CN109111958A - A kind of method that catalytic gasification coupled gasification ash extracts aluminium oxide - Google Patents

A kind of method that catalytic gasification coupled gasification ash extracts aluminium oxide Download PDF

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CN109111958A
CN109111958A CN201811062978.5A CN201811062978A CN109111958A CN 109111958 A CN109111958 A CN 109111958A CN 201811062978 A CN201811062978 A CN 201811062978A CN 109111958 A CN109111958 A CN 109111958A
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desiliconization
aluminium
residue
catalytic gasification
ash
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王志青
梅艳钢
黄戒介
房倚天
张永奇
宋双双
李莉
李翔宇
聂伟
余中亮
刘哲语
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
    • C01F7/141—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent
    • C01F7/142—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent with carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/20—Preparation of aluminium oxide or hydroxide from aluminous ores using acids or salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
    • C01F7/441—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by calcination
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/093—Coal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0983—Additives
    • C10J2300/0986—Catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1625—Integration of gasification processes with another plant or parts within the plant with solids treatment

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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Inorganic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
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Abstract

A kind of method that catalytic gasification coupled gasification ash extracts aluminium oxide is by high alumina coal and the catalyst containing Na or K, the mixing of catalyst containing Ca, the high alumina fine coal of supported catalyst is obtained after mixing, the high alumina fine coal of supported catalyst is at high temperature after catalytic gasification, obtain catalytic gasification ash, by directly leaching to obtain crude liquid containing aluminium and Al leaching residue, crude liquid containing aluminium by desiliconization obtain after desiliconization containing aluminum solutions and desiliconization residue, carbon point is carried out containing aluminum solutions after desiliconization, using filter, washing prepares aluminium hydroxide and alkali metal carbonate solution, Al leaches residue and desiliconization residue carries out high temperature hydro-thermal reaction dealkalize metal, recycle catalyst.The present invention have low energy consumption, advantage at low cost.

Description

A kind of method that catalytic gasification coupled gasification ash extracts aluminium oxide
Technical field
The invention belongs to the comprehensive utilizations of coal ash, and in particular to a kind of catalytic gasification coupled gasification ash extracts the side of aluminium oxide Method.
Background technique
Main aluminum-containing mineral matter is kaolinite (Al in high alumina coal2O3·2SiO2·2H2O) and boehmite (AlOOH), as Potential aluminium oxide supplier and bauxite replacer, extracting aluminium oxide from coal ash can be realized the resource utilization of coal ash, Greatly reduce coal ash simultaneously to the potential hazard of environment, thus, extracting aluminium oxide from coal ash is of great significance, and just becomes more The research emphasis of family R&D institution and enterprise.
The technique of the aluminium oxide of coal ash extraction at present is more, is broadly divided into acid system, alkaline process and calcination activation method.But mainly with combustion Coal-fired plant's combustion ash is raw material, in combustion process, the poor mullite of Al minerals generation of reactive after high temperature in coal, just Beautiful substance needs strong acid, soda acid to clear up under high temperature and pressure, or by activator high-temperature roasting activate after be just able to achieve compared with The leaching rate of high Al causes energy consumption and cost high.And during catalytic gasification, the base metal catalysts of addition can be with Aluminum silicon mineral qualitative response in coal generates reactivity relatively high alumino-silicate and nepheline class compound, makes the leaching of Al Relatively easily.Therefore extracting aluminium oxide using catalytic gasification ash has certain advantage.Based on this, limited public affairs are developed in New Austrian Science Department develops the patent of a kind of coal ash extraction aluminium oxide (103351014 A of CN) and aluminum contained compound (103349994 A of CN), Catalytic gasification ash is by water-soluble recovery section catalyst, then alkaline-earth metal Ca is added into residue, is soaked after roasting by aqueous slkali Take the leaching for realizing Al.The technique extracts aluminium oxide relative to traditional combustion ash and has a clear superiority, but the technique still needs Alkaline-earth metal Ca is added into catalyst recycling residue, and needs just to be able to achieve after high-temperature roasting the recycling of Al, there is roasting temperature Degree is high, and energy consumption is high, disadvantage at high cost.A kind of low energy consumption is thus developed, environmental-friendly coal ash, which extracts aluminium oxide method, to be had Significance.
