CN106145169B - A kind of method of the wet underwater welding aluminum oxide from aluminous fly-ash - Google Patents
A kind of method of the wet underwater welding aluminum oxide from aluminous fly-ash Download PDFInfo
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Abstract
The invention provides a kind of method of the wet underwater welding aluminum oxide from aluminous fly-ash, comprise the following steps：1) aluminous fly-ash is handled through pre-desiliconizing；2) pre-desiliconizing flyash is through low temperature wet method dissolution partial oxidation aluminium；3) low temperature dissolution slag is through high temperature wet dissolution aluminum oxide；4) step 2) and evaporating, concentrating and crystallizing after 3) dissolution fluid and seed precipitation solution mixing prepare aluminate hydrates sodium crystal, or evaporating, concentrating and crystallizing prepares aluminate hydrates sodium crystal after step 2) dissolution fluid and seed precipitation solution mixing, step 3) dissolution fluid is back to step 2) and is used as dissolution medium；5) aluminate hydrates sodium crystal is dissolved with sig water, obtains aluminium hydroxide through desiliconization, seeded precipitation, then obtain alumina product through calcining.Aluminum oxide step-leached in the present invention, leaching temperature and dissolution pressure are low, and energy consumption is low, and equipment material requires low, and technique is simple, and aluminium, silicon are utilized effectively, Whote-wet method flow, suitable for industrialized production.
Description
Technical field
The present invention relates to the utilization of aluminous fly-ash, more particularly to a kind of wet underwater welding aluminum oxide from aluminous fly-ash
Method.
Background technology
China's aluminum oxide yield accounts for the world 1/3, but the 3% of the bauxite resource reserves Jin Zhan worlds of China, resource guarantee year
Limiting less than 10 years, aluminum oxide external dependence degree is more than 50%, and mineral products export policy is tightened up by Indonesia of bauxite main body entrance state etc.,
China's bauxite resource supply contradiction.
The high alumina coal resource and the ground such as China Inner Mongol, Shanxi is richly stored with, stock number of the buried depth more than 500 meters
Have nearly 50,000,000,000 tons, will produce nearly 15,000,000,000 tons of aluminous fly-ash after high alumina coal power generation, wherein the content of aluminum oxide be 35%~
50%, this content equivalent to aluminum oxide in China's middle-low bauxite.At present, aluminous fly-ash total amount alreadys exceed 100,000,000
Ton, and also increase every year with about 25,000,000 tons of amplitude, take up an area and environmental pollution problem is serious, aluminous fly-ash is urgently opened
Hair utilizes.
Therefore, China's Aluminum is developed in a healthy way using aluminous fly-ash production aluminum oxide and environmental protection is significant.Mesh
Before, mainly there are acid system, sintering process, ammonium sulfate method etc. in China from flyash extraction aluminum oxide technology.Wherein there is equipment corruption in acid system
The shortcomings of erosion is serious, acid medium recovery is difficult, product quality can not be up to standard；Sintering temperature height, high energy consumption, tailings be present in sintering process
Measure the shortcomings of big；The shortcomings of equipment enlarging is difficult, tailings amount is big, ammonia emission amount is big be present in ammonium sulfate method.Recently, China is special
Profit application CN103663516A discloses a kind of method that aluminium hydroxide is prepared using aluminous fly-ash, and process characteristic mainly includes
Two step desiliconizations and two step high temperature dissolutions reaction, the technique can realize making full use of for aluminium and silicon components in flyash, but flow
Complexity, operating difficulties, pre-processed using two step desiliconizations, additionally use acid-wash activation, pickle recycles difficulty, easily causes ring
Border is polluted, and two step dissolution reaction conditions are all harsher, and energy consumption is larger.Chinese patent application CN104030331A discloses a kind of profit
With the method for aluminous fly-ash production aluminum oxide, process characteristic mainly includes pre-desiliconizing and alkali soluble goes out twice, and alkali soluble goes out to adopt twice
With the NaOH solution of various concentrations, but alkali soluble goes out that reaction temperature is still higher, and energy consumption is higher to the technique twice, and kind divides decomposition nut liquid to steam
An alkali soluble is returned to after hair concentration to go out, substantial amounts of aluminium returns to process in leaching, and the production efficiency of aluminium is relatively low.Because mullite structure is steady
It is fixed, generally believe that the decomposition of mullite in flyash needs to carry out at high temperature in the industry, therefore utilize flyash alkalinity extraction oxygen
Change the reaction temperature of aluminium at least more than 160 DEG C, not yet find to utilize flyash alkaline process dissolution aluminum oxide under lower temperature so far
Report.
