CN104150515A - Method for extracting alumina from fly ash based on ammonium sulfate method - Google Patents

Method for extracting alumina from fly ash based on ammonium sulfate method Download PDF

Info

Publication number
CN104150515A
CN104150515A CN201410390312.8A CN201410390312A CN104150515A CN 104150515 A CN104150515 A CN 104150515A CN 201410390312 A CN201410390312 A CN 201410390312A CN 104150515 A CN104150515 A CN 104150515A
Authority
CN
China
Prior art keywords
roasting
temperature
bed
ammonium sulfate
fixedly connected
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410390312.8A
Other languages
Chinese (zh)
Other versions
CN104150515B (en
Inventor
曾伟
郭新锋
梁兴国
钱永康
郭坤
杨超
高旋
王辉
李宁
王会宁
刘胜
丁建亮
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ACADEMY OF AEROSPACE PROPULSION TECHNOLOGY
China Shenhua Energy Co Ltd
Shenhua Zhunneng Resources Development and Utilisation Co Ltd
Original Assignee
ACADEMY OF AEROSPACE PROPULSION TECHNOLOGY
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ACADEMY OF AEROSPACE PROPULSION TECHNOLOGY filed Critical ACADEMY OF AEROSPACE PROPULSION TECHNOLOGY
Priority to CN201410390312.8A priority Critical patent/CN104150515B/en
Publication of CN104150515A publication Critical patent/CN104150515A/en
Application granted granted Critical
Publication of CN104150515B publication Critical patent/CN104150515B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Landscapes

  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

The invention relates to a method for extracting alumina from fly ash based on an ammonium sulfate method. The prior art utilizing fluidized bed-based roasting activation of fly ash to realize alumina extraction produces the problems of material caking and adhesion to the wall so that industrialization is realized difficultly and crude alumina produced by the prior art needs resolution impurity-removal so that processes are more, efficiency is low and energy consumption is high. The method comprises that fly ash, ammonium sulfate and a propping agent are mixed, the mixture is subjected to granulation, the granules are subjected to two-section fluidized bed roasting, the clinker is heated and dissolved by water, the filtrate is subjected to combined impurity-removal and then ammonia precipitation crystallization, and the crystals are calcined to form alumina. The method utilizes mixing granulation of fly ash, ammonium sulfate and the propping agent, oxygen-rich two-section fluidized bed roasting and heating dissolution by water, changes the order of the impurity-removal processes, utilizes a technical scheme comprising impurity-removal and then ammonia precipitation crystallization for high-purity aluminum hydroxide production to solve the problems of equipment corrosion, roasting-caused adhesion to the wall, clustering and coking of the prior art, shortens the integral main process and greatly reduces energy consumption and a cost of extraction of alumina from fly ash.