Summary of the invention
It is an object of the present invention to provide one kind, low energy consumption, and catalytic gasification coupled gasification ash at low cost extracts the side of aluminium oxide Method.
The technical solution adopted by the present invention is that: the high alumina coal of carrying alkali metal Na, K and alkaline-earth metal Ca are catalyzed at high temperature The activation process of ash is completed in gasification while gasification, obtains the catalytic gasification ash of activated mistake, the catalytic gasification ash after activation Without further activating, water, diluted alkaline, dilute Na can be passed through2CO3Solution, which directly leaches, obtains crude liquid containing aluminium, then passes through addition Ca (OH)2Aluminum hydroxide product is obtained after desiliconization, carbon point, filtering, the residue and desiliconization residue after aluminium leaching are anti-by high temperature hydro-thermal It answers, alkali metal leaches into solution, realizes base metal catalysts recycling.
The present invention is a kind of method that catalytic gasification coupled gasification ash extracts aluminium oxide, is included the following steps:
(a) high alumina coal is mixed with containing Na or K catalyst, catalyst containing Ca, the high alumina fine coal of supported catalyst is obtained after mixing, The high alumina fine coal of supported catalyst after catalytic gasification, obtains catalytic gasification ash at high temperature；
(b) catalytic gasification ash obtains crude liquid containing aluminium by directly leaching and Al leaches residue；
(c) crude liquid containing aluminium by desiliconization obtain after desiliconization containing carrying out carbon containing aluminum solutions after aluminum solutions and desiliconization residue, desiliconization Divide, prepare aluminium hydroxide and alkali metal carbonate solution using filter, washing, Aluminium hydroxide roasting obtains aluminium oxide；
(d) Al leaches residue and desiliconization residue carries out high temperature hydro-thermal reaction dealkalize metal, recycles catalyst.
In the step (a) containing Na or K catalyst be Na, K alkali or carbonate.Catalyst containing Ca is Ca (OH)2、CaO Or CaCO3。
Na or karat gold category load capacity are 0.8-1.6 times of coal ash weight in the step (a), are 1.1- with Ca/Si mass ratio 2.2 addition metal Ca, Si is Si contained in high alumina coal.
In the step (a) the main group of catalytic gasification ash become meta-aluminate, aluminate, low silica-alumina ratio alumino-silicate, Calcium silicates etc..
Technical solutions according to the invention step (b) are as follows:
Catalytic gasification ash consolidates mass ratio 10-100 by liquid, and passing through concentration at 40-150 DEG C is 0-5wt % (being water when 0%) NaOH Or Na2CO3After water-soluble liquid leaching 0.2-2 h, crude liquid containing aluminium is obtained by filtration and aluminium leaches residue.
Technical solutions according to the invention step (c) are as follows:
The desiliconization of the crude liquid containing aluminium is addition Ca (OH) into crude liquid containing aluminium20.5-2 h is mixed at 40-150 DEG C for emulsion Afterwards, contain aluminum solutions and desiliconization residue, desiliconization process Ca (OH) after desiliconization is obtained by filtration2Additive amount be crude liquid containing aluminium in Si matter 2.6-3.9 times of amount.
Technical solutions according to the invention step (c) are as follows:
Carbon point is to be passed through CO to containing aluminum solutions2, carbon divides process CO2Intake is 2-8 times of alkali metal molar content in solution, carbon Dividing temperature is 30-80 DEG C, and constant temperature keeps 0.5-2 h after carbon point.Using filter, washing after obtain aluminum hydroxide product, it is resulting Filtrate obtains alkali carbonate after heating, concentration, crystallization.
Technical solutions according to the invention step (d) are as follows:
The desiliconization residue that the aluminium that step (b) generates leaches residue and step (c) generation is consolidated into mass ratio 10-100 by liquid, in 150- At 250 DEG C with water after high temperature hydro-thermal reaction 2-20 h, the filtrate being obtained by filtration concentration, crystallization after carbonating obtain alkali gold Belong to carbonate.
The method that the catalytic gasification coupled gasification ash extracts aluminium oxide is different from traditional combustion ash and extracts aluminium oxide, is Catalytic gasification ash is subjected to alumina extraction.
