CN104030329B - A kind of method containing bauxite resource comprehensive utilization - Google Patents
A kind of method containing bauxite resource comprehensive utilization Download PDFInfo
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Abstract
The invention belongs to the method for comprehensive utilization of resources, particularly relate to a kind of method containing bauxite resource comprehensive utilization, comprise the steps: that ammonium sulfate heats by (1), decompose, produce monoammonium sulfate and ammonia; (2) mix containing the monoammonium sulfate of bauxite resource with step (1), and add water or washing lotion; (3) carry out solid-liquid separation and washing after reaction cooling, obtain the solution of aluminum ion and iron ion and excess sulfuric acid hydrogen ammonium solution and high white residue; (4) step (3) gained solution is added ammoniacal liquor or ammonia, obtain aluminium hydroxide and ferric hydroxide precipitate and ammoniumsulphate soln, then carry out solid-liquid separation washing; (5) ammoniumsulphate soln that step (4) obtains is carried out evaporative crystallization separation, obtain ammonium sulfate solids; (6) aluminium hydroxide step (4) obtained and ironic hydroxide solid is treated obtains metallurgical-grade aluminum oxide and high scum.Energy consumption of the present invention is low, and the leaching yield of aluminum oxide and iron is high, and effective constituent enrichment degree is high, and production cost is low.
Description
Technical field
The invention belongs to the method for comprehensive utilization of resources, particularly relate to a kind of method containing bauxite resource comprehensive utilization.
Background technology
For many years, along with the fast development of national economy, what China's aluminum i ndustry obtained develops on an unprecedented scale, aluminum oxide also develops very swift and violent as the raw material of electrolytic aluminum, become the first big producing country of aluminum oxide in the world, current China Alumina Enterprise reaches family more than 40, built and reach more than 5,050 ten thousand tons/year building production capacity, and the production capacity wherein processing domestic bauxite is 3,700 ten thousand tons/year.National aluminum oxide output 3769.6 ten thousand tons in 2012 is the large alumina producing state of the first in the world.But the country that to be bauxite resource relatively poor of China, current China find out and the bauxite resource reserves of inferring low to China's aluminum oxide industry guaranteed extent, and along with the continuous expansion of the consumption of Chinese aluminum oxide and throughput, the guaranteed extent of China's bauxite will reduce further, visible domestic bauxite resource shortage and contradiction in great demand, bauxite resource has become the bottleneck of restriction aluminum industry in China Sustainable development.The alumina-producing method of current employing mainly contains Bayer process, sintering process and integrated process, wherein Bayer process is topmost producing and manufacturing technique, simple sintering process is because the large cost height of energy consumption is substantially by market, and integrated process (comprising mixed combining method, multiple process and series process) also exists a small amount of application on process low grade ore.Because ore grade (ore alumina silica ratio) is very large on existing alumina production cost impact, the method existed at present is all not suitable for process low-grade bauxite or bauxite resource.So, develop the hot issue that new Technology process is current industry research containing bauxite resource (as aluminous fly-ash, iron aluminium mineral intergrowth, gibbsite, diaspore etc.).
Summary of the invention
The present invention is intended to overcome the deficiencies in the prior art part and provide a kind of energy consumption low, and the leaching yield of aluminum oxide and iron is high, and effective constituent enrichment degree is high, the method containing bauxite resource comprehensive utilization that production cost is low.
For solving the problems of the technologies described above, the present invention realizes like this.
Containing a method for bauxite resource comprehensive utilization, it is characterized in that, comprise the steps.
(1) ammonium sulfate is heated to 200 ~ 400 DEG C, decomposes, produce monoammonium sulfate and ammonia.
(2) monoammonium sulfate containing bauxite resource and step (1) after ore grinding is mixed, and add water or washing lotion, carry out reacting by heating.
(3) carry out solid-liquid separation and washing after reaction cooling, obtain the solution of aluminum ion and iron ion and excess sulfuric acid hydrogen ammonium solution and high white residue, realize ferro-aluminum and be separated with silicon.