Description

From flyash, extract the method for aluminum oxide based on ammonium sulfate method
Technical field
the present invention relates to a kind of alumina extraction method, be specifically related to a kind of method of extracting aluminum oxide based on ammonium sulfate method from flyash.
Background technology
Thermal power generation occupies dominant position in the electrification structure of China, and coal-fired thermal power generation occupies absolute ratio in thermal power generation, and flyash is the solid waste that coal-burning power plant dumps.
In recent years, along with the development of power industry, the quantity discharged sharp increase of flyash, according to the report in January, 2009 of Chinese coal TIA, the producing coal total amount of China in 2008 is 27.16 hundred million tons, and wherein most of for generating, the annual emissions of China's flyash has exceeded 200,000,000 tons, accumulative total volume of cargo in storage exceed 2,500,000,000 tons, taken a large amount of arable lands, on a large scale ground contamination environment.Therefore; carry out the comprehensive utilizating research of flyash, realize its resource utilization, be not only and be related to the significant problem urgently to be resolved hurrily that China's power industry and related industries Sustainable development face; and to protection land resources, minimizing and elimination environmental pollution, realize recycling economy significant.
The major ingredient containing in flyash has: Al 2o 3, SiO 2, Fe 2o 3, FeO, TiO 2, CaO, K 2o, MgO etc., wherein the content of aluminum oxide generally can reach 20%～40%, reaches as high as more than 50%, can replace bauxite to become a kind of well alumina resource.Because flyash is the product of high-temp combustion in burner hearth, so most flyash is to exist with vitreum form, its topology convergence degree is large, and chemical property is very stable.
The current method for aluminum oxide by coal ash for manufacturing both at home and abroad, is mainly pickling process, alkali fusion.
Pickling process (sulfuric acid directly leaches method, solubilization of ammonium fluoride method, exsiccated ammonium alum etc.) is from flyash, to extract aluminum oxide taking acid as preserved material, its shortcoming is that other metal containing in flyash also can enter leaching liquid with aluminium, affect the purity of alumina product, need manage to purify, and serious to equipment corrosion, pollute large.
Sintering alkali fusion (limestone sintering is from efflorescence method, soda-lime sintering process, sodium carbonate roasting method etc.) is to utilize alkali from flyash, to extract aluminum oxide, because silicon is dissolved in alkaline solution with aluminium, needs idea desiliconization.
Pickling process or sintering alkali fusion extract in the process of aluminum oxide, in order to remove the impurity in solution, have substantially all adopted the bayer's process removal of impurities of alumina industry, cause whole technology chain longer, and facility investment is large, and energy consumption is high; Meanwhile, being no matter flyash generates aluminum oxide and all needs to carry out roasting with mix heat or the calcination of aluminium salt of activated material, in roasting process, consume energy high, exhaust gas volumn large, bring difficulty to follow-up flue gas processing.In addition, extract aluminum oxide for ammonium sulfate roasting method, the industrialized the biggest problem of the method is that flyash and ammonium sulfate mixture are in roasting process, more than temperature to 220 DEG C time, the quick gelatinization of material, bonds agglomerating, the phenomenons such as sticky wall, caking or ring formation are inevitable, industry roasting apparatus rotary kiln overbalance, can not turn round, discharging difficulty; Fluidized-bed is due to material caking, sticky wall, destruction equipment, cannot move, and other baking modes industrial efficiencies is low, after roasting, materials from bonding becomes piece, discharging difficulty, after discharging, lumpy material also needs fragmentation just can carry out subsequent processing, and operation is many, efficiency is low, energy consumption is high, calcining process is difficult to realize industrialization, therefore,, because above-mentioned cost is high and technique is difficult to the reasons such as operation, make flyash extract aluminum oxide and cannot really realize suitability for industrialized production.
Summary of the invention
The object of this invention is to provide a kind of method of extracting aluminum oxide based on ammonium sulfate method from flyash, height corrosion (as: acid technological process), high energy consumption (as: sintering process) problem of prior art are effectively overcome, and change removal of impurities sequencing on stream, shorten the technology chain of overall main flow, solved a Technology difficult problem for material melting sticky wall, caking or ring formation.
The technical solution adopted in the present invention is:
The method of extracting aluminum oxide based on ammonium sulfate method from flyash, is characterized in that:
Realized by following steps:
Step 1: be 1:(5～10 in flyash and ammonium sulfate mol ratio) ratio, in flyash, add ammonium sulfate; Be 1:(0.05～0.35 in flyash and propping agent mass ratio again) ratio, add propping agent; Mixing granulation, the granularity of ball-type composite grain is diameter 0.5～10mm;
Described propping agent by two kinds of components by 1:(0.5～2) mass ratio mix, component one is selected from the one in cement, yellow mud, water glass, wilkinite, phosphoric acid salt, exsiccated ammonium alum, metal oxide, and component two is selected from the one in roasting grog, the white residue of vitriol, ammonium sulfate and flyash;
Step 2: particle is carried out to the roasting of two-part fluosolids roasting system:
A, granulation is carried out to cryodrying roasting:
Adopt low temperature drying system, granulation is carried out to cryodrying roasting, maturing temperature is 60～220 DEG C, and roasting time is 3 seconds～30 minutes, removes the free-water of particle surface;
In described low temperature drying system, low-temperature bake fluidized-bed body bottom connects low-temperature bake fluidized-bed air compartment, and bottom is fixedly connected with feed bin and feeding device, and top exit is fixedly connected with the first cyclonic separator top one side; Low-temperature bake fluidized bed combustor is installed on low-temperature bake fluidized-bed air compartment front side or low-temperature bake fluidized-bed body bottom; The first cyclonic separator bottom is fixedly connected with the first feeding back device one side, and the first feeding back device opposite side is fixedly connected with low-temperature bake fluidized-bed body bottom; One side on the first efficient cyclone separator top is fixedly connected with the first cyclonic separator top exit, and top exit is connected with the first air preheater one side, grog storehouse in the middle of outlet at bottom connects; The first air preheater opposite side connects the first sack cleaner one side, and the first sack cleaner opposite side is connected into ammonia absorption system;
B, the close conveying mutually of rare gas element:
Composite grain after cryodrying fluiddized-bed roasting is conveyed into high-temperature roasting circulating fluidized bed with the nitrogen after empty point;
C, material particles is carried out to high-temperature roasting:
Adopt high-temperature roasting alumina system, the close material particles transporting mutually after cryodrying roasting is carried out to circulating fluidized bed high-temperature roasting, maturing temperature is 80～800 DEG C, and roasting time is 3 seconds～30 minutes, finally generates grog;
In described high-temperature roasting alumina system, the outlet of roasting circulation spouting bed bodies top is fixedly connected with the second cyclonic separator top one side; Roasting circulation spouting bed burner can be installed and roasting circulating fluidized bed air compartment front side or roasting circulation spouting bed body bottom; The second cyclonic separator bottom is fixedly connected with the second feeding back device one side, and the second feeding back device opposite side is fixedly connected with roasting circulation spouting bed body bottom; One side on the second efficient cyclone separator top is fixedly connected with the second cyclonic separator top exit, top exit is connected with exhaust-heat boiler flue gas import, exhaust-heat boiler flue gas outlet connects the second sack cleaner one side, another side joint second air preheater one side of the second sack cleaner, the second air preheater opposite side connects the second soda-wash tower bottom, the second soda-wash tower top is connected with the second induced draft fan entrance, and the second induced draft fan outlet connects chimney; The second burner blower is connected with the second air preheater gas inlet, and the second air preheater air vout is connected with roasting circulating fluidized bed air compartment; The second feeding back device isocon is connected with multistage cross flow boiling cooling bed heat material entrance, and the second efficient cyclone separator, waste heat boiler and the second sack cleaner bottom are all connected with multistage cross flow boiling cooling bed heat material entrance; Cooling blower is connected with multistage cross flow boiling cooling bed bottom, and multistage cross flow boiling cooling bed top is connected with roasting circulation spouting bed body bottom or exhaust-heat boiler inlet;
Roasting process has experienced following reaction:
Al 2O 3 ＋4(NH 4) 2SO 4＝2NH 4 Al（SO 4） 2＋6 NH 3↑＋3H 2O
Al 2O 3 ＋3(NH 4) 2SO 4＝Al 2（SO 4） 3＋6 NH 3↑＋3H 2O
Fe 2O 3＋4(NH 4) 2SO 4＝2NH 4 Fe（SO 4） 2＋6 NH 3↑＋3H 2O
Fe 2O 3＋3(NH 4) 2SO 4＝Fe 2（SO 4） 3＋6 NH 3↑＋3H 2O
(NH 4) 2SO 4 → SO 3↑＋NH 3↑
Step 3: the grog water producing after roasting carries out the stripping of material at 60～160 DEG C of temperature, filters, and filtrate is NH 4al(SO 4) 2thick liquid, filter residue main component is silicon-dioxide;
Step 4: NH 4al(SO 4) 2thick liquid, after removal of impurities, obtains NH 4al(SO 4) 2seminal fluid;
Step 5: NH 4al(SO 4) 2seminal fluid adds 3～25% ammoniacal liquor, and the heavy reaction of ammonia occurs:
NH 4 Al（SO 4） 2＋3 NH 3＋3H 2O＝Al（OH） 3↓＋2（NH 4） 2SO 4
Ammoniacal liquor is absorbed the ammonia gained discharging in calcination process by water;
Step 6: the throw out Al(OH that step 5 is obtained) 3particle carries out circulating fluidized bed high-temperature roasting, and maturing temperature is 1100 DEG C, and roasting time is 3 seconds～30 minutes, finally generates metallurgical-grade aluminum oxide.
In step 4, described impurity-removing method is selected from:
Method one: crystallization-recrystallization method, realized by following steps:
