CN112358895A - Ash treatment system and method for high-silicon high-aluminum coal catalytic gasification process - Google Patents

Ash treatment system and method for high-silicon high-aluminum coal catalytic gasification process Download PDF

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CN112358895A
CN112358895A CN202011234007.1A CN202011234007A CN112358895A CN 112358895 A CN112358895 A CN 112358895A CN 202011234007 A CN202011234007 A CN 202011234007A CN 112358895 A CN112358895 A CN 112358895A
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water
aluminum
ash
catalyst
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毛燕东
李克忠
刘雷
武恒
芦涛
霍学斌
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Xinneng Energy Co Ltd
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Xinneng Energy Co Ltd
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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
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    • 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
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    • Y02P20/584—Recycling of catalysts

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Abstract

The invention discloses an ash processing system for a high-silicon high-aluminum coal catalytic gasification process, which comprises a water-soluble catalyst recovery unit, a water-insoluble catalyst recovery unit and an aluminum extraction unit; the water-soluble catalyst in the ash can be recovered, and the water-insoluble catalyst can also be recovered, so that the waste of the catalyst is avoided; meanwhile, aluminum resources in the coal can be recycled, and carbon residue in ash can be utilized through the high-temperature calcining device, so that the additional value of the system is improved, and the energy consumption of the system is reduced. The invention also discloses an ash treatment method for the high-silicon high-aluminum coal catalytic gasification process, which comprises the following steps: (1) recovering the water-soluble catalyst; (2) recovering the water-insoluble catalyst; (3) extracting aluminum; the recovery of water-soluble catalyst and water-insoluble catalyst can be realized; the extraction of the aluminum resource in the raw coal is realized; the carbon residue in the ash can be effectively utilized, the utilization rate of energy is improved, and the effects of energy conservation and consumption reduction are realized.

Description

Ash treatment system and method for high-silicon high-aluminum coal catalytic gasification process
The technical field is as follows:
the invention relates to the field of coal catalytic gasification, in particular to an ash treatment system and method for a high-silicon high-aluminum coal catalytic gasification process.
Background art:
the coal catalytic gasification refers to a process of directly reacting coal and water vapor to generate methane-rich gas under the action of a catalyst. The addition of the catalyst can effectively reduce the reaction temperature, improve the reaction rate and improve the content of methane in the crude gas. At present, an alkali metal catalyst is generally used, and the catalyst in the ash needs to be recycled in order to reduce the production cost due to higher cost.
Because the coal in inner Mongolia, Shanxi, Anhui and other places has the characteristics of high silicon and high aluminum, after the alkali metal catalyst is added, alkali metal is easy to react with silicon and aluminum to generate water-insoluble aluminosilicate in the gasification reaction process, the water-insoluble catalyst cannot be recovered through the conventional washing and digestion process, so that the alkali metal catalyst in ash is difficult to recover, and if the ash containing the catalyst is directly discharged, not only is the waste of the catalyst caused, but also the waste of aluminum resources in coal is caused, and the residual carbon in the ash is not fully utilized, so that the energy consumption of a system is large, and the economic benefit of an enterprise is seriously influenced.
The invention content is as follows:
the first purpose of the invention is to provide an ash processing system which has the advantages of energy saving, consumption reduction and high added value and is used for the catalytic gasification process of high-silicon high-aluminum coal;
the second purpose of the invention is to provide an ash treatment method which is resource-saving and has high energy utilization rate and is used for the high-silicon high-aluminum coal catalytic gasification process.
The first purpose of the invention is implemented by the following technical scheme:
the ash processing system for the high-silicon high-aluminum coal catalytic gasification process comprises a water-soluble catalyst recovery unit and a water-insoluble catalyst recovery unit;
the liquid outlet of the solid-liquid separation device of the water-soluble catalyst recovery unit is communicated with the liquid inlet of the catalyst recovery storage tank, the solid-phase outlet of the solid-liquid separation device is communicated with the feed inlet of the high-temperature calcination device of the water-insoluble catalyst recovery unit, and the liquid outlet of the primary filtering device of the water-insoluble catalyst recovery unit is communicated with the liquid inlet of the catalyst recovery storage tank.