(4) step (3) gained solution is added ammoniacal liquor or ammonia, obtain aluminium hydroxide and ferric hydroxide precipitate and ammoniumsulphate soln, then carry out solid-liquid separation washing.
(5) ammoniumsulphate soln that step (4) obtains is carried out evaporative crystallization separation, obtain ammonium sulfate solids.
(6) aluminium hydroxide step (4) obtained and ironic hydroxide solid obtain metallurgical-grade aluminum oxide and high scum through process.
As a kind of preferred version, in step of the present invention (6), the aluminium hydroxide obtain step (4) and ironic hydroxide solid obtain metallurgical-grade aluminum oxide and high scum through bayer process.
As a kind of preferred version, in step of the present invention (2), be heated to 80 ~ 280 DEG C and react, reaction times 5 ~ 150min.
Further, of the present invention is the resource of diaspore type bauxite, boehmite type bauxite, gibbsitic bauxite, iron aluminium mineral intergrowth, aluminous fly-ash or high alumina coal gangue containing aluminum oxide and metallic aluminium containing bauxite resource.
Further, in step of the present invention (5), after the ammonium sulfate solids obtained, return step (1) and recycle.
In addition, monoammonium sulfate of the present invention is 5 ~ 18 with the mol ratio containing aluminum oxide in bauxite resource and ferric oxide.
Further, in step of the present invention (6), high scum is as iron-smelting raw material or iron oxide red.
Containing a method for bauxite resource comprehensive utilization, when low containing iron level in bauxite resource, can comprise the steps.
(1) ammonium sulfate is heated to 200 ~ 400 DEG C, decomposes, produce monoammonium sulfate and ammonia.
(2) monoammonium sulfate containing bauxite resource and step (1) after ore grinding is mixed, and add water or washing lotion, carry out reacting by heating.
(3) carry out solid-liquid separation and washing after reaction cooling, obtain the solution of aluminum ion and iron ion and excess sulfuric acid hydrogen ammonium solution and high white residue, realize ferro-aluminum and be separated with silicon.
(4) deironing is carried out to the solution that step (3) obtains, make solution iron ion content be reduced to below 20mg/L.
(5) add ammoniacal liquor or ammonia, obtain aluminium hydroxide and ammoniumsulphate soln.
(6) aluminium hydroxide direct roasting prepares aluminum oxide, ammonium sulfate after evaporative crystallization is separated after return step (1) and recycle.
Containing a method for bauxite resource comprehensive utilization, when low containing iron level in bauxite resource, can comprise the steps.
(1) ammonium sulfate is heated to 200 ~ 400 DEG C, decomposes, produce monoammonium sulfate and ammonia.
(2) monoammonium sulfate containing bauxite resource and step (1) after ore grinding is mixed, and add water or washing lotion, carry out reacting by heating.
(3) carry out solid-liquid separation and washing after reaction cooling, obtain the solution of aluminum ion and iron ion and excess sulfuric acid hydrogen ammonium solution and high white residue, realize ferro-aluminum and be separated with silicon.
(4) deironing is carried out to the solution that step (3) obtains, make solution iron ion content be reduced to below 20mg/L.
(5) solution that step (4) obtains is carried out evaporative cooling crystallization, obtain exsiccated ammonium alum solid.
(6) exsiccated ammonium alum solid direct heating decomposes, and obtains aluminum oxide, ammonia and sulphur trioxide.
(7) ammonia and sulphur trioxide are absorbed by ammoniacal liquor, obtain ammoniumsulphate soln, return step (1) and recycle after evaporative crystallization is separated.
Further, in step of the present invention (3), gained height white residue is for the preparation of one or more the mixture in high silicon filler, white carbon black, silica gel, water glass, active calcium silicate and Starso; Described step (4) removing iron from solution adopts recrystallization deironing, resins exchange deironing, extraction deironing, separation of iron in goethite form or yellow ammonium ferrovanadium method.