Treat at room temperature stirred crystallization of removal of impurities filtrate, crystal is reheated in distilled water to dissolving, crystallisation by cooling, after filtering separation, can make most of foreign ion again be shunted in liquid phase, thereby reach the object of purified crystals;
Means re-crystallization is that the water that crystal is 1:4 with mass ratio mixes, and is heated to 98 DEG C of dissolution of crystals.
Method two: sedimentation method combined extraction process, realized by following steps:
A, to add organic precipitant oxalic acid or citric acid, massfraction be 5%～100%, and add-on is for to be as the criterion with point of equivalent, and part is removed calcium, magnesium, iron contamination;
B, to add organic extractant P204, massfraction be again 50%, and add-on is to treat that the mass ratio of removal of impurities filtrate and extraction agent is 1:(0.3～2), the degree of depth is removed calcium, magnesium, iron contamination.
Method three: film is analysed acid system co-precipitation method, is realized by following steps:
A, extract from treat removal of impurities filtrate based on film dialysis acid:
System pH reaches at 2.0 o'clock, and iron is separated out with ferric hydroxide precipitate; System pH reaches at 3.7 o'clock, has precipitated one-level dialysis, carries out solid-liquid separation thereupon, removes ironic hydroxide, continues to propose acid with film dialysis; System pH reaches at 3.8 o'clock, and aluminium is separated out with aluminum hydroxide precipitation; System pH reaches at 4.8 o'clock, and precipitation all completes, and continuously dialysis, until acid is all extracted, completes secondary dialysis, carries out solid-liquid separation thereupon, collects aluminum hydroxide precipitation, and other impurity is all retained in solution and is removed.
Method four: sorption-coprecipitation method, is realized by following steps:
In the acidic solution that is 1.6 in pH value, add potassium permanganate solution and manganese sulfate solution, Fe 2+be oxidized to Fe 3+after, be to be hydrolyzed for 2.0 o'clock in pH value, the Fe(OH of generation) 3with react newly-generated active MnO 2form immediately brown coprecipitate, remove impurity iron.
Method five: sedimentation method combined resin method, realized by following steps:
A, to add organic precipitant oxalic acid or citric acid, massfraction be 5%～100%, and add-on is for to be as the criterion with point of equivalent, and part is removed calcium, magnesium, iron contamination;
B, add resin again, carry out deep impurity-removing based on ion-exchange, the degree of depth is removed calcium, magnesium, iron contamination.
Ammoniumsulphate soln after step 5 is filtered carries out after condensing crystal, and the ammonium sulfate of recovery loops utilization, starts to reuse from step 1.
The present invention has the following advantages:
(1) the present invention's ammonium sulfate is that circulatory mediator extracts aluminum oxide; because ammonium sulfate does not react with silicon-dioxide; therefore in the process of extraction aluminum oxide; save numerous and diverse desiliconization process; ammonium sulfate corrodibility is little, and only water heating stripping, has overcome the deep-etching of traditional acid technological process to equipment; facility investment is little, and is conducive to environment protection.
(2) the present invention adopts first associating removal of impurities, and the heavy crystallization of rear ammonia generates the higher aluminium hydroxide technique of purity, has shortened the technology chain of overall main flow, has improved extraction yield and the purity of aluminum oxide, has reduced production cost.
(3) flyash and ammonium sulfate are carried out mixing granulation by the present invention, adopts oxygen enrichment two-part fluosolids roasting activating fly ash, makes that roasting process energy consumption is low, economy, exhaust gas volumn is little, cost is low.
(4) by adding propping agent, states of matter when change material is high temperature fluidized, and form priming reaction center, make activation temperature reduce by 60～110 DEG C, soak time shortens to original 1/3, greatly reduce priming reaction energy consumption, and solved a Technology difficult problem for material melting sticky wall, caking or ring formation.
Brief description of the drawings
Fig. 1 is the schema that the present invention extracts aluminum oxide from flyash.
Fig. 2 is oxygen-enriched combusting two-part fluosolids roasting system flowchart of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention will be described in detail.
A kind of method of extracting aluminum oxide based on ammonium sulfate method from flyash involved in the present invention, is realized by following steps:
Step 1: be 1:(5～10 in flyash and ammonium sulfate mol ratio) ratio, in flyash, add ammonium sulfate; Be 1:(0.05～0.35 in flyash and propping agent mass ratio again) ratio, add propping agent; Mixing granulation, the granularity of ball-type composite grain is diameter 0.5～10mm;
Described propping agent by two kinds of components by 1:(0.5～2) mass ratio mix, component one is selected from the one in cement, yellow mud, water glass, wilkinite, phosphoric acid salt (being selected from sodium phosphate, potassiumphosphate, ammonium phosphate etc.), exsiccated ammonium alum, metal oxide (being selected from aluminum oxide, sodium oxide, magnesium oxide etc.), and component two is selected from the one in roasting grog, the white residue of vitriol (being selected from sodium sulfate, potassium sulfate, ammonium sulfate etc.), ammonium sulfate and flyash.
Step 2: particle is carried out to the roasting of two-part fluosolids roasting system:
A, granulation is carried out to cryodrying roasting:
Adopt low temperature drying system, granulation is carried out to cryodrying roasting, maturing temperature is 60～220 DEG C, and roasting time is 3 seconds～30 minutes, removes the free-water of particle surface;
In described low temperature drying system, low-temperature bake fluidized-bed body bottom connects low-temperature bake fluidized-bed air compartment, and bottom is fixedly connected with feed bin and feeding device, and top exit is fixedly connected with the first cyclonic separator top one side; Low-temperature bake fluidized bed combustor is installed on low-temperature bake fluidized-bed air compartment front side or low-temperature bake fluidized-bed body bottom; The first cyclonic separator bottom is fixedly connected with the first feeding back device one side, and the first feeding back device opposite side is fixedly connected with low-temperature bake fluidized-bed body bottom; One side on the first efficient cyclone separator top is fixedly connected with the first cyclonic separator top exit, and top exit is connected with the first air preheater one side, grog storehouse in the middle of outlet at bottom connects; The first air preheater opposite side connects the first sack cleaner one side, and the first sack cleaner opposite side is connected into ammonia absorption system;
B, the close conveying mutually of rare gas element:
Composite grain after cryodrying fluiddized-bed roasting is conveyed into high-temperature roasting circulating fluidized bed with the nitrogen after empty point;
C, material particles is carried out to high-temperature roasting:
Adopt high-temperature roasting alumina system, the close material particles transporting mutually after cryodrying roasting is carried out to circulating fluidized bed high-temperature roasting, maturing temperature is 80～800 DEG C, and roasting time is 3 seconds～30 minutes, finally generates grog;
In described high-temperature roasting alumina system, the outlet of roasting circulation spouting bed bodies top is fixedly connected with the second cyclonic separator top one side; Roasting circulation spouting bed burner can be installed and roasting circulating fluidized bed air compartment front side or roasting circulation spouting bed body bottom; The second cyclonic separator bottom is fixedly connected with the second feeding back device one side, and the second feeding back device opposite side is fixedly connected with roasting circulation spouting bed body bottom; One side on the second efficient cyclone separator top is fixedly connected with the second cyclonic separator top exit, top exit is connected with exhaust-heat boiler flue gas import, exhaust-heat boiler flue gas outlet connects the second sack cleaner one side, another side joint second air preheater one side of the second sack cleaner, the second air preheater opposite side connects the second soda-wash tower bottom, the second soda-wash tower top is connected with the second induced draft fan entrance, and the second induced draft fan outlet connects chimney; The second burner blower is connected with the second air preheater gas inlet, and the second air preheater air vout is connected with roasting circulating fluidized bed air compartment; The second feeding back device isocon is connected with multistage cross flow boiling cooling bed heat material entrance, and the second efficient cyclone separator, waste heat boiler and the second sack cleaner bottom are all connected with multistage cross flow boiling cooling bed heat material entrance; Cooling blower is connected with multistage cross flow boiling cooling bed bottom, and multistage cross flow boiling cooling bed top is connected with roasting circulation spouting bed body bottom or exhaust-heat boiler inlet;
Roasting process has experienced following reaction:
Al 2O 3 ＋4(NH 4) 2SO 4＝2NH 4 Al（SO 4） 2＋6 NH 3↑＋3H 2O
Al 2O 3 ＋3(NH 4) 2SO 4＝Al 2（SO 4） 3＋6 NH 3↑＋3H 2O
Fe 2O 3＋4(NH 4) 2SO 4＝2NH 4 Fe（SO 4） 2＋6 NH 3↑＋3H 2O
Fe 2O 3＋3(NH 4) 2SO 4＝Fe 2（SO 4） 3＋6 NH 3↑＋3H 2O
(NH 4) 2SO 4 → SO 3↑＋NH 3↑。
Particle is carried out to the roasting of two-part fluosolids roasting system, be divided into low temperature and high-temperature roasting fluidised bed system two portions by material roasting, completely in parallel independent, can accomplish not interfere with each other.Low-temperature bake fluidized-bed inside is single-stage or plural serial stage ebullated bed, in stove, provide and mend right flame, can solve because a large amount of crystal water is concentrated and emit, heat energy undersupply, not in time, and there is the phenomenon of conglomeration, slagging scorification, to material crystal adhesive water wide accommodation.
Low temperature drying system carries out drying and dehydrating, oxidation by material in low-temperature bake fluidized-bed, removes the free-water of particle surface.Strictly control exit gas temperature simultaneously and outlet flue gas is carried out to multistage waste heat recovery, realizing minimizing of energy consumption, as much as possible the consumption of fuel.Finally low-temperature flue gas is absorbed.
Rare gas element is close to be carried mutually, and the composite grain after cryodrying fluiddized-bed roasting is conveyed into high-temperature roasting circulating fluidized bed with the nitrogen after empty point.Because nitrogen is to be come by space division system, that therefore can control nitrogen enters stove amount, greatly reduces NO xdischarge, and carry be totally-enclosed property, make whole course of conveying without dust from flying, environmentally safe.
