CN1108700A

CN1108700A - Preparation method of crystal form rare earth carbonate

Info

Publication number: CN1108700A
Application number: CN94110881A
Authority: CN
Inventors: 喻庆华; 李斯加; 朱惠英; 雷浩; 陈一波; 李先柏
Original assignee: Changsha Research Institute Of Mining And Metallurgy ministry Of Metallurgical Industry
Current assignee: Changsha Research Institute Of Mining And Metallurgy ministry Of Metallurgical Industry
Priority date: 1994-03-18
Filing date: 1994-03-18
Publication date: 1995-09-20
Anticipated expiration: 2014-03-18
Also published as: CN1042146C

Abstract

The invention belongs to a new process method in the field of rare earth extraction. It is characterized by that in the course of ore-leaching of ionic rare earth ore an additive is added, and the obtained leached mother liquor directly uses ammonium hydrogen carbonate as precipitant to prepare and extract crystal form rare earth carbonate. The invention can greatly reduce the production cost and overcome the problems of large volume, difficult filtration and purification before precipitation of the conventional rare earth carbonate. The product purity REO is more than 94 percent, and Al₂O₃Less than 0.3 percent, and the cost of the medicament is reduced by more than 60 percent compared with the cost of the oxalic acid process.

Description

Preparation method for crystal carbonated rare earth

The preparation method of crystal carbonated rare earth

What produce from ion type rareearth ore that crystal carbonated rare earth relates to is a kind of new processing method that rare earth extracts the field.

Ammonium sulfate maceration-oxalic acid precipitation-calcination explained hereafter rare earth oxide is adopted in the ion type rareearth mine usually.Make precipitation agent because oxalic acid costs an arm and a leg with oxalic acid, production cost is higher.Therefore people wish to obtain a kind of cheap, surrogate that market is easy to get, it is generally acknowledged that it is promising that bicarbonate of ammonia is used for the ion type rareearth ore precipitating rare earth as precipitation agent.But the sedimentary carbonated rare earth of ordinary method is amorphous flocks, and is bulky, and the dehydration difficulty contains assorted height, difficult quality guarantee, and before precipitation, need purification to remove aluminium, often reach 10%(in the loss of clean-up stage rare earth and see Chinese patent 86100671A).

Purpose of the present invention be exactly utilize bicarbonate of ammonia do precipitation agent from ion type rareearth, produce long-pending not quite, easily filter and precipitate before the crystal carbonated rare earth that need not purify.

Technical scheme of the present invention and preparation process are:

1) when the ammoniumsulphate soln maceration, add a kind of additive, aluminium is not leached, or the very fast hydrolysis again of aluminium of having been come out by leaching and being stored in the leached mud.This class additive can be the organic buffer agent, as acetate, urotropine etc.; Also can be inorganic salt, as molysite, ammonium salt, calcium salt or magnesium salts.The adding of this additive is leached rare earth does not have influence.Its process is: additive is sneaked in the ore of pond, or be dissolved in the soaking solution, the additive add-on is as the criterion with effluent liquid PH=5.0～6.0.

2) above-mentioned technology gained leach liquor is directly prepared crystal carbonated rare earth with bicarbonate of ammonia as precipitation agent.This process is divided into two steps, and promptly the preparation of crystal seed and crystalline duplicate.

Step 1: crystal seed preparation is under 10～50 ℃ temperature, with the REO in bicarbonate of ammonia (solid or solution) and the feed liquid by weight NH ₄HCO ₃The mixed of/REO=2～5:1, and control precipitated liquid PH stirred 0.5～60 minute between 6.5～8.5, treat mixing after room temperature leave standstill, ageing a couple of days, the crystal carbonated rare earth grows up to;

Step 2: crystal duplicate be crystal carbonated rare earth that step 1 is obtained as crystal seed, duplicate the carbonated rare earth crystal.It is identical that copy condition and method and crystal seed prepare, but at bicarbonate of ammonia and rare earth feed liquid blended simultaneously, need to add part and make crystal seed by the crystal of step 1 preparation.Crystal seed add-on (in REO) should be more than 1/4 of feed liquid rare earth.Digestion time 4～16 hours.This crystal that duplicates can be used as crystal seed and continues cycles prepare carbonated rare earth crystal.

Embodiment

The present invention carries out the technical scale experiment in certain rare-earth mineral, its main technical details and index such as following table:

Use this invented technology, reach 91% to the total recovery of carbonated rare earth, improve 5% than oxalic acid technology, reagent cost can reduce by 8000 yuan than oxalic acid technology rare earth oxide per ton.And, can calcination change into rare earth oxide and be directly used in the smelting separation because the solubility in acid of carbonated rare earth is good.

Claims

1, by the method for producing crystal carbonated rare earth in the ion type rareearth ore, it is characterized in that: add a kind of additive when the ammoniumsulphate soln maceration, the mother liquor that is drawn directly duplicates with crystal seed and the crystalline thereof that ammonium hydrogencarbonate is produced crystal carbonated rare earth as precipitation agent.

2, according to the preparation method of the described crystal carbonated rare earth of claim 1; It is characterized in that: ammoniumsulphate soln soak that additive can be organic salt in the ore deposit, as acetate, urotropine, also can be inorganic salt, as molysite, ammonium salt, calcium salt or magnesium salts, the consumption of additive is as the criterion with effluent liquid PH=5.0～6.0;

3, according to the preparation method of the described crystal carbonated rare earth of claim 1, it is characterized in that: directly prepare crystal carbonated rare earth as precipitation agent and divide the preparation of crystal seed and crystalline to duplicate two steps, that is: with ammonium hydrogencarbonate

Under 10～50 ℃ temperature, by weight the mixed of 2～5:1, the pH value of control precipitated liquid is 6.5～8.5, stirs 0.5～60 minute with the REO in bicarbonate of ammonia and the feed liquid, and even room temperature afterwards to be mixed leaves standstill, ageing a couple of days grows up to the carbonated rare earth crystal;

The crystal that said process makes is made crystal seed, join and treat in the sedimentary leaching mother liquor, prepare the crystal carbonated rare earth crystal with the condition identical with aforesaid method, the crystal that ageing was duplicated after 4～16 hours can continue circulation combinations type carbonated rare earth as crystal seed again, and the add-on of each crystal seed only accounts for when time more than 1/4 of feed liquid rare earth.