The content of the invention
It is an object of the present invention to provide a kind of method of the wet underwater welding aluminum oxide from aluminous fly-ash, this method
Using pre-desiliconizing, low temperature dissolution and the step dissolving-out process of high temperature dissolution two, have that energy consumption is low, equipment material requires low, waste residue
Discharge capacity is few, dissolution fluid silicon concentration it is low be advantageous to crystallization the advantages that, can be widely applied for industrialized production.
To reach above-mentioned purpose, present invention employs following technical scheme：
A kind of method of low cost wet underwater welding aluminum oxide from aluminous fly-ash, this method comprise the following steps：
1) aluminous fly-ash is subjected to pre-desiliconizing reaction, reaction temperature in the sodium hydroxide solution of mass fraction 10~20%
Spend for 80~120 DEG C, reaction is separated by filtration after terminating, and obtains pre-desiliconizing flyash and desiliconization liquid；
2) the pre-desiliconizing flyash is carried out to low temperature wet method molten in finite concentration sodium aluminate solution and under certain temperature
Go out reaction, reaction is separated by filtration after terminating, and obtains low temperature dissolution slag and low temperature dissolution fluid；
3) by the low temperature dissolution slag in a certain amount of calcium oxide of addition or calcium hydroxide or using calcium oxide as main component
High temperature dissolution reaction is carried out in the finite concentration sodium aluminate solution of waste residue at a certain temperature, reaction terminates rear filtration washing point
From obtaining carrying aluminium tailings and high temperature dissolution fluid；
4) the high temperature dissolution fluid and step 5) seed precipitation solution obtained low temperature dissolution fluid that step 2) obtains, step 3) mixes
Close, after evaporation and concentration, add crystal seed, crystallize under certain condition, obtain aluminate hydrates sodium crystal and crystalline mother solution, crystalline mother solution
For low temperature dissolution and high temperature dissolution；Or by the low temperature dissolution fluid that step 2) obtains and the seed precipitation solution that step 5) loops back
Mix, after evaporation and concentration, add crystal seed, crystallize under certain condition, obtain aluminate hydrates sodium crystal and crystalline mother solution, the knot
Brilliant mother liquor is used for the high temperature dissolution of step 3), and step 3) high temperature dissolution fluid is used for the low temperature dissolution of step 2)；
5) kind point：The aluminate hydrates sodium crystal that step 4) obtains is dissolved with sig water, the filtrate after desiliconization cleans, filtered
Added aluminium hydroxide crystal seed carries out seeded precipitation, obtains aluminum hydroxide crystals and seed precipitation solution, aluminum hydroxide crystals are scrubbed,
Calcining obtains alumina product, and seed precipitation solution returns to step 4).
Preferably, pre-desiliconizing is reacted in the step 1), and the volume mass ratio of sodium hydroxide solution and aluminous fly-ash is 3
~6：1 (ml/g), reaction time are 0.5~2h, and desiliconization rate is up to more than 40%, the alumina-silica amount ratio (A/ of pre-desiliconizing flyash
S) greatly improve, the desiliconization liquid can be used for preparing the products such as white carbon or active calcium silicate.
Preferably, the dissolution of low temperature wet method is reacted in the step 2), using Na2O concentration is 400~600g/L, Na2O with
Al2O3Mol ratio be 10~40 sodium aluminate solution, sodium aluminate solution and pre-desiliconizing flyash volume mass proportioning are 3~6：1
(ml/g), reaction temperature is 80~140 DEG C, and the reaction time is 0.5~3d.