Further, the water-soluble catalyst recovery unit comprises the first-stage wet grinding device, the first-stage water washing device and the solid-liquid separation device which are sequentially connected in series.
Further, the water-insoluble catalyst recovery unit comprises the high-temperature calcining device, a heat exchange device, a secondary wet grinding device, a desiliconization device, a secondary water washing device and a primary filtering device;
the discharge hole of the high-temperature calcining device is communicated with the heat medium inlet of the heat exchange device, and the heat medium gas phase outlet of the heat exchange device is communicated with CO of the gasification furnace2An inlet of the heat exchange device is communicated, a hot medium solid phase outlet of the heat exchange device is communicated with a feed inlet of the secondary wet grinding device, a discharge outlet of the secondary wet grinding device is communicated with a feed inlet of the desiliconization device, a discharge outlet of the desiliconization device is communicated with a feed inlet of the secondary washing device, and a discharge outlet of the secondary washing device is communicated with a feed inlet of the primary filtering device;
the feed inlet of the high-temperature calcining device is also connected with Ca (OH)2The material box is communicated; and the feed inlet of the desiliconization device is also respectively communicated with a CaO material box and a water source.
Further, the device also comprises an aluminum extracting unit; the liquid outlet of the primary filtering device is communicated with the feed inlet of the carbonating device of the aluminum extracting unit, and the liquid outlet of the secondary filtering device of the aluminum extracting unit is communicated with the liquid inlet of the catalyst recovery storage tank.
Further, the aluminum extraction unit comprises the carbonator, the secondary filter device and the aluminum extraction device; the discharge hole of the carbonating device is communicated with the feed inlet of the secondary filtering device, the solid phase outlet of the secondary filtering device is communicated with the feed inlet of the aluminum extracting device, and the discharge hole of the aluminum extracting device is communicated with Al2O3The product tanks are communicated;
the feed inlet of the carbonator is also connected with CO2The sources are connected.
The second purpose of the invention is implemented by the following technical scheme:
the ash slag treatment method for the high-silicon high-aluminum coal catalytic gasification process comprises the following steps:
(1) recovering the water-soluble catalyst: cooling and depressurizing ash generated by a catalytic gasification process, then feeding the ash into a water-soluble catalyst recovery unit, wet-grinding the ash by a primary wet grinding device, washing by a primary washing device, and separating by a solid-liquid separation device to obtain primary recovery liquid mainly containing a water-soluble catalyst and solid ash containing non-water-soluble catalyst aluminosilicate, and sending the primary recovery liquid to a catalyst recovery storage tank for mixing with raw coal;
(2) recovering the water-insoluble catalyst: sending the solid ash obtained in the step (1) for recovering the water-soluble catalyst to a high-temperature calcining device of a water-insoluble catalyst recovery unit, and firstly calcining the solid ash at high temperature by using water-insoluble catalyst aluminosilicate and Ca (OH)2Reacting to convert non-water-soluble catalyst aluminosilicate into water-soluble catalyst metaaluminate; the calcined material is cooled by a heat exchange device, wet-milled by a secondary wet milling device and then enters a desiliconization device, and because the raw coal contains SiO2By desiliconizing treatment, SiO contained therein2Reacting with water and CaO to precipitate silicon; then washing by a secondary washing device and filtering by a primary filtering device to obtain filtrate, namely water-soluble catalyst solution with the main component of meta-aluminate, and sending the filtrate to a catalyst recovery storage tank.