The method that the catalytic gasification coupled gasification ash extracts aluminium oxide, is the leaching that catalytic gasification ash is first carried out to Al Out, then the recycling of catalyst is carried out.
The method that the catalytic gasification coupled gasification ash extracts aluminium oxide is the leaching that catalytic gasification ash is directly carried out to Al Out, it is not necessarily to calcination activation process.
The base metal catalysts recycling realizes that crude liquid containing aluminium is by carbonating, being recovered by filtration in step (c) in two steps Partial alkaline-metal catalyst leaches remaining alkali metal in residue by high temperature hydro-thermal dealkalize metal recovery Al in step (d) and urges Agent.
Advantages of the present invention is as follows with technical effect:
1, aluminium oxide is extracted from coal ash compared to traditional soda lime roasting method, which completes aluminium during catalytic gasification The directly leaching of catalytic gasification ash is activated and used, saves high-temperature roasting activation process, low energy consumption, profitable；
2, process and high temperature hydro-thermal reaction alkali metal is divided to leach in carbon, alum recovery while realizes catalytic gasification base metal catalysts Recycling reduces the cost recovery of catalytic gasification catalyst；
3, using catalytic gasification ash as alumina raw material is extracted, the resource utilization of catalytic gasification ash is realized.
Technical solution provided by the invention extracts aluminium oxide from the resource utilization of coal ash, by catalytic gasification and coal ash It is coupled, the activation of Al in coal is completed during catalytic gasification, promotes the dissolution of Al；It is extracted in alumina process in coal ash Complete the recycling of catalyst in coal ash.Catalytic gasification coupling alumina extraction is the roasting process for saving coal ash and extracting aluminium oxide, The energy consumption that coal ash extracts aluminium oxide is reduced, and promotes the recycling of catalytic gasification catalyst, catalytic gasification and coal can be reduced simultaneously Ash extracts the cost of aluminium oxide, has good industrial applications prospect.
Specific embodiment
The present invention is described in further details below by embodiment, but invention protection scope do not limit to it is described interior Hold.
The minerals composition of 1 grandson family of table person of outstanding talent's coal ash
Grandson family's person of outstanding talent's coal Al2O3 SiO2 Fe2O3 TiO2 CaO MgO Na2O SO3 K2O P2O5
Form wt% 46.34 36.29 6.38 3.57 2.61 2.18 0.76 0.45 0.42 0.03
Embodiment 1: the present embodiment is using the bold and unconstrained high alumina coal of grandson family as raw material, with Na2CO3With Ca (OH)2For catalyst, urge at high temperature Change gasification, obtains catalytic gasification ash, catalytic gasification ash obtains crude liquid containing aluminium by water extraction, then passes through addition Ca (OH)2Desiliconization, Aluminum hydroxide product is obtained by filtration in carbon point, and the residue after aluminium leaching is leached into desiliconization residue by high temperature hydro-thermal reaction Na molten Liquid, Na2CO3Catalyst realizes recycling.
Specific step is as follows:
(1) generation of catalyst load and catalytic gasification ash: with Na2CO3It is that 0.8, Ca/Si mass ratio is with coal ash mass ratio 1.6, by the bold and unconstrained high alumina coal of grandson family, Na2CO3、Ca(OH)2Catalyst load is carried out, obtains the height of supported catalyst after ball mill mixing Aluminium powder coal.The high alumina fine coal of supported catalyst obtains catalytic gasification ash after 1200 DEG C of catalytic gasifications.
(2) it the leaching of the crude liquid containing aluminium: obtains catalytic gasification ash to consolidate mass ratio by liquid being 100,40 DEG C by 0.2 h of water extraction Afterwards, crude liquid containing aluminium is obtained by filtration and aluminium leaches residue.
(3) desiliconization of the crude liquid containing aluminium: with Ca (OH)2/ Si mass ratio is 3.9 additions Ca (OH) into crude liquid containing aluminium2Milkiness Liquid after 1 h is mixed at 60 DEG C, contains aluminum solutions and desiliconization residue after desiliconization is obtained by filtration.
