CN101700902A

CN101700902A - Method for manufacturing rare earth fluoride

Info

Publication number: CN101700902A
Application number: CN200910174475A
Authority: CN
Inventors: 尹祖平; 琚建勇; 梁行方; 徐志广; 贾恩泽; 王远锡; 孟兆东; 孟剑鸿; 邱桦林
Original assignee: BAOTOU RUIDA RARE EARTH MATERIAL Co Ltd; Ruike Rare Earth Metallurgy and Functional Materials National Engineering Research Center Co Ltd
Current assignee: Baotou Ruida Rare Earth Material Co., Ltd.; Baotou Ruixin Rare-earth Metallic Material Co., Ltd.; Ruike Rare Earth Metallurgy and Functional Materials National Engineering Research Center Co Ltd
Priority date: 2009-11-04
Filing date: 2009-11-04
Publication date: 2010-05-05
Anticipated expiration: 2029-11-04
Also published as: CN101700902B

Abstract

The invention relates to a method for manufacturing rare earth fluoride, which is characterized by comprising the steps: taking carbonic acid rare earth and HF gas as raw materials; directly filling the HF gas into a closed fluorination furnace, reacting the HF gas and the carbonic acid rare earth at 300-600 DEG C, and generating the rare earth fluoride, acid water and CO2; and finally preparing anhydrous rare earth fluoride; wherein the flow rate of the HF gas is 0.1-10kg/h, and the filling quantity of the gas is excessive 0-100wt%. The method has the advantages that the method is economical and environment-friendly, good in the using effect in the production and simple in operation; and more particularly, as fluoride-resistant material is adopted, the service life of a furnace body is prolonged by 3-5 times. By adopting gas method carbonic acid rare earth as raw material, the method reduces the cost of the raw materials, and the tail gas becomes hydrofluoric acid which can be directly sold after being sprayed and absorbed, so that the method is environment-friendly.

Description

A kind of manufacture method of rare earth fluorine

Technical field:

The present invention relates to a kind of manufacture method of rare earth fluorine, the making method of the high quality that particularly a kind of rare earth metal manufacturing, lubricant use, low cost, free of contamination rare earth fluorine belongs to the rare earth metallurgy field.

Background technology:

Existing rare earth fluoride adopts hydrofluoric acid (40wt%) and carbonated rare earth reaction, HF gas and rare earth oxide reaction to make.Preceding a kind of method rare-earth industry is called " wet processing ", production stage: excessive 20wt% hydrofluoric acid (concentration 40wt%) and carbonated rare earth (42-45wt%REO) are blended in 60 ℃ of reactions down, generate rare earth fluoride and water, CO ₂, be washed to PH=7, through filtering draining, slough crystal water in oven dry more than 500 ℃, make anhydrous rare earth fluorine.

The second method rare-earth industry is called " gas method ", production stage: feed excessive 10-20wt%HF gas and rare earth oxide in reaction more than 500 ℃, generate rare earth fluoride and water, make anhydrous rare earth fluorine.1 ton of rare earth fluoride of every production approximately produces 0.16 ton of waste acid water, but direct marketing realizes floride-free discharging.

The shortcoming that existing rare earth fluoride production technique exists is:

1) method 1 processing step is long, cause the rare earth yield on the low side about 96%, produce a large amount of waste water treatment cost height and be unfavorable for environmental protection (1 ton of rare earth fluoride of every production approximately produces waste acid water more than 2 tons, in needing and qualified discharge).

2) method 2 processing steps are short, and the rare earth yield is high by 99%, a small amount of waste water of generation can be done hydrofluoric acid and sell, and realizes floride-free discharging.Shortcoming: rare earth oxide will make from the carbonated rare earth high-temperature calcination, cost height, about 2000 yuan/ton.

Summary of the invention:

The purpose of this invention is to provide a kind of reaction under 300-600 ℃, generate rare earth fluoride and sour water, CO with carbonated rare earth and direct HF gas ₂, make the manufacture method of the rare earth fluorine of anhydrous rare earth fluorine, adopt present method neither to need the carbonated rare earth high-temperature calcination is become oxide compound, there are not a large amount of spent acid dischargings again, raw materials cost reduces about 2000 yuan/ton, and industrial promotion prospect is long-range.