Further, in the step (1), in the recovered water-soluble catalyst, the particle size of ash slag after wet grinding by a first-stage wet grinding device is less than 100 um; the washing time of the primary washing device is 15-60 min, the washing temperature is 50-80 ℃, and the mass ratio of the grain slag is (4-40): 1.
further, the step (2) recovers solid ash C, Ca (OH) in the water-insoluble catalyst entering the high-temperature calcination device2In a molar ratio of 1: (5-8): (2-4), the calcination temperature is 1000-1200 ℃, the calcination time is 0.5 &3 h; the particle size of ash slag after wet grinding by a secondary wet grinding device is below 80 um; the washing time of the secondary washing device is 10-30 min, the washing temperature is 40-60 ℃, and the mass ratio of water to slag is (3-6): 1.
further, the method also comprises the following steps of (3) extracting aluminum: sending the filtrate obtained in the step (2) for recovering the water-insoluble catalyst into a carbonator, and mixing with CO2The water is carbonated to precipitate the aluminum element contained in the meta-aluminate, and the carbonate catalyst solution with the main component of no aluminum is obtained as a secondary recovery solution and Al (OH)3And (4) sending the precipitate and the secondary recovery liquid to a catalyst recovery storage tank, and sending the precipitate to an aluminum extraction device for calcination to obtain an aluminum oxide product.
Further, in the aluminum extraction in the step (3), the reaction temperature of a carbonating device is 40-60 ℃, the reaction time is 10-20 min, and the pH value is 6-7; the calcining temperature of the aluminum extraction device is 600-900 ℃, and the calcining time is 1-2 h.
The invention has the advantages that:
the system firstly recovers the water-soluble catalyst in the ash through a first-stage wet grinding device, a first-stage water washing device and a solid-liquid separation device which are sequentially connected in series, recovers the water-insoluble catalyst in the ash through a high-temperature calcining device, a second-stage wet grinding device, a desiliconization device, a second-stage water washing device and a first-stage filtering device, and simultaneously recovers the aluminum resource through a carbonating device, a second-stage filtering device and an aluminum extraction device. The method can recover the water-soluble catalyst in the ash, and can also recover the water-insoluble catalyst, so that the waste of the catalyst is avoided; meanwhile, aluminum resources in the coal can be recycled, and carbon residue in ash can be utilized through the high-temperature calcining device, so that the additional value of the system is greatly improved, and the energy consumption of the system is reduced.
The method of the invention obtains primary recovery liquid with main components of water-soluble catalyst and solid ash containing water-insoluble catalyst after wet grinding, water washing and solid-liquid separation, and sends the primary recovery liquid to a catalyst recovery storage tank to realize the recovery of the water-soluble catalyst; in-line with the aboveThen, the water-insoluble catalyst is converted into a water-soluble catalyst through calcination, and the water-soluble catalyst is subjected to desiliconization treatment to ensure that silicon is precipitated and then discharged out of the system along with residues, and water washing and filtering are carried out to obtain an aqueous solution with the main component of the water-soluble catalyst; finally, carrying out carbonation treatment and filtration to obtain secondary recovery liquid mainly containing alkali metal carbonate, sending the secondary recovery liquid into a catalyst recovery storage tank for loading catalyst solution to realize cyclic utilization, and simultaneously, carrying out Al (OH)3Calcining the precipitate to obtain an alumina product, and extracting aluminum resources from the raw coal; in addition, the method can also effectively utilize the carbon residue in the ash, thereby improving the utilization rate of energy and realizing the effects of energy conservation and consumption reduction.
Description of the drawings:
in order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic view of the system configuration of embodiment 1;
FIG. 2 is a process flow diagram of example 2;
in the figure: a water-soluble catalyst recovery unit 1, a primary wet grinding device 1.1, a primary water washing device 1.2, a solid-liquid separation device 1.3, a water-insoluble catalyst recovery unit 2, a high-temperature calcining device 2.1, a heat exchange device 2.2, a secondary wet grinding device 2.3, a desiliconization device 2.4, a secondary water washing device 2.5, a primary filtering device 2.6, Ca (OH)2A material box 2.7, a CaO material box 2.8, a water source 2.9, an aluminum extraction unit 3, a carbonating device 3.1, a secondary filtering device 3.2, an aluminum extraction device 3.3 and CO2Source 3.4, Al2O3A product tank 3.5 and a catalyst recovery storage tank 4.