Advantageous effect of the present invention: the present invention does not add any auxiliary agent, can make effectively to leach containing aluminum oxide middle in bauxite resource and iron, the leaching yield of aluminum oxide can reach more than 85%, and the leaching yield of iron can reach more than 90%.Achieve the circulation of ammonium sulfate in present invention process flow process, obtain alumina product, high-quality iron-smelting raw material height scum, high white residue that silicon oxide enrichment degree is high, realize comprehensive utilization of resources, whole process does not have the discharge of waste gas, waste liquid, waste residue.Integrated artistic is mainly liquid phase reaction, and energy consumption is low, is especially applicable to siliceous high containing bauxite resource.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the invention will be further described.Protection scope of the present invention is not only confined to the statement of following content.
Fig. 1 is the method flow block diagram containing bauxite resource comprehensive utilization of the present invention.
Fig. 2 be iron level of the present invention low time containing a kind of embodiment FB(flow block) of bauxite resource method of comprehensive utilization.
Fig. 3 be iron level of the present invention low time containing the another kind of embodiment FB(flow block) of bauxite resource method of comprehensive utilization.
Embodiment
embodiment 1.
Ammonium sulfate is heated to 300 DEG C, decomposes, produce monoammonium sulfate and ammonia, ammonia water carries out absorption and makes ammoniacal liquor.Mix after 1000kg gibbsitic bauxite ore grinding with above-mentioned monoammonium sulfate, and add water, be heated to 90 DEG C and react, reaction times 60min, in monoammonium sulfate and gibbsitic bauxite, the mol ratio of aluminum oxide and ferric oxide is 7.Carry out solid-liquid separation and washing after reaction cooling, obtain the solution of aluminum ion and iron ion and excess sulfuric acid hydrogen ammonium solution and high white residue, realize ferro-aluminum and be separated with silicon; The ammoniacal liquor that above adding in the solution obtained prepared by Ammonia recovery obtains aluminium hydroxide and ferric hydroxide precipitate and ammoniumsulphate soln, then carries out solid-liquid separation washing; Ammoniumsulphate soln carries out evaporative crystallization separation, and the ammonium sulfate solids obtained is returned ammonium sulfate Decomposition Cycle and used, and realizes the circulation of ammonium sulfate in integrated artistic.Aluminium hydroxide and ironic hydroxide solid can obtain metallurgical-grade aluminum oxide and high scum through simple and easy bayer process.Bayer process comprises the operations such as material allocation, low temperature stripping, ironic hydroxide separating, washing, fine filtration of sodium aluminate solution, seminal fluid cooling, seeded precipitation, aluminium hydroxide filtration washing, Aluminium hydroxide roasting.Bayer process process for making alumina is that the aluminum oxide crystal seed in bauxite is separated out aluminium hydroxide from sodium aluminate solution, and dissolution rate slag and siliceous high ore are separately used sintering process process.Red mud in Bayer process after with oxygenation pretreatment, recyclable aluminum oxide.Sodium carbonate can also be reclaimed.
embodiment 2.
Ammonium sulfate is heated to 200 DEG C, decomposes, produce monoammonium sulfate and ammonia, ammonia water carries out absorption and makes ammoniacal liquor.Mix after 1000kg boehmite type bauxite Milling with above-mentioned monoammonium sulfate, and add water, be heated to 145 DEG C and react, reaction times 90min, in monoammonium sulfate and boehmite type bauxite, the mol ratio of aluminum oxide and ferric oxide is 12.Carry out solid-liquid separation and washing after reaction cooling, obtain the solution of aluminum ion and iron ion and excess sulfuric acid hydrogen ammonium solution and high white residue, realize ferro-aluminum and be separated with silicon; The ammoniacal liquor that above adding in the solution obtained prepared by Ammonia recovery obtains aluminium hydroxide and ferric hydroxide precipitate and ammoniumsulphate soln, then carries out solid-liquid separation washing; Ammoniumsulphate soln carries out evaporative crystallization separation, and the ammonium sulfate solids obtained is returned ammonium sulfate Decomposition Cycle and used, and realizes the circulation of ammonium sulfate in integrated artistic.Aluminium hydroxide and ironic hydroxide solid can obtain metallurgical-grade aluminum oxide and high scum through simple and easy bayer process.
embodiment 3.