Preferably, the high temperature dissolution reaction in the step 3), using Na2400~600g/L of O concentration, Na2O and Al2O3
Mol ratio be 20~40 sodium aluminate solution, sodium aluminate solution and pre-desiliconizing flyash are 6~15 by volume mass ratio：1ml/
G, reaction temperature are 200~300 DEG C, and the reaction time is 0.5~4h, calcium oxide or calcium hydroxide or using calcium oxide as main component
The addition of waste residue by Ca/Si mol ratios be 0.8~1.2 to be added.
Preferably, in the step 4), kind denominator that step 2) and the dissolution fluid that 3) obtains and step 5) loop back
After liquid mixing, it is 500~600g/L to be evaporated to oxidation na concn, then adds crystal seed and carries out crystallization reaction at 40~70 DEG C, obtains
To aluminate hydrates sodium crystal and crystalline mother solution, the crystalline mother solution returns to low temperature dissolution and high temperature process in leaching recycles.Or
Person, after the seed precipitation solution mixing that the low temperature dissolution fluid and step 5) that step 2) obtains loop back, being evaporated to oxidation na concn is
500~600g/L, then add crystal seed and carry out crystallization reaction at 40~70 DEG C, obtain aluminate hydrates sodium crystal and crystalline mother solution,
The crystalline mother solution returns to high temperature process in leaching and recycled, and the dissolution medium that step 3) high temperature dissolution fluid is used for step 2) is carried out
Low temperature dissolution.
, can further in the present invention, removing sodium reaction is hydrolyzed in the aluminium tailings that carries that step 3) is obtained in sig water,
Obtain removing sodium slag and removing sodium liquid.
Preferably, aluminium tailings is carried in Na2O concentration is that removing sodium reaction is hydrolyzed in 0~80g/L sig water, reaction temperature
Spend for 80~240 DEG C, the reaction time is 1~20h.
Preferably, resulting removing sodium slag can be used for the production building products such as white carbon or calcium silicate board.
Compared with prior art, the present invention has following obvious superiority：
1) present invention carries out pre-desiliconizing during using aluminous fly-ash extraction aluminum oxide using to aluminous fly-ash
The process of processing, can greatly improve the alumina silica ratio of aluminous fly-ash, while be advantageous to follow-up flyash and sodium aluminate solution
Dissolution is reacted.
2) process in leaching of aluminum oxide is carried out in two steps in the present invention, first using the portion in low temperature dissolution pre-desiliconizing flyash
Divide aluminum oxide, under conditions of this low energy consumption of low-temperature atmosphere-pressure, the digesting efficiency of alumina in aluminous fly-ash can be made left up to 50%
The right side, and because reaction temperature is low, equipment material requires low, and silicon concentration is low in dissolution fluid, is particularly conducive to follow-up sodium aluminate solution
Crystallization, energy consumption and equipment investment all substantially reduce, and technique simple possible.
3) second step depth extraction aluminum oxide is carried out to low temperature dissolution slag using high-temperature alkali leaching dissolution in the present invention, two steps are molten
The total dissolution rate gone out is up to more than 95%.
4) seed precipitation solution when recycling in the present invention, after being mixed with low temperature dissolution fluid and high temperature dissolution fluid (or only with it is low
Warm dissolution fluid mixing, and high temperature dissolution fluid returns to low temperature process in leaching), evaporating, concentrating and crystallizing, avoids conventional aluminium oxide together
The problem of aluminum oxide largely circulates in flow, the production efficiency of aluminum oxide is improved, and crystalline mother solution can return to low temperature dissolution
Recycled with high temperature process in leaching (or only returning to high temperature process in leaching).
5) raw material sources are extensive employed in the present invention, and while producing aluminum oxide, obtained desiliconization liquid can be used for preparing
The product such as white carbon or active calcium silicate, the building productses such as calcium silicate board can also be prepared by carrying aluminium tailings through hydrolyzing removing sodium, be realized high
The abundant high value added utilization of aluminium and silicon components in aluminium powder coal ash, there is great economy and the value of environmental protection.
6) method of present invention wet high-effective extraction aluminum oxide from aluminous fly-ash, reaction condition is gentle, both avoids
The high energy consumption of sintering process, tailings are big, the drawbacks of being difficult by, and the highly corrosive and acid medium that turn avoid acid system to equipment are difficult
The defects of recovery, it is thus also avoided that the shortcomings of two step alkali solution technique alkali lye internal circulating loads are big, equipment investment is high, the method tool that the present invention uses
There is energy consumption is low, equipment material requirement is low, production cost is low, waste sludge discharge amount is few, dissolution fluid silicon concentration is low to be advantageous to crystallize
The advantages that, it can be widely applied for industrialized production.
