CN100410399C - Method for nickel and cobalt recovery from laterite ores by reaction with concentrated acid and water leaching - Google Patents

Method for nickel and cobalt recovery from laterite ores by reaction with concentrated acid and water leaching Download PDF

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CN100410399C
CN100410399C CN 200580028497 CN200580028497A CN100410399C CN 100410399 C CN100410399 C CN 100410399C CN 200580028497 CN200580028497 CN 200580028497 CN 200580028497 A CN200580028497 A CN 200580028497A CN 100410399 C CN100410399 C CN 100410399C
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acid
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nickel
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CN101006190A (en
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D·纽道弗
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斯凯资源有限公司
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00Obtaining nickel or cobalt
    • C22B23/04Obtaining nickel or cobalt by wet processes
    • C22B23/0407Leaching processes
    • C22B23/0415Leaching processes with acids or salt solutions except ammonium salts solutions
    • C22B23/043Sulfurated acids or salts thereof
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00Obtaining nickel or cobalt
    • C22B23/04Obtaining nickel or cobalt by wet processes
    • C22B23/0453Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Process efficiency
    • Y02P10/21Process efficiency by recovering materials
    • Y02P10/212Recovering metals from waste

Abstract

一种两步法对含有褐铁矿和腐泥土的红土矿进行浸出的方法。 A two-step process of laterites comprising limonite and saprolite leaching method. 第一步包括将矿石与浓无机酸混合并发生反应,第二步包括制备酸/矿石混合物在水中的浆料并对混合物进行浸出以溶解镍和钴。 The first step includes mixing the ore with concentrated mineral acid and reacts, the second step comprises preparing a slurry acid / ore mixture in water and the mixture is leached to dissolve nickel and cobalt. 铁主要以黄钾铁矾以外的三价铁的氧化物或氢氧化物形式进入固体浸出残渣中,与镍和钴有效地分离。 Mainly iron entering the leach residue to the solid oxide or hydroxide of trivalent iron in the form other than jarosite, effectively separated from the nickel and cobalt.

Description

通过与浓酸反应及水浸出从红土矿石中回收镍和钴的方法相关申请的相互参引本申请要求享受2004年6月28日提交的美国临时专利申请No. 60/583243的优先权,现以引用的方式将其公开的内容纳入本说明书中。 By the reaction and associated with the concentrated acid method of recovering nickel and cobalt from laterite ore water leaching APPLICATIONS CROSS-REFERENCE This application claims the benefit of U.S. Provisional Patent June 28, 2004, filed Application No. 60/583243, now by reference into the disclosure of the present specification. 技术领域本发明涉及含镍的红土矿的湿法冶金处理,具体而言,涉及在同一工艺中对这种矿石的褐铁矿成分和腐泥土成分进行酸浸出的方法。 Technical Field The present invention relates to the hydrometallurgical processing of nickel containing laterite ore, in particular, it relates to acid leaching of limonite and saprolite components of this mineral components in the same process method. 背景技术红土矿是由邻近或处于地球表面的含镍的超基性(ultramaf ic)岩的。 BACKGROUND laterite by ultrabasic (ultramaf ic) containing nickel or near the earth's surface in rock. 它包含多种粘土、氧化物和硅酸盐矿物,有的富含镍和/或钴,这使其区别于另一大类镍矿—一硫化矿。 It contains a variety of clay, oxide and silicate minerals, some enriched in nickel and / or cobalt, which distinguishes it from another class of Nickel - a sulfide ore. 后者一般包含铁、镍和钴的硫化物矿物,通常含有铜和少量责金属,并与地壳中基性-超基性岩浆的侵入有关。 The latter typically contains sulfide minerals of iron, nickel and cobalt, copper, and typically contain a small amount of metal responsibilities, and with the base of the crust - invasive ultrabasic magmatic concerned. 风化过程一般产生层状沉积,其中在表面附近存在着完全的或最彻底的风化产物,随着深度增加渐变为程度较轻的风化产物,并最后在某个更深的深度处终止为未风化的岩石。 Weathering process typically produces a layer deposited near the surface where there is a complete or most thorough weathering products, with increasing depth to a lesser extent gradient weathering products, and finally terminating in unweathered to a deeper depth rock. 高度风化层通常将其含有的大部分镍细微分布在细碎的针铁矿颗粒中。 The highly weathered layer usually contains most of the nickel which is finely distributed in a finely divided goethite particles. 针铁矿是一种铁的鞋基氧化物(oxyhydroxide),化学式为Fe00H。 Goethite is an iron oxide-based shoe (oxyhydroxide), the formula Fe00H. 该层通常称为褐铁矿,它一般含有高比例的铁。 This layer is usually referred to as limonite, which typically contains a high proportion of iron. 钴通常与褐铁矿层伴生,并通常更主要地与氧化的锰矿物(含Mn (HI) 和/或Mn(IV)的氧化物和氢氧化物)伴生,通常称为钴土矿或锰土.风化较轻的层所含的镍一般更多地包含于各种硅酸镁矿物中,例如蛇紋岩。 Cobalt is usually associated with the limonite layer and is usually more important to the oxidation of manganese (containing Mn (HI) and / or Mn (IV) oxides and hydroxides) associated, commonly referred to as cobalt or manganese bauxite soil. the nickel layer contained in the light weathering more commonly included in various magnesium silicate minerals, such as serpentine. 蛇紋岩是一种镁的硅酸盐矿物,具有化学式3Mg0*2Si02*2H20, 一般认为蛇紋岩中镍取代了一部分镁。 Serpentine is a magnesium silicate mineral having the chemical formula 3Mg0 * 2Si02 * 2H20, serpentinite generally considered a part of the magnesium-substituted nickel. 镁也可被其他二价金属取代,例如亚铁(Fe".不完全风化带中可能有很多其他含有镍的硅酸盐矿物。部分风化的高含镁带通常称为腐泥土或硅镁镍矿。("硅镁镍矿"也用于描述一种特定的苹果绿色的具有可变组成的镁-镍硅酸盐矿物.)在一些矿床中还有另一种通常处于褐铁矿和腐泥土之间的主要含有绿脱石粘土的带;该绿脱石粘土为镁、铁和铝的硅酸盐,也可以舍镍。 在位于(目前)热带的多数矿床中,绿脱石带非常罕见,还应注意,风化带在矿物或化学组成上都不是均匀的,平行于地表的带之间的界面也不是均匀的。但是通常存在从铁含量高且镁含量相对低的矿石向镁含量相对高且铁含量较低——尽管铁含量是可变的—— 的矿石的相当急剧的转变,这在红土矿床中垂直距离l至3米内出现。 仅为说明目的,以下给出褐铁矿和腐泥土的典型化学组成: Magnesium may also be substituted by other divalent metals, such as ferrous (of Fe. "Incompletely weathered zone there may be many other silicate minerals containing nickel. Weathered portion with high magnesium saprolite or commonly referred garnierite . mine ( "garnierite" is also used to describe a particular apple-green having a variable composition of magnesium - nickel silicate minerals) in some deposits there is another typically in limonite and rot the main band containing between nontronite clay soil; the nontronite clays magnesium, iron and aluminum silicate, may be located in homes nickel (current) in most tropical deposits, with very nontronite. rare, should also be noted, with weathering on mineral or chemical composition is not uniform, parallel to the interface between the strip surface is not uniform, but is typically present from the high magnesium content of the iron content and the magnesium content of the ore to the relatively low high and relatively low iron content - although the iron content is variable - rather abrupt transition ore, which occur within a vertical distance l to 3 m in the laterite deposits purposes of illustration only, the following are given limonite saprolite and typical chemical composition: 褐铁矿:1. 0-1.8%Ni, 0.05-0. 3%Co, 35-50%Fe, 0. 2-3. 5%Mg 腐泥土: 1.2-3. 5%Ni, 0. 02-0. 07XCo, 7-20%Fe, 10-20XMg 在其他各种矿物中,各个带通常还含有相当浓度的铝、锰和铬,以及微量的其他重金属,例如铜和锌。将镍从红土矿中回收的一个困难之处在于,在进行化学处理分离镍有用成分之前通常不能通过物理方式充分富集这种金属有用成分(metal value),所述物理方式即称为选f广的技术。这使得红土;广的处理很昂贵,几十年来一直在寻找降低处理红土矿的成本的方法。而且,由于褐铁矿和腐泥土矿中不同的矿物和化学组成,这些矿石通常不适于使用同一处理技术进行处理。一种已知的用于镍红土矿的酸浸出方法是称为高压酸浸出(HPAL) 的方法(参见,例如"The Winning of Nickel Its Geology, Mining and Extractive Metallurgy,,的第437-453页,Joseph R. Boldt, Longmans Canada Ud. 1967 )。这 Limonite:.. 1 0-1.8% Ni, 0.05-0 3% Co, 35-50% Fe, 0. 2-3 5% Mg saprolite:.. 1.2-3 5% Ni, 0. 02- 0. 07XCo, 7-20% Fe, 10-20XMg in other various minerals, each band usually contain significant concentrations of aluminum, manganese and chromium, as well as traces of other heavy metals, such as copper and zinc. nickel from laterite ores recovered in a difficulty in that, before the chemical treatment is generally performed separating useful components of nickel is not sufficiently enriched by physical means such metals useful components (metal value), i.e., the physically selected f technology called wide. this making clay; extensive treatment is expensive, for decades has been cost-treated laterite find ways to reduce Moreover, since the limonite and saprolite ores and minerals of different chemical composition, these ores are usually not suitable for using the same process. process technology. One known acid leaching of nickel laterites method is a method called high pressure acid leaching (the HPAL) (see, for example, "the Winning of Nickel Its Geology, mining and Extractive Metallurgy ,, of 437 -453 page, Joseph R. Boldt, Longmans Canada Ud. 1967). this 种方法在20世纪50年代后期首次在古巴的Moa Bay使用,并在20世纪90年代后期在西澳大利亚建立了其它的工厂。这种方法使用硫酸在高温——通常为2501C——和高压下进行浸出;其中的蒸汽压在2S0t:下约为570psi。在这一温度下,矿石中含镍的矿物几乎完全溶解。溶解的铁在所采用的高温下迅速沉淀为赤铁矿(Fe203 ),这是由于在该温度下这种化合物即使是在微酸性溶液中也很难溶.镍留在溶液中,在冷却之后含铁的浸出残渣通过在一系列洗涤浓缩机(wash thickener)——所谓的逆流倾析洗涤(CCD)回路——中浓缩而从含镍的溶液中分离.