CN103936046B - The method of ore deposit calcification transition is added after in a kind of aluminum oxide production process - Google Patents
The method of ore deposit calcification transition is added after in a kind of aluminum oxide production process Download PDFInfo
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Abstract
The present invention relates to a kind of field of aluminum oxide production, after being specifically related to a kind of aluminum oxide production process, add the method for ore deposit calcification transition.Its step is in sodium aluminate solution, adopted by aluminum-containing mineral the mode of high temperature stripping to extract aluminum oxide wherein, and in ore pulp, adds siliceous that calcic material makes in stripping slag in cooling process after stripping all enter mutually in calcification slag.Calcification slag through the modes such as carbonization transformation, molten aluminium, heavy aluminium obtain calcium aluminate and as after add the calcium source of ore deposit calcification transformation process, the main component of molten aluminium slag is Calucium Silicate powder and calcium carbonate, can directly as the raw material of Cement industry.The solution that pressurization process in leaching produces obtains aluminium hydroxide through the mode such as solid-liquid separation, decomposition, and aluminium hydroxide obtains aluminum oxide through calcining.The present invention can improve the organic efficiency of aluminum oxide in bauxite and realize production process without solid waste discharge, and the mode adding calcium after employing also can reduce mass flow and the energy consumption of process in leaching, is a kind of alumina-producing method of high-efficiency environment friendly.
Description
Technical field
The present invention relates to field of aluminum oxide production, the present invention relates to a kind of field of aluminum oxide production, after being specifically related to a kind of aluminum oxide production process, add the method for ore deposit calcification transition.
Technical background
China is aluminum i ndustry big country, and along with the industrial scale of China's aluminum i ndustry and improving constantly of state of the art, the production capacity of China's aluminium has had development at full speed in recent years, ends 2013, and China's aluminum oxide production capacity reaches nearly 4,000 ten thousand tons.Aluminum oxide production process is one of key link of aluminium industrial chain, the production method of current aluminum oxide mostly is Bayer process, though adopt alumina producing Bayer process to have the advantages such as flow process is short, energy consumption is low, but use in this technical finesse middle-low grade raw material process and still there is following problem: one, because main component in the red mud of Bayer process production process generation is hydrated sodium aluminosilicate, therefore in this technical finesse low grade material process of use, the loss of aluminium is comparatively large, and comprehensive yield is lower; Two, contain a large amount of sodium oxides in red mud, not only cause the loss of alkali in production process, also increase the difficulty of red mud comprehensive utilization, make the process problem of red mud become the global problem of aluminum oxide industry.
China aluminum i ndustry person utilizes with regard to the high efficiente callback of aluminum oxide and red mud and has carried out large quantifier elimination, as Chinese Aluminium Co., Ltd Chen Xiang waits clearly " a kind of dressing process for desiliconizing bauxite; application number: 201210262148 " proposed to comprise bauxite at ore grinding, add flotation reagent and carry out roughly selecting, scanning and concentration step, underflow after roughly selecting is carried out classification, after coarse fraction product classification obtained carries out ore grinding, enter to roughly select flow process and carry out secondary and roughly select desiliconization; The fine fraction product that classification obtains feeds to be scanned flow process and carries out flotation desilication, improves the grade of bauxite by the way, thus improves the yield of aluminum oxide in concentrate in process in leaching; People's inventions such as Guiyang Institute of Al-Mg-Design Chen De " producing the technological process method of aluminum oxide with aluminous slag; application number: 200510200300 " is with the aluminous slag obtained after high-iron bauxite ironmaking, enter normal pressure digestion operation, red-mud separation sedimentation operation is delivered at the slip of normal pressure digestion operation stripping, the thick liquid overflowed is after desiliconization process, enter carbon and divide i.e. carbonation decomposition operation, obtain aluminium hydroxide after carbon divides, send calcining process process to obtain qualified alumina product.And the circulating mother liquor needed for stripping operation, by carbon evaporation mother liquor, red mud wash liquor and industrial ground caustic composition, can make full use of resource, carbon divides the CO of needs
2the means such as the flue gas supply that gas is produced by blast furnace realize having in such mineral the efficiency utilization of valency constituent element; " a kind of aluminum i ndustry technique waste residue all makes the transition as the technique of ecological architectural material and method; application number: 200710105971 " of the people such as Wang Wenju invention utilizes the material property of aluminum i ndustry the solid waste red mud (sintering process, Bayer process) of institute's output, boiler slag, milltailings, ashing slag, producer gas generator slag, mud six kinds of waste residues self in process of production, by drying, pulverizing, rational proportion, machine-shaping (roll, extrude) consolidation or sintering process, be converted into novel Load materials and construction material.
