CN101195873B

CN101195873B - Deposition gallium from water solution

Info

Publication number: CN101195873B
Application number: CN2007101520395A
Authority: CN
Inventors: 黄昌海; 向家武
Original assignee: Individual
Current assignee: Individual
Priority date: 2007-09-28
Filing date: 2007-09-28
Publication date: 2010-12-15
Anticipated expiration: 2027-09-28
Also published as: CN101195873A

Abstract

After aqueous solution including ethylenediamine tetra acetic acid-gallium is acidly or caustically pretreated, iron salt, nitrate, and hydrogen superoxide are added to react for 0.5 to 10 hours under the condition of 45 DEG C to 85 DEG C, and then alkali is added to cement out the gallium from the solution. The invention has the advantages that the process is simple, the efficiency is high, the cost of reagent is inexpensive and easy to be obtained, and the invention is easy to be industrialized.

Description

Deposition gallium from the aqueous solution

The technical field chemical precipitation

Background information

Gallium is a kind of eare scattered metals, weight in the earth's crust is 1.5 * 10-3%, content than antimony, silver, bismuth, tungsten is all high, but finds no the independent mineral of the gallium of extraction value at occurring in nature, has only a kind of extremely rare mineral---find content maximum (1.85%) in the germanite.Be contained in the sulphide ores of aluminium mineral (bauxitic clay, aluminosilicate), iron ore, plumbous zinc-copper and some coal dispersedly with the isomorphism state.

At present, the purposes of the maximum of gallium is to be used to produce the gallium arsenide compound semiconductor material, and this material is the sophisticated technology that Chinese government's emphasis is supported, can be rated as " heart " of information industry.The gallium arsenide compound semi-conductor can be used to create ultra-high speed, ultra-high frequency microwave and optical-fibre communications device, applies to fields such as radio communication, illumination, the energy, military affairs, medical treatment widely.12～13% of China's generated energy is used for illumination, and the turnover ratio of the development of LED technology, gallium solar cell reaches 41% and has the meaning of shocking development, will bring a revolutionary great development to lighting industry.

Because the rareness of gallium does not have the single gallium rich ore that contains to exploit, to refine for concentrating again, annual consumption is constantly increasing again.The demand that strategic analysis net gallium arsenide service center claims gallium arsenide in 2006 to be used for national defence increased by 9% than 2005, before 2010 with sustainable growth.The supply of gallium is becoming tight again day, and according to " Reference News " (2007.07.16), the existing reserves of gallium have been not enough to satisfy following needs at present.Therefore, reclaiming gallium from the various materials that contain gallium is a very significant job.

The deposition gallium method is a lot of from the aqueous solution, the earliest from the industrial sodium aluminate aqueous solution with secondary carbonation method deposition gallium, low because of its efficient, process is miscellaneous, has negative impact to be eliminated to alumina producing.

From sulphuric acid soln, make gallium become the ferrocyanide gallium precipitation of indissoluble with yellow prussiate of potash.It is to carry out under the heating condition in 70～80g/L solution that precipitation process requires at sulfuric acid concentration, and throw out adds alkali dissolution again, makes gallium be gallic acid sodium state and exists, and produces the sodium cyanide of severe toxicity simultaneously.Since reagent costliness, deposition condition harshness, no industrial utility value.

Use the organic precipitant deposition gallium, for example: with the cupferron that uses in the analytical chemistry, diethyl nabam, acetic acid etc., all because of the expensive no industrial utility value of reagent.

Summary of the invention:

Ethylenediamine tetraacetic acid (EDTA)---in the Gallium solution, ethylenediamine tetraacetic acid (EDTA) (or sodium salt) has powerful network and ability to gallium, and conventional precipitation agent can't make this complex compound dissociate, and gallium is precipitated out.Spent ion exchange resin, even common chelating resin all can't therefrom isolate gallium, adopts the method for this patent invention, uses cheap reagent that gallium precipitate from the aqueous solution and separates out, and is suitable for the large-scale commercial production use.

Specific implementation method:

Adding acid or alkali make ethylenediamine tetraacetic acid (EDTA) in beaker or in the industrial steel basin---and the PH of the aqueous solution of gallium is 1～4, add molysite, nitrate, aqueous hydrogen peroxide solution then, mix, heated and stirred, add alkali and make gallium become solid precipitation to separate out after 0.5～10 hour in reaction under 45～85 ℃.

Example 1:1 rises the ethylenediamine tetraacetic acid (EDTA) that PH0.3 contains gallium 1g/L---the aqueous solution of gallium, adding liquid caustic soda, to be neutralized to PH be 1.5, add ferric sulfate 2g, SODIUMNITRATE 8g, hydrogen peroxide 20ml 55 ℃ of reactions 8 hours, adds liquid caustic soda then and is neutralized to PH6.0, gallium becomes solid precipitation to separate out, and mother liquor of precipitation of ammonium contains gallium 45mg/L.

Example 2:1 rises the ethylenediamine tetraacetic acid (EDTA) that PH10 contains gallium 1g/L---and the aqueous solution of gallium adds nitric acid to PH3, adds ferrous sulfate 3g, ammonium nitrate 10g, hydrogen peroxide 25ml reacted 3 hours down at 80 ℃, added ammoniacal liquor then to be neutralized to PH7, gallium is solid precipitation separates out, and mother liquor of precipitation of ammonium contains gallium 38mg/L.

Claims

1. the method for a deposition gallium from the aqueous solution, it is meant the ethylenediamine tetraacetic acid (EDTA) that contains from any concentration---precipitation contains the solid sediment of gallium the acid of gallium or the alkaline aqueous solution, it is characterized in that: from the ethylenediamine tetraacetic acid (EDTA) that contains of any concentration---precipitate the acidity of gallium or the alkaline aqueous solution and contain before the solid sediment of gallium,---aqueous solution pre-treatment of gallium: the pre-treatment of acidic aqueous solution is to containing ethylenediamine tetraacetic acid (EDTA)---adds sodium hydroxide in the acidic aqueous solution of gallium to containing ethylenediamine tetraacetic acid (EDTA) earlier, potassium hydroxide, yellow soda ash, salt of wormwood, iron carbonate or their mixture, or liquid caustic soda, ammoniacal liquor, in and acidic aqueous solution to PH be 1～4; The pre-treatment of alkaline aqueous solution is to containing ethylenediamine tetraacetic acid (EDTA)---add sulfuric acid, nitric acid in the alkaline aqueous solution of gallium, the PH that makes the aqueous solution is 1～4; Then, in this solution, add molysite, nitrate, aqueous hydrogen peroxide solution again, after mixing, 45～85 ℃ of reactions 0.5～10 hour; Molysite here and nitrate are meant ferric sulfate, ferrous sulfate, iron nitrate, iron trichloride, SODIUMNITRATE, saltpetre, ammonium nitrate; The consumption of molysite is 0.5～5 times of amount of gallium in the aqueous solution, and the consumption of nitrate is 5～15 times of gallium, and the consumption of hydrogen peroxide is 5～40 times of gallium; After reaction finishes, add alkali PH4～8 that neutralize, gallium becomes solid sediment precipitate from the aqueous solution to separate out, and filtration obtains containing the solid concentrates of gallium; Here neutralize and be meant sodium hydroxide, potassium hydroxide, saleratus, bicarbonate of ammonia, yellow soda ash, sodium bicarbonate, liming, calcium oxide, lime carbonate, ammonia and ammoniacal liquor with alkali.