因此达到了浸出工艺的主要目的,即将镍与铁分离。 Ways for the first time at Moa Bay in Cuba in the late 1950s and the late 1990s to establish other factories in Western Australia this method using sulfuric acid at high temperature - generally carried out at a high pressure and 2501C-- leaching; wherein the vapor pressure at 2S0t: at 570psi at about this temperature, the nickel-containing ore minerals dissolved almost completely dissolved iron rapidly precipitated as hematite (Fe203) is used at a high temperature, it. Since this compound is difficult even dissolved in acidic solution at this temperature for a nickel remain in solution, after cooling the iron-containing leach residue was purified by washing in a series concentrator (wash thickener) -. the so-called counter current decantation (CCD) circuit - is separated from a concentrated nickel-containing solution thus achieving the primary object of the leaching process, i.e. the separation of nickel and iron. HPAL工艺的一大缺点是它需要复杂的高温高压釜以及相关的设备, 其安装与维护都很昂贵。 A disadvantage of the HPAL process is that it requires sophisticated high-temperature autoclave and associated equipment which are expensive to install and maintain. 此外,HPAL工艺消耗的硫酸比按化学计量溶解矿石中的非铁金属成分所需的硤酸更多,因为在高温下多数由硫酸提供的硫酸根离子停留在硫酸氢根离子(HSOD的形式.換句话说,碟酸(H2S(M在高温下只离解释放出一个质子(H+)。在浸出液冷却及中和时, 硫酸氢根离子分解成疏酸根(S042—)和另一个质子。因此后一个质子(酸) 没有充分用于浸出,并导致过量的必须要进行中和的破酸,例如使用石灰石进行中和。HPAL工艺的另一个缺点是它限于处理主要为褐铁矿类的原料,因为腐泥土的存在会导致疏酸消耗量的大量的并通常是不经济的增加,这是由于腐泥土中镁的浸出所引起的。这由于上述高温下的疏酸氢根"转变"问题而更加恶化。美国专利No. 4,097, 575描述了对HPAL工艺的改进,包括在约820 t:以下焙烧腐泥土矿以使矿石与硫酸的反应活性更强,然后使用焙 In addition, the HPAL process consumes sulfuric acid than is required for non-ferrous metal component is dissolved ore Kip acid stoichiometrically more, because the sulfate ion at a high temperature provided by the most remain in the sulfuric acid hydrogen sulfate ion (in the form of HSOD. in other words, disc acid (H2S (M only at a high temperature discharged from a proton interpreted (H +). leaching solution was cooled and neutralized, decomposed into hydrogen sulfate ion and phosphate repellent (S042-) and other protons. Thus the a proton (acid) is not sufficient for leaching and results in excess must be neutralized breaking acids, e.g. another disadvantage of using limestone and .HPAL process is that it is limited to dealing with material predominantly limonite class, because the presence of saprolite will cause a large amount is uneconomical and often sparse acid consumption increases, which is due to the leaching of magnesium saprolite caused. this is caused by hydrogen radicals in the high-temperature acid-repellent "transition" problem U.S. Pat worsened No. 4,097, 575 describes an improved process for the HPAL, comprising from about 820 t:. the following saprolite ore roasting the ore with sulfuric acid to make the reaction more active, then baking 炉的焙砂中和高压釜的排放物中过量的酸,在所述高压釜中发生褐铁矿的加压浸出.在这一中和过程中腐泥土矿中含有的镍大量溶解.据称这一工艺的优点为它在褐铁矿加压浸出过程中更好地利用添加的硫酸,减少了用于处理高压釜排放液体的石灰石或其他昂贵的中和试剂的消耗,并的能力。这一、工艺的缺点是它仍需要使用昂贵的高压k用于褐铁矿的浸出,而且需要对腐泥土矿进行焙烧处理,该处理在资金投入和操作成本上都是很昂责的。美国专利No. 6, 379, 636 B2描述了对美国专利No. 4, 097, 575中描述的工艺的进一步改进,其中去除了腐泥土焙烧步骤并将"自然"状态的腐泥土用于中和高压釜排放溶液中过量的酸,此外,可以向排放液中加入更多的酸以增加腐泥土的可浸出量。但是这种工艺仍然需要使用昂贵的高压釜。还记载了一些只使用大气压下酸浸 Calcine autoclave furnace and emissions in excess acid pressure leaching of limonite occurred in the autoclave. Saprolite ore containing nickel in this process and the amounts of dissolved allegedly the advantage of the process is the ability to pressure leaching process in which limonite better use of sulfuric acid added to reduce the consumption of limestone or other costly neutralizing agents for discharging liquid processing autoclave, and of which a disadvantage of the process is that it still requires the use of expensive high pressure leaching of limonite for k, and the need for saprolite ore roasting process, the process on the capital investment and operating costs are very expensive are responsible. U.S. Pat. No. 6, 379, 636 B2 describes 4, 097, further improvement of the process described in U.S. Pat. No. 575, wherein the saprolite roasting step is removed and the "natural" state for the saprolite and autoclave excess acid solution is discharged, in addition, more acid may be added to the effluent in order to increase the amount of saprolite leaching. However, this process still requires the use of an expensive autoclave. also described using only some of the atmospheric pressure acid leach 的工艺,它们消除了上迷的加压浸出的缺点.美国专利No. 3,793, 432描述了一种对红土矿石进行大气压漫出的工艺,其中使矿石与疏酸在沸点或低于沸点下进行反应,并通过加入铁沉淀剂,例如铵、钠、钾或锂离子使溶解的铁沉淀。尽管没有明确提出,说明书中引用的所有实例都使用了褐铁矿样品,这可由原料矿石的高铁含量和低镁含量证明。虽然这种工艺克服了加压浸出的缺点,但它具有其他的缺点。首先铁以黄钾铁矾化合物形式沉淀,这是铁的一种热力学不稳定的化合物,会随着时间而分解释放出硫酸,因此导致环境问题.(尽管黄钾铁矾并没有被明确提出,但对于本领域技术人员来说很明显在实例中所列出的条件下会沉淀出黄钾铁矾)。 Process, which eliminates the disadvantages of the above-pressure leaching. U.S. Pat. No. 3,793, 432 describes a process for laterite ore to diffuse out of the atmospheric pressure, wherein the ore with a hydrophobic acid at the boiling point or below the boiling point of the reaction, by addition of an iron precipitating agent such as ammonium, sodium, potassium or lithium ion precipitation of the dissolved iron. Although not clearly stated, all examples cited in the specification are used limonite sample, which may be a high iron content ore feed and demonstrated the low magnesium levels. While this process overcomes the disadvantages of pressure leaching, it has other disadvantages. first, iron is precipitated in the form of potassium alum yellow iron compound, which is a thermodynamically unstable compound of iron, will vary the time decomposition in sulfuric acid, thus causing environmental problems. (Although jarosite is not clearly stated, but under conditions of ordinary skill in the art apparent in the examples will be listed precipitated yellow iron potassium alum). 黄钟铁矾中每三摩尔铁对应含有两摩尔硫酸根,因此这种化合物意味着为提供必要的疏酸根离子而需要相当过量的疏酸消耗,第二,镍从矿石中的提取率明显较低。 Yellow bell jarosite three moles per two moles of the corresponding sulfate containing iron, so this means that the compound to provide the necessary hydrophobic ion and requires considerable excess of acid consumption sparse, second, the rate of nickel extraction from the ore significantly lower. 尽管提取芈没有明确给出, 根据残渣中镍的含量以及残渣重量必定大于原矿重量的亊实——这是由于黄钾铁矾中的铁百分含量比原矿中的低并且几乎全部铁都保留在残渣中,镍的提取率通常在60-65X的范围内。 Although not explicitly given extraction Mi, according to the residue and the weight of the residue content of nickel must be greater than the weight of the ore Shi solid - this is because the percentage content of iron jarosite is lower than the ore and retains almost all of the iron to the residue, nickel extraction rate typically in the range of 60-65X. 第三,需要非常长的浸出时间,量级为4-5天,第四,需要加入相对较贵的铁沉淀剂例如碳酸钾、碳酸钠等。 Third, a very long leaching time, the order of 4-5 days, the fourth, the need to add relatively expensive iron precipitating agents such as potassium carbonate and sodium carbonate. 美国专利No. 6, 261, 527 Bl以及6, 680, 035 B2描述了另一种大气压浸出工艺,其中首先使用浓硫酸对褐铁矿石进行"完全"浸出,即将镍和铁基本从针铁矿中溶解出来,然后在获得的褐铁矿浸出浆中对腐泥土矿进行浸出,同时通过加入黄钾铁矾沉淀剂使铁以黄钾铁矾的形式沉淀出来。 U.S. Patent No. 6, 261, 527 Bl and 6, 680, 035 B2 describe another atmospheric leaching process wherein the first concentrated sulfuric acid to limonite ore a "complete" leaching, i.e. substantially nickel and iron from the iron needle ore dissolved out, and then leaching the saprolite to limonite ore leach slurry obtained while jarosite by adding a precipitating agent to precipitate the iron in the form of jarosite. 这种工艺同样具有产生黄钾铁矾的缺点,需要对矿石的褐铁矿和腐泥土成分进行分别采矿和准备,并且只限用于很窄的腐泥土对褐铁矿之比的范围。 This process also has the disadvantage that the jarosite, the need for ores and limonite saprolite mining and separately prepared component, and for only a narrow range of saprolite to limonite ratio of the. 后一项缺点是由于腐泥土的有效可浸出量取决于褐铁矿浸出溶液中的铁的量。 The latter disadvantage may be due to an effective amount of saprolite leaching depends on the amount of iron in the limonite leach solution. W0 03/093517 Al描述了对这种工艺的一种改进,其中包括取消形成黄钾铁巩的离子例如钠、钾或铵的加入,并使铁以黄钾铁巩以外的化合物形式沉淀出来,例如针铁矿。 W0 03/093517 Al describes an improvement of such a process, which comprises forming cancellation Gong yellow ferric potassium ions such as sodium, potassium or ammonium, and iron is precipitated in the form of potassium compounds other than yellow iron Gong, such as goethite. 这种工艺克服了黄钾铁矾的缺点,但在所引用的实例中疏酸消耗量为0."至0. 87吨石克酸/吨矿石,在所引用的十一个实例中有九个超过了0. 72吨硫酸/吨矿石。美国专利No. 6, 261, 527 Bl和6, 680, 035 B2以及WO 03/093517 Al所描述的工艺基于针铁矿比通常的腐泥土矿物例如蛇纹岩更不易被酸浸出的亊实.