High-temperature roasting system can be adjusted roasting circulating fluidized bed operating temperature according to materials quality, as much as possible waste heat is reclaimed simultaneously, produces saturation steam preheating low-temperature bake fluidization air.
Step 3: the grog water producing after roasting carries out the stripping of material at 60～160 DEG C of temperature, filters, and filtrate is NH 4al(SO 4) 2thick liquid, filter residue main component is silicon-dioxide.
Step 4: NH 4al(SO 4) 2thick liquid, after removal of impurities, obtains NH 4al(SO 4) 2seminal fluid.
Step 5: NH 4al(SO 4) 2seminal fluid adds 3～25% ammoniacal liquor, and the heavy reaction of ammonia occurs:
NH 4 Al（SO 4） 2＋3 NH 3＋3H 2O＝Al（OH） 3↓＋2（NH 4） 2SO 4
Ammoniacal liquor is absorbed the ammonia gained discharging in calcination process by water.
Step 6: the throw out Al(OH that step 5 is obtained) 3particle carries out circulating fluidized bed high-temperature roasting, and maturing temperature is 1100 DEG C, and roasting time is 3 seconds～30 minutes, finally generates metallurgical-grade aluminum oxide.
The impurity-removing method adopting in step 4 can adopt following several:
Method one: crystallization-recrystallization method:
Treat at room temperature stirred crystallization of removal of impurities filtrate, crystal is reheated in distilled water to dissolving, crystallisation by cooling, after filtering separation, can make most of foreign ion again be shunted in liquid phase, thereby reach the object of purified crystals.
In crystallization, recrystallization process, need to stir, the one, can obtain evengranular crystal in order to lower step process, the 2nd, can better reach deimpurity object.
Means re-crystallization is that the water that crystal is 1:4 with mass ratio mixes, and is heated to 98 DEG C of dissolution of crystals, and its crystallization and recrystallization efficiency are respectively 88.72%, 83.20%.
Method two: sedimentation method combined extraction process:
A, to add organic precipitant oxalic acid or citric acid, massfraction be 5%～100%, and add-on, for to be as the criterion with point of equivalent, generates organic deposition, after precipitin reaction completes, and filtering separation solid precipitation, part is removed calcium, magnesium, iron contamination.
Chemical equation is: MCI 2+ H 2c 2o 4=MC 2o 4+ 2HCI
Wherein: M represents the positively charged ions such as calcium, magnesium, iron.
B, to add organic extractant P204, massfraction be again 50%, and add-on is to treat that the mass ratio of removal of impurities filtrate and extraction agent is 1:(0.3～2), make the Fe in solution 3+be combined into stable compound Deng foreign ion and organic extractant, by two phase stratification, liquid-liquid separation, the degree of depth is removed the impurity such as calcium, magnesium, iron.
Extraction agent extraction Fe 3+process be cationic exchange process, the H in P204 +exchange with the metal ions M e in solution, the metal ion in solution enters organic phase, the H in P204 +enter the aqueous solution.
Its chemical equation is: Me n++ nHR → MeRn+nH +
Can be found out by this reaction formula, when P204 extraction iron ion, ionize out H +therefore, in the time adopting the acid solution of lower concentration, be conducive to the extraction of metal ion.Difference according to P204 to each metal ion species extracting power, can separate iron with impurity.When the P204 of loaded metal ion and the acid solution of high density (example hydrochloric acid, sulfuric acid) are done the used time, due to H +concentration increases, and balance moves to contrary direction, and P204 is with the appearance of free state form, and the metal ion of extraction is again in the aqueous solution.Utilize this character, the organic phase of can regenerating.
Method three: film is analysed acid system co-precipitation method:
From treat removal of impurities filtrate, extract acid based on film dialysis:
Adopt film dialysis from acidic aluminum solution, to extract acid wherein, ooze acid for dynamic process.System pH reaches at 2.0 o'clock, and iron is separated out with ferric hydroxide precipitate; System pH reaches at 3.7 o'clock, has precipitated one-level dialysis, carries out solid-liquid separation thereupon, removes ironic hydroxide, continues to propose acid with film dialysis; System pH reaches at 3.8 o'clock, and aluminium is separated out with aluminum hydroxide precipitation; System pH reaches at 4.8 o'clock, and precipitation all completes, and continuously dialysis, until acid is all extracted, completes secondary dialysis, carries out solid-liquid separation thereupon, collects aluminum hydroxide precipitation, and other impurity is all retained in solution and is removed.
Its ionic equation is: Fe 3++ 3HO -=Fe(OH) 3↓
Al 3＋＋3HO －＝Al（OH） 3↓
Method four: sorption-coprecipitation method:
In the acidic solution that is 1.6 in pH value, add potassium permanganate solution and manganese sulfate solution, Fe 2+be oxidized to Fe 3+after, be to be hydrolyzed for 2.0 o'clock in pH value, the Fe(OH of generation) 3with react newly-generated active MnO 2form immediately brown coprecipitate, remove impurity iron.
MnO 4 -strong oxidizer, can be Fe 2+be oxidized to Fe 3+, reduzate is Mn 2+.Excessive MnO 4 -and Mn 2+there is redox reaction, and separate out active MnO 2.And Fe in solution 3+be to be hydrolyzed for 2.0 o'clock in pH value, the Fe(OH that hydrolysis generates) 3with react newly-generated active MnO 2form immediately brown coprecipitate, break Fe with this 3+hydrolysising balance makes it hydrolysis completely, thereby reaches the object of removing impurity iron.
Its chemical equation is:
MnO 4 - ＋ 5 Fe 2＋ ＋8 H ＋ ＝ Mn 2＋＋5Fe 3＋＋4HO －
2 MnO 4 -＋3 Mn 2＋＋2 H 2O＝5 MnO 2＋4H ＋
Fe 3＋＋3 H 2O＝Fe（OH） 3＋3H ＋。
Method five: sedimentation method combined resin method:
A, to add organic precipitant oxalic acid or citric acid, massfraction be 5%～100%, and add-on, for to be as the criterion with point of equivalent, generates organic deposition, after precipitin reaction completes, and filtering separation solid precipitation, part is removed calcium, magnesium, iron contamination;
Its chemical equation is: MCI 2+ H 2c 2o 4=MC 2o 4+ 2HCI
Wherein: M represents the positively charged ions such as calcium, magnesium, iron.
B, add resin again, carry out deep impurity-removing based on ion-exchange, the degree of depth is removed calcium, magnesium, iron contamination.2～15 grams of every liter of adsorbable impurity of resin.
Its chemical equation is: 3R-SO 3-h ++ Fe 3+=(R-SO 3-) 3fe 3++ 3H +
Wherein: R represents resin matrix ,-SO 3 -for function group, Fe 3+for foreign ion to be removed in solution.
Ammoniumsulphate soln after step 5 is filtered carries out after condensing crystal, and the ammonium sulfate of recovery loops utilization, starts to reuse from step 1.
Embodiment 1:
The method of extracting aluminum oxide based on ammonium sulfate method from flyash, is characterized in that:
Realized by following steps:
Step 1: the ratio that is 1:5 in flyash and ammonium sulfate mol ratio adds ammonium sulfate in flyash; The ratio that is 1:0.05 in flyash and propping agent mass ratio again, adds propping agent; Mixing granulation, the granularity of ball-type composite grain is diameter 0.5～10mm;
Described propping agent is mixed by the mass ratio of 1:0.5 by two kinds of components, and component one is selected from the one in cement, yellow mud, and component two is selected from vitriol (being selected from sodium sulfate, potassium sulfate, ammonium sulfate etc.);
Step 2: particle is carried out to the roasting of two-part fluosolids roasting system:
A, granulation is carried out to cryodrying roasting:
Adopt low temperature drying system, granulation is carried out to cryodrying roasting, maturing temperature is 60 DEG C, and roasting time is 3 seconds, removes the free-water of particle surface;
In described low temperature drying system, low-temperature bake fluidized-bed body bottom connects low-temperature bake fluidized-bed air compartment, and bottom is fixedly connected with feed bin and feeding device, and top exit is fixedly connected with the first cyclonic separator top one side; Low-temperature bake fluidized bed combustor is installed on low-temperature bake fluidized-bed air compartment front side or low-temperature bake fluidized-bed body bottom; The first cyclonic separator bottom is fixedly connected with the first feeding back device one side, and the first feeding back device opposite side is fixedly connected with low-temperature bake fluidized-bed body bottom; One side on the first efficient cyclone separator top is fixedly connected with the first cyclonic separator top exit, and top exit is connected with the first air preheater one side, grog storehouse in the middle of outlet at bottom connects; The first air preheater opposite side connects the first sack cleaner one side, and the first sack cleaner opposite side is connected into ammonia absorption system;
B, the close conveying mutually of rare gas element:
Composite grain after cryodrying fluiddized-bed roasting is conveyed into high-temperature roasting circulating fluidized bed with the nitrogen after empty point;
C, material particles is carried out to high-temperature roasting:
Adopt high-temperature roasting alumina system, the close material particles transporting mutually after cryodrying roasting is carried out to circulating fluidized bed high-temperature roasting, maturing temperature is 80～800 DEG C, and roasting time is 3 seconds～30 minutes, finally generates grog;
In described high-temperature roasting alumina system, the outlet of roasting circulation spouting bed bodies top is fixedly connected with the second cyclonic separator top one side; Roasting circulation spouting bed burner can be installed and roasting circulating fluidized bed air compartment front side or roasting circulation spouting bed body bottom; The second cyclonic separator bottom is fixedly connected with the second feeding back device one side, and the second feeding back device opposite side is fixedly connected with roasting circulation spouting bed body bottom; One side on the second efficient cyclone separator top is fixedly connected with the second cyclonic separator top exit, top exit is connected with exhaust-heat boiler flue gas import, exhaust-heat boiler flue gas outlet connects the second sack cleaner one side, another side joint second air preheater one side of the second sack cleaner, the second air preheater opposite side connects the second soda-wash tower bottom, the second soda-wash tower top is connected with the second induced draft fan entrance, and the second induced draft fan outlet connects chimney; The second burner blower is connected with the second air preheater gas inlet, and the second air preheater air vout is connected with roasting circulating fluidized bed air compartment; The second feeding back device isocon is connected with multistage cross flow boiling cooling bed heat material entrance, and the second efficient cyclone separator, waste heat boiler and the second sack cleaner bottom are all connected with multistage cross flow boiling cooling bed heat material entrance; Cooling blower is connected with multistage cross flow boiling cooling bed bottom, and multistage cross flow boiling cooling bed top is connected with roasting circulation spouting bed body bottom or exhaust-heat boiler inlet;