Adopt the mode of flotation to extract the grade improving bauxite can cause in production process not only can a large amount of waste residue of output, also can produce a large amount of flotation tailingss, increase solid waste content.Although adopt the method such as sintering production alumina process to obtain the requirement that tailings can meet building materials aspect, production process exists that energy consumption is high, high in cost of production problem.
Summary of the invention
In order to solve, aluminum oxide production process energy consumption is high, cost is high, and the loss of the aluminium of conventional Bayer process is large, and the problem that red mud cannot directly utilize the invention provides a kind of method adding ore deposit calcification transition after in aluminum oxide production process.The mode that the method adopts the interpolation of the cooling process after aluminum-containing mineral stripping calcic material to make the transition reduces mass flow in stripping temperature-rise period, thus reduce the energy consumption of production process, and avoid the problems such as the device processes amount reduction caused because lime adding amount is large.
To achieve these goals, technical scheme of the present invention is as follows:
Add the method for ore deposit calcification transition after in aluminum oxide production process, carry out according to the following steps:
(1) after first stripping, calcification makes the transition
(1a) stripping
The aluminum-containing mineral of fragmentation is mixed with sodium aluminate liquor, and 15 ~ 90min is reacted in stripping at the temperature of 100 ~ 300 DEG C, react through stripping, in mineral, a part of al dissolution is in sodium aluminate liquor, siliceously in mineral be all converted into hydrated sodium aluminosilicate mutually, obtain ore pulp after reaction, wherein liquid phase is sodium aluminate solution fluid, and solid phase main component is hydrated sodium aluminosilicate;
Al dissolution in aluminum-containing mineral is as follows in the solubilizing reaction of sodium aluminate solution:
(Al
2O
3)+2NaOH+3H
2O＝2NaAl(OH)
4(1)
Wherein, described aluminum-containing mineral is bauxite, nepheline, feldspar, kaolinite, flyash, alunite, iron aluminium mineral intergrowth or other aluminum-containing minerals;
Described sodium aluminate liquor is sodium oxide concentration 100 ~ 280g/L, and the mol ratio of sodium oxide and aluminum oxide is (2 ~ 4): the sodium aluminate solution of 1;
Described sodium aluminate solution fluid is sodium oxide and alumina molar ratio is (1.3 ~ 1.8): the sodium aluminate solution of 1;
(1b) calcification makes the transition
Temperature-fall period after mineral stripping, then add calcic material and carry out calcification isomerization, hydrated sodium aluminosilicate is converted into hydration ca aluminosilicate, after reaction, obtains dissolved mineral slurry;
Calcic raw material and hydrated sodium aluminosilicate occur to react as follows:
3(CaO)+Na
2O·Al
2O
3·nSiO
2·xH
2O+H
2O→3CaO·Al
2O
3·mSiO
2·xH
2O+NaOH(2)
The ratio of described calcic material and hydrated sodium aluminosilicate is: in calcic material, in calcium oxide and hydrated sodium aluminosilicate, the mass ratio of silicon oxide is (1.5 ~ 5.5): 1;
Described calcic material is the raw material containing calcium oxide such as lime, calcium aluminate, carbide slag;
The calcium source that described calcification process uses is different, and the crystallization degree of calcification product can be caused different;
(1c) ore pulp is separated
Ore pulp after dilution and solid-liquid separation, the calcification slag of solid phase to be main component be hydration ca aluminosilicate, liquid phase is sodium aluminate solution; Sodium aluminate solution is refining and add after aluminium hydroxide crystal seed makes sodium aluminate decompose, separates out aluminium hydroxide through adding milk of lime, obtain sodium oxide and alumina molar ratio is (1.3 ~ 1.8): the sodium aluminate decomposing solution of 1, then after evaporation reaches the concentration of step (1a) described sodium aluminate liquor, return step (1a) stripping reaction cycle use; The aluminium hydroxide obtained obtains alumina product through calcining;