这已被其他研究者所证实(参见,例如John H. Canterford "Leaching of Some Australian Nickeliferous Laterites with Sulfuric Acid at Atmospheric Pressure, " Proc. Australasian Inst. Min. Metall., 265 (1978), 19-26; NM Rice和LW Strong, "The Leaching of Lateritic Nickel Ores in Hydrochloric Acid, " Canadian Metallurgical Quarterly, 13 (3)(1974), 485-493;以及美国专利5, 571, 308的图5),因此,在浸出的第二阶段只有腐泥土可以有效地利用,在所述第二阶段中同时发生铁的沉淀。这是由于溶液的酸度必须相对较低以使得黄钾铁矾能够沉淀, This process overcomes the disadvantages of jarosite, but sparsely acid consumption in the examples cited 0. "stone g to 0.87 tons of acid / ton of ore, in nine of the eleven examples cited exceeds a / t of ore 0.72 tons of sulfuric acid. U.S. Pat. No. 6, 261, 527 Bl and processes described in 6, 680, 035 B2 and WO 03/093517 Al, for example, based on the goethite than typical saprolite minerals serpentine is less susceptible to acid leaching Shi solid. this has been confirmed by other researchers (see, e.g. John H. Canterford "leaching of Some Australian Nickeliferous Laterites with Sulfuric acid at Atmospheric Pressure," Proc. Australasian Inst. Min. Metall, 265 (1978), 19-26;. NM Rice and LW Strong, "The Leaching of Lateritic Nickel Ores in Hydrochloric Acid," Canadian Metallurgical Quarterly, 13 (3) (1974), 485-493; and U.S. Patent No. 5 , 571, 308 of FIG. 5), therefore, only saprolite can be effectively utilized in the second stage leach, iron precipitation occurs simultaneously in the second stage. this is due to the acidity of the solution must be relatively low so that the capable of precipitating jarosite, 至更低以使得针铁矿或三价铁的其它水解产物能够沉淀。褐铁矿中所含的针铁矿在这样的条件下浸出非常緩慢,因此在第一阶段使用相对较高的酸浓度对褐铁矿(主要为针铁矿)进行浸出并将铁和镍都带入溶液中。美国专利No. 3, 244, 513描述了一种方法,其中主要为褐铁矿类(定义为>25%铁)的红土矿在有限量的水的存在下与浓疏酸混合,然后将混合物在约500至7251C的温度下焙烧,以使镍、钴、镁和锰的有用成分优先于铁发生硫酸盐化。之后的水浸出可获得溶液中镍和钴的高提取率和铁的低提取率.该方法的优点在于它不需要使用昂贵的高压釜进行浸出.最主要的缺点是它需要进行昂责的焙烧步骤。美国专利No. 4, 125, 588描述了与美国专利No. 3, 244, 513中所描述的类似的方法,除了具有以下不同:省略了焙烧步壤,并且仔细控制矿石与浓硫酸的混合 So that to a lower goethite or other hydrolysis products of ferric iron can be precipitated. Goethite contained in limonite under such conditions extraction is very slow, so in the first stage using a relatively high acid concentration of limonite (predominantly goethite) and the leaching of iron and nickel are brought into solution. U.S. Patent No. 3, 244, 513 describes a process in which limonite main classes (defined as> 25% Fe) laterite ore mixed in the presence of a limited amount of water to the concentrated hydrophobic acid, and then the mixture was fired at a temperature of from about 500 to 7251C so that nickel, cobalt, magnesium and manganese useful components in preference to iron occurs aqueous leaching solution obtained nickel and cobalt sulfate. after high extraction rate and low rate of iron extraction. the advantage of this method is that it does not require the use of expensive autoclave leaching. the main drawback is that it requires . responsible for expensive baking step U.S. Patent No. 4, 125, 588 describes 3, 244, 513 similar to the method described in US Pat. No., with the following exception: calcination step is omitted soil, and careful control of ore mixed with concentrated sulfuric acid 在所述混合中首先在没有明显存在的水的条件下将矿石与浓硫酸混合,然后再加入控制量的水以引发矿石的硫酸化,最后再另外加入水对混合物进行浸出。 Mixing the first mixed in water under conditions of no significant presence of ore with concentrated sulfuric acid, and then water was added to initiate a controlled amount of sulfated ore, and finally water was added and the mixture was further leaching. 此方法的优点是其取消了美国专利No. 3, 244, 513所需的焙烧步骤.但是此方法也具有很大缺点。 The advantage of this method is that it canceled U.S. Patent No. 3, 244, 513 required calcination step. However, this method also has significant drawbacks. 缺点之一是所使用的矿石含有的水分应不高于1%,这意味着在大多数情况下矿石必须经过干燥,这是由于红土矿的原地含湿量通常为20%或更多。 One disadvantage is that the water contained in the ore used should be no higher than 1%, which means that in most cases the ore must be dried, which is due to in situ moisture content laterite generally 20% or more. 第二个缺点如该专利中引用的全部实例所示,该方法不提供镍优于铁的选择性溶解(>90^的铁提取率).将溶液中的镍与铁分离通常导致另外的镍损失。 The second drawback of the cited patent all illustrated example, this method does not provide selective dissolution of nickel than iron (> 90 ^ iron extraction rate). The solution generally leads to the separation of nickel and iron nickel additional loss. 此外,该方法只适用于含有"大量氧化镁和二氧化硅"的矿石,即腐泥土矿石或硅镁镍矿石.虽然没有在全部的实例中引迷矿石的精确组成,但从提供的数据可明显看出矿石含有的镁是铁的3至4倍,清楚地说明了没有考虑到褐铁矿石(铁/镁重量比为约10到90)。 Furthermore, the method applies only contains "substantial magnesia and silica" ore, or saprolite ore i.e. garnierite ore. Although no exact composition of lead ore fans all examples, but the data may be provided as is apparent magnesium containing ore is iron, 3 to 4 times, clearly illustrates the limonite ore is not considered (iron / magnesium weight ratio of about 10 to 90). 而且在该方法中酸消耗量非常高,为约0. 9至1. 1吨石危酸/吨矿石。 Also in this method, a very high acid consumption, risk acid / tonne of ore is from about 0.9 to 1.1 tons of stone. 美国专利No. 3, 093, 559描述了另一种使用相对较浓的硫酸(大约25至50%硫酸)处理红土矿的方法。 U.S. Patent No. 3, 093, 559 describes another use of a relatively more concentrated sulfuric acid (about 25 to 50% sulfuric acid) laterite processing method. 在该方法中,加入足量的酸以使包括铁在内的大多数或全部金属有用成分硫酸化。 In this process, a sufficient amount of acid is added so that most or all of the metal components including iron Useful sulfated. 然后通过将浸出溶液蒸发至干并在975至1050T下焙烧所获得的盐使铁转化为赤铁矿,从而将铁与镍分离.之后对焙砂的再浸出使镍进入溶液,铁留在残渣中。 The leach solution was then evaporated to dryness and the salt baked at 975 to the 1050T obtained hematite into iron, so that the iron-nickel separation. After then calcine leaching of nickel into solution, the iron in the residue left in. 如同上述的各种工艺,需要进行高温焙烧步骤是工艺中的一个显著缺点.美国专利No. 2, 899, 300描述了一种方法,其中使用浓硫酸对潮湿的红土矿进行处理,然后在1001C至1501C之间,优选125"C的温度下将混合物烘烤干燥,然后再进行水浸出以溶解矿石中的金属有用成分。 烘烤步骤是一个显著的缺陷,因为它需要大量热能以蒸发矿石/酸混合物中所含的水。而且,如说明书中给出的实例所述,镍的溶解率相对较低而铁的溶解率相对较高,分别为~77%和53%。据称可通过向第一阶段的残渣中另外加入硫酸并进行二次硫酸化和水浸出步骤,从而使镍提取率提高,但这会增加工艺的复杂性而且不能改善该工艺中铁/镍的分离。美国专利No. RE37, 251描述了一种工艺,其通过使用含有硫酸氩根和硫酸根离子以及卣素离子例如氯离子的酸性溶液和氧气对包括镍红土矿在内的 As the above-described various processes, the need for high-temperature calcination step is a significant disadvantage in the process. U.S. Pat. No. 2, 899, 300 describes a process in which concentrated sulfuric acid of wet laterite processed at 1001C and then to between 1501C, preferably 125 "C at a temperature baking and drying the mixture, and then the aqueous leaching to dissolve the metal ore useful components. bake step is a significant drawback because it requires a large amount of thermal energy to evaporate the ore / acid water contained in the mixture. Further, as described in the example given the relatively low rate of nickel dissolution rate of iron dissolved is relatively high, to 77% and 53%, respectively. allegedly by the the first stage residue was additionally added sulfuric acid and sulfuric acid and water leaching the second step, so that the nickel extraction rate, but will increase the complexity of the process and the process does not improve the separation of the iron / nickel. U.S. Pat. No. RE37, 251 describes a process by which the argon containing sulfate ions and sulfate ions and wine container element such as an acidic solution of chloride ions and oxygen gas including a nickel laterites, including 非亚铜矿石和浓缩物进行加压浸出。根据说明书,所需的温度和压力分别为225C和450psig 02。考虑到225t:下的蒸汽压大约为3"70psi,总压力应在8Wpsig的范围。 Non-copper ores and concentrates were leached 225C pressurized and 225t 450psig 02. Taking into account the description, the desired temperature and pressure: the vapor pressure of approximately 3 "70psi, the total pressure be in a range of 8Wpsig. 这些条件与高压酸浸出的条件非常相似,因此如上所述,需要使用昂贵的高压釜系统。 These conditions of high pressure acid leaching conditions are very similar, as described above, it is necessary to use an expensive autoclave system. 本发明的目的是消除或减少这些已知工艺的缺点.进一步的目的是提供一种对褐铁矿石和腐泥土矿石的混合物进行酸浸出的方法,所述褐铁矿石和腐泥土矿石的混合物通过对一般的红土矿矿体进行整体采矿而不进行任何后续的矿石种类分离而获得,本方法在大气压或较低压力下进行,可获得镍和钴的高提取率以及非常低的铁的最终提取率。 Object of the present invention is to eliminate or reduce these disadvantages of known processes. A further object is to provide a mixture of limonite and saprolite ore is iron ore acid leaching method, a mixture of brown iron ore and saprolite ore by laterite ore bodies general the whole mining ore without any subsequent kind of separation is obtained, the process is carried out at atmospheric pressure or a lower pressure, the final extract obtained high nickel and cobalt extraction rates and very low iron rate. 发明内容本发明提供一种浸出含有褐铁矿和腐泥土的红土矿的方法,包括以下步踝:(a) 将褐铁矿和腐泥土与足量的浓无机酸混合,以与矿石中可溶性非铁成分形成盐;(b) 对步骤(a)中的混合物进行水浸出,浸出时间和温度足以使溶解的三价铁水解、形成含铁的沉淀物,同时将镍和钴中的至少一种大量溶解到浸出溶液中;以及(c) 从浸出溶液中回收镍或钴的化合物中的至少一种。 