CN108745359B - Preparation method of core-shell structured composite phase-change heat-storage oxygen carrier for chemical-looping combustion - Google Patents

Preparation method of core-shell structured composite phase-change heat-storage oxygen carrier for chemical-looping combustion Download PDF

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CN108745359B
CN108745359B CN201810640945.8A CN201810640945A CN108745359B CN 108745359 B CN108745359 B CN 108745359B CN 201810640945 A CN201810640945 A CN 201810640945A CN 108745359 B CN108745359 B CN 108745359B
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CN108745359A (en
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王�华
田孟爽
李孔斋
张凌
陈艳鹏
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Kunming University of Science and Technology
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J23/74—Iron group metals
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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Abstract

The invention relates to a preparation method of a core-shell structured composite phase-change heat-storage oxygen carrier for chemical-looping combustion, and belongs to the technical field of heat storage materials. The invention adopts a coprecipitation method, adds the composite phase-change heat storage material with the core-shell structure into the mixed solution of aluminum salt and ferric salt, reacts under the condition of adjusting the pH value of the solution by ammonia water, and then is roasted at high temperature to obtain the composite phase-change heat storage oxygen carrier with the core-shell structure for chemical-looping combustion. The composite phase-change heat storage oxygen carrier is composed of a core phase-change heat storage material aluminum, an inner-layer aluminum nickel oxide, a middle-layer carbon fiber and a shell aluminum iron oxygen carrier, the heat storage type oxygen carrier structure is more stable due to the superposition of multiple shell layers, the aluminum in a core melting state can be effectively prevented from leaking, equipment is damaged, and economic loss is reduced. Meanwhile, the composite phase-change heat storage oxygen carrier has the characteristics of heat storage and oxygen carrying, can be repeatedly recycled, greatly saves the cost, and is economical and efficient.