(2) carbonization transformation
By clear water with calcification slag by liquid-solid ratio (3 ~ 15): after 1mL/g mixes in encloses container, in encloses container, pass into CO
2, CO
2gas first by its supercharging, makes CO in encloses container in venting process
2the dividing potential drop of gas reaches 0.8 ~ 1.8MPa, then under the condition of 90 ~ 150 DEG C, carbonization transformation reacts 10 ~ 240min, obtains ore pulp; Ore pulp through solid-liquor separation, the carbide slag of solid phase to be main component be Calucium Silicate powder, calcium carbonate and aluminium hydroxide, liquid phase is clear water;
The reaction of carbonization transformation is as follows:
3CaO·Al
2O
3·xSiO
2·(6-2x)H
2O+(3-2x)CO
2→xCa
2SiO
4+(3-2x)CaCO
3+2Al(OH)
3+(3-2x)H
2O(3)
Described carbonization transformation reaction is using clear water as medium transition, and clear water recycles in this step;
(3) the molten aluminium of low temperature
Under temperature of reaction 30 ~ 100 DEG C and reaction times 20 ~ 120min condition, naoh concentration is adopted to be that the carbide slag that the molten aluminium mother liquor of a low temperature of 30 ~ 200g/L and step (2) obtain reacts, extract the aluminium hydroxide in carbide slag, the liquid-solid ratio of a molten aluminium mother liquor of low temperature and carbide slag is (4 ~ 15): 1mL/g, the ore pulp be obtained by reacting is through solid-liquor separation, the novel texture red mud of solid phase to be main component be Calucium Silicate powder and calcium carbonate, liquid phase is the molten aluminium mother liquor of secondary low temperature containing sodium aluminate;
Molten aluminium main reaction is as follows:
Al(OH)
3+NaOH＝NaAl(OH)
4(4)
Described novel texture red mud, can be used as the raw material of Cement industry;
(4) heavy aluminium
Calcic material is added in the molten aluminium mother liquor of secondary low temperature that step (3) obtains, wherein in calcic material calcium oxide and in mother liquor quality of alumina than for (1.3 ~ 2.5): 1, under the condition of temperature of reaction 20 ~ 90 DEG C and reaction times 1 ~ 60min, obtain calcium aluminate precipitation and sodium hydroxide solution;
Described calcic material is the raw material containing calcium oxide such as lime, calcium aluminate, carbide slag;
The calcium aluminate be obtained by reacting returns step (1b) calcification isomerization and recycles as calcium source, and sodium hydroxide solution returns in the molten reactive aluminum of step (3) low temperature as a low temperature molten aluminium mother liquor and recycles.
Principle of the present invention: conventional by bauxite calcification stripping isomerization Aluminum, be all add in alkali lye by the solid calcic materials such as lime and bauxite, after heating, calcification stripping makes the transition, at stripping temperature-rise period, inventory is large, causes energy consumption high device processes amount to reduce.Bauxite first adds in alkali lye by present method, after intensification stripping, utilize temperature-fall period to add calcic material and carry out calcification transition, make to decrease in the temperature rise period inventory needing heating, and utilize the waste heat of cooling to carry out calcification transformation process, thus achieve reduction energy consumption, improve the object of device processes ability.
Compared with prior art, feature of the present invention and beneficial effect are:
(1) in calcification stripping isomerization, after employing, add the mode of calcic raw material, reduce the mass flow of process in leaching, reduce the energy consumption of this process, and avoid the problems such as the device processes amount reduction caused because lime adding amount is large.
(2) after calcification, carbonization and molten aluminium process, the tailings obtained in theory alkali-free, also not containing aluminium, improves the yield of aluminum oxide in production process.
(3) by process bauxite of the present invention, the main mine of the tailings obtained is Calucium Silicate powder, calcium carbonate mutually, directly as the raw material of Cement industry, fundamentally can solve red mud and take up an area the problems such as contaminate environment.
