CN1641054A - Method for treating smoke containing gallium - Google Patents
Method for treating smoke containing gallium Download PDFInfo
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- CN1641054A CN1641054A CNA2004100001388A CN200410000138A CN1641054A CN 1641054 A CN1641054 A CN 1641054A CN A2004100001388 A CNA2004100001388 A CN A2004100001388A CN 200410000138 A CN200410000138 A CN 200410000138A CN 1641054 A CN1641054 A CN 1641054A
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- flue dust
- gallium
- water
- sulfuric acid
- slurry
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The present invention is especially the treatment of gallium containing fume. The gallium containing fume treating process includes mixing the fume with water to form slurry, adding concentrated sulfuric acid into slurry, maturing the mixture, water soaking to extract, solid-liquid separation of the leached slurry, recovering gallium from the leached liquid in available method, recovering P, Zn, etc. in available method to produce fertilizer or other chemical product, returning the residual solution to leaching operation, and using the leached slag with silica as main component as building material. The said process can recover the valuable components from the fume and is environment friendly.
Description
Technical field
The invention belongs to chemical industry and field of metallurgy, relate to the processing of flue dust, especially contain the treatment process of gallium flue dust.
Background technology
Flue dust is the common solid emission in metallurgical and the chemical engineering industry.Both contain heavy metal and other poisonous elements in the flue dust, often contained various valuable elements again, the enrichment in flue dust usually of valuable rare elements.As processing and utilizing in addition not, in the process of storing up, be subjected to the erosion of various weather condition, dissolving entering environment gradually, and constantly polluted-water and soil also cause valuable element to lose in a large number.Therefore, contain the processing and the utilization of gallium flue dust, existing remarkable economical meaning has important Significance for Environment again.
Gallium is a kind of important dissipated metal, mainly as semiconductor compound, particularly gallium arsenide is widely used in electronic industry and other high-tech area such as unicircuit, information storage, microwave device, Laser Devices, telecommunication, solar cell, neutrino mensuration, specific alloy etc.And the demand of gallium that, is described as " electronic metal " along with high-tech develop rapidly is in continuous growth.
Gallium seldom is formed with the independent deposit of industrial value, and often is scattered in bauxite, zink sulphide, coal and the phosphatic rock with isomorphous impurity state.The content of gallium in these ores is all very low, is about 0.0001～0.003%, can not aim to extract gallium and exploitation processing economically.Therefore, all by-product recovery in other Metal Production of gallium so far.Wherein nearly 90% gallium reclaims from the circulating mother liquor of producing aluminum oxide, about 10% gallium reclaims from the zinc hydrometallurgy slag.It is very big that coal and phosphatic rock contain the gallium total amount, but the grade of gallium is low excessively, so that gallium wherein can't economic recovery.But, gallium wherein can be when phosphatic rock be produced yellow phosphorus enrichment in the flue dust of the flue dust of electrostatic precipitation and coal combustion, make it to become the new resources of gallium.The technical study of just extracting gallium at present from flue dust is very few, and this resource is still waiting exploitation.
The method of extracting gallium from flue dust that has now proposed has: with electric heating process yellow phosphorus factory electrostatic precipitation flue dust (being called for short electric dirt) and Na
2CO
3Mix, fusion at high temperature, the way of water logging reclaims gallium (Neylan Walters from electric dirt then, Gallium extraction from phosphorus flue dust, Proceedings of the InternationalSymposium on Recycle and Secondary Recovery ofMetals 1985); With the gallium (Stevens Harry M., Ballwin M., U.S.Appl.333,928,20 Feb 1973) in the basic solution leaching electric heating process yellow phosphorus factory electricity dirt; With hydrochloric acid leach gallium in the coal combustion flue dust (Founder, in the coal smoke dirt acidleach of gallium and with a kind of extraction of foam sponge, Central-South China Institute of Mining and Metallurgy's journal, 1994,25,762～763).United States Patent (USP) (H.E.Hirsch, S.C.Liang, U.S.Patent 4,071,422, Jan 31,1978 for T.L.Charlton, R.F.Redden) is handled electric heating process yellow phosphorus factory electricity dirt with the vitriol oil and is extracted wherein gallium.Sulfuric acid with 93% adds electric dirt, adds water then and leaches down at 85 ℃, and leaching yield only is 55%.Increase after the sulfuric acid add-on leaching yield of gallium and can bring up to 95%, but the residual sulfuric acid concentration of leach liquor had both increased the difficulty and the cost that reclaim gallium from leach liquor up to 25%, the corrosion of equipment also aggravates.Flue dust is heated to 150 ℃ earlier, add 93% sulfuric acid again and add water simultaneously, two sections adverse currents leach, first wash, the gallium leaching yield can reach 86%, add two sections countercurrent washings again and also can further improve, leach rear filtrate residual sulphur acid concentration and also can reduce to 2.5%, but complicated operation, and have silica gel in the leach liquor and form, cause the solid-liquid separation difficulty.