Brief description of the drawings
Fig. 1 is the process flow diagram of present invention wet underwater welding aluminum oxide from aluminous fly-ash.
Embodiment
With reference to the several specific embodiments of the present invention, the present invention is described in more detail, but following examples are only limitted to
The present invention is explained, is not intended to limit the scope of the present invention, interest field of the invention is defined by claims.
Embodiment 1
Exemplified by raw material uses Inner Mongol somewhere aluminous fly-ash, its main chemical compositions is as shown in table 1：
The chemical composition of the aluminous fly-ash of table 1
As shown in figure 1, a kind of method of the wet underwater welding aluminum oxide from aluminous fly-ash, methods described includes following step
Suddenly：
1. it is that 13.5% sodium hydroxide solution by volume mass ratio is 5 by the aluminous fly-ash described in table 1 and mass fraction：
1 (ml/g) is mixed, and carries out pre-desiliconizing reaction in a kettle, reaction temperature is 100 DEG C, reaction time 2h, after reaction terminates
It is separated by filtration, obtains pre-desiliconizing flyash and desiliconization liquid；Pre-desiliconizing flyash measures A/S as 2.4 after washing is dried.
2. by dried pre-desiliconizing flyash and oxidation na concn 600g/L, Na2O and Al2O3Mol ratio for 40 or
16 sodium aluminate solution is 5 by volume mass ratio：1 (ml/g) is mixed, and is placed in reactor, and 3d is incubated at 80 DEG C and carries out low temperature
Wet method dissolution is reacted, and reaction is separated by filtration after terminating, and obtains low temperature dissolution slag and low temperature dissolution fluid, dissolution fluid silica concentration
For 1~2g/L, and after carrying out a dissolution according to method disclosed in Chinese patent application CN103663516A, silica concentration
For 3.5~6g/L.
3. by low temperature dissolution slag and sodium oxide molybdena 600g/L, Na2O and Al2O3Mol ratio be 40 sodium aluminate solution press quality
Than for 6：1 mixing, it is 0.8 addition calcium oxide or calcium hydroxide or giving up using calcium oxide as main component by Ca/Si mol ratios
Slag, it is placed in reactor, the high temperature dissolution reaction 4h at 200 DEG C, reacts and be cooled to 100 DEG C after terminating, then filtration washing point
From obtaining carrying aluminium tailings and high temperature dissolution fluid；Carry and A/S is measured after the scrubbed drying of aluminium tailings as 0.12, be computed understanding, two steps
Total dissolution rate of dissolution is 95.0%.
4. low temperature dissolution fluid, high temperature dissolution fluid and seed precipitation solution are mixed, it is 600g/L to be evaporated to oxidation na concn, then
Add crystal seed and carry out crystallization reaction at 70 DEG C, crystallization time 10h, obtain aluminate hydrates sodium crystal and crystalline mother solution, crystalline mother solution
Crater corrosion 35, crystalline mother solution is returned into low temperature dissolution and high temperature process in leaching recycles.Or low temperature dissolution fluid and kind are divided
Mother liquor mix, be evaporated to oxidation na concn be 600g/L, then add crystal seed 70 DEG C progress crystallization reactions, crystallization time 10h,
Aluminate hydrates sodium crystal and crystalline mother solution are obtained, crystalline mother solution Crater corrosion 35, crystalline mother solution is returned into the circulation of high temperature process in leaching
Utilize, high temperature dissolution fluid is back to low temperature process in leaching and recycled.And disclosed according to Chinese patent application CN103663516A
Method carry out a dissolution, because silica concentration is high in solution, when it be 600g/L to aoxidize na concn, crystallizes 10h, tie
Brilliant mother liquor Crater corrosion is 18.