Embodiment
Illustrated embodiment of the present invention adopt alumina silica ratio be 3.29 low-grade bauxite be raw material, bauxite composition is by mass percentage: Al
2o
3-54.14%, SiO
2-16.55%, Fe
2o
3-7.16%, surplus is the water that cuts down according to the circumstance, TiO
2and impurity;
What adopt in illustrated embodiment of the present invention is low-grade bauxite, production content of the present invention is not limited to and adopts such mineral, any salic mineral comprise middle higher-grade bauxite, nepheline, feldspar, kaolinite, flyash, alunite, iron aluminium mineral intergrowth etc. all can adopt this technology to produce;
The CO adopted in illustrated embodiment of the present invention
2gas is the CO that lime sintering procedure produces
2waste gas, but production process of the present invention is not limited to use such gas, any containing CO
2gas all can be used as the raw material of carbonization transformation process;
Lime described in the present invention is that unslaked lime is fired, but calcification raw material is not limited to the lime fired, and it take calcium oxide as the material of principal constituent that the raw material of employing can comprise any, comprises lime, calcium aluminate, carbide slag etc.
Embodiment 1
Bauxite is crushed to-250 μm, and be 100g/L by the bauxite after fragmentation and starting point concentration, initial oxidation sodium and the mol ratio of the aluminum oxide sodium aluminate that is 4:1 mix after at 300 DEG C stripping 60min, react through stripping, in mineral, a part of al dissolution is in sodium aluminate solution, siliceously in mineral be all converted into hydrated sodium aluminosilicate mutually, be obtained by reacting ore pulp, the sodium aluminate solution fluid of the liquid phase of ore pulp to be sodium oxide and alumina molar ratio be 1.5:1, the solid phase main component of ore pulp is hydrated sodium aluminosilicate;
Cooling process after process in leaching adds calcium aluminate and lime in ore pulp, and in the total calcium oxide content in calcium aluminate and lime and mineral, the mass ratio of silicon oxide is 1.5:1, obtains calcification ore pulp after completing calcification transition;
Calcification ore pulp is after dilution and solid-liquid separation, liquid phase is sodium oxide and alumina molar ratio is the dissolution fluid of 1.5:1, dissolution fluid is refining and add aluminium hydroxide crystal seed and sodium aluminate is decomposed, separates out aluminium hydroxide through adding milk of lime, again through evaporation, to obtain concentration be the mol ratio of 100g/L, sodium oxide and aluminum oxide is return process in leaching after the sodium aluminate solution of 4:1 to recycle, and the aluminium hydroxide obtained obtains alumina product through calcining; The calcification slag of solid phase to be main component be hydration ca aluminosilicate;
After being mixed in encloses container by liquid-solid ratio 3:1mL/g with calcification slag by clear water, in encloses container, pass into CO
2, make CO in encloses container
2the dividing potential drop of gas reaches 1.8MPa, then under the condition of 90 DEG C, carbonization transformation reacts 90min, obtains ore pulp; Ore pulp through solid-liquor separation, the carbide slag of solid phase to be main component be Calucium Silicate powder, calcium carbonate and aluminium hydroxide, liquid phase is clear water; Carbonization transformation process is using clear water as medium transition, and clear water recycles in this step;
Carbide slag adopts the sodium hydroxide solution of 200g/L at 100 DEG C again, aluminium hydroxide under the low temperature leaching condition of stripping 20min in stripping carbide slag, the liquid-solid ratio 4:1mL/g of sodium hydroxide solution and carbide slag, the ore pulp be obtained by reacting is through solid-liquor separation, the novel texture red mud of solid phase to be main component be Calucium Silicate powder and calcium carbonate, liquid phase is sodium aluminate solution;
Add lime to sodium aluminate solution, wherein in lime calcium oxide and in solution quality of alumina than for 1.3:1, under the reaction conditions of precipitation temperature 90 DEG C and sedimentation time 1min, obtain calcium aluminate precipitation and sodium hydroxide solution; Cooling process after the calcium aluminate be obtained by reacting returns process in leaching recycles as calcium source, and sodium hydroxide solution returns in the molten aluminium process of low temperature as sodium hydroxide solution and recycles.
In tailings, alumina silica ratio is 0.45 after treatment, and soda content is 0.75%.