(4) carbon point, be filtered, washed and prepare aluminium hydroxide: be passed through excessive CO to containing aluminum solutions2, intake be Na moles contain 5 times of amount obtain aluminum hydroxide product after 60 DEG C of 1 h of constant temperature after being filtered, washed.Resulting filtrate is by heating, concentration, knot Na is obtained after crystalline substance2CO3。
(5) aluminium leaches residue and desiliconization residue high temperature hydro-thermal removes Na: the aluminium that step (2) are generated leaches residue and step (3) it is 100 that the desiliconization residue generated, which consolidates mass ratio by liquid, at 200 DEG C after high temperature hydro-thermal reaction 20h, filters resulting filter Liquid concentration, crystallization after carbonating obtain Na2CO3.It obtains aluminium hydroxide and roasts at 1200 DEG C to obtain aluminium oxide, aluminium oxide Effective content is 92.4%, and the leaching rate of aluminium is 84.7%, and the rate of recovery of catalyst n a is 88.6%.
Embodiment 2: the present embodiment is catalysis with NaOH and CaO using the bold and unconstrained high alumina coal of grandson family as raw material (forming same embodiment 1) Agent, catalytic gasification, obtains catalytic gasification ash at high temperature, and catalytic gasification ash leaches to obtain thick containing aluminium by 5 wt% NaOH solutions Liquid, then pass through addition Ca (OH)2Aluminum hydroxide product is obtained by filtration in desiliconization, carbon point, and the residue after aluminium leaches leads to desiliconization residue It crosses high-temperature water thermal response Na and leaches into solution, realize Na2CO3Catalyst recycling.
Specific step is as follows:
(1) generation of catalyst load and catalytic gasification ash: being 1.2, Ca/Si mass ratio for 2.2 with NaOH and coal ash mass ratio, The bold and unconstrained high alumina coal of grandson family, NaOH, CaO are subjected to catalyst load, obtain the high alumina fine coal of supported catalyst after ball mill mixing.It is negative The high alumina fine coal of carried catalyst obtains catalytic gasification ash after 1100 DEG C of catalytic gasifications.
(2) it the leaching of the crude liquid containing aluminium: obtains catalytic gasification ash to consolidate mass ratio by liquid being 50,150 DEG C by 5 wt% NaOH After solution leaches 0.5 h, crude liquid containing aluminium is obtained by filtration and aluminium leaches residue.
(3) desiliconization of the crude liquid containing aluminium: with Ca (OH)2/ Si mass ratio is 2.6 additions Ca (OH) into crude liquid containing aluminium2Milkiness Liquid after 2 h are mixed at 40 DEG C, contains aluminum solutions and desiliconization residue after desiliconization is obtained by filtration.
(4) carbon point, be filtered, washed and prepare aluminium hydroxide: be passed through excessive CO to containing aluminum solutions2, intake be Na moles contain 5 times of amount obtain aluminum hydroxide product after 60 DEG C of 1 h of constant temperature after being filtered, washed.Resulting filtrate is by heating, concentration, knot Na is obtained after crystalline substance2CO3。
(5) aluminium leaches residue and desiliconization residue high temperature hydro-thermal takes off Na: the aluminium that step 2 generates being leached residue and is produced with step 3 It is at 10,150 DEG C after 2 h of high temperature hydro-thermal reaction that raw desiliconization residue, which consolidates mass ratio by liquid, and the filtrate being obtained by filtration is by carbon It is concentrated after acidification, crystallization obtains Na2CO3.It obtains aluminium hydroxide and roasts at 1200 DEG C to obtain aluminium oxide, aluminium oxide effective content It is 96.4%, the leaching rate of aluminium is 63.7%, and the rate of recovery of catalyst n a is 80.9%.
Embodiment 3: the present embodiment is using the bold and unconstrained high alumina coal of grandson family as raw material (forming same embodiment 1), with NaOH and CaCO3To urge Agent, catalytic gasification, obtains catalytic gasification ash at high temperature, and catalytic gasification ash passes through 1 wt% Na2CO3Solution, which leaches, to be contained Aluminium crude liquid, then pass through addition Ca (OH)2Aluminum hydroxide product is obtained by filtration in desiliconization, carbon point, and the residue and desiliconization after aluminium leaching are residual Slag leaches into solution by high temperature hydro-thermal reaction Na, realizes Na2CO3The recycling of catalyst.