5. the aluminate hydrates sodium crystal is dissolved with sig water, add desiliconization agent and carry out desiliconization, filtrate is through adding after filtering
Hydrogenation alumina seed carries out kind of a point decomposition, obtains aluminum hydroxide crystals and seed precipitation solution, aluminum hydroxide crystals are scrubbed, calcining
Alumina product is obtained, seed precipitation solution returns to be utilized with low temperature dissolution fluid mixing circulation.
6. by the aluminium tailings that carries in Na2O concentration is that removing sodium reaction, reaction temperature are hydrolyzed in 10g/L sig water
For 80 DEG C, time 20h, removing sodium slag and removing sodium liquid are obtained, removing sodium liquid is used to dissolve aluminate hydrates sodium crystal, in removing sodium slag
Na2O content is 0.93%, available for the production building products such as white carbon or calcium silicate board.
Embodiment 2
As shown in figure 1, a kind of method of the wet underwater welding aluminum oxide from aluminous fly-ash, methods described includes following step
Suddenly：
1. it is that 20% sodium hydroxide solution by volume mass ratio is 3 by the aluminous fly-ash described in table 1 and mass fraction：1
(ml/g) mix, carry out pre-desiliconizing reaction in a kettle, reaction temperature is 120 DEG C, reaction time 0.5h, after reaction terminates
It is separated by filtration, obtains pre-desiliconizing flyash and desiliconization liquid；Pre-desiliconizing flyash measures A/S as 2.4 after washing is dried.
2. dried pre-desiliconizing flyash and oxidation na concn 400g/L, Na2O and Al2O3Mol ratio be 20 or 10
Sodium aluminate solution by volume mass ratio be 3：1 (ml/g) is mixed, and is placed in reactor, and 1d is incubated at 110 DEG C and carries out low temperature
Wet method dissolution is reacted, and reaction is separated by filtration after terminating, and obtains low temperature dissolution slag and low temperature dissolution fluid, dissolution fluid silica concentration
For 1~2g/L, and after carrying out a dissolution according to method disclosed in Chinese patent application CN103663516A, silica concentration
For 3.5~6g/L.
3. by low temperature dissolution slag and oxidation na concn 400g/L, Na2O and Al2O3Mol ratio be 20 sodium aluminate solution press
Volume mass ratio is 15：1 mixing, it is 1.2 addition calcium oxide or calcium hydroxide by Ca/Si mol ratios, is placed in reactor,
1h is reacted in high temperature dissolution at 260 DEG C, and reaction is cooled to 100 DEG C after terminating, reaction terminates rear filtration washing separation, obtains carrying aluminium tail
Slag and high temperature dissolution fluid；Carry and A/S is measured after the scrubbed drying of aluminium tailings as 0.08, be computed understanding, total dissolution of two step dissolutions
Rate is 96.7%.
4. low temperature dissolution fluid, high temperature dissolution fluid and seed precipitation solution are mixed, it is 500g/L to be evaporated to oxidation na concn, then
Add crystal seed and carry out crystallization reaction at 40 DEG C, crystallization time 20h, obtain aluminate hydrates sodium crystal and crystalline mother solution, crystalline mother solution
Crater corrosion 25, crystalline mother solution is returned into low temperature dissolution and high temperature process in leaching recycles.Or low temperature dissolution fluid and kind are divided
Mother liquor mix, be evaporated to oxidation na concn be 500g/L, then add crystal seed 40 DEG C progress crystallization reactions, crystallization time 20h,
Aluminate hydrates sodium crystal and crystalline mother solution are obtained, crystalline mother solution Crater corrosion 25, crystalline mother solution is returned into the circulation of high temperature process in leaching
Utilize, high temperature dissolution fluid is back to low temperature process in leaching and recycled.And disclosed according to Chinese patent application CN103663516A
Method carry out a dissolution, because silica concentration is high in solution, when it be 500g/L to aoxidize na concn, crystallizes 20h, tie
Brilliant mother liquor Crater corrosion is 14.
5. the aluminate hydrates sodium crystal is dissolved with sig water, add desiliconization agent and carry out desiliconization, filtrate is through adding after filtering
Hydrogenation alumina seed carries out kind of a point decomposition, obtains aluminum hydroxide crystals and seed precipitation solution, aluminum hydroxide crystals are scrubbed, calcining
Obtain alumina product.