The specific implementation mode is as follows:
the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the ash handling system for the high-silicon high-aluminum coal catalytic gasification process as shown in figure 1 comprises a water-soluble catalyst recovery unit 1 and a water-insoluble catalyst recovery unit 2;
the water-soluble catalyst recovery unit 1 comprises a first-stage wet grinding device 1.1, a first-stage water washing device 1.2 and a solid-liquid separation device 1.3 which are sequentially connected in series. The water-insoluble catalyst recovery unit 2 comprises a high-temperature calcining device 2.1, a heat exchange device, a secondary wet grinding device 2.3, a desiliconization device 2.4, a secondary washing device 2.5 and a primary filtering device 2.6; the embodiment also comprises an aluminum extracting unit 3; the aluminium extraction unit 3 comprises a carbonator 3.1, a secondary filtration device 3.2 and an aluminium extraction device 3.3.
The slag outlet of the slag discharging unit of the gasification furnace is communicated with the feed inlet of a first-stage wet grinding device 1.1 of a water-soluble catalyst recovery unit 1, the liquid outlet of a solid-liquid separation device 1.3 of the water-soluble catalyst recovery unit 1 is communicated with the liquid inlet of a catalyst recovery storage tank 4, the solid-phase outlet of the solid-liquid separation device 1.3 is communicated with the feed inlet of a high-temperature calcining device 2.1 of a non-water-soluble catalyst recovery unit 2, and the feed inlet of the high-temperature calcining device 2.1 is also communicated with Ca (2The material box 2.7 is communicated; the discharge port of the high-temperature calcining device 2.1 is communicated with the heat medium inlet of the heat exchange device 2.2, and the heat medium gas phase outlet of the heat exchange device 2.2 is communicated with CO of the gasification furnace2The inlet is communicated, the heat medium solid phase outlet of the heat exchange device 2.2 is communicated with the feed inlet of the second-stage wet grinding device 2.3, the discharge outlet of the second-stage wet grinding device 2.3 is communicated with the feed inlet of the desiliconization device 2.4, and the feed inlet of the desiliconization device 2.4 is also respectively communicated with the CaO feed box 2.8 and the water source 2.9. A discharge hole of the desiliconization device 2.4 is communicated with a feed inlet of the secondary washing device 2.5, and a discharge hole of the secondary washing device 2.5 is communicated with a feed inlet of the primary filtering device 2.6; the liquid outlet of the primary filter device 2.6 is communicated with the feed inlet of a carbonator 3.1 of the aluminum extracting unit 3 for carbonatingThe feed inlet of the device 3.1 is also connected with CO2The source 3.4 is connected. The discharge port of the carbonator 3.1 is communicated with the feed inlet of the second-stage filter device 3.2, the liquid outlet of the second-stage filter device 3.2 is communicated with the liquid inlet of the catalyst recovery storage tank 4, the solid phase outlet of the second-stage filter device 3.2 is communicated with the feed inlet of the aluminum extraction device 3.3, and the discharge port of the aluminum extraction device 3.3 is communicated with the Al2O3The product tank 3.5 is communicated.
In this embodiment, the primary wet grinding device 1.1 and the secondary wet grinding device 2.3 are both wet grinders; the first-stage water washing device 1.2 and the second-stage water washing device 2.5 are water washing tanks with stirring; the high-temperature calcining device 2.1 and the aluminum extracting device 3.3 are calcining furnaces; the desiliconization device 2.4 is a desiliconization tower, namely a tower-shaped reactor; the carbonator 3.1 is a gas-liquid two-phase reactor, and reacts with the solution phase by introducing carbon dioxide; the heat exchange device 2.2 is a shell-and-tube heat exchanger.