Summary of the invention
The objective of the invention is to: in order to overcome the low or residual acid concentration height of the metal recovery rate that exists in the above-mentioned dust treatment method, and form silica gel and be difficult to problem such as filtrations, provide a kind of can fully reclaim gallium in the flue dust and valuable components such as zinc, phosphorus effectively, economy and environment amenable dust treatment method.
The treatment process of flue dust provided by the invention, this method comprises: flue dust and water are mixed make slurry, join the vitriol oil in the slurry then and be mixed to evenly, water logging was extracted after resulting sulfuric acid-water-flue dust mixture was placed and carried out the slaking certain hour.
Adopt method of the present invention to handle flue dust, granularity is preferably less than 0.15mm, makes flue dust be convenient to handle and be beneficial to flue dust and fully contact with reactant.
In the methods of the invention, flue dust and water are mixed make slurry earlier, wherein the mass ratio of water and flue dust is (0.5-4): 1; With the vitriol oil, preferably adopt the vitriol oil of undiluted mistake then, join in the above-mentioned slurry of making and uniform mixing, the mass ratio of sulfuric acid and flue dust (0.2-5): 1.
Mixing acid phase, vigorous reaction takes place rapidly in the mixture of sulfuric acid-water and flue dust, makes essential mineral decomposition in the flue dust, and components such as the gallium in the mineral lattice, phosphorus, zinc change into water soluble sulfate.Emitting a large amount of heat simultaneously provides the temperature of reaction needed and evaporates redundant moisture, and makes the silicon-dioxide partial dehydration.
The mixture of the above-mentioned sulfuric acid-water that obtains-flue dust is remained on 0.2h to 8h between about 50 ℃ to 250 ℃, make the mineral decomposition in the flue dust more abundant,, silicon-dioxide is further dewatered, the solid-liquid separation after helping leaching to improve the leaching yield of metal.
Adopt the inventive method to handle the last resulting material of flue dust, further water or dilute acid soln leach wherein gallium, phosphorus, zinc etc., the liquid-solid ratio, the temperature and time that leach can in very large range change with the composition and the different of character of processed flue dust, liquid-solid ratio generally can be at 1-10, extraction temperature is at 20-100 ℃, and extraction time is from 10min to 5h.Leaching the resulting leach liquor in back can make it to separate with insoluble leached mud with any known solid-liquid separating method, and alternative solid-liquid separating method comprises sedimentation, dense and filtration; Gallium useable solvents extracting and separating enrichment-electrolytic process in the leach liquor or other any known methods reclaim; Phosphorus, zinc etc. can be recycled into compound manure or other Chemicals with any known technology, and the solution after the recovery valuable constituent returns to leach makes liquid; Leached mud mainly contains silicon-dioxide, can be used as material of construction.
The inventive method is particularly useful for containing the processing of gallium flue dust, because carry out in the maturing process in the adding vitriol oil and placement in slurry, sulfuric acid-water-flue dust mixture reacts, metals such as gallium wherein, phosphorus, zinc are converted into water-soluble form, can and separate with unreacted flue dust residue by aqueous solution leaching.
The treatment process of flue dust provided by the invention is for fully reclaiming effective, the economic and environment amenable gallium dust treatment method that contains of the valuable components such as gallium, phosphorus and zinc in the flue dust, in simple machine and under the simple operations condition valuable component in the flue dust is converted into form soluble in water with inexpensive and well-off chemical, water leaches and reclaims with various known technology again.Whole process is not used the high equipment of cost, does not produce to hinder filtering colloidal state silicon.
Embodiment
The following examples just are used for specifically describing the present invention, and the present invention is not limited to these embodiment.
Embodiment 1
A kind of electric heating process yellow phosphorus factory's electrostatic precipitation flue dust slurry (abbreviation electric dust slurry), its chemical constitution (weight percent) is as table 1.