6. by the aluminium tailings that carries in Na2O concentration is that removing sodium reaction is hydrolyzed in 80g/L sig water, reaction temperature
Spend for 150 DEG C, reaction time 8h, wash through multi-stage countercurrent to obtain removing sodium slag and removing sodium liquid after reaction, removing sodium liquid is used for molten
Aluminate hydrates sodium crystal is solved, Na in removing sodium slag2O content is 0.88%, available for the production building such as white carbon or calcium silicate board production
Product.
Embodiment 3
1. it is that 10% sodium hydroxide solution by volume mass ratio is 6 by the aluminous fly-ash described in table 1 and mass fraction：1
(ml/g) mix, carry out pre-desiliconizing reaction in a kettle, reaction temperature is 80 DEG C, reaction time 2h, mistake after reaction terminates
Filter separation, obtains pre-desiliconizing flyash and desiliconization liquid；Pre-desiliconizing flyash measures A/S as 2.4 after washing is dried
2. dried pre-desiliconizing flyash and oxidation na concn 500g/L, Na2O and Al2O3Mol ratio be 30 or 13
Sodium aluminate solution by volume mass ratio be 4：1 (ml/g) is mixed, and is placed in reactor, and it is low that 0.5d progress is incubated at 140 DEG C
Warm and humid method dissolution reaction, reaction are separated by filtration after terminating, and obtain low temperature dissolution slag and low temperature dissolution fluid, dissolution fluid silica is dense
Spend for 1~2g/L, and after carrying out a dissolution according to method disclosed in Chinese patent application CN103663516A, silica is dense
Spend for 3.5~6g/L.
3. by low temperature dissolution slag and oxidation na concn 500g/L, Na2O and Al2O3Mol ratio be 30 sodium aluminate solution press
Volume mass ratio is 10：1 mixing, it is 1.0 addition calcium oxide or calcium hydroxide by Ca/Si mol ratios, is placed in reactor,
0.5h is reacted in high temperature dissolution at 300 DEG C, and reaction is cooled to 100 DEG C after terminating, reaction terminates rear filtration washing separation, obtains carrying aluminium
Tailings and high temperature dissolution fluid；Carry and A/S measured after the scrubbed drying of aluminium tailings as 0.03, be computed understanding, two step dissolutions it is total molten
Extracting rate is 98.7%.
4. low temperature dissolution fluid, high temperature dissolution fluid and seed precipitation solution are mixed, it is 560g/L to be evaporated to oxidation na concn, then
Add crystal seed and carry out crystallization reaction at 55 DEG C, crystallization time 18h, obtain aluminate hydrates sodium crystal and crystalline mother solution, crystalline mother solution
Crater corrosion 30, crystalline mother solution is returned into low temperature dissolution and high temperature process in leaching recycles.Or low temperature dissolution fluid and kind are divided
Mother liquor mixes, and it is 560g/L to be evaporated to oxidation na concn, then adds crystal seed and carries out crystallization reaction 18h at 55 DEG C, is hydrated
Aluminic acid sodium crystal and crystalline mother solution, crystalline mother solution Crater corrosion 30, crystalline mother solution return high temperature process in leaching is recycled, high temperature
Dissolution fluid is back to low temperature process in leaching and recycled.And carried out according to method disclosed in Chinese patent application CN103663516A
Dissolution, because silica concentration is high in solution, when it is 560g/L to aoxidize na concn, crystallize 18h, crystalline mother solution causticity
Than for 15.
5. the aluminate hydrates sodium crystal is dissolved with sig water, add desiliconization agent and carry out desiliconization, filtrate is through adding after filtering
Hydrogenation alumina seed carries out kind of a point decomposition, obtains aluminum hydroxide crystals and seed precipitation solution, aluminum hydroxide crystals are scrubbed, calcining
Obtain alumina product.
6. by the aluminium tailings that carries in Na2O concentration is that removing sodium reaction is hydrolyzed in 40g/L sig water, reaction temperature
Spend for 240 DEG C, reaction time 1h, wash through multi-stage countercurrent to obtain removing sodium slag and removing sodium liquid after reaction, removing sodium liquid is used for molten
Aluminate hydrates sodium crystal is solved, Na in removing sodium slag2O content is 0.57%, available for the production building such as white carbon or calcium silicate board production
Product.