Ammonium sulfate is heated to 400 DEG C, decomposes, produce monoammonium sulfate and ammonia, ammonia water carries out absorption and makes ammoniacal liquor.Mix after 1000kg aluminous fly-ash ore grinding with above-mentioned monoammonium sulfate, and add water, be heated to 280 DEG C and react, reaction times 30min, in monoammonium sulfate and aluminous fly-ash, the mol ratio of aluminum oxide and ferric oxide is 18.Carry out solid-liquid separation and washing after reaction cooling, obtain the solution of aluminum ion and iron ion and excess sulfuric acid hydrogen ammonium solution and high white residue, realize ferro-aluminum and be separated with silicon; The ammoniacal liquor that above adding in the solution obtained prepared by Ammonia recovery obtains aluminium hydroxide and ferric hydroxide precipitate and ammoniumsulphate soln, then carries out solid-liquid separation washing; Ammoniumsulphate soln carries out evaporative crystallization separation, and the ammonium sulfate solids obtained is returned ammonium sulfate Decomposition Cycle and used, and realizes the circulation of ammonium sulfate in integrated artistic.Aluminium hydroxide and ironic hydroxide solid can obtain metallurgical-grade aluminum oxide and high scum through simple and easy bayer process.
embodiment 4.
Ammonium sulfate is heated to 300 DEG C, decomposes, produce monoammonium sulfate and ammonia, ammonia water carries out absorption and makes ammoniacal liquor.Mix after 1000kg diaspore type bauxite ore grinding with above-mentioned monoammonium sulfate, and add water, be heated to 200 DEG C and react, reaction times 180min, in monoammonium sulfate and diaspore type bauxite, the mol ratio of aluminum oxide and ferric oxide is 15.Carry out solid-liquid separation and washing after reaction cooling, obtain the solution of aluminum ion and iron ion and excess sulfuric acid hydrogen ammonium solution and high white residue, realize ferro-aluminum and be separated with silicon; The ammoniacal liquor that above adding in the solution obtained prepared by Ammonia recovery obtains aluminium hydroxide and ferric hydroxide precipitate and ammoniumsulphate soln, then carries out solid-liquid separation washing; Ammoniumsulphate soln carries out evaporative crystallization separation, and the ammonium sulfate solids obtained is returned ammonium sulfate Decomposition Cycle and used, and realizes the circulation of ammonium sulfate in integrated artistic.Aluminium hydroxide and ironic hydroxide solid can obtain metallurgical-grade aluminum oxide and high scum through simple and easy bayer process.
embodiment 5.
Ammonium sulfate is heated to 300 DEG C, decomposes, produce monoammonium sulfate and ammonia, subsequent technique delivered to by ammonia compressor.Mix after 1000kg high alumina coal gangue ore grinding with above-mentioned monoammonium sulfate, and add water, be heated to 160 DEG C and react, reaction times 120min, in monoammonium sulfate and high alumina coal gangue, the mol ratio of aluminum oxide and ferric oxide is 12.Carry out solid-liquid separation and washing after reaction cooling, obtain the solution of aluminum ion and iron ion and excess sulfuric acid hydrogen ammonium solution and high white residue, realize ferro-aluminum and be separated with silicon; In the solution obtained, pass into ammonia that ammonia compressor sends here obtain aluminium hydroxide and ferric hydroxide precipitate and ammoniumsulphate soln, then carry out solid-liquid separation washing; Ammoniumsulphate soln carries out evaporative crystallization separation, and the ammonium sulfate solids obtained is returned ammonium sulfate Decomposition Cycle and used, and realizes the circulation of ammonium sulfate in integrated artistic.Aluminium hydroxide and ironic hydroxide solid can obtain metallurgical-grade aluminum oxide and high scum through simple and easy bayer process.
embodiment 6.