Description

Preparation method of core-shell structured composite phase-change heat-storage oxygen carrier for chemical-looping combustion
Technical Field
The invention relates to a preparation method of a core-shell structured composite phase-change heat-storage oxygen carrier for chemical-looping combustion, belonging to the technical field of oxygen carriers.
Background
With the rapid development of science and technology and the rapid increase of population, energy becomes an important factor restricting the social development. While traditional fossil energy is being consumed, the amount of stored energy is also being increasedIn the process of continuously reducing and utilizing fossil energy, a plurality of byproducts are inevitably generated, especially, the pollutants are various and large in quantity. Wherein CO is2Is the most dominant greenhouse gas responsible for global warming. In recent years, production and life of people around the world are lost, which is difficult to estimate, by global warming. Therefore, CO2Emission reduction and recycling become global problems to be solved urgently. Thus, Chemical Looping Combustion (CLC) takes place.
CLC is a new non-mixed combustion technology without direct contact of fuel and air, and has CO2Internal separation and low NOxThe high efficiency combustion process of emissions has been of great interest to researchers since its inception. The CLC system mainly comprises three parts, namely an oxidation reactor, a reduction reactor and an oxygen carrier. The CLC technology realizes flameless combustion of fuel by linking oxidation reaction and reduction reaction with oxygen carrier and separating fuel and air. While the key to the performance of CLC systems lies in the choice of oxygen carrier.
Currently, oxygen carriers are classified into metal oxide oxygen carriers and non-metal oxide oxygen carriers. Among them, metal oxygen carriers have been studied intensively because of their advantages such as easy availability, low cost, and simple operation. Fe. Ni, Co, Cu, Mn, Cd and the like are metal oxygen carriers with wide application, and Al is mostly adopted as an inert carrier2O3、TiO2、MgO、SiO2YSZ and CaSO4And the like.
Although Ni-based oxygen carriers have very high reactivity, they easily generate toxic sulfides during the reaction, and their own porous nature causes the reaction rate not to be high; the Cu-based oxygen carrier is easily decomposed into Cu under the low-temperature reaction condition2And O, which is often sintered due to the low melting point under the high temperature reaction condition, and the reaction rate of the Cu-based oxygen carrier is rapidly reduced after several cycles of reaction. Co, Mn, Cd, etc. have good properties but high costs. The Fe-based oxygen carrier has low price, but the oxygen storage amount is not high, and the cycle period is not long. The oxygen carrier material can be a chemical chain combustion material with wide material source, low price, environmental friendliness, no toxicity, excellent cycle performance and the likeThe industrialization provides the premise.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a composite phase-change heat-storage oxygen carrier with a core-shell structure for chemical-looping combustion, wherein the phase-change temperature of an inner core Al of the composite phase-change heat-storage oxygen carrier is 660 ℃, the composite phase-change heat-storage oxygen carrier has larger melting heat (about 396.09J/g), high heat conductivity coefficient, low evaporation pressure and low heat storage cost, an aluminum nickel oxide at the inner layer of a shell has higher structural stability and high-temperature stability, and can uniformly wrap an inner core material, and the catalytic action of nickel can catalyze methane to crack to generate carbon to cover the surface of the aluminum nickel oxide shell; the middle carbon fiber can enhance the sealing performance of the shell layer, enhance the thickness of the shell layer on the surface of the heat storage material, increase the heat transfer area, and increase the ductility of the carbon fiber, so that the mechanical strength of the heat storage material is increased; the aluminum ferrite carrier is uniformly coated outside the middle-layer carbon fiber shell, so that the composite phase-change heat storage oxygen carrier integrates heat storage and oxygen storage, and the problem that a fixed bed is easy to generate hot spots in the chemical looping combustion process can be solved.
The invention adopts a coprecipitation method, adds the composite phase-change heat storage material with the core-shell structure into the mixed solution of aluminum salt and ferric salt, reacts under the condition of adjusting the pH value of the solution by ammonia water, and then is roasted at high temperature to obtain the composite phase-change heat storage oxygen carrier with the core-shell structure for chemical-looping combustion. The composite phase-change heat storage oxygen carrier is composed of a core phase-change heat storage material aluminum, an inner layer aluminum nickel oxide, a middle layer carbon fiber and a shell aluminum iron oxygen carrier, and the superposition of multiple shell layers enables the heat storage type oxygen carrier to have a more stable structure, so that the leakage of aluminum in a core molten state can be effectively prevented, equipment is prevented from being damaged, and economic loss is reduced; meanwhile, the composite phase-change heat storage oxygen carrier has the characteristics of heat storage and oxygen carrying, can be repeatedly recycled, greatly saves the cost, and is economical and efficient.