Example 2
As shown in FIG. 2, the method for treating ash by using the ash treatment system for the high-silicon high-aluminum coal catalytic gasification process provided in example 1 comprises the following steps:
(1) recovering the water-soluble catalyst: cooling and depressurizing ash generated by a catalytic gasification process, then feeding the ash into a water-soluble catalyst recovery unit 1, wet-grinding the ash by a primary wet grinding device 1.1, washing the ash by a primary washing device 1.2, and carrying out solid-liquid separation by a solid-liquid separation device 1.3 in sequence to obtain primary recovery liquid mainly containing a water-soluble catalyst and solid ash containing non-water-soluble catalyst aluminosilicate, and sending the primary recovery liquid to a catalyst recovery storage tank 4 for mixing with raw coal;
the particle size of ash slag after wet grinding by a first-stage wet grinding device 1.1 is below 100 um; the primary washing device 1.2 is used for washing for 15-60 min, the washing temperature is 50-80 ℃, and the mass ratio of water to slag is (4-40): 1.
(2) recovering the water-insoluble catalyst: sending the solid ash obtained in the step (1) for recovering the water-soluble catalyst to a high-temperature calcining device 2.1 of a water-insoluble catalyst recovery unit 2, and firstly calcining the solid ash at high temperature by using water-insoluble catalyst aluminosilicate and Ca (OH)2Reacting to convert water insoluble catalyst aluminosilicate into water soluble catalyst metaaluminateAn acid salt; the calcined material is cooled by a heat exchange device 2.2, wet-milled by a secondary wet milling device 2.3 and enters a desiliconization device 2.4, and because the raw coal contains SiO2By desiliconizing treatment, SiO contained therein2Reacting with water and CaO to precipitate silicon; then the water is washed by a secondary washing device 2.5 and filtered by a primary filtering device 2.6, and the filtrate, namely the water-soluble catalyst solution with the main component of meta-aluminate, is obtained.
Solid ash C, Ca (OH) entering the high temperature calcination device 2.12In a molar ratio of 1: (5-8): (2-4), wherein the calcining temperature is 1000-1200 ℃, and the calcining time is 0.5-3 h; CaO and SiO in the desiliconization device 2.42The mol ratio of the SiO in the material entering the desiliconization device 2.4 is (1.2-2) to 1 (1.5-3)2Detecting the content according to the proportion and SiO2The content further determines the amount of the material entering the desilication device 2.4; the particle size of ash slag after wet grinding by a secondary wet grinding device 2.3 is below 80 um; the washing time of the secondary washing device 2.5 is 10-30 min, the washing temperature is 40-60 ℃, and the mass ratio of water to slag is (3-6): 1.
(3) aluminum extraction: sending the filtrate obtained in the step (2) for recovering the water-insoluble catalyst into a carbonator 3.1 to react with CO2The water is carbonated to precipitate the aluminum element contained in the meta-aluminate, and the secondary filter device 3.2 filters the aluminum element to obtain a carbonate catalyst solution with the main component of aluminum-free as a secondary recovery solution and Al (OH)3And (4) sending the precipitate and the secondary recovery liquid to a catalyst recovery storage tank 4, and sending the precipitate to an aluminum extraction device 3.3 for calcination to obtain an aluminum oxide product.
The reaction temperature of the carbonator 3.1 is 40-60 ℃, the reaction time is 10-20 min, and the pH value is 6-7; the calcining temperature of the aluminum extraction device 3.3 is 600-900 ℃, and the calcining time is 1-2 h.