Specific step is as follows:
(1) generation of catalyst load and catalytic gasification ash: being 0.8, Ca/Si mass ratio for 1.1 with NaOH and coal ash mass ratio, By the bold and unconstrained high alumina coal of grandson family, NaOH, CaCO3Catalyst load is carried out, obtains the high alumina fine coal of supported catalyst after ball mill mixing. The high alumina fine coal of supported catalyst obtains catalytic gasification ash after 1000 DEG C of catalytic gasifications.
(2) it the leaching of the crude liquid containing aluminium: obtains catalytic gasification ash to consolidate mass ratio by liquid being 10, passes through 1 wt% at 80 DEG C Na2CO3After solution leaches 1 h, crude liquid containing aluminium is obtained by filtration and aluminium leaches residue.
(3) desiliconization of the crude liquid containing aluminium: with Ca (OH)2/ Si mass ratio is 2.6 additions Ca (OH) into crude liquid containing aluminium2Milkiness Liquid after 2 h are mixed at 150 DEG C, contains aluminum solutions and desiliconization residue after desiliconization is obtained by filtration.
(4) carbon point, be filtered, washed and prepare aluminium hydroxide: be passed through excessive CO to containing aluminum solutions2, intake be Na moles contain 4 times of amount obtain aluminum hydroxide product after 60 DEG C of 1 h of constant temperature after being filtered, washed.Resulting filtrate is by heating, concentration, knot Na is obtained after crystalline substance2CO3。
(5) aluminium leaches residue and desiliconization residue high temperature hydro-thermal takes off Na: the aluminium that step 2 generates being leached residue and is produced with step 3 It is 50 that raw desiliconization residue, which consolidates mass ratio by liquid, at 250 DEG C after 10 h of high temperature hydro-thermal reaction, filters resulting filtrate and passes through It is concentrated after carbonating, crystallization obtains Na2CO3.It obtains aluminium hydroxide and roasts at 1200 DEG C to obtain aluminium oxide, aluminium oxide effectively contains Amount is 90.4%, and the leaching rate of aluminium is 74.3%, and the rate of recovery of catalyst n a is 84.5%.
Embodiment 4: the present embodiment is using the bold and unconstrained high alumina coal of grandson family as raw material (forming same embodiment 1), with Na2CO3With Ca (OH)2 For catalyst, catalytic gasification, obtains catalytic gasification ash at high temperature, and catalytic gasification ash obtains crude liquid containing aluminium by water extraction, then By adding Ca (OH)2Aluminum hydroxide product is obtained by filtration in desiliconization, carbon point, and the residue after aluminium leaches passes through height with desiliconization residue Warm water thermal response Na leaches into solution, realizes Na2CO3The recycling of catalyst.
Specific step is as follows:
(1) generation of catalyst load and catalytic gasification ash: with Na2CO3It is 1.2, Ca/Si mass ratio with coal ash mass ratio is 2, By the bold and unconstrained high alumina coal of grandson family, Na2CO3、Ca(OH)2Catalyst load is carried out, obtains the high-alumina fly of supported catalyst after ball mill mixing Coal.The high alumina fine coal of supported catalyst obtains catalytic gasification ash after 1200 DEG C of catalytic gasifications.
(2) it the leaching of the crude liquid containing aluminium: obtains catalytic gasification ash to consolidate mass ratio by liquid being 50, passes through water extraction 1 at 60 DEG C After h, crude liquid containing aluminium is obtained by filtration and aluminium leaches residue.
(3) desiliconization of the crude liquid containing aluminium: with Ca (OH)2/ Si mass ratio is 3.1 additions Ca (OH) into crude liquid containing aluminium2Milkiness Liquid after 1 h is mixed at 150 DEG C, contains aluminum solutions and desiliconization residue after desiliconization is obtained by filtration.
(4) carbon point, be filtered, washed and prepare aluminium hydroxide: be passed through excessive CO to containing aluminum solutions2, intake be Na moles contain 5 times of amount obtain aluminum hydroxide product after 60 DEG C of 1 h of constant temperature after being filtered, washed.Resulting filtrate is by heating, concentration, knot Na is obtained after crystalline substance2CO3。
(5) aluminium leaches residue and desiliconization residue high temperature hydro-thermal takes off Na: the aluminium that step 2 generates being leached residue and is produced with step 3 It is 40 that raw desiliconization residue, which consolidates mass ratio by liquid, at 150 DEG C after 4 h of high temperature hydro-thermal reaction, filters resulting filtrate and passes through It is concentrated after carbonating, crystallization obtains Na2CO3.It obtains aluminium hydroxide and roasts at 1200 DEG C to obtain aluminium oxide, aluminium oxide effectively contains Amount is 92.4%, and the leaching rate of aluminium is 84.5%, and the rate of recovery of catalyst n a is 71.4%.