Method of the present invention is as follows:

With carbonated rare earth and HF gas is raw material, with HF gas directly feed airtight fluoridize in the stove 300-600 ℃ down with carbonated rare earth reaction, generation rare earth fluoride, sour water and CO ₂, make anhydrous rare earth fluorine, wherein: the gas flow of HF is 0.1-10kg/h, gas feeding amount is excessive 0-100wt%;

Described carbonated rare earth is one or more the mixture in praseodymium carbonate neodymium, Phosbloc, cerous carbonate, praseodymium carbonate, neodymium carbonate, samaric carbonate, europium carbonate, gadolinium carbonate, terbium carbonate, dysprosium carbonate, carbonic acid holmium, carbonic acid erbium, thulium carbonate, yttrium carbonate, ytterbium carbonate, carbonic acid lutetium, the scandium carbonate;

Described HF gas is to adopt anhydrous HF, is heated into gas at 19-100 ℃;

The container material is with the material of anti-the fluorine, and polluted product can not make the high quality rare earth fluoride.

Advantage of the present invention is: this method economy, environmental protection, result of use is good, simple to operate on producing, particularly adopt the material of anti-the fluorine after, body of heater prolongs 3-5 doubly work-ing life.Adopt the gas method carbonated rare earth to make raw material, can reduce about 2000 yuan/ton of raw materials cost, tail gas becomes the hydrofluoric acid direct marketing after spray absorbs, and environmental protection is good.

Embodiment:

Embodiment 1

300kg praseodymium carbonate neodymium (REO45wt%) packed into fluoridize in the stove, 0-300 ℃ of intensification 6h, remove moisture, use anhydrous 99.99%HF, be heated into gas, directly feed airtight fluoridizing in the stove at 19-100 ℃, fluoridize stove with 300-600 ℃ of intensification 12h, make the reaction of HF gas and carbonated rare earth, the excessive 10wt% of HF gas (purity 99.99%), gas flow 0.1-10kg/h.Reaction accessory products water spray absorbs into hydrofluoric acid, CO ₂Emptying.

The product rate of fluoridizing is not less than 99%, O＜0.05wt%, F 〉=28.11wt%, rare earth yield＞99%.

Embodiment 2

300kg gadolinium carbonate (REO50wt%) packed into fluoridize in the stove, 0-300 ℃ of intensification 6h, remove moisture, use anhydrous 99.99%HF, be heated into gas, directly feed airtight fluoridizing in the stove at 19-100 ℃, fluoridize stove with 300-600 ℃ of intensification 12h, make the reaction of HF gas and carbonated rare earth, the excessive 20wt% of HF gas (purity 99.99%), gas flow 0.1-10kg/h.Reaction accessory products water spray absorbs into hydrofluoric acid, CO ₂Emptying.

The product rate of fluoridizing is not less than 99%, O＜0.05%, F 〉=26.58%, rare earth yield＞99%.

Embodiment 3

300kg neodymium carbonate (REO50.32wt%) packed into fluoridize in the stove, 0-300 ℃ of intensification 6h, remove moisture, use anhydrous 99.99%HF, be heated into gas, directly feed airtight fluoridizing in the stove at 19-100 ℃, fluoridize stove with 300-600 ℃ of intensification 12h, make the reaction of HF gas and carbonated rare earth, the excessive 20wt% of HF gas (purity 99.99%), gas flow 0.1-10kg/h.Reaction accessory products water spray absorbs into hydrofluoric acid, CO ₂Emptying.

The product rate of fluoridizing is not less than 99%, O＜0.05%, F 〉=26.78%, rare earth yield＞99%.

Claims

1. the manufacture method of a rare earth fluorine, it is characterized in that: with carbonated rare earth and HF gas is raw material, with HF gas directly feed airtight fluoridize in the stove 300-600 ℃ down with carbonated rare earth reaction, generation rare earth fluoride, sour water and CO ₂, make anhydrous rare earth fluorine, wherein: the gas flow of HF is 0.1-10kg/h, gas feeding amount is excessive 0-100wt%.

2. the manufacture method of rare earth fluorine according to claim 1 is characterized in that: described carbonated rare earth is one or more the mixture in praseodymium carbonate neodymium, Phosbloc, cerous carbonate, praseodymium carbonate, neodymium carbonate, samaric carbonate, europium carbonate, gadolinium carbonate, terbium carbonate, dysprosium carbonate, carbonic acid holmium, carbonic acid erbium, thulium carbonate, yttrium carbonate, ytterbium carbonate, carbonic acid lutetium, the scandium carbonate.

3. the manufacture method of rare earth fluorine according to claim 1 is characterized in that: described HF gas is to adopt anhydrous HF, is heated into gas at 19-100 ℃.