The working principle is as follows:
raw coal loaded with an alkali metal catalyst (specifically, a K or Na salt, in this embodiment, a K salt is taken as an example) enters a pressurized fluidized bed gasifier, a gasifying agent mainly comprising water vapor, oxygen and carbon dioxide enters a reactor through the bottom of the gasifier, coal powder and the gasifying agent perform catalytic gasification reaction under the action of the catalyst, the operating pressure of the gasifier is controlled to be 2-4 MPa, the temperature is controlled to be 700-850 ℃, crude gas mainly comprising methane, carbon monoxide, hydrogen and carbon dioxide is generated and enters a subsequent purification and separation unit, and methane-rich crude gas and tar products are obtained through separation.
Discharging high-temperature ash containing a certain amount of carbon residue and a catalyst (including a water-soluble catalyst and a water-insoluble catalyst) obtained after gasification from the bottom of a gasification furnace, cooling by a slag discharging unit, recovering waste heat, and reducing pressure to obtain ash containing a certain amount of carbon residue and a catalyst, sending the ash into a first-stage wet grinding device 1.1, grinding to obtain fine-particle ash below 100um, then sending the ash into a first-stage washing device 1.2, adding water, controlling the water-slag ratio to be 4-40, the temperature to be 50-80 ℃, washing for 15-60 min, and washing to dissolve the water-soluble catalyst in the water; and (3) sending the slag-containing solution after the washing treatment into a solid-liquid separation device 1.3 for solid-liquid separation treatment, sending the obtained primary recovery liquid into a catalyst recovery storage tank 4 for mixing with raw coal, realizing the recycling of the water-soluble catalyst, and simultaneously obtaining solid ash containing the water-insoluble catalyst (potassium aluminosilicate).
Solid ash containing water-insoluble catalyst (potassium aluminosilicate) enters a high-temperature calcining device 2.1, and Ca (OH) is introduced into the high-temperature calcining device 2.12And oxygen-containing gas and a certain amount of raw material containing carbon (the amount of the raw material containing carbon to be newly added can be determined according to the amount of carbon residue in the ash) are subjected to high-temperature calcination treatment, and the solid ash containing the water-insoluble catalyst, C, Ca (OH) are maintained2In a molar ratio of 1: (5-8): (2-4), keeping the calcining temperature at 1000-1200 ℃ and the calcining time at 0.5-3 h. The charcoal is combusted with oxygen-containing gas to provide the heat for the reaction, and Ca (OH) is added2Can be combined with carbon dioxide obtained by combustion to generate calcium carbonate, and simultaneously releases a large amount of reaction heat to provide heat for calcination, so that the total consumption of carbon can be reduced. The calcination process takes place as follows:
C+O2→CO2
CO2+Ca(OH)2→CaCO3↓+H2O
Ca(OH)2+KAlSiO4→KAlO2+Ca2SiO4↓
after the calcined product is subjected to waste heat recovery through the heat exchange device 2.2, the waste heat is used for preheating a gasifying agent or co-producing steam of the gasification furnace, so that waste heat recovery and reutilization are realized, and the effect of energy conservation is achieved; with CO2Mainly sending the tail gas into a gasification furnace as a gasification agent to participate in gasification reaction; with KAlO2、Ca2SiO4And sending solid-phase materials mainly comprising silicon oxide and other coal ash mineral substances contained in the raw coal into a secondary wet grinding device 2.3, and crushing to obtain fine particles below 80 um.
Since the raw coal contains silica, it is easy to mix with KAlO2The reaction is converted into water-insoluble potassium aluminosilicate, so that the solid material crushed by the secondary wet grinding device 2.3 is firstly sent into a desiliconization device 2.4 for desiliconization treatment, and water and CaO are introduced into the desiliconization device 2.4 to react as follows:
CaO+SiO2+H2O→Ca2SiO4↓
the desiliconized material enters a secondary washing device 2.5 for washing, and the mass ratio of the introduced water to the solid-phase material is kept between (3-6): 1, washing with water at the temperature of 40-60 ℃ for 10-30 min; then filtering the solid-containing solution to obtain a residue and a water-soluble catalyst (KAlO)2) While Ca is added to the solution of2SiO4And the silicon slag is discharged out of the system along with the residues, so that the aim of desiliconization is fulfilled.