Embodiment 5: the present embodiment is using the bold and unconstrained high alumina coal of grandson family as raw material (forming same embodiment 1), with K2CO3With Ca (OH)2For Catalyst, catalytic gasification, obtains catalytic gasification ash, catalytic gasification ash obtains crude liquid containing aluminium by water extraction, then leads at high temperature Cross addition Ca (OH)2Aluminum hydroxide product is obtained by filtration in desiliconization, carbon point, and the residue after aluminium leaches passes through high temperature with desiliconization residue Hydro-thermal reaction K leaches into solution, realizes K2CO3The recycling of catalyst.
Specific step is as follows:
(1) generation of catalyst load and catalytic gasification ash: with K2CO3It is 1.6, Ca/Si mass ratio with coal ash mass ratio is 2, By the bold and unconstrained high alumina coal of grandson family, K2CO3、Ca(OH)2Catalyst load is carried out, obtains the high-alumina fly of supported catalyst after ball mill mixing Coal.The high alumina fine coal of supported catalyst obtains catalytic gasification ash after 1200 DEG C of catalytic gasifications.
(2) it the leaching of the crude liquid containing aluminium: obtains catalytic gasification ash to consolidate mass ratio by liquid being 20, passes through water extraction 1 at 40 DEG C After h, crude liquid containing aluminium is obtained by filtration and aluminium leaches residue.
(3) desiliconization of the crude liquid containing aluminium: with Ca (OH)2/ Si mass ratio is 3.9 additions Ca (OH) into crude liquid containing aluminium2Milkiness Liquid after 2 h are mixed at 40 DEG C, contains aluminum solutions and desiliconization residue after desiliconization is obtained by filtration.
(4) carbon point, be filtered, washed and prepare aluminium hydroxide: be passed through excessive CO to containing aluminum solutions2, intake is K molar content 6 times, aluminum hydroxide product is obtained after being filtered, washed after 60 DEG C of 1 h of constant temperature.Resulting filtrate is by heating, concentration, crystallization After obtain K2CO3。
(5) aluminium leaches residue and desiliconization residue high temperature hydro-thermal takes off K: the aluminium that step 2 generates being leached residue and is generated with step 3 Desiliconization residue by liquid consolidate mass ratio be 100, at 190 DEG C after 4 h of high temperature hydro-thermal reaction, filter resulting filtrate pass through carbon It is concentrated after acidification, crystallization obtains K2CO3.It obtains aluminium hydroxide and roasts at 1200 DEG C to obtain aluminium oxide, aluminium oxide effective content is 92.1%, the leaching rate of aluminium is 84.5%, and the rate of recovery of catalyst K is 83.4%.
Embodiment 6: the present embodiment is using the bold and unconstrained high alumina coal of grandson family as raw material (forming same embodiment 1), with K2CO3With Ca (OH)2For Catalyst, catalytic gasification, obtains catalytic gasification ash, catalytic gasification ash obtains crude liquid containing aluminium by water extraction, then leads at high temperature Cross addition Ca (OH)2Aluminum hydroxide product is obtained by filtration in desiliconization, carbon point, and the residue after aluminium leaches passes through high temperature with desiliconization residue Hydro-thermal reaction K leaches into solution, realizes K2CO3The recycling of catalyst.
Specific step is as follows:
(1) generation of catalyst load and catalytic gasification ash: with K2CO3It is that 1.2, Ca/Si mass ratio is with coal ash mass ratio 1.5, by the bold and unconstrained high alumina coal of grandson family, K2CO3、Ca(OH)2Catalyst load is carried out, obtains the height of supported catalyst after ball mill mixing Aluminium powder coal.The high alumina fine coal of supported catalyst obtains catalytic gasification ash after 900 DEG C of catalytic gasifications.