The present invention provides a method for leaching laterites comprising limonite and saprolite, comprising the steps ankle: (a) mixing the limonite and saprolite with a sufficient amount of concentrated inorganic acid, and soluble ores non-ferrous salt forming component; (b) the mixture of step (a) is performed in a water leaching, ferric hydrolysis leaching time and temperature sufficient to dissolve the formed precipitate iron, nickel and cobalt while at least one of a large number of species dissolved in the leach solution; and (c) recovering at least one compound of nickel or cobalt from the leach solution. 该方法可从褐铁矿石和腐泥土矿石中将镍和钴充分浸出。 This method is sufficiently leached from the ore and in the limonite saprolite nickel and cobalt. 所述褐铁矿石和腐泥土矿石可以通过对一般的镍红土矿床进行整体采矿获得,本方法分为两个阶段,第一阶段包括将矿石与浓无机酸混合并发生反应,第二阶段包括制备酸/矿石混合物在水中的浆料并对混合物进行浸出以溶解镍和钴。 The limonite and saprolite ore may be iron ore by the general overall mining Ni laterite deposits obtained, the process is divided into two stages, the first comprising mixing ore with concentrated mineral acid and reaction, the second stage comprising preparing the acid / ore mixture in water slurry and the mixture is leached to dissolve nickel and cobalt. 铁主要作为黄钟铁巩以外的三价铁的氧化物或氢氧化物i^固体環出残渣,与镍和钴有效地分开。 Than iron mainly as Huang Zhong Gong ferric iron oxides or hydroxides i ^ solid residue out of the ring, and effectively separated from nickel and cobalt. 本方法还可以包括在水浸出之前对混合的矿石和酸进行熟化,矿石在与酸混合并反应之前首先将其破碎。 The method may further include curing the mixed ore and acid prior to water leaching, the ore prior to mixing with the acid and the reaction is first crushed. 优选单独破碎腐泥土,然后再与褐铁矿混合。 Preferably crushed separately the saprolite, limonite and then mixed. 更优选先将酸与褐铁矿混合,然后再加入腐泥土。 More preferably first acid mixed with the limonite, saprolite then added. 水浸出可有利地在适当提高的温度下进行。 Water leaching can be advantageously carried out at a suitable elevated temperature. 对于大气压浸出,优选在95-1051C的温度范围内进行。 To atmospheric leaching is preferably carried out in a temperature range of 95-1051C. 或者,可通过在高压釜中在最高至约1501C 的温度下进行浸出以获得更快的浸出。 Alternatively, leaching may be performed by up to a temperature of about 1501C in an autoclave to obtain a faster leaching. 对应的压力为最高至70psia,例如15-70psia的压力范围内,大约等于该浸出温度下的饱和蒸汽压。 Corresponding to a pressure of up to 70 psia, for example in a pressure range of 15-70psia, approximately equal to the saturation vapor pressure at the leaching temperature. 水浸出可分两个阶段进行,第一阶段在大气压下、在最高至浸出溶液的沸点的温度下进行,第二阶段在高压釜中、在最高至150X:的温度下进行。 Flooding carried out in two stages, the first stage, at a temperature up to the boiling point of the leach solution at atmospheric pressure, a second phase, up to 150X autoclave: carried out at a temperature. 所用的酸优选选自硫酸、盐酸或硝酸,更优选硫酸。 Preferably selected from sulfuric acid, hydrochloric acid or nitric acid is used, more preferably sulfuric acid. 也可使用上述酸的混合物。 Mixtures of the abovementioned acids may also be used. 当所用的酸为硫酸时,步骤(a)中形成的盐包括硫酸盐。 When sulfuric acid is used, a salt in step (a) comprises a sulphate formed. 有利地,在水浸出过程中可加入还原剂例如二氧化硫、硫化氢、可溶的亚硫酸氩盐和亚硫酸盐化合物或可溶的亚铁化合物以增强钴的溶解。 Advantageously, the water extract can be added during a reductant such as sulfur dioxide, hydrogen sulfide, soluble bisulfite and sulfite compounds argon salts or soluble ferrous compound to enhance the dissolution of cobalt. 步骤(c)中从浸出溶液中对至少一种镍或钴的化合物进行的回收可包括向浸出溶液中加入离子交换树脂而不预先进行固/液分离。 Recovery step (c) is at least one compound of nickel or cobalt from the leach solution carried may comprise an ion exchange resin was added to the leach solution without prior solid / liquid separation. 也可首先将浸出溶液与沉淀物分离,然后再从浸出溶液中回收至少一种镍或钴的化合物。 May first be separated from the leach solution from the precipitate, at least one compound of nickel or cobalt and then recovered from the leach solution. 本发明的方法避免了使用高成本的高压釜并减少了黄钟铁巩化合物的生成。 The method of the present invention avoids the costly use of an autoclave, and reduces the production of yellow bell Gong iron compound. 在一些实施方式中,还免除了对褐铁矿类矿石和腐泥土类矿石进行分别开采和分别处理的必要,还使得能够处理大范围的腐泥土对褐铁矿比例的矿石。 In some embodiments, it eliminates the need for further classes limonite and saprolite ores are mined ore type and treatment separately, also makes it possible to handle a wide range of limonite to saprolite ore ratio. 还发现本发明能获得至少约80%的镍提取率和多达95%或更高的钴提取率,同时具有低于约15%的铁提取率。 The present invention further found that the nickel extraction can be obtained at least about 80% and up to or more cobalt extraction rate of 95%, while the rate of extraction of iron having less than about 15%. 附图说明图1为以简化形式显示了本发明方法的一种实施方式的流程图。 Figure 1 is a flowchart showing an embodiment of the method of the present invention in a simplified form. 图2显示了本发明方法的另一实施方式,其中将一部分浸出残渣重复利用作为铁沉淀的晶种。 Figure 2 shows another embodiment of the method of the present invention, wherein a portion of the leach residue is reused as a seed crystal precipitated iron. 图3显示了本发明方法的第三种实施方式,其中首先将全部的所需酸与褐铁矿石混合,然后再将腐泥土矿石与获得的褐铁矿/酸混合物混合。 Figure 3 shows a third embodiment of the method of the present invention, wherein the first mixing all of the desired acid to limonite ore, saprolite ore and then get mixed with the limonite / acid mixture. 图4显示了本发明方法的第四种实施方式,其中首先将全部的所需酸与褐铁矿石混合,然后将破碎的腐泥土矿石和水加入获得的褐铁矿/酸混合物中,之后将所得的混合物研磨再进行大气压浸出。 4 shows a fourth embodiment of the method of the present invention, wherein the first mixing all of the desired acid to limonite ore, and then crushed saprolite ore and water were added to the limonite / acid mixture obtained, after the resulting mixture was then triturated atmospheric leaching. 具体实施方式本发明提供一种改进的方法用于从含镍的红土矿,提取镍和钴,同时将矿石中所含的大部分铁排除在固体浸出残渣中。 DETAILED DESCRIPTION The present invention provides an improved process for nickel from laterites, nickel and cobalt extraction, while most of the iron contained in the ore leach out of the solid residue. 本方缺不需要预先进行褐铁矿石与腐泥土矿石的分离,并且能够处理两种类型矿石的混合物。 This lack of side does not need to previously separate the limonite saprolite ore iron ore, and a mixture of two types of ores can be processed. 但是在便于分别开采褐铁矿石和腐泥土矿石的情况下,可以通过首先直接使酸与褐铁矿石反应然后再加入腐泥土矿石的方法获得镍的高提取率。 However, in each case to facilitate the exploitation of brown iron ore and saprolite ore, by first exposing the acid to limonite ore direct reaction method and then saprolite ore is added to obtain a high nickel extraction rate. 参见图1,首先将由褐铁矿和腐泥土的混合物组成的红土矿原矿石破碎到约5mm至10mm上限粒度。 Referring to Figure 1, by first crushing the mixture of limonite and saprolite ore raw laterite composition to a top particle size of about 5mm to 10mm. 然后将破碎的矿石与浓无机酸在合适的设备例如混磨机中混合,所述无机酸选自硫酸、盐酸和硝酸或上述酸的混合物。 Then the crushed ore with concentrated mineral acid in a suitable mixing apparatus such as compounding mill, a mixture of the mineral acid is selected from sulfuric acid, hydrochloric acid and nitric acid, or above. 矿石一般在原矿状态下含有大量游离水分,在加入浓酸之前不必对矿石进行干燥。 Ore typically contains a lot of free water in the state ore, the ore drying is not necessary prior to the addition of concentrated acid. 酸的加入量至少为在后续的浸出阶段按化学计量溶解矿石中可溶的'非铁金属(不包括铁)所需的量,所述非铁金属即矿石中的大部分镍、钴、 镁、铝、铜、锌和一小部分铬。 The amount of acid added is at least stoichiometric in the subsequent dissolution of the ore leaching stage is soluble 'non-ferrous metals (excluding Fe) of the desired amount, i.e., the non-ferrous metal ores most of the nickel, cobalt, magnesium , aluminum, copper, zinc, and a small portion of the chromium. 加入少量过量的酸以在后续的浸出阶段提供一定的游离酸度,从而浸出少量的铁,并且保证镍和钴的最大提取率。 Adding a small amount to provide an excess of acid leaching stage subsequent free acidity constant, so that a small amount of iron leached, and to ensure maximum extraction of nickel and cobalt. 限制酸的加入量以保证从矿浆中提取铁的最终提取率最小。 To limit the amount of acid added to ensure that the final extraction rate of iron extraction from the pulp minimum. 在一些情况下, 一些镁和铝可能是不溶的,需要将这种情况考虑在内以确定确切的酸加入量'酸混合过程中水的加入量被减少至能够使与矿物反应的酸达到最高浓度的程度。 In some cases, some of the magnesium and aluminum may be insoluble, it is necessary to take this into account to determine the exact amount of acid added to 'the acid added during the mixing amount of water is reduced to enable the reaction of the acid with a mineral highest the degree of concentration. 只有矿石/酸混合物硬到不能完全混合或不易处理时才有必要加入水。 Only the ore / acid mixture to the hard or difficult to handle not only complete mixing is necessary to add water. 向潮湿的矿石中加入浓酸导致产生大量的热,使得混合物的温度升高至——甚至高于——水的沸点并导致水的大量蒸发。 Concentrated acid was added to the moist ore results in a large amount of heat, so that the temperature of the mixture was raised to - even higher than - the boiling point of water and lead to substantial evaporation of water. 如果需要,可体的程度。 If desired, the extent of the body. 