Embodiment 2
Bauxite is crushed to-250 μm, and be 280g/L by the bauxite after fragmentation and starting point concentration, initial oxidation sodium and the mol ratio of the aluminum oxide sodium aluminate solution that is 2:1 mix after at 100 DEG C stripping 15min, react through stripping, in mineral, a part of al dissolution is in sodium aluminate solution, siliceously in mineral be all converted into hydrated sodium aluminosilicate mutually, be obtained by reacting ore pulp, the sodium aluminate solution fluid of the liquid phase of ore pulp to be sodium oxide and alumina molar ratio be 1.8:1, the solid phase main component of ore pulp is hydrated sodium aluminosilicate;
Cooling process after process in leaching adds calcium aluminate, and in the total calcium oxide content in calcium aluminate and mineral, the mass ratio of silicon oxide is 5.5:1, obtains calcification ore pulp after completing calcification transition;
Calcification ore pulp is after dilution and solid-liquid separation, liquid phase is sodium oxide and alumina molar ratio is the dissolution fluid of 1.8:1, dissolution fluid is refining and add aluminium hydroxide crystal seed and sodium aluminate is decomposed, separates out aluminium hydroxide through adding milk of lime, again through evaporation, concentration is 280g/L, the mol ratio of initial oxidation sodium and aluminum oxide is return process in leaching after the sodium aluminate solution of 2:1 to recycle; The calcification slag of solid phase to be main component be hydration ca aluminosilicate;
After being mixed in encloses container by liquid-solid ratio 15:1mL/g with calcification slag by clear water, in encloses container, pass into CO
2, make CO in encloses container
2the dividing potential drop of gas reaches 0.8MPa, then under the condition of 150 DEG C, carbonization transformation reacts 240min, obtains ore pulp; Ore pulp through solid-liquor separation, the carbide slag of solid phase to be main component be Calucium Silicate powder, calcium carbonate and aluminium hydroxide, liquid phase is clear water; Carbonization transformation process is using clear water as medium transition, and clear water recycles in this step;
Carbide slag adopts the sodium hydroxide solution of 30g/L at 30 DEG C again, aluminium hydroxide under the low temperature leaching condition of stripping 20min in stripping carbide slag, the ore pulp that the liquid-solid ratio 15:1mL/g of sodium hydroxide solution and carbide slag is obtained by reacting is through solid-liquor separation, the novel texture red mud of solid phase to be main component be Calucium Silicate powder and calcium carbonate, liquid phase is sodium aluminate solution;
Add lime to sodium aluminate solution, wherein in lime calcium oxide and in solution quality of alumina than for 2.5:1, under the reaction conditions of precipitation temperature 20 DEG C and sedimentation time 60min, obtain calcium aluminate precipitation and sodium hydroxide solution; Cooling process after the calcium aluminate be obtained by reacting returns process in leaching recycles as calcium source, and sodium hydroxide solution returns in the molten aluminium process of low temperature as sodium hydroxide solution and recycles.
In tailings, alumina silica ratio is 0.45 after treatment, and soda content is 1.0%.
Embodiment 3
Bauxite is crushed to-250 μm, be 240g/L with starting point concentration, initial oxidation sodium and the mol ratio of the aluminum oxide sodium aluminate solution that is 3:1 mix after at 240 DEG C stripping 45min, react through stripping, in mineral, a part of al dissolution is in sodium aluminate solution, siliceously in mineral be all converted into hydrated sodium aluminosilicate mutually, be obtained by reacting ore pulp, the sodium aluminate solution fluid of the liquid phase of ore pulp to be sodium oxide and alumina molar ratio be 1.3:1, the solid phase main component of ore pulp is hydrated sodium aluminosilicate;
Cooling process after process in leaching adds calcium aluminate and carbide slag, and in the total calcium oxide content in calcium aluminate and carbide slag and mineral, the mass ratio of silicon oxide is 2.5:1, obtains calcification ore pulp after completing calcification transition;
Calcification ore pulp is after dilution and solid-liquid separation, liquid phase is sodium oxide and alumina molar ratio is the dissolution fluid of 1.3:1, dissolution fluid is refining and add aluminium hydroxide crystal seed and sodium aluminate is decomposed, separates out aluminium hydroxide through adding milk of lime, again through evaporation, obtain that concentration is 240g/L, the mol ratio of initial oxidation sodium and aluminum oxide is return process in leaching after the sodium aluminate solution of 3:1 to recycle; The calcification slag of solid phase to be main component be hydration ca aluminosilicate;
