CN1295357C

CN1295357C - Recovery method of valuable element in neodymium iron boron waste material

Info

Publication number: CN1295357C
Application number: CNB2005100426452A
Authority: CN
Inventors: 周成钢
Original assignee: XI'AN XIJUN NEW MATERIAL CO Ltd
Current assignee: XI'AN XIJUN NEW MATERIAL CO Ltd
Priority date: 2005-05-08
Filing date: 2005-05-08
Publication date: 2007-01-17
Anticipated expiration: 2025-05-08
Also published as: CN1693493A

Abstract

本发明公开了一种钕铁硼废料中有价元素的回收方法，该方法包括稀土萃取回收分离工艺、氧化钴回收分离工艺、氧化铁回收工艺和排放液回收工艺四个工序，稀土萃取回收分离工艺得到纯度为99.5%氧化钕、纯度为99.5%氧化镝和纯度为99.5%氧化铽；氧化钴回收分离工艺得到纯度为99.5%氧化钴产品；氧化铁回收工艺得到磁粉级纯度为98.5%氧化铁；排放液回收工艺得到15%的盐酸副产品和蒸溜冷凝水。本发明可使钕铁硼废料中的钕、镝、铽、钴、铁全部分离为单一的氧化物产品，同时所用的辅料—硫酸和碳酸氢铵最终以农用级硫酸铵产品进行回收，工艺流程达到了有价元素全回收，工艺过程完全闭环，基本达到无排放、成本低、无污染、无公害的要求。The invention discloses a method for recovering valuable elements in NdFeB waste. The method comprises four processes: rare earth extraction recovery and separation process, cobalt oxide recovery and separation process, iron oxide recovery process and discharge liquid recovery process. Rare earth extraction recovery and separation The purity of neodymium oxide is 99.5%, the purity of dysprosium oxide is 99.5%, and the purity of terbium oxide is 99.5%; the cobalt oxide recovery and separation process is 99.5% cobalt oxide; the iron oxide recovery process is magnetic powder grade with a purity of 98.5% iron oxide ; The discharge liquid recovery process obtains 15% hydrochloric acid by-products and distilled condensed water. The invention can separate the neodymium, dysprosium, terbium, cobalt and iron in the NdFeB waste into a single oxide product, and at the same time, the auxiliary materials used—sulfuric acid and ammonium bicarbonate are finally recycled as agricultural grade ammonium sulfate products, the process flow It achieves full recovery of valuable elements, complete closed-loop process, and basically meets the requirements of no emission, low cost, no pollution, and no pollution.

Description

The recovery method of valuable element in the neodymium iron boron waste material

Technical field

The present invention relates to derived energy chemical and resource clean utilization technical field, particularly relate to the recovery method of valuable element in a kind of neodymium iron boron waste material.

Background technology

Nd-Fe-B permanent magnet is a kind of permanent magnet material of superior performance, is widely used in high-tech every field, and the industrialization process of the industry has only nearly 10 years history, belongs to new industry.Because the factor of production technique and use, can produce 30% scrap stock and substandard product in production process and the use, but its moiety and finished product are in full accord, its composition is about Nd:25%, Dy:2-8%, Co:1-4%, Fe:60-65% also exists with alloy morphology, all valuable elements are all recyclable sharp again, ton surplus the annual Nd-Fe-B permanent magnet output about 40,000 in the whole world, about 14000 tons of the scrap stock utmost point unacceptable product that produces, the output of prediction global Nd-Fe-Bo permanent magnet material in 2010 will reach 14.6 ten thousand tons, the output value reaches 8,000,000,000 dollars, wherein the output of China will reach 5.4 ten thousand tons, the output value reaches more than 20 hundred million dollars, and the related device output value reaches 100～15,000,000,000 dollars.Reclaim for now as with these waste material resources, can reduce the annual about 50,000 tons of rare-earth mineral of China (in the packet header raw ore) from exploiting the wasting of resources and the environmental pollution that process for processing is brought.So not only rationally utilized resource, and Chinese rare earth resources and environment have been played provide protection.

At present, the production technique that the recovery of neodymium iron boron waste material is generally adopted, focus on the recovery of the fluorochemical precipitator method and double salt precipitation method to rare earth, other valuable element cobalt, iron discharge with acid waste liquid, reclaim the used auxiliary material of rare earth finally with a large amount of ammonia nitrogen waste water dischargings, wasted a large amount of valuable resources, severe contamination environment, and the rare earth that reclaims is not single product.

