为 50-300L/hr， NaOH溶液的加料速度由控制的 pH来匹配，反应温度为 40-70°C，搅拌速度为 70-250转 /分，控制结晶晶体的平均粒径为 2-15微米；平均反应时间为 2-50小时，制成球状或类球状前驱体氢氧化钴晶体；或为： The purified cobalt chloride or cobalt sulfate solution is adjusted to a concentration of 50-140 g / l and a 5% by weight NaOH solution prepared in a concentration of 15 to 35 % is sprayed into the reaction vessel in a mist, mixed and stirred, while adding 10% by weight — 30% concentration of NH ₃ solution or NH ₃ gas with a purity of 98% or more by weight. The amount of NH ₃ gas added is determined by the concentration of free . Co ²⁺ in the solution. The amount of NH ₃ added is controlled so that the concentration of free Co ²⁺ is 0.5-200 mg / 1, the pH of the reaction solution is 7-14, the feed rate of Co ²⁺ solution is 50-300 L / hr, the feed rate of the NaOH solution is matched by the controlled pH, and the reaction temperature is 40-70 ° C , stirring speed is 70-250 rpm, controlling the average crystal grain size of the crystal crystal is 2-15 microns; the average reaction time is 2-50 hours, forming a spherical or spheroidal precursor cobalt hydroxide crystal; or:

所述精制氯化钴或硫酸钴溶液调整浓度为 10-100g/L，沉淀剂为浓度为 0.1-3.0mol/L的草酸铵与比重 d= 0.5-0.95 的丽₃ · ¾0和重量百分比浓度为 10-35%的 NaOH两个中的任意一种或两种的混合物，以雾状喷射到反应釜中，混合搅拌， Co²⁺液的加料速度为 30-300L/hr，反应液的 pH为 7-12，或为 7.5-9.5，反应温度为 50-75°C , 或为 60-70°C，通过调节 ΝΗ₃ · H₂0和 /或 NaOH的加入量来保持 pH稳定，反应中保持温度、加料速度稳定，加料速度同样通过用定量泵加料方式维持恒定；平均反应时间为 5-1200分钟，或为 20-40分钟，通过控制各反应条件生成纤维状或类纤维状的草酸钴和氢氧化钴混合的复合钴盐。 The refined cobalt chloride or cobalt sulfate solution is adjusted to a concentration of 10-100 g/L, and the precipitant is a concentration of 0.1-3.0 mol/L of ammonium oxalate and a specific gravity d=0.5-0.95 of Li ₃ · 3⁄40 and a concentration by weight of A mixture of any one or two of 10-35% NaOH is sprayed into the reaction vessel in a mist form, mixed and stirred, and the feed rate of the Co ²⁺ liquid is 30-300 L/hr, and the pH of the reaction liquid is 7-12, or 7.5-9.5, reaction temperature 50-75 ° C, or 60-70 ° C, to maintain pH stability by adjusting the amount of ΝΗ ₃ · H ₂ 0 and / or NaOH added, keep the reaction The temperature and feed rate are stable, and the feed rate is also maintained constant by the metering method; the average reaction time is 5-120 minutes, or 20-40 minutes, and the fibrous or fibrillar-like cobalt oxalate is produced by controlling the reaction conditions. Cobalt hydroxide mixed composite cobalt salt.

10、根据权利要求 9所述的循环技术生产超细钴粉的制造方法，其特征在于：在所述雾化水解过程中，所述反应物的投料为对冲方式，即在反应器中的上部和下部分设都设有进料喷嘴，上面一个喷嘴喷口向下，下面一个喷嘴喷口向上喷出物料；所述钴液从在上的喷嘴向下喷出，所述沉淀剂从在下的喷嘴向上喷出。 10. The method for producing ultrafine cobalt powder according to the recycling technique according to claim 9, wherein: in the atomization and hydrolysis process, the reactant is charged in a hedging manner, that is, in an upper portion of the reactor. And the lower part is provided with a feeding nozzle, the upper nozzle nozzle is downward, and the lower nozzle nozzle ejects the material upward; the cobalt liquid is sprayed downward from the upper nozzle, and the precipitant is upward from the lower nozzle ejection.

11、根据权利要求 6所述的循环技术生产超细钴粉的制造方法，其特征在于：所述还原过程为***热还原，其分预还原、还原和冷却三个阶段- 11. The method for producing ultrafine cobalt powder according to the recycling technique of claim 6, wherein: the reduction process is a blasting heat reduction, and the pre-reduction, reduction and cooling are carried out in three stages -

( 1 ) 预还原： (1) Pre-reduction:

将所述前驱体在还原气体保护性气体]^₂或 C0₂的保护气氛中，温度为 200 - 500°C , 还原 1-5 小时，在该还原阶段使晶体脱水和进行预还原，草酸钴或碳酸钴晶体裂解释放二氧化碳和一氧化碳的混合气体，具有还原性质，使草酸钴或碳酸钴晶体中的二氧化碳溢出，其使晶体堆变得疏松，即进行所谓的***；The precursor is subjected to a protective atmosphere of a reducing gas protective gas of ₂ or C0 ₂ at a temperature of 200 to 500 ° C for 1-5 hours, in which the crystal is dehydrated and pre-reduced, cobalt oxalate Or The crystal of cobalt carbonate crystals releases a mixed gas of carbon dioxide and carbon monoxide, and has a reducing property, causing carbon dioxide in the crystal of cobalt oxalate or cobalt carbonate to overflow, which makes the crystal pile loose, that is, so-called blasting;

(2) 还原： (2) Restore:

( 3 ) 冷却 (3) cooling

在 N₂或 C0₂的保护气氛中将晶体冷却、惰化至室温，即制成粒径在 0.1〜 2.0 μ m的纤维状或球状或类球状超细钴粉。 The crystal is cooled and inerted to room temperature in a protective atmosphere of N ₂ or C _{2 2 to} form a fibrous or spherical or spheroidal ultrafine cobalt powder having a particle diameter of 0.1 to 2.0 μm.