如果不加入水,根据矿石的含湿i:以及净发热量,、也可能会形成干燥、粉末状的反应产物。 If no water is added, according to the moisture ore i: ,, and the net calorific value may also form a dry, powdery reaction product. (可能会形成糊状流体和干燥粉末状物质的中间状态,即坚硬的乳脂糖状混合物,该混合物可能更难于处理)。 (Intermediate state may form a fluid paste and a dry powder substance, i.e. hard toffee-like mixture, the mixture may be more difficult to process). 理论上,混合物既可以具有糊状流体的稠度也可以是干燥粉末状的稠度以使其易于处理。 In theory, either a mixture of pasty consistency having a fluid may be a dry powder-like consistency so that it is easy to handle. 所得的酸/矿石混合物一或者"泥料"一可以在室温下进行"熟化",熟化时间应足以使无机酸与矿石中的矿物成分几乎完全反应。 The resulting acid / ore mixture, or a "mud" may be a "aged" at room temperature, the curing time should be sufficient to allow the mineral component of the inorganic acid and ore is almost complete reaction. 所述熟化可以通过将泥料存放在准备好的无渗透性的垫上并使泥料在垫上静置几天,然后将材料回收并用于下一步处理来完成。 The ripening can be stored in mud prepared rather impermeable mud mat and the mat was allowed to stand a few days, and then recovered for further processing to complete the material. 为便于存放和回收,可能需要在存放前通过对材料进行例如挤出或造粒以形成小份的不连续的泥料。 To facilitate storage and recycling may be required before storing the material, for example, by extrusion or pelletized to form small discrete parts mud. 但是发现使用最少的熟化时间或无熟化时间可能获得满意的结果。 But I found that using a minimum of aging time or no aging time possible to obtain satisfactory results. 在这种情况下,可将酸/矿石混合物直接与水混合。 In this case, the acid / ore mixture may be directly mixed with water. 如杲在加入酸之前研磨矿石,则之后不必要进行研磨。 Gao The ground ore before adding the acid, it is necessary after grinding. 更长时间的熟化可能使之后的水浸出步骤获得略高一点的镍提取率和更低的铁提取率。 After the water leaching step may cause longer curing to obtain a nickel extraction rate slightly higher and lower iron extraction rate. 熟化之后,将泥料研磨至足以在搅拌槽中进行浸出的颗粒大小。 After ripening, the mud is ground to a particle size sufficient for leaching in a stirred tank. 方便地,可以将所需用于形成浸出浆料的水在研磨之前加入,以使研磨步骤在湿润状态下进行。 Conveniently water, may be used to form the desired leached slurry is added before grinding, milling step is carried out so that in a wet state. 泥料研磨所达到的颗粒大小应足以使得大部分颗粒在不需要过多的搅拌能量输入的条件下在浆料中成为离开底面的悬浮固体。 Pug milled particle size achieved should be sufficient such that the majority of the particles become suspended solids away from the bottom surface of the slurry without requiring excessive energy input stirring. 需要使浆料在浸出过程中在保证混合良好的情况下尽可能浓稠,从而使所需水量最少并生成最浓的含镍和钴的浸出母液。 Necessary to the slurry in the leaching process in the case of thick as possible to ensure good mixing, such that a minimum amount of water required to produce the most concentrated and the pregnant leach solution containing nickel and cobalt. 将所得的浸出浆料在分批浸出反应器中按需要加热,或者,如果过程连续进行则在一系列浸出反应器中按需要加热。 The resultant leached slurry is heated as necessary in a batch leaching reactor, or, if the process is carried out continuously in a series of heat needed in the leaching reactor. 浸出浆料的温度优选控制在浸出液的标准沸点或接近该沸点, 一般为95至IOO"C。为达到这一目的可以使用新鲜蒸汽注入或其它方法增加热能。一部分所需的热由酸混合步骤中形成的含有过量的酸和金属盐的溶液的热量提供。此外,可以在泥料形成过程中通过用浸出时需要使用的水对泥料反应器进行降温从而将水预热,或者通过回收酸矿石反应过程中产生的蒸汽,从而回收另一部分热量。可以使浸出混合物进行反应直到矿石中的大部分的镍和钴溶解并且大部分的铁进入固体浸出残渣中。搅拌浸出的保持时间的量级为12至48 小时。 一般在约15小时或更少的时间内可以获得满意的结果。在一些情况下,可能需要向浸出浆料中加入控制量的还原剂以增强矿石中与氧化的锰矿物(例如钴土)共生的钴的浸出.例如,可以有控制地加入二氧化硫以提高钴(和锰的 Leached slurry temperature is preferably controlled to the normal boiling point of the leaching solution at or near the boiling point, usually 95 to IOO "C. For this purpose use can increase the thermal energy of fresh steam injection or other methods. Portion of the heat required by the step of mixing the acid heat of solution containing excess acid and metal salt formed is provided. Further, when using an acid leaching process by the need to use water to cool the reactor mud so as to preheat the water, or it may be formed by recovering pug ore steam produced during the reaction, thereby recovering another part of the heat may cause most of the leached mixture to react until the nickel and cobalt ore is dissolved into the iron and most of the solids in the leach residue. agitation leaching of the order of retention time generally satisfactory results can be obtained within about 15 hours or less for 12 to 48 hours. in some cases, the control amount of reductant added to the leach slurry may be required to enhance the oxidation of manganese ore was (e.g. asbolane) symbiotic leaching cobalt. For example, the controlled addition of sulfur dioxide to increase the cobalt (manganese and 出),这对于本领域的技术人员是显而易见的。还可以使用其它能够将三价和四价铥氧化物还原至二价态的还原剂。可以通过使用高于沸点的温度以大幅度加快浸出过程,例如通过在高压釜中将浸出浆料加热到约150X:,可以将浸出时间减少到约1小时。进一步提高温度可能是有益的,但本发明的一个目的是消除与高压浸出有关的复杂性。应指出在15ox:下浸出泥料加水的浆料所需的压力只有约70psia (150"C下的蒸汽压)。 Out), to which those skilled in the art will be apparent. It may also be capable of reducing the use of other trivalent and tetravalent thulium oxide twenty reducing valence can be used to significantly speed up the leaching by a temperature above the boiling point process, for example by heating in an autoclave leach slurry to about 150X :, leaching time can be reduced to about 1 hour. further increasing the temperature may be beneficial, but an object of the present invention to eliminate the complexity associated with the high pressure leaching sexual should be noted that in 15ox: only about 70psia (150 vapor pressure at C ") required under leaching mud slurry with water pressure. 在这一压力下,可以使用常规离心泵将浆料泵至高压釜,并且降压系统可以是非常简单的单级阀或节流门(choke), 适用于本发明的高压蒼设备与在250匸左右的温度和450-500psia左右的压力下进行高压浸出所需的高压釜大不相同,这对于本领城的技术人员是显而易见的。 Under this pressure, using conventional centrifugal slurry pump to the autoclave, and depressurization system can be very simple single-stage valve or throttle (Choke), suitable for high pressure apparatus according to the present invention and the dark green 250 required high pressure leaching autoclave is very different from a temperature of about about 450-500psia Xi and pressure, which for the city skilled in the art will be apparent. 使用高于沸点的温度还可在溶液中获得更高的镍/铁比,这对于浸出溶液的下游处理是有益的。 A temperature above the boiling point may also be used to obtain higher nickel / iron ratio in solution, which for the downstream processing of the leach solution is advantageous. 这是由于在多数情况下在进行镍和钴的回收之前必须将几乎所有铁从溶液中去除。 This is because prior to recovery of nickel and cobalt is performed in most cases virtually all iron must be removed from the solution. 通常,通过向浸出浆料中加入碱,例如碳酸钙,并沉淀出羟基氧化铁(iron oxyhydroxide)化合物而除去溶液中残留的铁。 Typically, by adding a base to the leach slurry, such as calcium carbonate, and precipitated iron oxyhydroxide (iron oxyhydroxide) compound to remove residual iron in solution. 一部分镍会与铁共沉淀而导致该有价值金属(paymetal) 的损失,此外中和剂也意味着工艺中额外的操作成本。 A portion of the nickel and iron will lead to the loss of the co-precipitation of valuable metal (paymetal), and further neutralizer means of the additional operating cost of the process. 使用较高温度的另一个优点是最终浸出浆料的固/液分离性能得到提高,因为在较高的浸出温度下可获得较高的沉降速度。 Another advantage of using high temperatures is the final leach slurry separation performance solid / liquid is increased, because at higher settling velocity obtain higher leaching temperature. 在一些情况下,依次使用大气压浸出和后续的中等压力浸出可能是有利的。 In some cases, the sequential use of atmospheric pressure leaching and subsequent extraction medium may be advantageous. 可以最方便地在大气压浸出阶段加入用于浸出氧化的锰矿物和所含的钴和镍有用成分的二氧化疏或其它的还原剂。 Most conveniently at atmospheric leaching stage sparse dioxide or other added reducing agents were used for the leaching of manganese oxide and cobalt and nickel contained in the useful components. 还可以使用后续的加压浸出步骤实现上一段中指出的优点。 You may also be used in the subsequent step of pressure leaching to achieve the advantages noted in the preceding paragraph. 本发明可获得至少80%、可高达90-95%的镍提取率以及对应的低至5-10%的铁提取率。 The present invention can be obtained at least 80%, up to 90-95% of nickel extraction and low iron extraction rate of 5-10% of the corresponding. 此外,浸出残渣中一般含有不超过约1_2%的疏,说明残渣中的铁化合物主要不是黄钾铁矾类。 Additionally, the leach residue generally contains no more than about 1_2% hydrophobic, residue iron compound described is not primarily based jarosite. 在将硫酸用作浸出剂时,本发明的这一浸出工艺与现有技术例如美国专利No. 3, 244, 513的不同之处在于,现有技术在酸混合后使用焙烧步骤以将酸混合时形成的全部硫酸铁转化为氧化铁。 When sulfuric acid is used as the leaching agent, the leaching process of the present invention with the prior art, for example, U.S. Pat. No. 3, 244, 513 differs from that in the prior art to use baking step after mixing the acid to a mixed acid when all of the ferric iron oxide is formed into. 在该转化过程中释放出三氧化硫(S03)气体,三氧化疏气体与非铁金属氧化物例如Ni0和Mg0反应形成非铁硫酸盐。 Release of sulfur trioxide (S03) in which a gas conversion process, sparse trioxide gas and non-ferrous metals and oxides such as Ni0 Mg0 react to form a non-ferrous sulphate. 