Summary of the invention

The purpose of this invention is to provide the complete closed loop of a kind of technological process, reach the recovery method that does not have valuable element in discharging, low, pollution-free, the non-harmful neodymium iron boron waste material of cost substantially.This method makes neodymium, dysprosium, terbium, cobalt, the iron in the neodymium iron boron waste material all be separated into single oxide product, and used auxiliary material-sulfuric acid and bicarbonate of ammonia finally reclaims with the agricultural grade ammonium sulfate product simultaneously.

The object of the present invention is achieved like this: the recovery method of valuable element in a kind of neodymium iron boron waste material, and this method may further comprise the steps:

(1) rare earth reclaims separating technology: it is PH=4.5-5 that neodymium iron boron waste material is made final acidity with the dilute sulphuric acid dissolving, make not molten suspended substance cohesion with No. 3 flocculation agents, filtration obtains filter residue and feed liquid, filter residue returns molten batch can and continues dissolving, feed liquid enters the multi-stage solvent extraction groove and carries out iron and Rare Earth Separation, the raffinate product is the feed liquid that contains cobalt and iron, the extracted organic phase process multi-stage solvent extraction separation that contains rare earth obtains 99.5% Neodymium trichloride, 99.5% Dysprosium trichloride, 99.5% terbium chloride feed liquid, obtain rare earth carbonate and ammonium chloride waste-water through carbon ammonium precipitation-washing-dehydration again, calcination is the oxygenated products of corresponding purity to each rare earth carbonate through 900 ℃ of high-temperature roasting kilns;

(2) cobalt oxide reclaims separating technology: the product of the raffinate behind the above-mentioned extracting and separating rear earth-iron content cobalt feed liquid is added a certain amount of sodium sulphite in the chemical reaction container, iron powder, SULPHUR POWDER, stirred 0.5～1 hour down at 30～70 ℃, filtration obtains containing cobalt filter cake and iron content feed liquid, contain the cobalt filter cake through oven dry, with oven dry a certain amount of water logging of weight of material molten 2-4 hour, with bicarbonate of ammonia readjustment material PH=4.5-6, make not molten suspended substance cohesion with flocculation agent, filtration obtains filter cake and cobalt feed liquid, filter cake returns step (1) and raw material together dissolves, the cobalt feed liquid is carried out the liquid that precipitin reaction-washing-dehydration obtains cobalt oxalate and contains dilute sulphuric acid and trace cobalt with oxalic acid under 35-80 ℃ of condition, the liquid that contains dilute sulphuric acid and trace cobalt returns step (1) and joins dissolving raw material usefulness behind the sulfuric acid, and cobalt oxalate carries out roasting under 600-650 ℃ the condition in roasting kiln to obtain purity be 99.5% cobalt oxide product;

(3) ferric oxide reclaims technology: step (2) is removed the iron content feed liquid that obtains behind the cobalt add after bicarbonate of ammonia or its solution carries out precipitin reaction, the water that adds 2 times of iron protocarbonate volumes washs iron protocarbonate or countercurrent washing-dehydration obtains the liquid of iron protocarbonate and sulfur acid ammonium, iron protocarbonate in rotary kiln or other roasting kilns under 750-900 ℃ of condition roasting 1.5-2 hour, carrying out oxidation, to obtain magnetic level purity be 98.5% ferric oxide;

(4) relief liquor reclaims technology: step (1) ammonium sulfate that ammonium chloride feed liquid and step (3) obtain containing of obtaining is mixed storing, adding quantitative sulfuric acid makes ammonium chloride wherein change into ammonium sulfate, in the triple effect graphite evaporator, carry out evaporative crystallization, obtain ammonium sulfate crystallization, obtain farming fertilizer level ammonium sulfate product through centrifugal oven dry, vaporised gas obtains 15% hydrochloric acid byproduct and steams the slide water of condensation through the dilute hydrochloric acid upgrading tower.

Advantage of the present invention is: the present invention utilizes the composite technology of P507-kerosene extraction method-precipitator method-hydrometallurgys such as condensing crystal method, make neodymium, dysprosium, terbium, cobalt, iron in the neodymium iron boron waste material all be separated into single oxide product, used auxiliary material-sulfuric acid and bicarbonate of ammonia finally reclaims with the agricultural grade ammonium sulfate product simultaneously, technical process has reached valuable element and has reclaimed entirely, the complete closed loop of technological process, reaching does not substantially have discharging, low, pollution-free, the non-harmful requirement of cost.