12、根据权利要求 11所述的循环技术生产超细钴粉的制造方法，其特征在于：所述还原阶段分成多个升温阶段：前低温段、高温段，所述前低温段比高温段的温度低 30— 5(TC _;所述冷却阶段分成若干个温降阶梯，每个阶梯的温差在 40— 80°C。 12. The method for producing ultrafine cobalt powder according to the recycling technique of claim 11, wherein: the reduction stage is divided into a plurality of temperature rising stages: a front low temperature section, a high temperature section, and the front low temperature section is higher than the high temperature section. The temperature is 30-5 (TC _; the cooling phase is divided into several steps of temperature drop, and the temperature difference of each step is 40-80 °C.

13、根据权利要求 11所述的循环技术生产超细钴粉的制造方法，其特征在于：所述冷却阶段分成若干个温降阶梯，每个阶梯的温差在 40— 80°C。 13. The method for producing ultrafine cobalt powder according to the recycling technique according to claim 11, wherein the cooling stage is divided into a plurality of temperature drop steps, and the temperature difference of each step is 40-80 °C.

14、一种循环技术生产超细钴粉的制造设备，其特征在于：包括溶解设备、提纯设备、雾化水解反应器和还原设备，所述溶解设备为带有加热装置的反应器或带有加热装置及电解装置的反应器，所述提纯装置为萃取箱或带有加热装置及电解装置的反应器、所述还原设备为液压和机械传动的多段推舟； 14. A manufacturing apparatus for producing ultrafine cobalt powder by a recycling technique, comprising: a dissolving device, a purifying device, an atomization hydrolysis reactor and a reducing device, wherein the dissolving device is a reactor with a heating device or a heating device and a reactor of the electrolysis device, wherein the purifying device is an extraction tank or a reactor with a heating device and an electrolysis device, and the reducing device is a multi-stage push boat that is hydraulically and mechanically driven;

所述多段式推舟，包括三个通道壳体，其间通过输送管路相连接构成一个狭长的通道，在该通道的两端设有进口和出口，所述三个壳体从入口到出口顺序形成三个区域：为预还原区域、还原区域和冷却区域，所述推舟各区域通过不锈钢挂帘隔开或者设置自动控制的炉门或闸板，以限制各区的气体互相流动；该挂帘设在各区域之间的连接管路内和出口上，所述挂帘的上端与管壁铰接连接，其下端为自由端，各区域连接在一起，在推舟内形成一个可通过各个腔室的管状通道，在该管状通道中彼此相接触地设有若干个物料舟，在推舟的进口处设有可将物料舟推入所述管状通道中的物料舟推进装置，在所述在各个烧结腔室中设有加热装置和温度检测及调节装置，用以给各个腔室提供所需的温度；在所述各个腔室中还设有一个或多个进气口和排气口；所述冷却腔室中设有冷却装置； The multi-stage push boat comprises three channel shells connected by a conveying pipeline to form an elongated passage, and an inlet and an outlet are arranged at both ends of the passage, and the three shells are arranged from the inlet to the outlet. Forming three regions: a pre-reduction zone, a reduction zone and a cooling zone, the zones of the push boat are separated by a stainless steel curtain or an automatically controlled furnace door or shutter is provided to restrict the mutual flow of gases in the zones; The upper end of the curtain is hingedly connected to the tube wall, and the lower end is a free end, and the regions are connected together to form a chamber through the chamber. a tubular passage in which a plurality of material boats are placed in contact with each other, and at the inlet of the push boat is provided a material boat propulsion device capable of pushing the material boat into the tubular passage, a heating device and a temperature detecting and regulating device are provided in the sintering chamber for providing the required temperature to each chamber; and one or more air inlets are also provided in each of the chambers And a vent; the cooling chamber is provided with a cooling device;

在各区域的机壳的顶部设有进气口和排气口，在所述预还原区域和还原区域中，所述进气口和排气口设在该区域的两端且进出气口与推舟的行进方向相反；在每个区域中又通过隔板分隔成若干分段空间，该隔板在其下方设有通道孔使各分段空间连通令所述推舟通过；在预还原区域和还原区域中的分别设有若干个分段空间，在各分段空间中分别设置加热器以在不同分段空间形成不同的温度，在冷却区域也设有若干个分段空间，在各分段空间中分别设有冷却器；在冷却区域的前面几个分段空间中的中部机壳顶部设有进气口，在最后一个分段空间中部机壳顶部设有排气口。 An air inlet and an exhaust port are provided at a top of the casing of each area, and in the pre-reduction area and the reduction area, the air inlet and the exhaust port are disposed at both ends of the area, and the air inlet and outlet are pushed The traveling direction of the boat is opposite; in each area, it is divided into a plurality of segmented spaces by a partition plate, and the partition plate is provided with a passage hole below the space for connecting the segments to pass the push boat; in the pre-reduction area and There are several segment spaces in the reduction area, heaters are respectively arranged in each segment space to form different temperatures in different segment spaces, and several segment spaces are also arranged in the cooling region, in each segment. Coolers are respectively arranged in the space; an air inlet is arranged at the top of the middle casing in the first segment space of the cooling zone, and an exhaust port is arranged at the top of the middle casing of the last segment space.