因此在现有技术的方法中非铁金属优先硫酸化。 Thus in the process of sulfation preferentially Africa prior art ferrous metal. 但是,现在令人惊讶地发现,耗资巨大并且需要大量昂责的燃料能量以达到所需的焙烧温度例如500-7001C的焙烧步骤,并不是为达到非铁金属的选择性硫酸化、从而在对矿石/酸混合物进行水浸出后获得含有大部分的可溶非铁金属——尤其是镍和钴——以及相对较少的铁的浸出母液所必要的。 However, now surprisingly it has been found that, costly and requires a lot of expensive fuel energy responsibility to achieve the desired firing temperature of 500-7001C, for example, the calcining step is not to achieve selective sulfation of non-ferrous metal, for so particularly nickel and cobalt - - and the relatively few pregnant leach solution containing iron necessary for most of the soluble non-ferrous metal ore / acid mixture was obtained flooding. 所需的只是在水浸出过程中提供足够的时间和温度以实现所需的反应。 Is required is to provide sufficient time and temperature in the water leaching process to achieve the desired reaction. 因此取消焙烧步骤体现出相对于现有技术的一大优点。 Thus the calcination step reflects a big advantage over the prior art. 水浸出之后,通过过滤或浓缩对浸出浆料进行固/液分离,以获得含有矿石中所含的大部分镍和钴的浸出母液以及含有矿石中所含的大部分铁的固体残渣。 After the aqueous leaching, solid / liquid separation by filtration or the leached slurry was concentrated to obtain a solid residue containing most of the iron in the leach liquor most nickel and cobalt contained in the ore as well as contained in ores containing. 有利地,在一系列浓缩器中在洗涤水流和浸出浆料逆流的情况下进行浓缩,以从浸出残渣中将携带的大部分金属有用成分洗涤出来,这种方法称为逆流倾析洗涤(CCD)。 Advantageously, in a series of concentrators in washing water was concentrated and leached slurry counterflow situation, most of the metal to carry a useful component in the leach residue from washing out, this method is called counter-current decantation washing (CCD ). 金属有用成分主要向第一浓缩器的浓缩器溢流(overflow)中汇聚,得到浸出母液。 Useful metal composed mainly concentrated to the first concentrator overflow (overflow) in convergence, obtained pregnant leach solution. 浸出母液接着通过本领域技术人员已知的方法进行镍和钴的回收, 所述方法例如溶剂萃取、离子交换、使用硫化剂例如硫化氩进行硫化物沉淀,或使用例如氧化镁作为沉淀剂进行氢氧化物沉淀。 Pregnant leach solution is then carried out by methods known to those of skill in the recovery of nickel and cobalt, the method such as solvent extraction, ion exchange, for example using a vulcanizing agent for vulcanizing argon sulfide precipitation, such as magnesium oxide or hydroxide as a precipitating agent oxide precipitation. 还可以不先进行固/液分离而使用矿浆树脂交换工艺将镍和钴从漫出浆料中回收。 May not first subjected to solid / liquid separation process using the pulp exchange resin from nickel and cobalt diffuse out of the slurry recovered. 在此工艺中,向浸出浆料中直接加入提取镍及可能的钴的离子交换树脂。 In this process, may be added directly to the extraction of nickel and cobalt to leach slurry ion exchange resin. 提取结束后,通过筛分使树脂与已去除镍的浸出浆料分离。 After the extraction, by sieving the resin with removal of nickel leached slurry is separated. 清洗树脂以除去固体后,可使用新鲜的酸溶液将镍从树脂上洗脱下来。 After washing the resin to remove solids, the nickel can be eluted from the resin with fresh acid solution. 在通过上述方法之一回收镍和钴的过程中或在此之前,可使用碱, 例如碳酸钾、氧化镁、碳酸钠等中和浸出溶液,以中和从浸出步骤中残留下来的游离酸度并沉淀少量的三价铁、铝和铬,同时使镍和钴的共沉淀最小化。 In this prior process through recovery of nickel and cobalt or in one of the above methods, may be used a base, such as potassium carbonate, magnesium carbonate, sodium carbonate and the like and the leach solution to neutralize residual leaching step down from the free acidity and the precipitate small amounts of ferric iron, aluminum and chromium, nickel and cobalt while minimizing co-precipitation. 这一过程可通过单个或多个步骤完成,多个步稞中间间隔固/液分离.在本发明的一种实施方式中,可在将浸出残渣与浸出溶液分离之前进行第一步中和。 This process may be completed by a single or multiple steps, among a plurality of steps spaced wheat solid / liquid separation. In one embodiment of the present invention, and the first step may be carried out prior to separation of the leach solution and leach residue. 然后可将合并的浸出和中和残渣通过过滤或浓缩从部分中和的浸出溶液中分离,如上所述.根据所选的从浸出母液中回收镍和钴的方法,可能还需要第二步中和.在第二步中和之后,可通过过滤或浓缩将获得的中和残渣与中和后的浸出溶液分离。 Then the combined leach and neutralization residue may be separated or concentrated by filtration from the partially neutralized leach solution, as described above. The method for recovering nickel and cobalt from the pregnant leach solution is selected, the second step may also be required and separating the leach solution in a second step and then, by filtration or by concentration and the residue obtained after the neutralization. 第二步中和残渣最好返回至第一步中和,以重新溶解任何共沉淀的镍和钴.程中进行分别的不同的处理而将二者分离。 The residue and the second step is preferably returned to the first step and to re-dissolve any co-precipitated nickel and cobalt. Each treatment is different and the two separating process. 而且,只要达到至少某一腐泥土/褐铁矿的最小比值,此工艺不限于任何特定的腐泥土/褐铁矿比。 Further, as long as at least a minimum ratio of saprolite / limonite reached, this process is not limited to any particular saprolite / limonite ratio. 可以根据腐泥土/揭铁矿矿石混合物中非铁金属的含量,针对腐泥土/ 褐铁矿的比值范围调整加入矿石的酸的量。 May saprolite / expose ores Africa ferrous metal content of the mixture, the range for the ratio of saprolite / limonite adjustment amount of acid added to the ore. 还令人惊讶地发现不必像美国专利No. 3, 793, 432中一样向浸出浆料中加入铁沉淀剂.加入铁沉淀剂例如钠、钾和铵离子是不利的,因为这些离子促使生成含铁的黄钾铁矾化合物,黄钾铁矾化合物是热力学不稳定的,会随着时间而緩慢分解释放出硫酸,从而导致浸出残渣中金属杂质的重新溶解并可能导致环境污染。 It has also been surprisingly found that do not like the U.S. Patent No. 3, 793, 432 as the iron precipitating agent was added to the leach slurry was added iron precipitating agent such as sodium, potassium and ammonium ions are disadvantageous because they promote the formation of ions containing jarosite iron compound, jarosite compounds are thermodynamically unstable, break down over time slowly releasing sulfuric acid, resulting in the leaching residue re-dissolved metal impurities and may cause environmental pollution. 此外,浸出过程中需要频外的硫酸以满足形成黄钾铁矾所需的硫酸根离子。 Further, sulfuric acid leaching process outside the frequency needed to satisfy the required form jarosite sulfate ion. 在本发明的方法中,将例如硫酸加入矿石中时,在酸/矿石混合步骤中镍、钴和铁以及矿石中其他非铁金属被无选择地硫酸化,即转化为疏酸盐。 In the method of the present invention, for example sulfuric acid added to the ore, in the acid / ore mixing step of nickel, cobalt and iron ore as well as other non-ferrous metals is not selective sulfation, i.e. converted into salt sparse. 在后续的浸出步骤中硫酸盐易于在水中溶解。 In the subsequent leaching step Sulfate readily dissolved in water. 但是由于最初加入的酸的量不足以使包括铁在内的所有金属转化为硫酸盐,因此最初的镍和钴的提取是不完全的。 However, since the initial amount of acid added is insufficient to all metals including iron sulfate is converted, so the initial extraction of nickel and cobalt is incomplete. 因此,相当数量的铁与镍、钴、镁、铝、铬、 铜和锌一起进入溶液.但是通过最初的硫酸盐溶解步骤之后继续的浸出过程,溶液中铁含量降低,并从固相中进一步提取出镍和钴.确切的铁浸出和再沉淀反应仍为未知,但最终残渣中的硫含量很低,通常小于2%,说明黄钾铁矾的形成并没有达到显著的程度。 Thus, a considerable amount of iron and nickel, into the cobalt, magnesium, aluminum, chromium, copper and zinc with a solution. However, continuing leaching process, the iron content in solution decreased by initially sulfate after dissolving step and further extracted from the solid phase the nickel and cobalt. the exact leaching and iron precipitation reactions is still unknown again, but the final sulfur content of the residue is low, typically less than 2%, indicating the formation of jarosite, and did not reach a significant degree. 在本发明的一种优选的实施方式中,在水浸出步骤的开始阶段向浸出浆料中加入含铁的"晶种"材料,目的是加速溶解的铁的沉淀以及加速从固相中提取剩余的镍和钴。 In a preferred embodiment of the present invention, the iron is added to the leach slurry at the beginning of the flooding step of "seed" material, the purpose of accelerating the precipitation of dissolved iron, and the acceleration phase from the solid residual extract nickel and cobalt. 晶种颗粒的表面为铁的水解和沉淀—— 例如以氢氧化铁、针铁矿或赤铁石的形式——提供了低活化能位点,晶种材料最好是含有沉淀的铁化合物的最终浸出残渣本身的一部分.困2 显示了一种使用晶种循环实施工艺的方法,在本发明的另一种实施方式中,首先将矿石中的褐铁矿部分与浓酸混合,酸的量按照与前述相同的方法计算,然后将矿石中的腐泥土部分加入褐铁矿/酸混合物中.可以将腐泥土矿石以破碎的腐泥土或研磨的腐泥土形式加入褐铁矿/酸混合物中。 Surface of the seed particles hydrolysis and precipitation of iron - for example in the form of iron hydroxide, goethite or Hematite - A low activation energy sites is provided, preferably containing seed material is finally precipitated iron compounds a portion of the leach residue itself. trapped 2 illustrates a method embodiment of the process cycle using a seed crystal, in another embodiment of the present invention, first mixed limonite fraction of the ore with a concentrated acid, in accordance with the amount of the acid the method of calculating the same, and then saprolite ore is added portion limonite / acid mixture. saprolite ore or saprolite to break ground saprolite may be added in the form of a limonite / acid mixture. 对于前一种情况,在进行水浸出之前先对矿石/酸混合物进行研磨,可以在不加水的情况下进行研磨. 有利地,可以在进行大气压水浸出之前向矿石/酸混合物中加入水并进行湿研磨。 