After being mixed in encloses container by liquid-solid ratio 9:1mL/g with calcification slag by clear water, in encloses container, pass into CO
2, make CO in encloses container
2the dividing potential drop of gas reaches 1.2MPa, then under the condition of 120 DEG C, carbonization transformation reacts 10min, obtains ore pulp; Ore pulp through solid-liquor separation, the carbide slag of solid phase to be main component be Calucium Silicate powder, calcium carbonate and aluminium hydroxide, liquid phase is clear water; Carbonization transformation process is using clear water as medium transition, and clear water recycles in this step;
Carbide slag adopts the sodium hydroxide solution of 60g/L at 60 DEG C again, aluminium hydroxide under the low temperature leaching condition of stripping 120min in stripping carbide slag, the liquid-solid ratio 8:1mL/g of sodium hydroxide solution and carbide slag, the ore pulp be obtained by reacting is through solid-liquor separation, the novel texture red mud of solid phase to be main component be Calucium Silicate powder and calcium carbonate, liquid phase is sodium aluminate solution;
Add lime to sodium aluminate solution, wherein in lime calcium oxide and in solution quality of alumina than for 1.7:1, under the reaction conditions of precipitation temperature 40 DEG C and sedimentation time 30min, obtain calcium aluminate precipitation and sodium hydroxide solution; Cooling process after the calcium aluminate be obtained by reacting returns process in leaching recycles as calcium source, and sodium hydroxide solution returns in the molten aluminium process of low temperature as sodium hydroxide solution and recycles.
In tailings, alumina silica ratio is 0.38 after treatment, and soda content is 0.43%.
Embodiment 4
After the sodium aluminate solution that to be crushed to by bauxite after-250 μm with starting point concentration be 200g/L, initial oxidation sodium and the mol ratio of aluminum oxide are 3:1 mixes at 260 DEG C stripping 60min, react through stripping, in mineral, a part of al dissolution is in sodium aluminate solution, siliceously in mineral be all converted into hydrated sodium aluminosilicate mutually, be obtained by reacting ore pulp, the sodium aluminate solution fluid of the liquid phase of ore pulp to be sodium oxide and alumina molar ratio be 1.5:1, the solid phase main component of ore pulp is hydrated sodium aluminosilicate;
Cooling process after process in leaching adds calcium aluminate and lime, and in the total calcium oxide content in calcium aluminate and lime and mineral, the mass ratio of silicon oxide is 3:1, obtains calcification ore pulp after completing calcification transition;
Calcification ore pulp is after dilution and solid-liquid separation, liquid phase is sodium oxide and alumina molar ratio is the dissolution fluid of 1.5:1, dissolution fluid is refining and add aluminium hydroxide crystal seed sodium aluminate is decomposed through adding milk of lime, separate out the aluminium hydroxide in mother liquor, again through evaporation, to obtain concentration be concentration is 200g/L, the mol ratio of initial oxidation sodium and aluminum oxide is return process in leaching after the sodium aluminate of 3:1 to recycle; The calcification slag of solid phase to be main component be hydration ca aluminosilicate;
After being mixed in encloses container by liquid-solid ratio 12:1mL/g with calcification slag by clear water, in encloses container, pass into CO
2, make CO in encloses container
2the dividing potential drop of gas reaches 1.5MPa, then under the condition of 100 DEG C, carbonization transformation reacts 30min, obtains ore pulp; Ore pulp through solid-liquor separation, the carbide slag of solid phase to be main component be Calucium Silicate powder, calcium carbonate and aluminium hydroxide, liquid phase is clear water; Carbonization transformation process is using clear water as medium transition, and clear water recycles in this step;
Carbide slag adopts the sodium hydroxide solution of 60g/L at 60 DEG C again, aluminium hydroxide under the low temperature leaching condition of stripping 50min in stripping carbide slag, the liquid-solid ratio 12:1mL/g of sodium hydroxide solution and carbide slag, the ore pulp be obtained by reacting is through solid-liquor separation, the novel texture red mud of solid phase to be main component be Calucium Silicate powder and calcium carbonate, liquid phase is sodium aluminate solution;
Add lime to sodium aluminate solution, wherein in lime calcium oxide and in solution quality of alumina than for 2:1, under the reaction conditions of precipitation temperature 70 DEG C and sedimentation time 50min, obtain calcium aluminate precipitation and sodium hydroxide solution; Cooling process after the calcium aluminate be obtained by reacting returns process in leaching recycles as calcium source, and sodium hydroxide solution returns in the molten aluminium process of low temperature as sodium hydroxide solution and recycles.