Roasting process has experienced following reaction:
Al 2O 3 ＋4(NH 4) 2SO 4＝2NH 4 Al（SO 4） 2＋6 NH 3↑＋3H 2O
Al 2O 3 ＋3(NH 4) 2SO 4＝Al 2（SO 4） 3＋6 NH 3↑＋3H 2O
Fe 2O 3＋4(NH 4) 2SO 4＝2NH 4 Fe（SO 4） 2＋6 NH 3↑＋3H 2O
Fe 2O 3＋3(NH 4) 2SO 4＝Fe 2（SO 4） 3＋6 NH 3↑＋3H 2O
(NH 4) 2SO 4 → SO 3↑＋NH 3↑
Step 3: the grog water producing after roasting carries out the stripping of material at 60 DEG C of temperature, filters, and filtrate is NH 4al(SO 4) 2thick liquid, filter residue main component is silicon-dioxide;
Step 4: NH 4al(SO 4) 2thick liquid, after removal of impurities, obtains NH 4al(SO 4) 2seminal fluid;
Step 5: NH 4al(SO 4) 2seminal fluid adds 3～25% ammoniacal liquor, and the heavy reaction of ammonia occurs:
NH 4 Al（SO 4） 2＋3 NH 3＋3H 2O＝Al（OH） 3↓＋2（NH 4） 2SO 4
Ammoniacal liquor is absorbed the ammonia gained discharging in calcination process by water;
Step 6: the throw out Al(OH that step 5 is obtained) 3particle carries out circulating fluidized bed high-temperature roasting, and maturing temperature is 1100 DEG C, and roasting time is 3 seconds, finally generates metallurgical-grade aluminum oxide.
In step 4, described impurity-removing method can adopt crystallization-recrystallization method, is realized by following steps:
Treat at room temperature stirred crystallization of removal of impurities filtrate, crystal is reheated in distilled water to dissolving, crystallisation by cooling, after filtering separation, can make most of foreign ion again be shunted in liquid phase, thereby reach the object of purified crystals;
Means re-crystallization is that the water that crystal is 1:4 with mass ratio mixes, and is heated to 98 DEG C of dissolution of crystals.
Ammoniumsulphate soln after step 5 is filtered carries out after condensing crystal, and the ammonium sulfate of recovery loops utilization, starts to reuse from step 1.
Embodiment 2:
Step 1: the ratio that is 1:7 in flyash and ammonium sulfate mol ratio adds ammonium sulfate in flyash; The ratio that is 1:15 in flyash and propping agent mass ratio again, adds propping agent; Mixing granulation, the granularity of ball-type composite grain is diameter 0.5～10mm;
Described propping agent is mixed by the mass ratio of 1:1 by two kinds of components, and component one is selected from the one in water glass, wilkinite, and component two is the roasting grog of ammonium sulfate and flyash;
Step 2: particle is carried out to the roasting of two-part fluosolids roasting system:
A, granulation is carried out to cryodrying roasting:
Adopt low temperature drying system, granulation is carried out to cryodrying roasting, maturing temperature is 110 DEG C, and roasting time is 10 minutes, removes the free-water of particle surface;
In described low temperature drying system, low-temperature bake fluidized-bed body bottom connects low-temperature bake fluidized-bed air compartment, and bottom is fixedly connected with feed bin and feeding device, and top exit is fixedly connected with the first cyclonic separator top one side; Low-temperature bake fluidized bed combustor is installed on low-temperature bake fluidized-bed air compartment front side or low-temperature bake fluidized-bed body bottom; The first cyclonic separator bottom is fixedly connected with the first feeding back device one side, and the first feeding back device opposite side is fixedly connected with low-temperature bake fluidized-bed body bottom; One side on the first efficient cyclone separator top is fixedly connected with the first cyclonic separator top exit, and top exit is connected with the first air preheater one side, grog storehouse in the middle of outlet at bottom connects; The first air preheater opposite side connects the first sack cleaner one side, and the first sack cleaner opposite side is connected into ammonia absorption system;
B, the close conveying mutually of rare gas element:
Composite grain after cryodrying fluiddized-bed roasting is conveyed into high-temperature roasting circulating fluidized bed with the nitrogen after empty point;
C, material particles is carried out to high-temperature roasting:
Adopt high-temperature roasting alumina system, the close material particles transporting mutually after cryodrying roasting is carried out to circulating fluidized bed high-temperature roasting, maturing temperature is 280 DEG C, and roasting time is 10 minutes, finally generates grog;
In described high-temperature roasting alumina system, the outlet of roasting circulation spouting bed bodies top is fixedly connected with the second cyclonic separator top one side; Roasting circulation spouting bed burner can be installed and roasting circulating fluidized bed air compartment front side or roasting circulation spouting bed body bottom; The second cyclonic separator bottom is fixedly connected with the second feeding back device one side, and the second feeding back device opposite side is fixedly connected with roasting circulation spouting bed body bottom; One side on the second efficient cyclone separator top is fixedly connected with the second cyclonic separator top exit, top exit is connected with exhaust-heat boiler flue gas import, exhaust-heat boiler flue gas outlet connects the second sack cleaner one side, another side joint second air preheater one side of the second sack cleaner, the second air preheater opposite side connects the second soda-wash tower bottom, the second soda-wash tower top is connected with the second induced draft fan entrance, and the second induced draft fan outlet connects chimney; The second burner blower is connected with the second air preheater gas inlet, and the second air preheater air vout is connected with roasting circulating fluidized bed air compartment; The second feeding back device isocon is connected with multistage cross flow boiling cooling bed heat material entrance, and the second efficient cyclone separator, waste heat boiler and the second sack cleaner bottom are all connected with multistage cross flow boiling cooling bed heat material entrance; Cooling blower is connected with multistage cross flow boiling cooling bed bottom, and multistage cross flow boiling cooling bed top is connected with roasting circulation spouting bed body bottom or exhaust-heat boiler inlet;
Roasting process has experienced following reaction:
Al 2O 3 ＋4(NH 4) 2SO 4＝2NH 4 Al（SO 4） 2＋6 NH 3↑＋3H 2O
Al 2O 3 ＋3(NH 4) 2SO 4＝Al 2（SO 4） 3＋6 NH 3↑＋3H 2O
Fe 2O 3＋4(NH 4) 2SO 4＝2NH 4 Fe（SO 4） 2＋6 NH 3↑＋3H 2O
Fe 2O 3＋3(NH 4) 2SO 4＝Fe 2（SO 4） 3＋6 NH 3↑＋3H 2O
(NH 4) 2SO 4 → SO 3↑＋NH 3↑
Step 3: the grog water producing after roasting carries out the stripping of material at 90 DEG C of temperature, filters, and filtrate is NH 4al(SO 4) 2thick liquid, filter residue main component is silicon-dioxide;
Step 4: NH 4al(SO 4) 2thick liquid, after removal of impurities, obtains NH 4al(SO 4) 2seminal fluid;
Step 5: NH 4al(SO 4) 2seminal fluid adds 10% ammoniacal liquor, and the heavy reaction of ammonia occurs:
NH 4 Al（SO 4） 2＋3 NH 3＋3H 2O＝Al（OH） 3↓＋2（NH 4） 2SO 4
Ammoniacal liquor is absorbed the ammonia gained discharging in calcination process by water;
Step 6: the throw out Al(OH that step 5 is obtained) 3particle carries out circulating fluidized bed high-temperature roasting, and maturing temperature is 1100 DEG C, and roasting time is 10 minutes, finally generates metallurgical-grade aluminum oxide.
In step 4, described impurity-removing method can adopt sedimentation method combined extraction process, is realized by following steps:
A, to add organic precipitant oxalic acid or citric acid, massfraction be 5%～100%, and add-on is for to be as the criterion with point of equivalent, and part is removed calcium, magnesium, iron contamination;
B, to add organic extractant P204, massfraction be again 50%, and add-on is to treat that the mass ratio of removal of impurities filtrate and extraction agent is 1:(0.3～2), the degree of depth is removed calcium, magnesium, iron contamination.
Ammoniumsulphate soln after step 5 is filtered carries out after condensing crystal, and the ammonium sulfate of recovery loops utilization, starts to reuse from step 1.
Embodiment 3:
Step 1: the ratio that is 1:9 in flyash and ammonium sulfate mol ratio adds ammonium sulfate in flyash; The ratio that is 1:25 in flyash and propping agent mass ratio again, adds propping agent; Mixing granulation, the granularity of ball-type composite grain is diameter 0.5～10mm;
Described propping agent is mixed by the mass ratio of 1:1.5 by two kinds of components, and component one is selected from the one in phosphoric acid salt (being selected from sodium phosphate, potassiumphosphate, ammonium phosphate etc.), exsiccated ammonium alum, and component two is the one in white residue;
Step 2: particle is carried out to the roasting of two-part fluosolids roasting system:
A, granulation is carried out to cryodrying roasting:
Adopt low temperature drying system, granulation is carried out to cryodrying roasting, maturing temperature is 160 DEG C, and roasting time is 20 minutes, removes the free-water of particle surface;
In described low temperature drying system, low-temperature bake fluidized-bed body bottom connects low-temperature bake fluidized-bed air compartment, and bottom is fixedly connected with feed bin and feeding device, and top exit is fixedly connected with the first cyclonic separator top one side; Low-temperature bake fluidized bed combustor is installed on low-temperature bake fluidized-bed air compartment front side or low-temperature bake fluidized-bed body bottom; The first cyclonic separator bottom is fixedly connected with the first feeding back device one side, and the first feeding back device opposite side is fixedly connected with low-temperature bake fluidized-bed body bottom; One side on the first efficient cyclone separator top is fixedly connected with the first cyclonic separator top exit, and top exit is connected with the first air preheater one side, grog storehouse in the middle of outlet at bottom connects; The first air preheater opposite side connects the first sack cleaner one side, and the first sack cleaner opposite side is connected into ammonia absorption system;
B, the close conveying mutually of rare gas element:
Composite grain after cryodrying fluiddized-bed roasting is conveyed into high-temperature roasting circulating fluidized bed with the nitrogen after empty point;
C, material particles is carried out to high-temperature roasting:
Adopt high-temperature roasting alumina system, the close material particles transporting mutually after cryodrying roasting is carried out to circulating fluidized bed high-temperature roasting, maturing temperature is 400 DEG C, and roasting time is 20 minutes, finally generates grog;
In described high-temperature roasting alumina system, the outlet of roasting circulation spouting bed bodies top is fixedly connected with the second cyclonic separator top one side; Roasting circulation spouting bed burner can be installed and roasting circulating fluidized bed air compartment front side or roasting circulation spouting bed body bottom; The second cyclonic separator bottom is fixedly connected with the second feeding back device one side, and the second feeding back device opposite side is fixedly connected with roasting circulation spouting bed body bottom; One side on the second efficient cyclone separator top is fixedly connected with the second cyclonic separator top exit, top exit is connected with exhaust-heat boiler flue gas import, exhaust-heat boiler flue gas outlet connects the second sack cleaner one side, another side joint second air preheater one side of the second sack cleaner, the second air preheater opposite side connects the second soda-wash tower bottom, the second soda-wash tower top is connected with the second induced draft fan entrance, and the second induced draft fan outlet connects chimney; The second burner blower is connected with the second air preheater gas inlet, and the second air preheater air vout is connected with roasting circulating fluidized bed air compartment; The second feeding back device isocon is connected with multistage cross flow boiling cooling bed heat material entrance, and the second efficient cyclone separator, waste heat boiler and the second sack cleaner bottom are all connected with multistage cross flow boiling cooling bed heat material entrance; Cooling blower is connected with multistage cross flow boiling cooling bed bottom, and multistage cross flow boiling cooling bed top is connected with roasting circulation spouting bed body bottom or exhaust-heat boiler inlet;
Roasting process has experienced following reaction:
Al 2O 3 ＋4(NH 4) 2SO 4＝2NH 4 Al（SO 4） 2＋6 NH 3↑＋3H 2O
Al 2O 3 ＋3(NH 4) 2SO 4＝Al 2（SO 4） 3＋6 NH 3↑＋3H 2O
Fe 2O 3＋4(NH 4) 2SO 4＝2NH 4 Fe（SO 4） 2＋6 NH 3↑＋3H 2O
Fe 2O 3＋3(NH 4) 2SO 4＝Fe 2（SO 4） 3＋6 NH 3↑＋3H 2O
(NH 4) 2SO 4 → SO 3↑＋NH 3↑
Step 3: the grog water producing after roasting carries out the stripping of material at 120 DEG C of temperature, filters, and filtrate is NH 4al(SO 4) 2thick liquid, filter residue main component is silicon-dioxide;
Step 4: NH 4al(SO 4) 2thick liquid, after removal of impurities, obtains NH 4al(SO 4) 2seminal fluid;
Step 5: NH 4al(SO 4) 2seminal fluid adds 17% ammoniacal liquor, and the heavy reaction of ammonia occurs:
NH 4 Al（SO 4） 2＋3 NH 3＋3H 2O＝Al（OH） 3↓＋2（NH 4） 2SO 4
Ammoniacal liquor is absorbed the ammonia gained discharging in calcination process by water;
Step 6: the throw out Al(OH that step 5 is obtained) 3particle carries out circulating fluidized bed high-temperature roasting, and maturing temperature is 1100 DEG C, and roasting time is 20 minutes, finally generates metallurgical-grade aluminum oxide.
In step 4, described impurity-removing method can adopt film to analyse acid system co-precipitation method, is realized by following steps:
A, extract from treat removal of impurities filtrate based on film dialysis acid:
System pH reaches at 2.0 o'clock, and iron is separated out with ferric hydroxide precipitate; System pH reaches at 3.7 o'clock, has precipitated one-level dialysis, carries out solid-liquid separation thereupon, removes ironic hydroxide, continues to propose acid with film dialysis; System pH reaches at 3.8 o'clock, and aluminium is separated out with aluminum hydroxide precipitation; System pH reaches at 4.8 o'clock, and precipitation all completes, and continuously dialysis, until acid is all extracted, completes secondary dialysis, carries out solid-liquid separation thereupon, collects aluminum hydroxide precipitation, and other impurity is all retained in solution and is removed.
Ammoniumsulphate soln after step 5 is filtered carries out after condensing crystal, and the ammonium sulfate of recovery loops utilization, starts to reuse from step 1.
Embodiment 4:
Step 1: the ratio that is 1:10 in flyash and ammonium sulfate mol ratio adds ammonium sulfate in flyash; The ratio that is 1:0.35 in flyash and propping agent mass ratio again, adds propping agent; Mixing granulation, the granularity of ball-type composite grain is diameter 0.5～10mm;
Described propping agent is mixed by the mass ratio of 1:2 by two kinds of components, and component one is selected from metal oxide (being selected from aluminum oxide, sodium oxide, magnesium oxide etc.), and component two is white residue;
Step 2: particle is carried out to the roasting of two-part fluosolids roasting system:
A, granulation is carried out to cryodrying roasting:
Adopt low temperature drying system, granulation is carried out to cryodrying roasting, maturing temperature is 220 DEG C, and roasting time is 30 minutes, removes the free-water of particle surface;
In described low temperature drying system, low-temperature bake fluidized-bed body bottom connects low-temperature bake fluidized-bed air compartment, and bottom is fixedly connected with feed bin and feeding device, and top exit is fixedly connected with the first cyclonic separator top one side; Low-temperature bake fluidized bed combustor is installed on low-temperature bake fluidized-bed air compartment front side or low-temperature bake fluidized-bed body bottom; The first cyclonic separator bottom is fixedly connected with the first feeding back device one side, and the first feeding back device opposite side is fixedly connected with low-temperature bake fluidized-bed body bottom; One side on the first efficient cyclone separator top is fixedly connected with the first cyclonic separator top exit, and top exit is connected with the first air preheater one side, grog storehouse in the middle of outlet at bottom connects; The first air preheater opposite side connects the first sack cleaner one side, and the first sack cleaner opposite side is connected into ammonia absorption system;
B, the close conveying mutually of rare gas element:
Composite grain after cryodrying fluiddized-bed roasting is conveyed into high-temperature roasting circulating fluidized bed with the nitrogen after empty point;
C, material particles is carried out to high-temperature roasting:
Adopt high-temperature roasting alumina system, the close material particles transporting mutually after cryodrying roasting is carried out to circulating fluidized bed high-temperature roasting, maturing temperature is 800 DEG C, and roasting time is 30 minutes, finally generates grog;
In described high-temperature roasting alumina system, the outlet of roasting circulation spouting bed bodies top is fixedly connected with the second cyclonic separator top one side; Roasting circulation spouting bed burner can be installed and roasting circulating fluidized bed air compartment front side or roasting circulation spouting bed body bottom; The second cyclonic separator bottom is fixedly connected with the second feeding back device one side, and the second feeding back device opposite side is fixedly connected with roasting circulation spouting bed body bottom; One side on the second efficient cyclone separator top is fixedly connected with the second cyclonic separator top exit, top exit is connected with exhaust-heat boiler flue gas import, exhaust-heat boiler flue gas outlet connects the second sack cleaner one side, another side joint second air preheater one side of the second sack cleaner, the second air preheater opposite side connects the second soda-wash tower bottom, the second soda-wash tower top is connected with the second induced draft fan entrance, and the second induced draft fan outlet connects chimney; The second burner blower is connected with the second air preheater gas inlet, and the second air preheater air vout is connected with roasting circulating fluidized bed air compartment; The second feeding back device isocon is connected with multistage cross flow boiling cooling bed heat material entrance, and the second efficient cyclone separator, waste heat boiler and the second sack cleaner bottom are all connected with multistage cross flow boiling cooling bed heat material entrance; Cooling blower is connected with multistage cross flow boiling cooling bed bottom, and multistage cross flow boiling cooling bed top is connected with roasting circulation spouting bed body bottom or exhaust-heat boiler inlet;
Roasting process has experienced following reaction:
Al 2O 3 ＋4(NH 4) 2SO 4＝2NH 4 Al（SO 4） 2＋6 NH 3↑＋3H 2O
Al 2O 3 ＋3(NH 4) 2SO 4＝Al 2（SO 4） 3＋6 NH 3↑＋3H 2O
Fe 2O 3＋4(NH 4) 2SO 4＝2NH 4 Fe（SO 4） 2＋6 NH 3↑＋3H 2O
Fe 2O 3＋3(NH 4) 2SO 4＝Fe 2（SO 4） 3＋6 NH 3↑＋3H 2O
(NH 4) 2SO 4 → SO 3↑＋NH 3↑
Step 3: the grog water producing after roasting carries out the stripping of material at 160 DEG C of temperature, filters, and filtrate is NH 4al(SO 4) 2thick liquid, filter residue main component is silicon-dioxide;
Step 4: NH 4al(SO 4) 2thick liquid, after removal of impurities, obtains NH 4al(SO 4) 2seminal fluid;
Step 5: NH 4al(SO 4) 2seminal fluid adds 25% ammoniacal liquor, and the heavy reaction of ammonia occurs:
NH 4 Al（SO 4） 2＋3 NH 3＋3H 2O＝Al（OH） 3↓＋2（NH 4） 2SO 4
Ammoniacal liquor is absorbed the ammonia gained discharging in calcination process by water;
Step 6: the throw out Al(OH that step 5 is obtained) 3particle carries out circulating fluidized bed high-temperature roasting, and maturing temperature is 1100 DEG C, and roasting time is 30 minutes, finally generates metallurgical-grade aluminum oxide.
In step 4, described impurity-removing method can adopt sorption-coprecipitation method, is realized by following steps:
In the acidic solution that is 1.6 in pH value, add potassium permanganate solution and manganese sulfate solution, Fe 2+be oxidized to Fe 3+after, be to be hydrolyzed for 2.0 o'clock in pH value, the Fe(OH of generation) 3with react newly-generated active MnO 2form immediately brown coprecipitate, remove impurity iron.
Or sedimentation method combined resin method, realized by following steps:
A, to add organic precipitant oxalic acid or citric acid, massfraction be 5%～100%, and add-on is for to be as the criterion with point of equivalent, and part is removed calcium, magnesium, iron contamination;
B, add resin again, carry out deep impurity-removing based on ion-exchange, the degree of depth is removed calcium, magnesium, iron contamination.
Ammoniumsulphate soln after step 5 is filtered carries out after condensing crystal, and the ammonium sulfate of recovery loops utilization, starts to reuse from step 1.
It is cited that content of the present invention is not limited to embodiment, and the conversion of any equivalence that those of ordinary skill in the art take technical solution of the present invention by reading specification sheets of the present invention, is claim of the present invention and contains.

