CN1149294C - Method for extracting metal gallium from flue dust from corundum electric arc furnace smelting - Google Patents

Abstract

The invention discloses a method for extracting gallium metal from corundum electric arc furnace smelting fume. The method adds ingredients CaCO ₃ and K ₂ CO ₃ to the corundum fume, and then undergoes material preparation, roasting, grinding, alkali leaching, separation, alkali Gallium metal is prepared by immersion, electrolysis, refining and purification. The amount of _CaCO3 added is based on the _weight ratio of corundum fume: corundum fume: _CaCO3 = 1.00: 1.30～1.45; the amount of _K2CO3 added is based on the weight ratio of corundum fume The weight ratio is: corundum soot: K ₂ CO ₃ =1.00:0.14-0.19. The invention adopts an alkali method to extract metal gallium products from corundum fumes, and has the advantages of simple process, low cost, high extraction rate, high product purity, little environmental pollution, and the by-products can be recycled.

Description

From the corundum arc furnace smelting smoke dust, extract the method for gallium

At present, only there is the hydrochloric acid-extraction of employing technology from corundum arc smelting flue dust, to extract gallium in the prior art, when extracting gallium with the high silicon corundum of hydrochloric acid-extraction art breading flue dust, mainly exist complex process, cost height, big for environment pollution, extraction yield is low and byproduct that produced is difficult to shortcomings such as recycling, therefore adopt hydrochloric acid-extraction technology from the corundum flue dust, to extract gallium, because technically, on the technology, also have a series of problem to exist in the environmental protection, suitability for industrialized production so far is unrealized.

The objective of the invention is: provide that a kind of technology is simple, at the bottom of the cost, extraction yield height, environmental pollution be little, and the method for extracting gallium from the corundum arc furnace smelting smoke dust that can its byproduct of comprehensive reutilization.

The present invention is achieved in that it adds batching CaCO in the corundum flue dust ₃And K ₂CO ₃, then through system material, roasting, levigate, alkali soaks, separation, alkali are soaked, electrolysis, refining are purified and made gallium, the CaCO in the batching ₃And K ₂CO ₃Add-on is according to SiO in the corundum flue dust ₂, Al ₂O ₃, K ₂O, SO ₄ ^2-, Fe ₂O ₃Content determine and K ₂CO ₃Adopt the K in the circulating mother liquor ₂CO ₃Replenish CaCO ₃And K ₂CO ₃Add-on also should satisfy K in the roasting ₂OAl ₂O ₃, K ₂OGa ₂O ₃, β-2CaOSiO ₂, K ₂OFe ₂O ₃CaO and K when cenotype generates ₂The reaction measuring requirement of O, CaCO in the batching ₃And K ₂CO ₃The concrete add-on and the concrete grammar of each procedure as follows:

CaCO ₃Add-on by weight ratio be with the corundum flue dust:

Corundum flue dust: CaCO ₃=1.00: 1.30～1.45

K ₂CO ₃Add-on by weight ratio be with the corundum flue dust:

Corundum flue dust: K ₂CO ₃=1.00: 0.14～0.19

When material system, with add batching corundum flue dust mixing after more than 12 hours ageing handle compression moulding again, making its water content is 12%～14%, and then with semidrying extrusion forming clamp dog;

During roasting, with clamp dog 300 ℃ of following temperature through roasting under 1200 ℃～1250 ℃ high temperature again after the processed, make it finish the cenotype conversion reaction;

To be ground to less than 200 orders after the roasting material pulverizing, put it into then and carry out agitation leach in the alkali immersion liquid, when agitation leach, controlling its liquid-solid ratio is 3: 1, extraction temperature is greater than 80 ℃, and extraction time 20 minutes～40 minutes washs leached mud once under above-mentioned parameter then again, and wash water is returned down batch of material leach use, the K of leach liquor and the circulating mother liquor that is used for leaching ₂CO ₃Content is controlled at 10～20 grams per liters, send concrete product plant directly to make raw material the silico-calcium slag of gained and uses.

During separation, Al (OH) will be added after the purification of leaching liquor desiliconization ₃Crystal seed stirs at a slow speed under 40 ℃～50 ℃ temperature, with decomposition of crystal seed method separating most Al, makes K ₂OAl ₂O ₃Most of with Al (OH) ₃Separation is separated out in the form hydrolysis, with CO ₂Be carbonating agent, under 40 ℃～50 ℃ temperature, carry out degree of depth carbonating and handled 5～6 hours that the terminal point pH value is controlled at 8.5～9.0, makes the Al that residues in the solution be converted into K ₂OAl ₂O ₃2CO ₂2H ₂O forms and K ₂OGa ₂O ₃2CO ₂2H ₂O separates out with precipitation forms together, and obtains rich gallium product;