In tailings, alumina silica ratio is 0.41 after treatment, and soda content is 0.62%.
Embodiment 5
Bauxite is crushed to-250 μm, be 150g/L with starting point concentration, initial oxidation sodium and the mol ratio of the aluminum oxide sodium aluminate solution that is 4:1 mix after at 150 DEG C stripping 90min, react through stripping, in mineral, a part of al dissolution is in sodium aluminate solution, siliceously in mineral be all converted into hydrated sodium aluminosilicate mutually, be obtained by reacting ore pulp, the sodium aluminate solution fluid of the liquid phase of ore pulp to be sodium oxide and alumina molar ratio be 1.6:1, the solid phase main component of ore pulp is hydrated sodium aluminosilicate;
Cooling process after process in leaching adds calcium aluminate and lime, and in the total calcium oxide content in calcium aluminate and lime and mineral, the mass ratio of silicon oxide is 4:1, obtains calcification ore pulp after completing calcification transition;
Calcification ore pulp is after dilution and solid-liquid separation, liquid phase is sodium oxide and alumina molar ratio is the dissolution fluid of 1.6:1, dissolution fluid is refining and add aluminium hydroxide crystal seed sodium aluminate is decomposed through adding milk of lime, separate out the aluminium hydroxide in mother liquor, again through evaporation, to obtain concentration be concentration is 150g/L, the mol ratio of initial oxidation sodium and aluminum oxide is return process in leaching after the sodium aluminate solution of 4:1 to recycle; The calcification slag of solid phase to be main component be hydration ca aluminosilicate;
After being mixed in encloses container by liquid-solid ratio 6:1mL/g with calcification slag by clear water, in encloses container, pass into CO
2, make CO in encloses container
2the dividing potential drop of gas reaches 1.0MPa, then under the condition of 100 DEG C, carbonization transformation reacts 120min, obtains ore pulp; Ore pulp through solid-liquor separation, the carbide slag of solid phase to be main component be Calucium Silicate powder, calcium carbonate and aluminium hydroxide, liquid phase is clear water; Carbonization transformation process is using clear water as medium transition, and clear water recycles in this step;
Carbide slag adopts the sodium hydroxide solution of 150g/L at 60 DEG C again, aluminium hydroxide under the low temperature leaching condition of stripping 60min in stripping carbide slag, the liquid-solid ratio 12:1mL/g of sodium hydroxide solution and carbide slag, the ore pulp be obtained by reacting is through solid-liquor separation, the novel texture red mud of solid phase to be main component be Calucium Silicate powder and calcium carbonate, liquid phase is sodium aluminate solution;
Add lime to sodium aluminate solution, wherein in lime calcium oxide and in solution quality of alumina than for 2.2:1, under the reaction conditions of precipitation temperature 55 DEG C and sedimentation time 30min, obtain calcium aluminate precipitation and sodium hydroxide solution; Cooling process after the calcium aluminate be obtained by reacting returns process in leaching recycles as calcium source, and sodium hydroxide solution returns in the molten aluminium process of low temperature as sodium hydroxide solution and recycles.
In tailings, alumina silica ratio is 0.48 after treatment, and soda content is 0.75%.