Claims (3)

1. the method for extracting aluminum oxide based on ammonium sulfate method from flyash, is characterized in that:
Realized by following steps:
Step 1: be 1:(5～10 in flyash and ammonium sulfate mol ratio) ratio, in flyash, add ammonium sulfate; Be 1:(0.05～0.35 in flyash and propping agent mass ratio again) ratio, add propping agent; Mixing granulation, the granularity of ball-type composite grain is diameter 0.5～10mm;
Described propping agent by two kinds of components by 1:(0.5～2) mass ratio mix, component one is selected from the one in cement, yellow mud, water glass, wilkinite, phosphoric acid salt, exsiccated ammonium alum, metal oxide, and component two is selected from the one in roasting grog, the white residue of vitriol, ammonium sulfate and flyash;
Step 2: particle is carried out to the roasting of two-part fluosolids roasting system:
A, granulation is carried out to cryodrying roasting:
Adopt low temperature drying system, granulation is carried out to cryodrying roasting, maturing temperature is 60～220 DEG C, and roasting time is 3 seconds～30 minutes, removes the free-water of particle surface;
In described low temperature drying system, low-temperature bake fluidized-bed body bottom connects low-temperature bake fluidized-bed air compartment, and bottom is fixedly connected with feed bin and feeding device, and top exit is fixedly connected with the first cyclonic separator top one side; Low-temperature bake fluidized bed combustor is installed on low-temperature bake fluidized-bed air compartment front side or low-temperature bake fluidized-bed body bottom; The first cyclonic separator bottom is fixedly connected with the first feeding back device one side, and the first feeding back device opposite side is fixedly connected with low-temperature bake fluidized-bed body bottom; One side on the first efficient cyclone separator top is fixedly connected with the first cyclonic separator top exit, and top exit is connected with the first air preheater one side, grog storehouse in the middle of outlet at bottom connects; The first air preheater opposite side connects the first sack cleaner one side, and the first sack cleaner opposite side is connected into ammonia absorption system;
B, the close conveying mutually of rare gas element:
Composite grain after cryodrying fluiddized-bed roasting is conveyed into high-temperature roasting circulating fluidized bed with the nitrogen after empty point;
C, material particles is carried out to high-temperature roasting:
Adopt high-temperature roasting alumina system, the close material particles transporting mutually after cryodrying roasting is carried out to circulating fluidized bed high-temperature roasting, maturing temperature is 80～800 DEG C, and roasting time is 3 seconds～30 minutes, finally generates grog;
In described high-temperature roasting alumina system, the outlet of roasting circulation spouting bed bodies top is fixedly connected with the second cyclonic separator top one side; Roasting circulation spouting bed burner can be installed and roasting circulating fluidized bed air compartment front side or roasting circulation spouting bed body bottom; The second cyclonic separator bottom is fixedly connected with the second feeding back device one side, and the second feeding back device opposite side is fixedly connected with roasting circulation spouting bed body bottom; One side on the second efficient cyclone separator top is fixedly connected with the second cyclonic separator top exit, top exit is connected with exhaust-heat boiler flue gas import, exhaust-heat boiler flue gas outlet connects the second sack cleaner one side, another side joint second air preheater one side of the second sack cleaner, the second air preheater opposite side connects the second soda-wash tower bottom, the second soda-wash tower top is connected with the second induced draft fan entrance, and the second induced draft fan outlet connects chimney; The second burner blower is connected with the second air preheater gas inlet, and the second air preheater air vout is connected with roasting circulating fluidized bed air compartment; The second feeding back device isocon is connected with multistage cross flow boiling cooling bed heat material entrance, and the second efficient cyclone separator, waste heat boiler and the second sack cleaner bottom are all connected with multistage cross flow boiling cooling bed heat material entrance; Cooling blower is connected with multistage cross flow boiling cooling bed bottom, and multistage cross flow boiling cooling bed top is connected with roasting circulation spouting bed body bottom or exhaust-heat boiler inlet;
Roasting process has experienced following reaction:
Al 2O 3 ＋4(NH 4) 2SO 4＝2NH 4 Al（SO 4） 2＋6 NH 3↑＋3H 2O
Al 2O 3 ＋3(NH 4) 2SO 4＝Al 2（SO 4） 3＋6 NH 3↑＋3H 2O
Fe 2O 3＋4(NH 4) 2SO 4＝2NH 4 Fe（SO 4） 2＋6 NH 3↑＋3H 2O
Fe 2O 3＋3(NH 4) 2SO 4＝Fe 2（SO 4） 3＋6 NH 3↑＋3H 2O
(NH 4) 2SO 4 → SO 3↑＋NH 3↑
Step 3: the grog water producing after roasting carries out the stripping of material at 60～160 DEG C of temperature, filters, and filtrate is NH 4al(SO 4) 2thick liquid, filter residue main component is silicon-dioxide;
Step 4: NH 4al(SO 4) 2thick liquid, after removal of impurities, obtains NH 4al(SO 4) 2seminal fluid;
Step 5: NH 4al(SO 4) 2seminal fluid adds 3～25% ammoniacal liquor, and the heavy reaction of ammonia occurs:
NH 4 Al（SO 4） 2＋3 NH 3＋3H 2O＝Al（OH） 3↓＋2（NH 4） 2SO 4
Ammoniacal liquor is absorbed the ammonia gained discharging in calcination process by water;
Step 6: the throw out Al(OH that step 5 is obtained) 3particle carries out circulating fluidized bed high-temperature roasting, and maturing temperature is 1100 DEG C, and roasting time is 3 seconds～30 minutes, finally generates metallurgical-grade aluminum oxide.
2. the method for extracting aluminum oxide based on ammonium sulfate method from flyash according to claim 1, is characterized in that:
In step 4, described impurity-removing method is selected from:
Method one: crystallization-recrystallization method, realized by following steps:
Treat at room temperature stirred crystallization of removal of impurities filtrate, crystal is reheated in distilled water to dissolving, crystallisation by cooling, after filtering separation, can make most of foreign ion again be shunted in liquid phase, thereby reach the object of purified crystals;
Means re-crystallization is that the water that crystal is 1:4 with mass ratio mixes, and is heated to 98 DEG C of dissolution of crystals;
Method two: sedimentation method combined extraction process, realized by following steps:
A, to add organic precipitant oxalic acid or citric acid, massfraction be 5%～100%, and add-on is for to be as the criterion with point of equivalent, and part is removed calcium, magnesium, iron contamination;
B, to add organic extractant P204, massfraction be again 50%, and add-on is to treat that the mass ratio of removal of impurities filtrate and extraction agent is 1:(0.3～2), the degree of depth is removed calcium, magnesium, iron contamination;
Method three: film is analysed acid system co-precipitation method, is realized by following steps:
A, extract from treat removal of impurities filtrate based on film dialysis acid:
System pH reaches at 2.0 o'clock, and iron is separated out with ferric hydroxide precipitate; System pH reaches at 3.7 o'clock, has precipitated one-level dialysis, carries out solid-liquid separation thereupon, removes ironic hydroxide, continues to propose acid with film dialysis; System pH reaches at 3.8 o'clock, and aluminium is separated out with aluminum hydroxide precipitation; System pH reaches at 4.8 o'clock, and precipitation all completes, and continuously dialysis, until acid is all extracted, completes secondary dialysis, carries out solid-liquid separation thereupon, collects aluminum hydroxide precipitation, and other impurity is all retained in solution and is removed;
Method four: sorption-coprecipitation method, is realized by following steps:
In the acidic solution that is 1.6 in pH value, add potassium permanganate solution and manganese sulfate solution, Fe 2+be oxidized to Fe 3+after, be to be hydrolyzed for 2.0 o'clock in pH value, the Fe(OH of generation) 3with react newly-generated active MnO 2form immediately brown coprecipitate, remove impurity iron;
Method five: sedimentation method combined resin method, realized by following steps:
A, to add organic precipitant oxalic acid or citric acid, massfraction be 5%～100%, and add-on is for to be as the criterion with point of equivalent, and part is removed calcium, magnesium, iron contamination;
B, add resin again, carry out deep impurity-removing based on ion-exchange, the degree of depth is removed calcium, magnesium, iron contamination.
3. the method for extracting aluminum oxide based on ammonium sulfate method from flyash according to claim 1 and 2, is characterized in that:
Ammoniumsulphate soln after step 5 is filtered carries out after condensing crystal, and the ammonium sulfate of recovery loops utilization, starts to reuse from step 1.
CN201410390312.8A 2014-08-11 2014-08-11 From flyash, the method for aluminum oxide is extracted based on ammonium sulfate method Active CN104150515B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410390312.8A CN104150515B (en) 2014-08-11 2014-08-11 From flyash, the method for aluminum oxide is extracted based on ammonium sulfate method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410390312.8A CN104150515B (en) 2014-08-11 2014-08-11 From flyash, the method for aluminum oxide is extracted based on ammonium sulfate method