Ammonium sulfate is heated to 300 DEG C, decomposes, produce monoammonium sulfate and ammonia, ammonia water carries out absorption and makes ammoniacal liquor.Mix after 1000kg iron aluminium mineral intergrowth ore grinding with above-mentioned monoammonium sulfate, and add water, be heated to 80 DEG C and react, reaction times 180min, in monoammonium sulfate and iron aluminium mineral intergrowth, the mol ratio of aluminum oxide and ferric oxide is 9.Carry out solid-liquid separation and washing after reaction cooling, obtain the solution of aluminum ion and iron ion and excess sulfuric acid hydrogen ammonium solution and high white residue, realize ferro-aluminum and be separated with silicon; The ammoniacal liquor that above adding in the solution obtained prepared by Ammonia recovery obtains aluminium hydroxide and ferric hydroxide precipitate and ammoniumsulphate soln, then carries out solid-liquid separation washing; Ammoniumsulphate soln carries out evaporative crystallization separation, and the ammonium sulfate solids obtained is returned ammonium sulfate Decomposition Cycle and used, and realizes the circulation of ammonium sulfate in integrated artistic.Aluminium hydroxide and ironic hydroxide solid can obtain metallurgical-grade aluminum oxide and high scum through simple and easy bayer process.
embodiment 7.
Ammonium sulfate is heated to 300 DEG C, decomposes, produce monoammonium sulfate and ammonia, ammonia water carries out absorption and makes ammoniacal liquor.Mix after 1000kg aluminous fly-ash ore grinding with above-mentioned monoammonium sulfate, and add water, be heated to 170 DEG C and react, reaction times 120min, in monoammonium sulfate and high alumina coal gangue, the mol ratio of aluminum oxide and ferric oxide is 9.Carry out solid-liquid separation and washing after reaction cooling, obtain the solution of aluminum ion and iron ion and excess sulfuric acid hydrogen ammonium solution and high white residue, realize ferro-aluminum and be separated with silicon; The solution obtained carries out the deironing of employing resins exchange, makes solution iron ion content be reduced to below 20mg/L; After deironing, in solution, add ammoniacal liquor prepared by Ammonia recovery, obtain aluminium hydroxide and ammoniumsulphate soln; Aluminium hydroxide direct roasting prepares aluminum oxide, and ammonium sulfate returns Decomposition of ammonium sulfate and recycles after evaporative crystallization is separated.
embodiment 8.
Ammonium sulfate is heated to 300 DEG C, decomposes, produce monoammonium sulfate and ammonia, ammonia water carries out absorption and makes ammoniacal liquor.Mix after 1000kg aluminous fly-ash ore grinding with above-mentioned monoammonium sulfate, and add water, be heated to 230 DEG C and react, reaction times 90min, in monoammonium sulfate and high alumina coal gangue, the mol ratio of aluminum oxide and ferric oxide is 5.Carry out solid-liquid separation and washing after reaction cooling, obtain the solution of aluminum ion and iron ion and excess sulfuric acid hydrogen ammonium solution and high white residue, realize ferro-aluminum and be separated with silicon; The solution obtained carries out the deironing of employing recrystallization, makes solution iron ion content be reduced to below 20mg/L; Solution carries out evaporative cooling crystallization, obtains exsiccated ammonium alum solid; Exsiccated ammonium alum solid direct heating decomposes, and obtains aluminum oxide, ammonia and sulphur trioxide; Ammonia and sulphur trioxide are absorbed by ammoniacal liquor obtained above, obtain ammoniumsulphate soln, and after evaporative crystallization is separated, Decomposition of ammonium sulfate recycles.
embodiment 9.
Deironing adopts extraction deironing, and other implementation condition is identical with embodiment 7.
embodiment 10.
Deironing adopts separation of iron in goethite form, and other implementation condition is identical with embodiment 8.
embodiment 1.