Embodiment

Below in conjunction with embodiment in detail the present invention is described in detail:

Embodiment

The recovery method of valuable element may further comprise the steps in the neodymium iron boron waste material of the present invention:

(1) rare earth extraction reclaims separating technology: acidproof and have a sulphuric acid soln that is mixed with 2-2.5mol/l in the exhausting dissolver with the vitriol oil, under agitation slowly add neodymium iron boron waste material, it is PH=4.5-5 that dissolving makes final acidity, add an amount of No. 3 flocculation agents (0.3% aqueous solution) and make not molten suspended substance cohesion, obtain filter residue and feed liquid with the plate-and-frame filter press filtration, filter residue returns molten batch can and continues dissolving, filtrate enters 23 grades of extraction tanks of P507-kerosene system and carries out iron and Rare Earth Separation, extraction tank will seal and prevent that iron is oxidized, 3 grades of wherein saponification sections, 10 grades of extraction sections, 10 grades of washing sections, the raffinate product is that the feed liquid that contains cobalt and iron goes to cobalt recovery separating technology operation, the extracted organic phase that contains rare earth obtains 99.5% Neodymium trichloride feed liquid through 150 grades of extracting and separating, 99.5% Dysprosium trichloride feed liquid and 99.5% terbium chloride feed liquid, each rare-earth products feed liquid obtains corresponding product carbonate and ammonium chloride solution through carbon ammonium precipitation-washing-dehydration, calcination is that corresponding purity is 99.5% Neodymium trioxide to each rare earth carbonate through 900 ℃ of high-temperature roasting kilns, 99.5% dysprosium oxide and 99.5% terbium sesquioxide product contain the chlorination ammonium solution and go to (4) operation and reclaim.

(2) cobalt reclaims separating technology: the sodium sulphite that adds 1.3～1.7 times of weight of cobalt in the chemical reaction container under the raffinate iron content cobalt feed liquid behind the extracting and separating rear earth is stirred respectively, 1.1～1.3 times iron powder, 0.3～0.6 times SULPHUR POWDER, stirred 0.5～1 hour down at 30-70 ℃, obtain containing cobalt filter cake and iron content feed liquid with the plate-and-frame filter press filtration, the iron content feed liquid is changeed preface to iron and is reclaimed technique process, it is red to the color purpling 70-300 ℃ oven dry kiln dry to contain the cobalt filter cake, stir at 0-60 ℃ (generally at 20-30 ℃) with oven dry weight of material 3.5-4 water doubly and to soak molten 2-4 hour, slowly adjust back material to PH=4.5-6 with bicarbonate of ammonia, add an amount of No. 3 flocculation agents and make not molten suspended substance cohesion, obtain filter cake and cobalt feed liquid with the plate-and-frame filter press filtration, filter cake returns step (1) and raw material together dissolves, cobalt feed liquid weight ratio is that 1: 2.5 oxalic acid is 35-80 ℃ of precipitin reaction, add material: water (available recycle-water)=1: 2 (volume) washing or countercurrent washing, 5 washings, obtain cobalt oxalate and the liquid that contains dilute sulphuric acid and trace cobalt after the dehydration, the liquid that contains dilute sulphuric acid and trace cobalt returns step (1) join sulfuric acid after dissolving raw material use, cobalt oxalate carries out roasting under 600-650 ℃ the condition in roasting kiln, obtain 99.5% cobalt oxide product.

(3) iron reclaims technology and product: after step (2) is removed the iron content feed liquid that obtains behind the cobalt slowly adds the bicarbonate of ammonia of 3.0～3.5 times of iron weight or its equal solute equably in the chemical reaction stirred vessel ammonium bicarbonate soln and carried out precipitin reaction, the water that adds 2 times of iron protocarbonate volumes washs iron protocarbonate or countercurrent washing 4 times, dehydration obtains the liquid of iron protocarbonate and sulfur acid ammonium, the liquid of sulfur acid ammonium goes to subsequent processing and reclaims, iron protocarbonate is in rotary kiln or other roasting kilns, under 750-900 ℃ of condition roasting 1.5-2 hour, carrying out oxidizing roasting, to obtain magnetic level purity be 98.5% ferric oxide.