Mixing the mixture with a water-soluble catalyst (KAlO)2) The solution is sent to a carbonator 3.1 for carbonating treatment to make KAlO2Precipitating the mainly aluminum-containing substance and simultaneously making KAlO-containing substance2Conversion to K2CO3Namely, the following reaction occurs:
KAlO2+CO2+H2O→Al(OH)3↓+K2CO3
the conditions under which the carbonation reaction occurs are: the reaction time is 10-20 min at 40-60 ℃, and the pH value is controlled to be 6-7.
Filtering the carbonated material againMixing Al (OH)3The precipitate is filtered off to give the alkali metal carbonate (K)2CO3) The primary secondary recovery liquid is sent into the catalyst recovery storage tank 4 to be mixed with the raw coal, so that the recycling of the catalyst is realized.
Simultaneously, filtering out Al (OH)3Calcining, introducing a certain amount of carbon-containing raw material and oxygen-containing gas, controlling the temperature at 600-900 ℃, and reacting for 1-2 hours, so that the aluminum hydroxide can be converted into an aluminum oxide product, and the extraction of aluminum resources in the raw coal is realized.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. The ash processing system for the high-silicon high-aluminum coal catalytic gasification process is characterized by comprising a water-soluble catalyst recovery unit and a water-insoluble catalyst recovery unit;
the feed inlet of a first-stage wet grinding device of the water-soluble catalyst recovery unit is communicated, the liquid outlet of a solid-liquid separation device of the water-soluble catalyst recovery unit is communicated with the liquid inlet of the catalyst recovery storage tank, the solid-phase outlet of the solid-liquid separation device is communicated with the feed inlet of a high-temperature calcination device of the water-insoluble catalyst recovery unit, and the liquid outlet of a first-stage filtering device of the water-insoluble catalyst recovery unit is communicated with the liquid inlet of the catalyst recovery storage tank.
2. The ash handling system for the catalytic gasification process of high-silicon high-aluminum coal according to claim 1, wherein the water-soluble catalyst recovery unit comprises the primary wet grinding device, the primary water washing device and the solid-liquid separation device in series in sequence.
3. The ash handling system for the catalytic gasification process of high-silicon high-aluminum coal according to claim 1, wherein the water-insoluble catalyst recovery unit comprises the high-temperature calcination device, a heat exchange device, a secondary wet grinding device, a desilication device, a secondary water washing device and a primary filtering device;
the discharge hole of the high-temperature calcining device is communicated with the heat medium inlet of the heat exchange device, the heat medium solid phase outlet of the heat exchange device is communicated with the feed hole of the secondary wet grinding device, the discharge hole of the secondary wet grinding device is communicated with the feed hole of the desiliconization device, the discharge hole of the desiliconization device is communicated with the feed hole of the secondary washing device, and the discharge hole of the secondary washing device is communicated with the feed hole of the primary filtering device;
the feed inlet of the high-temperature calcining device is also connected with Ca (OH)2The material box is communicated; and the feed inlet of the desiliconization device is also respectively communicated with a CaO material box and a water source.
4. The ash handling system for a high-silicon high-aluminum coal catalytic gasification process according to claim 1, further comprising an aluminum extraction unit; the liquid outlet of the primary filtering device is communicated with the feed inlet of the carbonating device of the aluminum extracting unit, and the liquid outlet of the secondary filtering device of the aluminum extracting unit is communicated with the liquid inlet of the catalyst recovery storage tank.
5. The ash handling system for a high-silicon high-aluminum coal catalytic gasification process according to claim 4, wherein the aluminum extraction unit comprises the carbonation device, the secondary filtration device and the aluminum extraction device; the discharge hole of the carbonating device is communicated with the feed inlet of the secondary filtering device, the solid phase outlet of the secondary filtering device is communicated with the feed inlet of the aluminum extracting device, and the discharge hole of the aluminum extracting device is communicated with Al2O3The product tanks are communicated;
the feed inlet of the carbonator is also connected with CO2The sources are connected.