The composition of the electric dirt of table 1
Composition P
2O
5F CaO Al
2O
3Fe
2O
3K
2O
(w)/％ 26.32 4.19 14.90 3.42 2.20 8.89
Composition SiO
2S MgO ZnO Na Ga
(w)/％ 17.64 0.42 0.63 4.64 0.62 0.053
After electric dust slurry inspissation, filtration, drying, levigate and sieve with standard sieve.Get each 300g of levigate electric dirt of three kinds of granularities, place the 1000mL beaker respectively, add 150mL water, fully mix, add commercially available 93% sulfuric acid of 100mL then while stirring rapidly.Vigorous reaction takes place in this moment immediately, and follows a large amount of heat releases, and temperature moment is increased to boils.This sulfuric acid-water-electric dirt mixture is maintained the temperature at 2h more than 75 ℃, add water to liquid-solid ratio then and leach at 3: 1.85 ℃ of extraction temperatures, extraction time 3h.Slurries filtration after the leaching, filtrate and filter cake are analyzed its chemical constitution respectively, and analytical results calculates leaching yield such as following table in view of the above:
Size, mesh gallium content (%) leaching yield, %
-35 0.0533 89.21
-150 0.0531 89.58
-340 0.0538 90.09
Embodiment 2
A kind of coal-fired cigarette ash, its chemical constitution such as table 2.
Composition SiO
2Al
2O
3Fe
2O
3CaO MgO K
2O Na
2O
(w)/％ 50.3 26.2 9.55 5.18 1.25 3.36 2.06
Composition Cu Pb Ni Ga Zn Cr Mn
(w)/％ 0.011 0.008 0.016 0.009 0.12 0.08 0.05
Coal-fired cigarette ash is milled to-200 order 〉=70%, gets 100 g levigated stove flue dust and place the 500mL beaker, add 80mL water, fully mix, add commercially available 95% sulfuric acid of 60mL then while stirring.This sulfuric acid-water-flue dust mixture is maintained the temperature at 2h more than 150 ℃, add water to liquid-solid ratio then and leach at 3: 1.85 ℃ of extraction temperatures, extraction time 3h.Leaching yield is: Ga 87.56%, and Al 90.12%, and Fe 4.66%.
Claims (7)
1. the treatment process of a flue dust is characterized in that: this method comprises flue dust and water mixed makes slurry, joins the vitriol oil in the slurry then and is mixed to evenly, and resulting sulfuric acid-water-flue dust mixture is placed and carried out slaking.
2. treatment process as claimed in claim 1 is characterized in that: the consumption of described water and flue dust is that the mass ratio of water and flue dust is (0.2-3): 1.
3. treatment process as claimed in claim 1 is characterized in that: the consumption of the described vitriol oil is that the mass ratio of sulfuric acid and flue dust is (0.5-5): 1.
4. treatment process as claimed in claim 1 is characterized in that: it is between 50 ℃ to 400 ℃ that described sulfuric acid-water-flue dust mixture is placed the temperature of carrying out slaking.
5. treatment process as claimed in claim 1 is characterized in that: it is 0.2h to 8h that described sulfuric acid-water-flue dust mixture is placed the time of carrying out slaking.
6. treatment process as claimed in claim 1 is characterized in that: described flue dust is the flue dust that contains gallium.
7. as claim 1 or 6 described treatment processs, it is characterized in that: described flue dust is the flue dust that granularity is not more than 0.15mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2004100001388A CN1641054A (en) | 2004-01-06 | 2004-01-06 | Method for treating smoke containing gallium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2004100001388A CN1641054A (en) | 2004-01-06 | 2004-01-06 | Method for treating smoke containing gallium |
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| Publication Number | Publication Date |
|---|---|
| CN1641054A true CN1641054A (en) | 2005-07-20 |
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ID=34866644
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2004100001388A Pending CN1641054A (en) | 2004-01-06 | 2004-01-06 | Method for treating smoke containing gallium |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103388159A (en) * | 2012-05-11 | 2013-11-13 | 深圳市格林美高新技术股份有限公司 | Method for recovering gallium from gallium nitride-containing wastes |
| CN107988486A (en) * | 2017-12-08 | 2018-05-04 | 江西自立环保科技有限公司 | A kind of method that zinc is recycled in the cigarette ash from fuming furnace |
-
2004
- 2004-01-06 CN CNA2004100001388A patent/CN1641054A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103388159A (en) * | 2012-05-11 | 2013-11-13 | 深圳市格林美高新技术股份有限公司 | Method for recovering gallium from gallium nitride-containing wastes |
| CN103388159B (en) * | 2012-05-11 | 2016-08-03 | 格林美股份有限公司 | A kind of method reclaiming gallium from nitrogen gallium garbage |
| CN107988486A (en) * | 2017-12-08 | 2018-05-04 | 江西自立环保科技有限公司 | A kind of method that zinc is recycled in the cigarette ash from fuming furnace |
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