Claims (7)
1. add the method for ore deposit calcification transition after in aluminum oxide production process, it is characterized in that, carry out according to the following steps:
(1) after first stripping, calcification makes the transition
(1a) stripping
Mixed with sodium aluminate liquor by aluminum-containing mineral, and 15 ~ 90min is reacted in stripping at the temperature of 100 ~ 300 DEG C, be obtained by reacting ore pulp through stripping, liquid phase is wherein sodium aluminate solution fluid, and solid phase main component is wherein hydrated sodium aluminosilicate;
(1b) calcification makes the transition
Ore pulp temperature-fall period after mineral stripping, then calcic material is added in ore pulp, hydrated sodium aluminosilicate is converted into hydration ca aluminosilicate, completes calcification and obtain dissolved mineral slurry transition;
(1c) ore pulp is separated
Dissolved mineral slurry after dilution and solid-liquid separation, the calcification slag of solid phase to be main component be hydration ca aluminosilicate, liquid phase is sodium aluminate solution; Sodium aluminate solution is refining and add after aluminium hydroxide crystal seed makes sodium aluminate decompose, separates out aluminium hydroxide through adding milk of lime, obtains sodium aluminate decomposing solution; The aluminium hydroxide obtained obtains alumina product through calcining;
Described sodium aluminate decomposing solution returns step (1a) stripping reaction and recycles as sodium aluminate liquor after evaporation reaches the concentration of step (1a) described sodium aluminate liquor;
(2) carbonization transformation
By clear water with calcification slag by liquid-solid ratio (3 ~ 15): after 1mL/g mixes in encloses container, in encloses container, pass into CO
2, make CO in encloses container
2the dividing potential drop of gas reaches 0.8 ~ 1.8MPa, then under the condition of 90 ~ 150 DEG C, carbonization transformation reacts 10 ~ 240min, obtains ore pulp; Ore pulp through solid-liquor separation, the carbide slag of solid phase to be main component be Calucium Silicate powder, calcium carbonate and aluminium hydroxide, liquid phase is clear water;
The clear water be obtained by reacting recycles in the reaction of step (2) carbonization transformation;
(3) the molten aluminium of low temperature
Naoh concentration is adopted to be that the molten aluminium mother liquor of a low temperature of 30 ~ 200g/L and carbide slag react, extract the aluminium hydroxide in carbide slag, a molten aluminium mother liquor of low temperature and carbide slag liquid-solid ratio are (4 ~ 15): 1mL/g, temperature of reaction 30 ~ 100 DEG C, reaction times 20 ~ 120min, the ore pulp be obtained by reacting is through solid-liquor separation, and liquid phase is the molten aluminium mother liquor of secondary low temperature containing sodium aluminate, the novel texture red mud of solid phase to be main component be Calucium Silicate powder and calcium carbonate;
(4) heavy aluminium
In the molten aluminium mother liquor of secondary low temperature, add calcic material, be obtained by reacting calcium aluminate precipitation and sodium hydroxide solution;
The calcium aluminate that heavy reactive aluminum obtains returns step (1b) calcification isomerization and recycles as calcium source; The sodium hydroxide solution obtained returns in the molten reactive aluminum of step (3) low temperature as a low temperature molten aluminium mother liquor and recycles.
2. add the method for ore deposit calcification transition after in a kind of aluminum oxide production process according to claim 1, it is characterized in that, described aluminum-containing mineral is bauxite, nepheline, feldspar, kaolinite, flyash, alunite or iron aluminium mineral intergrowth.
3. after in a kind of aluminum oxide production process according to claim 1, add the method for ore deposit calcification transition, it is characterized in that, in described step (1a), sodium aluminate liquor is the mol ratio of sodium oxide concentration 100 ~ 280g/L, sodium oxide and aluminum oxide is (2 ~ 4): the sodium aluminate solution of 1; Sodium aluminate solution fluid is sodium oxide and alumina molar ratio is (1.3 ~ 1.8): the sodium aluminate solution of 1.
4. add the method for ore deposit calcification transition after in a kind of aluminum oxide production process according to claim 1, it is characterized in that, described calcic material is the raw material containing calcium oxide, comprises lime, calcium aluminate, carbide slag.
5. after in a kind of aluminum oxide production process according to claim 1, add the method for ore deposit calcification transition, it is characterized in that, the ratio of the described calcic material of step (1b) and hydrated sodium aluminosilicate is: in calcic material, in calcium oxide and hydrated sodium aluminosilicate, the mass ratio of silicon oxide is (1.5 ~ 5.5): 1.
6. after in a kind of aluminum oxide production process according to claim 1, add the method for ore deposit calcification transition, it is characterized in that, in step (4) described calcic material, calcium oxide and quality of alumina in the molten aluminium mother liquor of secondary low temperature are than being (1.3 ~ 2.5): 1.
7. after in a kind of aluminum oxide production process according to claim 1, add the method for ore deposit calcification transition, it is characterized in that, the reaction conditions of the molten aluminium mother liquor of step (4) described secondary low temperature and calcic material is: temperature of reaction 20 ~ 90 DEG C and reaction times 1 ~ 60min.
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