When rich gallium material leaches, leach and in high density KOH solution, carry out, and agitation leach under 80 ℃～90 ℃ temperature, and according to K in the rich gallium material ₂OAl ₂O ₃2CO ₂2H ₂O and K ₂OGa ₂O ₃2CO ₂2H ₂O and KHCO ₃Chemical constitution and metering, calculate its leach in the consumption of KOH, said components is separately converted to KAlO in guaranteeing to leach ₂, KGaO ₂, K ₂CO ₃Cenotype enters solution;

When the electrowinning gallium, electrolyte temperature is controlled at 35 ℃～50 ℃, bath voltage is 5～6V, current density is 0.3～0.5A/cm ², be anode with the Ni plate, stainless steel plate is a negative electrode; At Al ₂O ₃Content is less than 150g/L, and Ga can be at α during greater than 2g/L _kIn～1.6 solution, directly carry out electrolysis;

With the further refining of thick gallium that obtains in the above-mentioned technology, during purification, in KOH aqueous medium of 25%～30%, carry out, and be anode with thick gallium, as negative electrode, other condition is identical with the electrowinning gallium with platinum.

Owing to adopted technique scheme, the present invention compares with existing hydrochloric acid-extraction technology, the present invention has adopted the method that is different from prior art fully, the present invention adopts alkaline process to extract the gallium product from the corundum flue dust, not only realized the changing rejected material to useful resource target, opened up the new source of rich gallium resource, also realized substep comprehensive reutilization valuable constituents such as Ga, K, Al, Si in the corundum flue dust, in addition, the main supplementary material CaCO that on technology, adopts of the present invention ₃, CO ₂Cheap etc. price, draw materials easily, and whole process flow has realized closed cycle, has not produced at the bottom of secondary pollution, easy handling, the energy consumption, its electrolytic recovery rate average out to 84.7%, the electrolysis current consumption of every gram gallium is 0.56 degree, the thick gallium purity of extracting can reach 99.0%, thick gallium is behind further refining, its purity can reach 99.98%, thus the present invention has that technology is simple, at the bottom of the cost, extraction yield height, product purity height, environmental pollution be little, and can recycle the advantage of its byproduct.

Embodiments of the invention: get corundum flue dust 100 grams, press corundum flue dust and CaCO ₃Weight ratio be: corundum flue dust: CaCO ₃=1.00: 1.30～1.45 formula adds CaCO ₃Amount 140 grams,

And press corundum flue dust and K ₂CO ₃The weight ratio formula: corundum flue dust: K ₂CO ₃Add K at=1.00: 0.14～0.19 ₂CO ₃Amount 16 grams will add batching CaCO ₃And K ₂CO ₃Corundum flue dust mixing after more than 12 hours ageing handle compression moulding, making its water content is 13%, and then gets the piece material with the semidrying extrusion forming; With the piece material under 300 ℃ of temperature through roasting under 1200 ℃～1250 ℃ high temperature again after the processed, make it finish the cenotype conversion reaction; To be ground to less than 200 orders after the roasting material pulverizing, material after will grinding is then put into the alkali immersion liquid and is carried out agitation leach, when agitation leach, controlling its liquid-solid ratio is 3: 1, and extraction temperature kept greater than 80 ℃, extraction time is 30 minutes, washing is once again under above-mentioned parameter with its leached mud, and wash water is returned down batch of material leach use, the K of leach liquor and the circulating mother liquor that is used for leaching ₂CO ₃Content is controlled at 12 grams per liters, and send concrete product plant to do the raw material use silico-calcium slag of gained; Al (OH) will be added after the purification of leaching liquor desiliconization ₃Crystal seed stirs at a slow speed under 45 ℃ of temperature, with decomposition of crystal seed method separating most Al, makes K ₂OAl ₂O ₃Most of with Al (OH) ₃Separation is separated out in the form hydrolysis, with CO ₂Be carbonating agent, under 40 ℃～50 ℃ temperature, carry out degree of depth carbonating and handled 5～6 hours that the terminal point pH value is controlled at 8.5～9.0, makes the Al that residues in the solution be converted into K ₂OAl ₂O ₃2CO ₂2H ₂O forms and K ₂OGa ₂O ₃2CO ₂2H ₂O separates out with precipitation forms together, thereby obtains rich gallium product; When rich gallium material leaches, leach and in high density KOH solution, carry out, and agitation leach under 80 ℃～90 ℃ temperature, and according to K in the rich gallium material ₂OAl ₂O ₃2CO ₂2H ₂O, K ₂OGa ₂O ₃2CO ₂2H ₂O and KHCO ₃Chemical constitution and metering, calculate its leach in the consumption of KOH, said components is separately converted to KAlO in guaranteeing to leach ₂, KGaO ₂, K ₂CO ₃Cenotype enters solution; When the electrowinning gallium, the leach liquor temperature is controlled at 35 ℃～50 ℃, bath voltage is 5～6V, current density is 0.3～0.5A/cm ², be anode with the Ni plate, stainless steel plate is a negative electrode; At Al ₂O ₃Content is less than 150g/L, and Ga can be at α during greater than 2g/L _kIn～1.6 solution, directly carry out electrolysis; With the thick gallium that obtains in the above-mentioned technology further refining again, during purification, in KOH aqueous medium of 25%～30%, carry out, and be anode with thick gallium, as negative electrode, other condition is identical with the electrowinning gallium to get final product with platinum.