It should be noted last that the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted.Although ginseng
The present invention is described in detail according to embodiment, it will be apparent to an ordinarily skilled person in the art that the technical side to the present invention
Case is modified or equivalent substitution, and without departure from the spirit and scope of technical solution of the present invention, it all should cover in the present invention
Right among.
Claims (10)
1. a kind of method of the wet underwater welding aluminum oxide from aluminous fly-ash, the described method comprises the following steps：
1) pre-desiliconizing：Aluminous fly-ash is subjected to pre-desiliconizing reaction in the sodium hydroxide solution of mass fraction 10~20%, instead
It is 80~120 DEG C to answer temperature, and reaction is separated by filtration after terminating, and obtains pre-desiliconizing flyash and desiliconization liquid；
2) low temperature dissolution：The pre-desiliconizing flyash that step 1) is obtained carries out reaction temperature as 80~140 in sodium aluminate solution
DEG C the dissolution of low temperature wet method reaction, reaction terminate after be separated by filtration, obtain low temperature dissolution slag and low temperature dissolution fluid；
3) high temperature dissolution：The low temperature dissolution slag that step 2) obtains is being added calcium oxide or calcium hydroxide or is being main using calcium oxide
High temperature dissolution reaction is carried out in the sodium aluminate solution of the waste residue of composition, reaction terminates rear filtration washing separation, obtains carrying aluminium tailings
With high temperature dissolution fluid；
4) crystallize：The seed precipitation solution that step 2) loops back with the dissolution fluid and step 5) 3) obtained is mixed, is concentrated by evaporation
Afterwards, seeded crystallization is added, obtains aluminate hydrates sodium crystal and crystalline mother solution, crystalline mother solution is used for step 2) and dissolution 3)；Or
Person mixes the low temperature dissolution fluid that step 2) obtains and the seed precipitation solution that step 5) loops back, and after evaporation and concentration, adds crystal seed
Crystallization, aluminate hydrates sodium crystal and crystalline mother solution are obtained, crystalline mother solution is used for the dissolution of step 3), and step 3) high temperature dissolution fluid is used
In the dissolution of step 2)；
5) kind point：The aluminate hydrates sodium crystal that step 4) obtains is dissolved with sig water, filtrate is through adding after desiliconization cleans, filtered
It is hydrogenated with alumina seed and carries out seeded precipitation, obtains aluminum hydroxide crystals and seed precipitation solution, aluminum hydroxide crystals are scrubbed, calcining
Alumina product is obtained, seed precipitation solution returns to step 4).
A kind of 2. method of wet underwater welding aluminum oxide from aluminous fly-ash according to claim 1, it is characterised in that institute
In the pre-desiliconizing reaction for stating step 1), the volume mass ratio of sodium hydroxide solution and aluminous fly-ash is 3~6：1mL/g, reaction
Time is 0.5~2h.
A kind of 3. method of wet underwater welding aluminum oxide from aluminous fly-ash according to claim 1, it is characterised in that institute
State the low temperature wet method dissolution reaction in step 2)：Using Na2O concentration is 400~600g/L, Na2O and Al2O3Mol ratio be 10
~40 sodium aluminate solution, sodium aluminate solution are 3~6 with pre-desiliconizing flyash volume mass proportioning：1mL/g, reaction time is
0.5~3d.
A kind of 4. method of wet underwater welding aluminum oxide from aluminous fly-ash according to claim 1, it is characterised in that institute
State the high temperature dissolution reaction in step 3)：Using Na2400~600g/L of O concentration, Na2O and Al2O3Mol ratio be 20~40
Sodium aluminate solution, sodium aluminate solution are 6~15 by volume mass ratio with pre-desiliconizing flyash：1mL/g, reaction temperature be 200~
300 DEG C, the reaction time is 0.5~4h.
A kind of 5. method of wet underwater welding aluminum oxide from aluminous fly-ash according to claim 1, it is characterised in that institute
State the high temperature dissolution reaction in step 3)：Calcium oxide or calcium hydroxide or addition using calcium oxide as the waste residue of main component are pressed
Ca/Si mol ratios are added for 0.8~1.2.