Deironing adopts the deironing of yellow ammonium ferrovanadium method, and other implementation condition is identical with embodiment 7.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (3)
1., containing a method for bauxite resource comprehensive utilization, it is characterized in that, comprise the steps:
(1) ammonium sulfate is heated to 200 ~ 400 DEG C, decomposes, produce monoammonium sulfate and ammonia;
(2) monoammonium sulfate containing bauxite resource and step (1) after ore grinding is mixed, and add water or washing lotion, carry out reacting by heating; Be heated to 80 ~ 280 DEG C react, reaction times 5 ~ 150min; Described is the resource of diaspore type bauxite, boehmite type bauxite, gibbsitic bauxite, iron aluminium mineral intergrowth, aluminous fly-ash or high alumina coal gangue containing aluminum oxide and metallic aluminium containing bauxite resource;
(3) carry out solid-liquid separation and washing after reaction cooling, obtain the solution of aluminum ion and iron ion and excess sulfuric acid hydrogen ammonium solution and high white residue, realize ferro-aluminum and be separated with silicon;
(4) step (3) gained solution is added ammoniacal liquor or ammonia, obtain aluminium hydroxide and ferric hydroxide precipitate and ammoniumsulphate soln, then carry out solid-liquid separation washing;
(5) ammoniumsulphate soln that step (4) obtains is carried out evaporative crystallization separation, obtain ammonium sulfate solids; After the ammonium sulfate solids obtained, return step (1) and recycle;
(6) aluminium hydroxide step (4) obtained and ironic hydroxide solid obtain metallurgical-grade aluminum oxide and high scum through bayer process; Described monoammonium sulfate is 5 ~ 18 with the mol ratio containing aluminum oxide in bauxite resource and ferric oxide; High scum is as iron-smelting raw material or iron oxide red.
2., containing a method for bauxite resource comprehensive utilization, it is characterized in that, comprise the steps:
(1) ammonium sulfate is heated to 200 ~ 400 DEG C, decomposes, produce monoammonium sulfate and ammonia;
(2) monoammonium sulfate containing bauxite resource and step (1) after ore grinding is mixed, and add water or washing lotion, carry out reacting by heating;
(3) carry out solid-liquid separation and washing after reaction cooling, obtain the solution of aluminum ion and iron ion and excess sulfuric acid hydrogen ammonium solution and high white residue, realize ferro-aluminum and be separated with silicon; Gained height white residue is for the preparation of one or more the mixture in high silicon filler, white carbon black, silica gel, water glass, active calcium silicate and Starso;
(4) deironing is carried out to the solution that step (3) obtains, solution iron ion content is made to be reduced to below 20mg/L, wherein, described step (4) removing iron from solution adopts recrystallization deironing, resins exchange deironing, extraction deironing, separation of iron in goethite form or yellow ammonium ferrovanadium method;
(5) add ammoniacal liquor or ammonia, obtain aluminium hydroxide and ammoniumsulphate soln;
(6) aluminium hydroxide direct roasting prepares aluminum oxide, ammonium sulfate after evaporative crystallization is separated after return step (1) and recycle.
3., containing a method for bauxite resource comprehensive utilization, it is characterized in that, comprise the steps:
(1) ammonium sulfate is heated to 200 ~ 400 DEG C, decomposes, produce monoammonium sulfate and ammonia;
(2) monoammonium sulfate containing bauxite resource and step (1) after ore grinding is mixed, and add water or washing lotion, carry out reacting by heating;
(3) carry out solid-liquid separation and washing after reaction cooling, obtain the solution of aluminum ion and iron ion and excess sulfuric acid hydrogen ammonium solution and high white residue, realize ferro-aluminum and be separated with silicon;
(4) deironing is carried out to the solution that step (3) obtains, make solution iron ion content be reduced to below 20mg/L;
(5) solution that step (4) obtains is carried out evaporative cooling crystallization, obtain exsiccated ammonium alum solid;
(6) exsiccated ammonium alum solid direct heating decomposes, and obtains aluminum oxide, ammonia and sulphur trioxide;
(7) ammonia and sulphur trioxide are absorbed by ammoniacal liquor, obtain ammoniumsulphate soln, return step (1) and recycle after evaporative crystallization is separated.
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| CN104030329A (en) | 2014-09-10 |
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