6. The method for treating ash by using the ash treatment system for the high-silicon high-aluminum coal catalytic gasification process as claimed in claims 1 to 5, which is characterized by comprising the following steps:
(1) recovering the water-soluble catalyst: cooling and depressurizing ash generated by a catalytic gasification process, then feeding the ash into a water-soluble catalyst recovery unit, wet-grinding the ash by a primary wet grinding device, washing by a primary washing device, and separating by a solid-liquid separation device to obtain primary recovery liquid mainly containing a water-soluble catalyst and solid ash containing non-water-soluble catalyst aluminosilicate, and sending the primary recovery liquid to a catalyst recovery storage tank for mixing with raw coal;
(2) recovering the water-insoluble catalyst: sending the solid ash obtained in the step (1) for recovering the water-soluble catalyst to a high-temperature calcining device of a water-insoluble catalyst recovery unit, and firstly calcining the solid ash at high temperature by using water-insoluble catalyst aluminosilicate and Ca (OH)2Reacting to convert non-water-soluble catalyst aluminosilicate into water-soluble catalyst metaaluminate; the calcined material is cooled by a heat exchange device, wet-milled by a secondary wet milling device and then enters a desiliconization device to ensure that the SiO contained in the calcined material is2Reacting with water and CaO to precipitate silicon; then washing by a secondary washing device and filtering by a primary filtering device to obtain filtrate, namely water-soluble catalyst solution with the main component of meta-aluminate, and sending the filtrate to a catalyst recovery storage tank.
7. The ash processing method for the catalytic gasification process of the high-silicon high-aluminum coal according to claim 6, wherein in the step (1) of recovering the water-soluble catalyst, the particle size of the ash after wet grinding by a primary wet grinding device is less than 100 um; the washing time of the primary washing device is 15-60 min, the washing temperature is 50-80 ℃, and the mass ratio of the grain slag is (4-40): 1.
8. the ash handling method for the catalytic gasification of high-silica high-alumina coal according to claim 6, wherein the step (2) recovers solid ash C, Ca (OH) from the water-insoluble catalyst in the high-temperature calcination device2In a molar ratio of 1: (5-8): (2-4), wherein the calcining temperature is 1000-1200 ℃, and the calcining time is 0.5-3 h; the particle size of ash slag after wet grinding by a secondary wet grinding device is below 80 um; when the second-stage washing device is used for washingThe time is 10-30 min, the washing temperature is 40-60 ℃, and the mass ratio of water to slag is (3-6): 1.
9. the ash treatment method for the catalytic gasification process of high-silicon high-aluminum coal according to claim 6, further comprising the step (3) of extracting aluminum: sending the filtrate obtained in the step (2) for recovering the water-insoluble catalyst into a carbonator, and mixing with CO2The water is carbonated to precipitate the aluminum element contained in the meta-aluminate, and the carbonate catalyst solution with the main component of no aluminum is obtained as a secondary recovery solution and Al (OH)3And (4) sending the precipitate and the secondary recovery liquid to a catalyst recovery storage tank, and sending the precipitate to an aluminum extraction device for calcination to obtain an aluminum oxide product.
10. The ash treatment method for the high-silicon high-aluminum coal catalytic gasification process according to claim 9, wherein in the step (3) of extracting aluminum, the reaction temperature of the carbonator is 40-60 ℃, the reaction time is 10-20 min, and the pH value is 6-7; the calcining temperature of the aluminum extraction device is 600-900 ℃, and the calcining time is 1-2 h.
CN202011234007.1A 2020-11-07 2020-11-07 Ash treatment system and method for high-silicon high-aluminum coal catalytic gasification process Pending CN112358895A (en)

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