A kind of 6. method of wet underwater welding aluminum oxide from aluminous fly-ash according to claim 1, it is characterised in that institute
State in step 4), after the seed precipitation solution mixing that step 2) and the dissolution fluid 3) obtained and step 5) loop back, be evaporated to oxygen
Change na concn is 500~600g/L, then add crystal seed 40~70 DEG C carry out crystallization reactions, obtain aluminate hydrates sodium crystal and
Crystalline mother solution, the crystalline mother solution returns to low temperature dissolution and high temperature process in leaching recycles.
A kind of 7. method of wet underwater welding aluminum oxide from aluminous fly-ash according to claim 1, it is characterised in that institute
State in step 4), after the seed precipitation solution mixing that the low temperature dissolution fluid and step 5) that step 2) obtains loop back, be evaporated to oxidation
Na concn is 500~600g/L, then adds crystal seed and carries out crystallization reaction at 40~70 DEG C, obtains aluminate hydrates sodium crystal and knot
Brilliant mother liquor, the crystalline mother solution are back to step 3) and are used as dissolution medium, and step 3) high temperature dissolution fluid is back to step 2) conduct
Dissolution medium.
8. according to a kind of method of any described wet underwater welding aluminum oxide from aluminous fly-ash of claim 1-7, its feature
It is, removing sodium reaction is hydrolyzed in the aluminium tailings that carries that step 3) is obtained in sig water, obtains removing sodium slag and removing sodium liquid.
9. the method for a kind of wet underwater welding aluminum oxide from aluminous fly-ash according to claim 8, it is characterised in that carry
Aluminium tailings is in Na2O concentration is that removing sodium reaction is hydrolyzed in 0~80g/L sig water, and reaction temperature is 80~240 DEG C, the time
For 1~20h.
A kind of 10. method of wet underwater welding aluminum oxide from aluminous fly-ash according to claim 8, it is characterised in that
The removing sodium slag is used to produce white carbon or calcium silicate board.
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| CN201510164903.8A CN106145169B (en) | 2015-04-09 | 2015-04-09 | A kind of method of the wet underwater welding aluminum oxide from aluminous fly-ash |
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| CN201510164903.8A CN106145169B (en) | 2015-04-09 | 2015-04-09 | A kind of method of the wet underwater welding aluminum oxide from aluminous fly-ash |
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| CN106145169A CN106145169A (en) | 2016-11-23 |
| CN106145169B true CN106145169B (en) | 2018-02-13 |
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| US4362703A (en) * | 1982-03-01 | 1982-12-07 | Iowa State University Research Foundation, Inc. | Process for preparing cryolite from fly ash |
| CN102476820A (en) * | 2010-11-25 | 2012-05-30 | 中国科学院过程工程研究所 | Method for extracting alumina from coal ash through wet process |
| CN104030331A (en) * | 2014-06-27 | 2014-09-10 | 大唐国际发电股份有限公司高铝煤炭资源开发利用研发中心 | Method for producing aluminum oxide by utilizing high-alumina fly ash |
| CN104073651A (en) * | 2013-03-29 | 2014-10-01 | 中国科学院过程工程研究所 | Method for extracting aluminum and iron from high iron gibbsite-type bauxite |
| CN103303952B (en) * | 2012-03-06 | 2015-07-01 | 中国科学院过程工程研究所 | Method for linked preparation of sodium aluminate and production of silica-based material by means of high-alumina fly ash low-temperature liquid-phase alkali dissolving |
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| US4362703A (en) * | 1982-03-01 | 1982-12-07 | Iowa State University Research Foundation, Inc. | Process for preparing cryolite from fly ash |
| CN102476820A (en) * | 2010-11-25 | 2012-05-30 | 中国科学院过程工程研究所 | Method for extracting alumina from coal ash through wet process |
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| CN104073651A (en) * | 2013-03-29 | 2014-10-01 | 中国科学院过程工程研究所 | Method for extracting aluminum and iron from high iron gibbsite-type bauxite |
| CN104030331A (en) * | 2014-06-27 | 2014-09-10 | 大唐国际发电股份有限公司高铝煤炭资源开发利用研发中心 | Method for producing aluminum oxide by utilizing high-alumina fly ash |
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