(4) relief liquor reclaims technology: the liquid that contains the sulfur acid ammonium that chlorination ammonium solution and step (3) obtain that step (1) is obtained adds the vitriol oil of 0.5 times of chlorine mole number total content in the chemical reaction stirred vessel, in the triple effect graphite evaporator, carry out evaporative crystallization, obtain ammonium sulfate crystallization, ammonium sulfate crystallization obtains farming fertilizer level ammonium sulfate product through centrifugal oven dry, and vaporised gas obtains 15% hydrochloric acid byproduct and steams the slide water of condensation through the dilute hydrochloric acid upgrading tower.

Claims

1. A method for recovering valuable elements in NdFeB waste, characterized in that the method comprises the following steps:

(1) Rare earth extraction, recovery and separation process: Dissolve NdFeB waste with dilute sulfuric acid to make the final acidity PH = 4.5-5, use No. The material tank continues to dissolve, and the feed liquid enters the multi-stage extraction tank for iron and rare earth separation. The raffinate product is a feed liquid containing cobalt and iron. Dysprosium chloride, 99.5% terbium chloride feed solution, and then through ammonium bicarbonate precipitation-washing-dehydration to obtain carbonate and ammonium chloride wastewater, each rare earth carbonate is burned by a high-temperature roasting kiln at 900 ° C to obtain a purity of 99.5% oxidation Neodymium, 99.5% pure dysprosium oxide and 99.5% pure terbium oxide;

(2) Cobalt oxide recovery and separation process: add the raffinate product after the above-mentioned extraction and separation of rare earths-iron-cobalt-containing liquid into a chemical reaction vessel, add sodium sulfide 1.3-1.7 times the weight of cobalt, and iron powder 1.1-1.3 times the weight of cobalt and sulfur powder 0.3 to 0.6 times the weight of cobalt, stirred at 30 to 70°C for 0.5 to 1 hour, filtered to obtain cobalt-containing filter cake and iron-containing feed liquid, the cobalt-containing filter cake was dried, and the dried material weight was 3.5- 4 times of water soaking and dissolving for 2-4 hours, using ammonium bicarbonate to adjust the pH of the material to 4.5-6, coagulating the undissolved suspended matter with a flocculant, filtering to obtain a filter cake and cobalt feed liquid, and returning the filter cake to step (1) and The raw materials are dissolved together, and the cobalt feed solution is subjected to precipitation reaction-washing-dehydration with oxalic acid at 35-80°C to obtain cobalt oxalate and a liquid containing dilute sulfuric acid and a small amount of cobalt, and the liquid containing dilute sulfuric acid and a small amount of cobalt is returned to step (1) and The dilute sulfuric acid in the step (1) is mixed and used to dissolve the raw materials, and the cobalt oxalate is roasted under the condition of 600-650°C in a roasting kiln to obtain a cobalt oxide product with a purity of 99.5%.

(3) Iron oxide recovery process: the iron-containing feed liquid that step (2) obtains after removing cobalt is added ammonium bicarbonate or its solution and carries out precipitation reaction, generates ferrous carbonate, adds the water of ferrous carbonate volume 2 times to ferrous carbonate Iron is washed or countercurrent washed-dehydrated to obtain ferrous carbonate and liquid containing ammonium sulfate. Ferrous carbonate is roasted at 750-900°C for 1.5-2 hours in a rotary kiln or other roasting kiln, and oxidized to obtain a magnetic powder grade with a purity of 98.5 % iron oxide;

(4) Discharge liquid recovery process: the ammonium chloride-containing feed liquid obtained in step (1) and the ammonium sulfate obtained in step (3) are mixed and stored, and the concentrated sulfuric acid with a total content of 0.5 times the molar amount of chlorine is added to make the chlorinated sulfuric acid wherein Ammonium is converted into ammonium sulfate, evaporated and crystallized in a three-effect graphite evaporator to obtain ammonium sulfate crystals, and the agricultural fertilizer grade ammonium sulfate product is obtained through centrifugal drying, and the evaporated gas passes through a dilute hydrochloric acid concentration tower to obtain 15% hydrochloric acid by-products and distilled condensed water .

2. The method for recovering valuable elements in NdFeB waste according to claim 1, characterized in that: Ammonium bicarbonate 3.0 to 3.5 times the weight of iron is added to the iron-containing liquid in step (3), or ammonium bicarbonate is added A solution containing ammonium bicarbonate 3.0 to 3.5 times the weight of iron.