Publications (2)

Publication Number Publication Date
CN104150515A true CN104150515A (en) 2014-11-19
CN104150515B CN104150515B (en) 2015-08-26

Family

ID=51876186

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410390312.8A Active CN104150515B (en) 2014-08-11 2014-08-11 From flyash, the method for aluminum oxide is extracted based on ammonium sulfate method

Country Status (1)

Country Link
CN (1) CN104150515B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106495193A (en) * 2016-10-31 2017-03-15 航天推进技术研究院 Based on the method that ethanol auxiliary agent extracts aluminum oxide in flyash using ammonium sulfate method
CN114644928A (en) * 2022-04-12 2022-06-21 中国环境科学研究院 Process for producing and processing soil conditioner by taking fly ash as raw material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0731957A (en) * 1993-07-16 1995-02-03 Hideo Tomoyasu Method for recycling collected ash of petroleum combustion boiler
CN102583468A (en) * 2012-03-08 2012-07-18 航天推进技术研究院 Method for extracting aluminum oxide from fly ash based on ammonium sulfate activation process
CN202369408U (en) * 2011-10-26 2012-08-08 北京航天动力研究所 Clinkering-free multistage differential temperature fluidized roasting system for crystal aluminum salt
CN103086412A (en) * 2013-02-28 2013-05-08 山东科院天力节能工程有限公司 Method for extracting alumina through coal ash
CN103449483A (en) * 2012-05-29 2013-12-18 西安航天动力试验技术研究所 Impurity removing method in process of preparing alumina from fly ash by utilizing acid method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0731957A (en) * 1993-07-16 1995-02-03 Hideo Tomoyasu Method for recycling collected ash of petroleum combustion boiler
CN202369408U (en) * 2011-10-26 2012-08-08 北京航天动力研究所 Clinkering-free multistage differential temperature fluidized roasting system for crystal aluminum salt
CN102583468A (en) * 2012-03-08 2012-07-18 航天推进技术研究院 Method for extracting aluminum oxide from fly ash based on ammonium sulfate activation process
CN103449483A (en) * 2012-05-29 2013-12-18 西安航天动力试验技术研究所 Impurity removing method in process of preparing alumina from fly ash by utilizing acid method
CN103086412A (en) * 2013-02-28 2013-05-08 山东科院天力节能工程有限公司 Method for extracting alumina through coal ash

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
晋新亮等: "硫酸铵焙烧法提取粉煤灰中氧化铝的工艺技术研究", 《非金属矿》 *
李来时等: "以粉煤灰为原料制备高纯氧化铝", 《化工学报》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106495193A (en) * 2016-10-31 2017-03-15 航天推进技术研究院 Based on the method that ethanol auxiliary agent extracts aluminum oxide in flyash using ammonium sulfate method
CN114644928A (en) * 2022-04-12 2022-06-21 中国环境科学研究院 Process for producing and processing soil conditioner by taking fly ash as raw material

Also Published As

Publication number Publication date
CN104150515B (en) 2015-08-26

Similar Documents

Publication Publication Date Title
CN102583468B (en) From flyash, the method for aluminum oxide is extracted based on ammonium sulfate activation process
CN103146930B (en) Method for preparing vanadium oxide
CN101775505B (en) Method and device for extracting lithium from lapidolite by chloridizing roasting method
CN102698737B (en) Method for preparing selective catalytic reduction SCR flue gas denitration catalyst and method for preparing raw material titanium-tungsten powder of SCR flue gas denitration catalyst
CN106477609B (en) Method for producing alumina by coal ash sulfuric acid curing
CN104445313B (en) Method for extracting aluminum oxide from fly ash by acid-base combination
CN108480360A (en) Novel method for recycling fly ash resources and discharging tail gas in ultra-clean mode by adopting rotary kiln melting method
CN104445312B (en) Method for extracting aluminum oxide by synergistic treatment of fly ash and coal gangue
CN106048230B (en) The separation of tungsten and vanadium, recovery method in a kind of useless SCR denitration
CN113479920B (en) Aluminum ash resource utilization method
JP6371015B2 (en) Purification system and method for divanadium pentoxide
CN104495899A (en) Method for synergic resource utilization of acetylene sludge and coal ash
CN104649306A (en) Method for extracting aluminium oxide from coal ash
CN105779757A (en) Method for leaching extracted vanadium from vanadium-containing raw material roasted clinker through ammonium oxalate
CN103466661B (en) One kind utilizes potassium feldspar calcium sulfate mineralising CO2The method of co-producing sulfuric acid potassium
CN105385844B (en) One kind roasting defluorinate device and technique
CN109573955B (en) Device and process for preparing sulfur and recovering desulfurizer through sulfate carbon thermal reduction
CN103011272A (en) Method for concentrating and purifying titanium dioxide waste acid by using complex acid
CN103290217B (en) Technology for extracting lithium by processing lithium ores through high-pressure steaming process
CN104817099A (en) Improved method for extracting alkali metal compound from solid fluorine reconstruction lepidolite
CN105648226A (en) Method for separating antimony from arsenic in antimony-arsenic soot
CN103159263B (en) Treatment method of artificial rutile mother solution
US11292718B2 (en) Process for preparing sulfur from reduction of sulfate/ nitrate by iron-carbon and recovering desulfurization/ denitration agents
CN102101686B (en) Process method for ultra-high purity alumina preparation by utilizing coal ash and comprehensive utilization of ultra-high purity alumina
CN104150515B (en) From flyash, the method for aluminum oxide is extracted based on ammonium sulfate method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C41 Transfer of patent application or patent right or utility model
CB03 Change of inventor or designer information

Inventor after: Zeng Wei

Inventor after: Gao Xuan

Inventor after: Wang Hui

Inventor after: Li Ning

Inventor after: Wang Huining

Inventor after: Liu Sheng

Inventor after: Ding Jianliang

Inventor after: Guo Zhaohua

Inventor after: Liang Xingguo

Inventor after: Guo Xinfeng

Inventor after: Zhang Xiaodong

Inventor after: Qian Yongkang

Inventor after: Guo Kun

Inventor after: Tu Ya

Inventor after: Yang Chao

Inventor before: Zeng Wei

Inventor before: Wang Huining

Inventor before: Liu Sheng

Inventor before: Ding Jianliang

Inventor before: Guo Xinfeng

Inventor before: Liang Xingguo

Inventor before: Qian Yongkang

Inventor before: Guo Kun

Inventor before: Yang Chao

Inventor before: Gao Xuan

Inventor before: Wang Hui

Inventor before: Li Ning

COR Change of bibliographic data
TR01 Transfer of patent right

Effective date of registration: 20161122

Address after: 100011 Beijing, Dongcheng District Anwai Binhe West Road No. 22 Shenhua building

Patentee after: China Shenhua Energy Co., Ltd.

Patentee after: Zhun Neng resource synthetic development Co., Ltd of Shenhua

Patentee after: Academy of Aerospace Propulsion Technology

Address before: 710100 Shaanxi city of Xi'an province No. 67 West Southern Aerospace Aerospace base

Patentee before: Academy of Aerospace Propulsion Technology