(2) it the leaching of the crude liquid containing aluminium: obtains catalytic gasification ash to consolidate mass ratio by liquid being 20, passes through water extraction 1 at 40 DEG C After h, crude liquid containing aluminium is obtained by filtration and aluminium leaches residue.
(3) desiliconization of the crude liquid containing aluminium: with Ca (OH)2/ Si mass ratio is 3.9 additions Ca (OH) into crude liquid containing aluminium2Milkiness Liquid after 3 h are mixed at 60 DEG C, contains aluminum solutions and desiliconization residue after desiliconization is obtained by filtration.
(4) carbon point, be filtered, washed and prepare aluminium hydroxide: be passed through excessive CO to containing aluminum solutions2, intake is K molar content 6 times, aluminum hydroxide product is obtained after being filtered, washed after 60 DEG C of 1 h of constant temperature.Resulting filtrate is by heating, concentration, crystallization After obtain K2CO3。
(5) aluminium leaches residue and desiliconization residue high temperature hydro-thermal takes off K: the aluminium that step 2 generates being leached residue and is generated with step 3 Desiliconization residue by liquid consolidate mass ratio be 100, at 250 DEG C after 4 h of high temperature hydro-thermal reaction, filter resulting filtrate pass through carbon It is concentrated after acidification, crystallization obtains K2CO3.It obtains aluminium hydroxide and roasts at 1200 DEG C to obtain aluminium oxide, aluminium oxide effective content is 91.4%, the leaching rate of aluminium is 64.2%, and the rate of recovery of catalyst K is 89.7%.
Embodiment 7: the present embodiment is using the bold and unconstrained high alumina coal of grandson family as raw material (forming same embodiment 1), with K2CO3With Ca (OH)2For Catalyst, catalytic gasification, obtains catalytic gasification ash, catalytic gasification ash obtains crude liquid containing aluminium by water extraction, then leads at high temperature Cross addition Ca (OH)2Aluminum hydroxide product is obtained by filtration in desiliconization, carbon point, and the residue after aluminium leaches passes through high temperature with desiliconization residue Hydro-thermal reaction K leaches into solution, realizes K2CO3The recycling of catalyst.
Specific step is as follows:
(1) generation of catalyst load and catalytic gasification ash: with K2CO3It is 1, Ca/Si mass ratio with coal ash mass ratio is 2, it will Grandson family's person of outstanding talent's high alumina coal, K2CO3、Ca(OH)2Catalyst load is carried out, obtains the high alumina fine coal of supported catalyst after ball mill mixing. The high alumina fine coal of supported catalyst obtains catalytic gasification ash after 1300 DEG C of catalytic gasifications.
(2) it the leaching of the crude liquid containing aluminium: obtains catalytic gasification ash to consolidate mass ratio by liquid being 50, passes through water extraction 1 at 100 DEG C After h, crude liquid containing aluminium is obtained by filtration and aluminium leaches residue.
(3) desiliconization of the crude liquid containing aluminium: with Ca (OH)2Ca (OH) is added into crude liquid containing aluminium for/Si mass ratio 3.12Emulsion, After 2 h are mixed at 80 DEG C, contain aluminum solutions and desiliconization residue after desiliconization is obtained by filtration.
(4) carbon point, be filtered, washed and prepare aluminium hydroxide: be passed through excessive CO to containing aluminum solutions2, intake is K molar content 6 times, aluminum hydroxide product is obtained after being filtered, washed after 60 DEG C of 1 h of constant temperature.Resulting filtrate is by heating, concentration, crystallization After obtain K2CO3。
(5) aluminium leaches residue and desiliconization residue high temperature hydro-thermal takes off K: the aluminium that step 2 generates being leached residue and is generated with step 3 Desiliconization residue by liquid consolidate mass ratio be 60, at 250 DEG C after 4 h of high temperature hydro-thermal reaction, filter resulting filtrate pass through carbon It is concentrated after acidification, crystallization obtains K2CO3.It obtains aluminium hydroxide and roasts at 1200 DEG C to obtain aluminium oxide, aluminium oxide effective content is 92.4%, the leaching rate of aluminium is 90.2%, and the rate of recovery of catalyst K is 84.7%.
Leaching rate, alumina content and the catalyst recovery yield of the Al of embodiment under one, different condition of table.