In the former case, the first of the ore / acid mixture is ground prior to the flooding, can be ground without the addition of water. Advantageously, the atmospheric pressure can be performed before the water is added to the aqueous leaching the ore / acid mixture and wet grinding. 对于后一种情况,可以在干燥条件下对腐泥土矿石进行研磨然后再与水一起加入酸/褐铁矿混合物中,或者湿研磨并以浆料或滤饼的形式加入褐铁矿/酸混合物中。 In the latter case, drying can be performed under conditions of saprolite ore triturated with water and then added with the acid / limonite mixture, or wet-milled and added to the limonite / acid mixture in the form of a slurry or cake in. 然后如前所述对所得的混合的矿石与酸进行水浸出。 As described above is then mixed with an acid of ore was subjected to water leaching.本方法最大可能地将红土矿中的针铁矿成分硫酸化。图3显示了进行本发明的这种实施方式的流程图。以下的实施例说明了本发明的方法。这些实施例中使用的矿石来自中美洲红土矿矿床.实施例l-3所用矿石中的褐铁矿和腐泥土成分具有表l中给出的组成。将腐泥土矿石在用于试验之前破碎至约-6. 4mm。表l <table>table see original document page 16</column></row> <table>实施例1在球磨机中将约lkg腐泥土矿石湿研磨至约100%通过100目篩。将研磨后的浆料过滤以制得含湿量为41%的研磨腐泥土.将425. 2g潮湿的研磨腐泥土与381. 7g潮湿的褐铁矿石混合以制得500g具有1:1 的褐铁矿/腐泥土比(以干燥固体计)的浸出原料。将矿石混合物放入4. 5升细颈玻璃瓶,将瓶在瓶滚动设备(bottle rolling device)上以与水平方向略微倾斜的角度在大约47至48rpm 的速度下滚动。用约30分钟将312. 5g 96%的硫酸加入瓶中的矿石混合物中。全部酸加入后,将矿石与酸混合约30分钟。混合结束时矿石和酸形成半流体物料,温度升高到约70到ioor;之间。将瓶从滚动设备上取下,使酸和矿石的混合物在室温下熟化约72 小时。然后向熟化的物料中加入622mL水,搅拌混合物直至形成均一的浸出浆料.将浸出浆料转移到装有一个机械搅拌器、4个塑料挡板(baffle)和一个紧密配合盖的2升圃筒形反应釜中,所迷紧密配合盖装有向大气敞开的水冷凝器.使用外置电热套对反应釜进行加热。将浸出浆料加热到约96-99"C并保持在此温度下48小时,同时剧烈搅拌。浸出5小时后,向反应釜中加入129g磨细的工业级赤铁矿作为铁沉淀的"晶种"。定期采集浸出液样品以进行化学分析。48小时浸出过程结束时,将全部浆料过滤,在新鲜水中将滤饼进行两次再浆化以洗出携带的金属有用成分。然后将滤饼干燥称重。分別分析干燥固体、 滤液和合并的洗涤水。本试验结果由以下的表2和3给出。表2<table>table see original document page 17</column></row> <table>表3 <table>table see original document page 17</column></row> <table>'基于最终残渣和最终溶液的重量、体积和分析结果的Ni、 Fe和Mg 的提取率结果表明获得了较高的镍提取率,同时对矿石中铁的提取很少。此外,残渣中的硫含量相当低,Fe/S比接近44:l。硫酸中所含的低于5% 的硫酸根进入残渣中。如果矿石中全部的铁都形成黄钾铁矾 最终残渣中的Fe/S比应接近4. 3。此外,对残渣的X射线衍射分析说明了只出现了最初的矿石中的赤铁矿、针铁矿和尖晶石相。动力学数据说明需要进行略多于24-32小时的浸出以达到溶液中最终的铁浓度。可以通过使用碱例如石灰石进行中和而将残留的铁从溶液中除去,而不产生镍进入固相的显著损失。实施例2将381. 7g褐铁矿石样品与317. 7g破碎的腐泥土矿石和95g水在2 升平底玻璃烧杯中混合。加入水是为了模拟原矿矿石的预计含湿量,应认识到样品比其在原处的状态略干.用约30分钟向烧杯中加入312. 5g 96X的硫酸。使用搅拌器在60rpm的转速下将酸与矿石混合.酸的加入量足以使得酸对矿石之比为约600kg 112304/吨矿石(以干品计)。将矿石与酸形成的半流体物料倾倒至浅盘中以在室温下熟化约72 小时。在此过程中一部分混合物没有被回收,以重量回收率计,估 约13%的混合物没有被回收。熟化过程后,将已显著变硬的酸/矿石混合物破碎成块并转移到小型研磨机中。向研磨机中加入300g水,使用石介质研磨混合物约1小时以将最大顆粒大小降至约100目。向研磨机中另外加入水以将浆料冲洗到2升浸出反应器中。用这种方法制备l, 858g浸出浆料,将反应器加热到95至105t:,同时进行搅拌,并持续进行44小时的浸出.浸出5小时后,向反应器中加入129g磨细的工业级赤铁矿作为铁沉淀的"晶种"。定期采集浸出液样品以进行化学分析,48小时浸出过程结束时, 将全部浆料过滤。在新鲜水中将滤饼进行两次再浆化以洗出携带的金属有用成分。然后将滤饼干燥称重.分别分析干燥固体、滤液和合并的洗涤水。本试验结果由以下的表4和5给出。表4<table>table see original document page 18</column></row> <table>

表5<table>table see original document page 18</column></row> <table>'基于最终残渣和最终溶液的重量、体积和分析结果的Ni、 Fe和Mg 的提取率本试验模拟本发明的一个优选的实施方式,其中腐泥土矿石在与褐铁矿石混合及加酸之前不进行研磨.代之以在熟化之后对酸/矿石混合物进行研磨。 Table 5 <table> table see original document page 18 </ column> </ row> <table> ', Fe and Mg extraction rate based on the weight of the final residue and of the final solution volume and analysis of Ni This test simulates the present invention a preferred embodiment, which is not polished saprolite ore prior to mixing with brown iron ore and the acid addition. instead of grinding the acid / ore mixture after aging. 本试验的结果类似于实施例1的结果,但镍提取率略低。 Result of this test is similar to the results of Example 1 but slightly lower rate of nickel extraction. 实施例3本试验进行的方式类似于实施例2,同时具有以下区别.酸混合过程中以及之后的浸出过程中,褐铁矿石、破碎的腐泥土矿石、水、酸以及赤铁矿晶种的用量分别为336. 9g、 280. 3g、 84g、 275. 8g和113g. 矿石、水和酸的比例与实施例2中相同。 Example 3 This manner similar to Example 2 Test, also has the following differences. Acid leaching process during and after mixing, the brown iron ore, crushed saprolite ore, water, acid, and hematite seed are used in an amount of 336. 9g, 280. 3g, 84g, and 113 g. ores, the proportion of water and acid in Example 275. 8g 2 in. 将矿石与酸混合后,将混合物转移到浅盘上并熟化仅1小时,然后转移到研磨机中以进行湿研磨,之后进行水浸出。 After mixing the ore with an acid, the mixture was transferred to a tray and aged for only an hour, and then transferred to a mill for wet grinding, followed by flooding. l小时的熟化之后, 混合物仍为流体并可以被倾倒入研磨机中。 After l hour aging, the mixture was still fluid and could be poured into the mill. 制备了1,776g浸出浆料并用与实施例2完全一样的方法进行浸出。 Preparing 1,776g leached slurry is leached and treated with 2 with exactly the same manner as in Example. 酸/矿石混合物的回收率接近96%。 Recovery of the acid / ore mixture closed to 96%. 本试验结杲由以下的表6和7给出。 Gao present test results given by the following Table 6 and 7. 表6<table>table see original document page 19</column></row> <table> 表7 <table>table see original document page 19</column></row> <table> '基于最终残渣和最终溶液的重量、体积和分析结果的Ni、 Fe和Mg 的提取率本试验的结果类似于之前的实施例,证明了不必在浸出之前对矿石/酸混合物进行长时间的熟化*实施例4本试验中使用的矿石具有表8中给出的组成。 Table 6 <table> table see original document page 19 </ column> </ row> <table> Table 7 <table> table see original document page 19 </ column> </ row> <table> 'based on the final residue and final weight of the solution, the results of Ni, Fe and Mg extraction rate and volume of analysis results of this test is similar to the previous embodiments, does not have to prove long-time aging of the ore / acid mixture prior to leaching * test Example 4 ore used had the composition given in table 8. 表8<table>table see original document page 20</column></row> <table>将409. 6g (以湿品计)褐铁矿石放入装有0. 6-1. 9cm资球的乾球磨机中。 Table 8 <table> table see original document page 20 </ column> </ row> <table> to 409. 6g (wet product) was put into a limonite ore 0. 6-1. 9cm ball funding dry ball mill. 在加入矿石之前,将研磨机和研磨介质预热到约ioox:。 Prior to addition of the ore, the grinding media and mill preheated to about ioox :. 这是为了模拟工艺连续进行时的热条件。 This is to simulate the thermal conditions during the process continuously. 研磨机装有中心有孔的塑料盖,通过所述孔可以添加硫酸.使用实施例1中的滚动机旋转研磨机.用约1.5分钟向研磨机中加入338. 5g 96%的疏酸,使褐铁矿石与酸反应15 分钟。 Mill equipped with a central hole of a plastic cover, may be added to sulfuric acid through the holes using a rotary rolling mill machine in Example 1 was added 338. 5g 96% hydrophobic acid to the mill for about 1.5 minutes for brown iron ore with an acid for 15 minutes. 在反应过程中使用手持式激光温度计监测研磨机内的温度。 The temperature monitored by a thermometer handheld laser mill during the reaction. 测得的温度在97至121C之间变化,在酸加入完成后约1分钟记录到最高温度。 Measured temperature changes between 97 to 121C, for about 1 minute to a maximum temperature recorded after the acid addition was complete. 反应完成时,将研磨机从滚动机上取下,摘下盖子,向褐铁矿/ 酸混合物中加入306. lg (以湿品计)破碎的腐泥土矿石和510g 30g/L 的Mg (为MgS04)水溶液。 Upon completion of the reaction, the rolling mill is removed from the machine, the lid off, 306. lg was added to the limonite / acid mixture (wet product) crushed saprolite ore and 510g 30g / L of Mg (MgS04 is ) aqueous solution. 使用MgS04溶液是为了模拟在工艺中使用经过纯化和镍/钴回收后剩余的贫液作为回用(make-up)水的效果。 MgS04 was used to simulate the lean liquid after purification using nickel / cobalt recovery and the remainder is recycled (make-up) effect of water in the process. 使用紧密配合的瓷盖封闭研磨机,将全部矿石/酸混合物研磨近60分钟,直到大部分固体颗粒尺寸低于100目。 Using a close-fitting lid is closed porcelain mill, grinding the mixture of all the ore / acid nearly 60 minutes until most of the solid particle size below 100 mesh. 根据矿石样品的重量和含湿量,以干品计的总的腐泥土/褐铁矿比为1.1,总的酸/矿石比为0.65 (以千矿石和100%H2SO^i")。然后将研磨机的内容物排出至与实施例1中所用的相同的反应釜。 使用粗篩截留研磨介质,使用764g的30g/LMg溶液冲洗球磨机和研磨介质。将冲洗溶液加入反应釜中。将反应釜加热到95-1001C并搅拌。进行24小时浸出。浸出的前5 小时中,向浸出浆料中鼓泡通入二氧化硫气体以将浆料的氧化还原电位控制在540到600mV之间(相对于饱和Ag/AgCl参比电极).整个浸出过程中均采集浆料样品,过滤、洗涤固体,对溶液和固体进行分析。浸出过程完成时,在951C下用约2小时向浸出浆料中加入20X的石灰石浆料以将浸出浆料中和至pH为3.0。对中和后的浸出浆料取样, 然后过滤全部浆料。浸出过程的结果由表9给出.表9<table>table see original document page 21</column></row> <tabl The weight and moisture content of the ore samples, the total dry product saprolite / limonite ratio was 1.1, the total of the acid / ore ratio of 0.65 (in thousands of ore and 100% H2SO ^ i "). Then grinder contents are discharged into the same reactor described in Example 1 was used using a coarse sieve cutoff abrasive medium, using 764g of 30g / LMg solution, rinse mill and milling media. the rinse solution was added to the kettle. the kettle and heated to 95-1001C with stirring. leaching for 24 hours. 5 hours prior to leaching, the slurry was reduced to oxidation leached slurry to the sulfur dioxide gas was bubbled through the potential control between 540 to 600mV (with respect to saturation Ag / AgCl reference electrode). throughout the leaching process slurry sample were collected, filtered and the solid washed on the solution and solids analysis. leaching process is complete, the leached slurry was added to the 20X at 951C for about 2 hours limestone slurry to leach slurry to a pH of 3.0. leaching slurry and after sampling, the whole slurry was then filtered. the results of the leaching process are given in table 9. table 9 <table> table see original document page 21 </ column> </ row> <tabl e>浸出过程结束时的固体的分析结果为0.21%Ni、 0. 