Claims (1)

1, a kind of method of extracting gallium from the corundum arc furnace smelting smoke dust is characterized in that: it adds batching CaCO in the corundum flue dust ₃And K ₂CO ₃, then through system material, roasting, levigate, alkali soaks, separation, alkali are soaked, electrolysis, refining are purified and made gallium, the CaCO in the batching ₃And K ₂CO ₃Add-on is according to SiO in the corundum flue dust ₂, Al ₂O ₃, K ₂O, SO ₄ ^2-, Fe ₂O ₃Content determine and K ₂CO ₃Adopt the K in the circulating mother liquor ₂CO ₃Replenish CaCO ₃And K ₂CO ₃Add-on also should satisfy K in the roasting ₂OAl ₂O ₃, K ₂OGa ₂O ₃, β-2CaOSiO ₂, K ₂OFe ₂O ₃CaO and K when cenotype generates ₂The reaction measuring requirement of O, CaCO in the batching ₃And K ₂CO ₃The concrete add-on and the concrete grammar of each procedure as follows:

CaCO ₃Add-on by weight ratio be with the corundum flue dust:

Corundum flue dust: CaCO ₃=1.00: 1.30～1.45

K ₂CO ₃Add-on by weight ratio be with the corundum flue dust:

Corundum flue dust: K ₂CO ₃=1.00: 0.14～0.19

When material system, with add batching corundum flue dust mixing after more than 12 hours ageing handle compression moulding again, making its water content is 12%～14%, and then with semidrying extrusion forming clamp dog;

During roasting, with clamp dog 300 ℃ of following temperature through roasting under 1200 ℃～1250 ℃ high temperature again after the processed, make it finish the cenotype conversion reaction;

To be ground to less than 200 orders after the roasting material pulverizing, put it into then and carry out agitation leach in the alkali immersion liquid, when agitation leach, controlling its liquid-solid ratio is 3: 1, extraction temperature is greater than 80 ℃, and extraction time 20 minutes～40 minutes washs leached mud once under above-mentioned parameter then again, and wash water is returned down batch of material leach use, the K of leach liquor and the circulating mother liquor that is used for leaching ₂CO ₃Content is controlled at 10～20 grams per liters;

During separation, Al (OH) will be added after the purification of leaching liquor desiliconization ₃Crystal seed stirs at a slow speed under 40 ℃～50 ℃ temperature, with decomposition of crystal seed method separating most Al, makes K ₂OAl ₂O ₃Most of with Al (OH) ₃Separation is separated out in the form hydrolysis, with CO ₂Be carbonating agent, under 40 ℃～50 ℃ temperature, carry out degree of depth carbonating and handled 5～6 hours that the terminal point pH value is controlled at 8.5～9.0, makes the Al that residues in the solution be converted into K ₂OAl ₂O ₃2CO ₂2H ₂O forms and K ₂OGa ₂O ₃2CO ₂2H ₂O separates out with precipitation forms together, and obtains rich gallium product;

When rich gallium material leaches, leach and in high density KOH solution, carry out, and agitation leach under 80 ℃～90 ℃ temperature, and according to K in the rich gallium material ₂OAl ₂O ₃2CO ₂2H ₂O and K ₂OGa ₂O ₃2CO ₂2H ₂O and KHCO ₃Chemical constitution and metering, calculate its leach in the consumption of KOH, said components is separately converted to KAlO in guaranteeing to leach ₂, KGaO ₂, K ₂CO ₃Cenotype enters solution;

When the electrowinning gallium, electrolyte temperature is controlled at 35 ℃～50 ℃, bath voltage is 5～6V, current density is 0.3～0.5A/cm ², be anode with the Ni plate, stainless steel plate is a negative electrode; At Al ₂O ₃Content is less than 150g/L, and Ga can be at α during greater than 2g/L _kIn～1.6 solution, directly carry out electrolysis;

With the further refining of thick gallium that obtains in the above-mentioned technology, during purification, in KOH aqueous medium of 25%～30%, carry out, and be anode with thick gallium, as negative electrode, other condition is identical with the electrowinning gallium with platinum.