。

Claims (8)

1. a kind of method that catalytic gasification coupled gasification ash extracts aluminium oxide, it is characterised in that include the following steps:
(a) high alumina coal is mixed with containing Na or K catalyst, catalyst containing Ca, the high alumina fine coal of supported catalyst is obtained after mixing, The high alumina fine coal of supported catalyst after catalytic gasification, obtains catalytic gasification ash at high temperature；
(b) catalytic gasification ash obtains crude liquid containing aluminium by directly leaching and Al leaches residue；
(c) crude liquid containing aluminium by desiliconization obtain after desiliconization containing carrying out carbon containing aluminum solutions after aluminum solutions and desiliconization residue, desiliconization Divide, prepare aluminium hydroxide and alkali metal carbonate solution using filter, washing；
(d) Al leaches residue and desiliconization residue carries out high temperature hydro-thermal reaction dealkalize metal, recycles catalyst.
2. the method that a kind of catalytic gasification coupled gasification ash as described in claim 1 extracts aluminium oxide, it is characterised in that described The alkali or carbonate for being Na or K containing Na or K catalyst in step (a), catalyst containing Ca are Ca (OH)2, CaO or CaCO3。
3. the method that a kind of catalytic gasification coupled gasification ash as described in claim 1 extracts aluminium oxide, it is characterised in that described Na or karat gold category load capacity are 0.8-1.6 times of coal ash weight in step (a), are that 1.1-2.2 adds metal with Ca/Si mass ratio Ca, Si are Si contained in high alumina coal.
4. the method that a kind of catalytic gasification coupled gasification ash as described in claim 1 extracts aluminium oxide, it is characterised in that described The main group of catalytic gasification ash becomes the alumino-silicate and calcium silicates of meta-aluminate, aluminate, low silica-alumina ratio in step (a).
5. the method that a kind of catalytic gasification coupled gasification ash as described in claim 1 extracts aluminium oxide, it is characterised in that described The step of (b) specifically:
Catalytic gasification ash consolidates mass ratio 10-100 by liquid, passes through 0-5wt % (being water when 0%) NaOH or Na at 40-150 DEG C2CO3 After water-soluble liquid leaching 0.2-2 h, crude liquid containing aluminium is obtained by filtration and aluminium leaches residue.
6. the method that a kind of catalytic gasification coupled gasification ash as described in claim 1 extracts aluminium oxide, it is characterised in that described The step of (c) desiliconization specifically:
The logical desiliconization of crude liquid containing aluminium is addition Ca (OH) into crude liquid containing aluminium20.5-2 h is mixed at 40-150 DEG C for emulsion Afterwards, contain aluminum solutions and desiliconization residue, Ca (OH) in desiliconization process after desiliconization is obtained by filtration2Additive amount is Si matter in crude liquid containing aluminium 2.6-3.9 times of amount.
7. the method that a kind of catalytic gasification coupled gasification ash as described in claim 1 extracts aluminium oxide, it is characterised in that described The step of (c) in carbon point, be filtered, washed specifically:
CO is passed through to containing aluminum solutions2, carbon divides process CO2Intake is 2-8 times of alkali metal molar content in solution, and carbon divides temperature It is 30-80 DEG C, constant temperature keeps 0.5-2 h after carbon divides, and using aluminum hydroxide product is obtained after filter, washing, resulting filtrate is passed through Alkali carbonate is obtained after crossing heating, concentration, crystallization.
8. the method that a kind of catalytic gasification coupled gasification ash as described in claim 1 extracts aluminium oxide, it is characterised in that described The step of (d) specifically:
The desiliconization residue that the aluminium that step (b) generates leaches residue and step (c) generation is consolidated into mass ratio 10-100 by liquid, in 150- At 250 DEG C with water after high temperature hydro-thermal reaction 2-20 h, the filtrate being obtained by filtration concentration, crystallization after carbonating obtain alkali gold Belong to carbonate.
CN201811062978.5A 2018-09-12 2018-09-12 A kind of method that catalytic gasification coupled gasification ash extracts aluminium oxide Pending CN109111958A (en)

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CN101484554A (en) * 2006-06-01 2009-07-15 格雷特波因特能源公司 Catalytic steam gasification process with recovery and recycle of alkali metal compounds
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