006%Co、 3UFe、 0. 65%Mg、 14. 9%Si和1. 39%S。 Ni及Co的提取率通过"硅束绰(silicon tie)"法(假设没有将硅浸出,使用矿石和残渣的硅的分析结果计算浸出残渣的重量,并使用矿石和残渣重量以及分析结果计算提取率)进行计算,分别约为93. 1%和95. 5%。铁提取率约为9%。中和至pH3之后,溶液分析结果为6. 23g/L Ni, 0. 29g/L Co和3. 24g/LFe。固体分析结果为0. 22% Ni、 0. 009%Co、 26. 5% Fe和11. 7% Si。浸出溶液中约74%的铁在中和过程中沉淀;因此中和后铁的净提取率只有约2%,约2%的镍和494的钴在中和过程中与铁共沉淀.这一实施例说明了本发明的一种优选实施方式的一些重要特点:可高的镍提取率;向浸出浆料中加入还原剂——在此例中为二氧化硫气体——可以提高钴提取率;不需要通过酸/矿石反应混合物的熟化来获得高提取率 The results e> solids at the end of the leaching process was 0.21% Ni, 0. 006% Co, 3UFe, 0. 65% Mg, 14. 9% Si and 1. 39% S. Ni and Co extraction rate by " Chuo beam silicon (silicon tie) "method (the results of the analysis, assuming no silicon silicon leaching, the ore used to calculate the weight of the residue and leach residue of the ore and the weight of the residue and using the results of calculation and analysis extraction rate) are calculated, respectively, approximately 93.1% and 95.5% iron extraction rate of about 9%. after neutralized to pH3, solution analysis results 6. 23g / L Ni, 0. 29g / L Co and 3. 24g / LFe. solids analysis results of 0. 22% Ni, 0. 009% Co, 26. 5% Fe, and 11. 7% Si leach solution for about 74% and iron precipitation in the process; net and after extraction rate so the iron only about 2%, about 2% of nickel and cobalt co-precipitate with the iron 494 and in the process of this Example illustrate some important features of a preferred embodiment of the present invention: a high nickel extraction rate;. adding a reducing agent to the leach slurry - as sulfur dioxide gas in this case - can increase the rate of extraction of cobalt; no reaction mixture was aged by acid / ore to obtain a high extraction rate ;硫酸与矿石之间的反应极快并大量放热,使得在酸/矿石反应过程中可获得非常高的温庋,从而提高反应动力并使得所需用于进行硫酸化步骤的设备体积非常小;可以在浸出之后对浸出浆料进行不完全中和以去除浸出的小比例的铁中的大部分,并使镍和钴的损失最小。本领域的技术人员当然应认识到本方法在本发明的宽泛范围内可有多种变化,本领域的技术人员应认识到,作为说明书之根本的本发明可按其它的能实现本发明目的并完成本发明目标的实施方式使用,本发明的方法广泛适用于既含褐铁矿也含腐泥土的镍红土矿体,包括了红土矿体的大多数.本方法的腐泥土/褐铁矿比可宽泛地变化,只要在本方法中满足腐泥土/褐铁矿比的某最小值.当使用例如硫酸时, 通过使褐铁矿石和腐泥土矿石中的"可硫酸化"的铁成分以三价铁的氧化物或氢氧化物的 ; Reaction between sulfuric acid and ore fast and highly exothermic, so that very high temperatures can be obtained in the approach of taking the acid / ore reaction process, thereby increasing the volume of the reaction kinetics and that the apparatus required for carrying out the sulfation step is very small ;. can be leached slurry after leaching to incomplete neutralization and removal of most of the iron leached small proportion, and to minimize the loss of nickel and cobalt skilled in the art will of course be appreciated that in the process of the present invention, Many variations may be within the broad scope of the skilled in the art will recognize that, as a fundamental specification of the present invention may be further object of the present invention is to achieve complete certain embodiments of the present invention, the method of the present invention is widely Ni laterite ore body suitable for containing both limonite saprolite also contain, comprises most of. the present method saprolite / limonite ratio may vary widely, as long as the present process saprolite laterite ore / limonite ratio of a minimum value. when using sulfuric acid, for example, by limonite ore and "sulfation" the iron content of saprolite ore to iron oxide or ferric hydroxide 式水解或沉淀而生成一些硫酸,最小比值可通过计算腐泥土矿石中的可被这些硫酸硫酸化的非铁成分的量来大致确定。 Hydrolytic precipitation generate some or sulfuric acid, may be substantially the minimum ratio may be determined by the amount of sulfated iron component of these non-sulfated saprolite ore calculation. 比值可以是任何等于或大于此最小值的数值,只要酸的加入量是按前述的方法计算而得,即足以与褐铁矿石和腐泥土矿石中可硫酸化的非铁成分反应的酸的量加上用于少量可溶解的铁以及用于促使反应完成的略微过量的量。 Any ratio may be equal to or greater than this minimum value, as long as the amount of acid added is calculated from the method according to the preceding, i.e. an amount sufficient to react with the acid of brown iron ore and saprolite ore may be non-sulfated iron component plus a slight excess amount to complete the reaction a small amount of soluble iron, and for causing. 以上所公开的内容是为了进行说明,而本发明的范围由以下权利要求限定。 SUMMARY disclosed above are for purposes of illustration, and the scope of the present invention is defined by the following claims.

Claims (16)

1. 一种漫出含有褐铁矿和腐泥土的红土矿的方法,包括以下步骤: (a)将褐铁矿和腐泥土与足量的浓无机酸混合,以与矿石中可溶性非铁成分形成盐; (b)对步骤(a)中的混合物进行水漫出,浸出时间和温度足以使溶解的三价铁水解、形成含铁的沉淀物,同时将镍和钴中的至少一种大量溶解到漫出溶液中;以及(c)从浸出溶液中回收镍或钴的化合物中的至少一种。 CLAIMS 1. A method for diffuse out of laterites comprising limonite and saprolite, comprising the steps of: (a) mixing the limonite and saprolite with a sufficient amount of concentrated mineral acid, with the non-ferrous ore soluble component forming a salt; mixture (a) in (b) water diffuse out of the step, the hydrolysis of ferric leaching time and temperature sufficient to dissolve the formed precipitate iron, while at least one of a number of nickel and cobalt to diffuse out of the dissolved solution; and at least one compound (c) recovering nickel and cobalt from the leach solution in the.
2. 权利要求1的方法,其中步骤(a)中首先将酸与褐铁矿混合,然后再加入腐泥土。 The method of claim 1, wherein step (a) is first mixed with an acid limonite, saprolite then added.
3. 权利要求1或2的方法,其中将矿石的至少一部分破碎以促进酸与矿石的均匀混合。 The method of claim 1 or claim 2, wherein at least a portion of crushed ore to promote uniform mixing of the ore with acid.
4. 权利要求2的方法,其中将腐泥土矿石单独破碎,然后再加入褐铁矿与酸的混合物中。 The method of claim 2, wherein the saprolite ore crushed separately and then added to the mixture and limonite acid.
5. 权利要求1的方法,其中将褐铁矿和腐泥土共同破碎并研磨然后再与酸混合。 The method of claim 1, wherein the limonite and saprolite crushed and ground together then mixed with an acid.
6. 权利要求1、 2、 4或5所述的方法,其中步骤(b)中的水漫出在高压釜中在最高至1501C的温度下进行。 1, 2, 4 or claim 5, wherein the step (b) is carried out in water diffuse out up to a temperature of 1501C in an autoclave.
7. 权利要求6所述的方法,其中步稞(b)中的水浸出在95-1051C的温度范围内进行。 The method according to claim 6, wherein the wheat step (b) in water leaching at a temperature range of 95-1051C.
8. 权利要求1、2、4或5所述的方法,其中步骤(b)中的水浸出在95-105 C的温度范围内、15-70psia的压力范围内进行。 The method of claim 4 or claim 5, wherein the step (b) in water leaching, pressure range 15-70psia performed in the temperature range of 95-105 C.
9. 权利要求4或5的方法,其中步稞(b)中的水浸出分两个阶段进行, 第一阶段在大气压下、在最高至浸出溶液的沸点的温度下进行,第二阶段在高压釜中、在最高至1501C的温度下进行。 9. A method as claimed in claim 4 or 5, wherein the wheat step (b) in water leaching in two stages, the first stage, at a temperature up to the boiling point of the leach solution at atmospheric pressure, a second high pressure stage kettle, carried out at a temperature up to 1501C.
10. 权利要求4或5的方法,其中酸选自疏酸、盐酸和贿酸或其混合物。 10. The method of claim 4 or claim 5, wherein the acid is selected from hydrophobic acid, hydrochloric acid or mixtures thereof, and bribery.
11. 权利要求8的方法,其中酸为硫酸并且步骤(a)中形成的盐包括硫 Salt 11. The method of claim 8, wherein the acid is sulfuric acid and step (a) comprises forming of sulfur
12. 权利要求1、 2、 4或5所述的方法,其中步骤(c)中从漫出溶液中对至少一种镍或钴的化合物进行的回收包括向浸出溶液中加入离子交换树脂而不预先进行固/液分离。 12. The method of 1, 2, 4 or claim 5, wherein step (c) recovering from the solution to diffuse out of at least one compound of nickel or cobalt ion is added to the leach solution comprises exchange resin without previously subjected to solid / liquid separation.
13. 权利要求1、 2、 4或5所述的方法,其中步骤(c)中首先将浸出溶液与沉淀物分离,然后再从浸出溶液中回收至少一种镍或钴的化合物, 13. The method of 1, 2, 4 or claim 5, wherein step (c) in the leach solution is first separated from the precipitate, at least one compound of nickel or cobalt and then recovered from the leach solution,
14. 权利要求1、 2、 4或5所述的方法,其中在步骤(b)中的水浸出过程中加入还原剂以增强矿石中钴的溶解。 14. The method of 1, 2, 4 or claim 5, wherein the reducing agent is added to the flooding in step (b) in the process to enhance the dissolution of cobalt ore.
15. 权利要求14的方法,其中还原剂选自二氣化碟、硫化氩、可溶性亚硫酸氢盐和亚硫酸盐化合物、或可溶的亚铁化合物. The method of 14 wherein the reducing agent is selected from di gasification Singles, argon sulfide, soluble bisulfite and sulfite compounds, or soluble ferrous compound as claimed in claim 15,.
16. 权利要求1或2的方法,进一步包括对步骤(a)中的混合物进行熟化的步骤,然后再进行步骤(b)的水浸出, 16. A method as claimed in claim 1 or 2, further comprising the step of the mixture from step (a) is aged, and then flooding step (b) is out,
CN 200580028497 2004-06-28 2005-06-27 Method for nickel and cobalt recovery from laterite ores by reaction with concentrated acid and water leaching CN100410399C (en)

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