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

The present invention discloses a method for recovering valuable elements in Nd-Fe-B waste materials. The present invention comprises four processing steps of rare-earth extracting, recovering and separating technology, cobalt oxide recovering and separating technology, iron oxide recovering technology and discharged liquid recovering technology, wherein 99.5% purity of neodymium oxide, 99.5% purity of dysprosium oxide and 99.5% purity of terbium oxide are obtained in the rare-earth extracting, recovering and separating technology, and 99.5% purity of cobalt oxide products are obtained in the cobalt oxide recovering and separating technology. 98.5% magnetic-powder purity of iron oxide is obtained in the iron oxide recovering technology, and 99.5% purity of cobalt oxide products are obtained in the cobalt oxide recovering and separating technology. The present invention completely separates Nd, Dy, Tb, Co and Fe in the Nd-Fe-B waste materials into single oxide products, and simultaneously, adjuvant materials-sulfuric acid and ammonium bicarbonate in use are finally recovered by agricultural-use ammonium sulfate products. The technological process of the present invention achieves full-recovery of valuable elements and is completely sealed, so the present invention basically achieves the requirements of no discharge, low cost, no pollution and no public harm.

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, the recovery method of valuable element in a kind of neodymium iron boron waste material is characterized in that this method may further comprise the steps:

(1) rare earth extraction 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 carbonate and ammonium chloride waste-water through carbon ammonium precipitation-washing-dehydration again, calcination is that purity is 99.5% Neodymium trioxide to each rare earth carbonate through 900 ℃ of high-temperature roasting kilns, purity is that 99.5% dysprosium oxide and purity are 99.5% terbium sesquioxide;

(2) cobalt oxide reclaims separating technology: the sodium sulphite that the product of the raffinate behind the above-mentioned extracting and separating rear earth-iron content cobalt feed liquid is added 1.3～1.7 times of weight of cobalt in the chemical reaction container, the SULPHUR POWDER that iron powder that weight of cobalt is 1.1～1.3 times and weight of cobalt are 0.3～0.6 times, 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 doubly the molten 2-4 of water logging hour of oven dry weight of material 3.5-4, 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 mixes back dissolving raw material usefulness with dilute sulphuric acid in the step (1), 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 adding bicarbonate of ammonia or its solution that obtain behind the cobalt carry out precipitin reaction, generate iron protocarbonate, 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, the vitriol oil that adds 0.5 times of chlorine mole number total content, make 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.

2, the recovery method of valuable element in the neodymium iron boron waste material according to claim 1, it is characterized in that: add the bicarbonate of ammonia of 3.0～3.5 times of iron weight in the iron content feed liquid in the step (3), or add the solution of the bicarbonate of ammonia that contains 3.0～3.5 times of iron weight.