A preparation method of a core-shell structured composite phase-change heat-storage oxygen carrier for chemical-looping combustion comprises the following specific steps:
(1) dispersing the Al @ C composite phase-change heat storage material with the core-shell structure into deionized water or ultrapure water to prepare an Al @ C composite phase-change heat storage material turbid liquid with the core-shell structure;
(2) mixing Fe (NO)3)3·9H2O and Al (NO)3)3·9H2Adding O into deionized water or ultrapure water to prepare a solution B;
(3) adding the Al @ C composite phase change heat storage material suspension into the solution B to react for 0.1-1 h under the stirring condition at the temperature of 40-90 ℃; dropwise adding ammonia water to adjust the pH value of the solution to 9-10, reacting for 0.5-3 h, and then carrying out constant-temperature aging treatment for 1-12 h; carrying out solid-liquid separation, alternately washing the solid for 3-5 times according to the sequence of water-absolute ethyl alcohol-water, and drying the solid for 3-24 h at the temperature of 50-100 ℃;
(4) roasting the solid dried in the step (3) at a high temperature of 600-800 ℃ for 1-5 h to obtain the core-shell structure Fe for chemical-looping combustion2O3-Al2O3V (Al @ C) composite heat storage type oxygen carrier;
the preparation method of the Al @ C composite phase change heat storage material with the core-shell structure comprises the following specific steps:
(1) respectively mixing aluminium powder and NiCl2、NH4F is added into deionized water or ultrapure water to prepare aluminum powder turbid liquid and NiCl2Solution and NH4F solution;
(2) placing the aluminum powder turbid liquid obtained in the step (1) in ultrasonic waves for ultrasonic treatment for 5-30 min to obtain an aluminum powder turbid liquid;
(3) adding gelatin to the NiCl of step (1)2Uniformly stirring the solution at the temperature of 35-55 ℃, then adding the aluminum powder suspension obtained in the step (2), and reacting for 5-20 min at the temperature of 35-55 ℃ under stirring to obtain a solution A;
(4) dropwise adding NH in the step (1) into the solution A in the step (3) at the temperature of 35-55 ℃ under the stirring condition4Continuously reacting the solution F for 0.5-3 h; washing for 3-5 times alternately according to the sequence of water, absolute ethyl alcohol and water, carrying out solid-liquid separation, and drying the solid at the temperature of 50-100 ℃;
(5) uniformly heating the solid dried in the step (4) to 600-800 ℃ and roasting at high temperature for 2-16 h to obtain a precursor Al @ Al2O3；
(6) Will be step (5)Precursor Al @ Al of2O3Placing the material in a fixed bed, introducing a methane-inert gas mixed gas, and carrying out methane catalytic cracking reaction for 0.2-5 h at the temperature of 500-750 ℃ to obtain the Al @ C composite phase change heat storage material with the core-shell structure;
further, in the step (1) of the preparation method of the Al @ C composite phase change heat storage material with the core-shell structure, aluminum powder and NiCl2、NH4The molar ratio of F is (5-20): (0.5-2): 1-3), the concentration of aluminum powder in the aluminum powder turbid liquid is 0.5-2 mol/L, and NiCl2NiCl in solution2The concentration of (A) is 0.05-0.2 mol/L, NH4NH in solution F4The concentration of F is 0.1-0.3 mol/L; the ultrasonic power is 40-80W;
further, in the step (3) of the preparation method of the Al @ C composite phase change heat storage material with the core-shell structure, gelatin and NiCl are adopted2The solid-liquid ratio g of the solution to L is (3-15) to 1.
Further, the speed of dropwise adding in the step (4) of the preparation method of the Al @ C composite phase-change heat storage material with the core-shell structure is 1-5 drops/s.
Further, in the preparation method of the Al @ C composite phase-change heat storage material with the core-shell structure, in the step (5), the constant temperature rise rate is 1-10 ℃/min.
Further, in the preparation method of the Al @ C composite phase-change heat storage material with the core-shell structure, in the step (6), the volume fraction of methane in the methane-inert gas mixed gas is 1-100%, and the inert gas is nitrogen or argon.
Further, said Fe3+And Al3+The molar ratio of (1) to (3); fe in solution A3+And Al3+The total concentration of (a) is 0.1-0.6 mol/L; the concentration of the Al @ C composite phase-change heat storage material suspension is 70-90 g/L; with Fe3+And Al3+The total molar weight of the Al @ C composite phase change heat storage material is 3-12 g/mol.
The invention also aims to provide the composite phase-change heat-storage oxygen carrier prepared by the preparation method of the core-shell structure composite phase-change heat-storage oxygen carrier for chemical looping combustion;
the composite phase-change heat-storage oxygen carrier can be used as a chemical-looping combustion catalyst for application;
the invention relates to a core-shell structured composite phase-change heat storage oxygen carrier for chemical-looping combustion, wherein a core heat storage material is spherical metal aluminum particles, two shells of the heat storage material are respectively aluminum nickel oxide and carbon, and the outermost layer is uniformly coated with an iron-aluminum oxide oxygen carrier; the core aluminum is melted and solidified along with the temperature change, the heat absorption and release of the composite phase-change heat storage oxygen carrier are realized, the phenomenon that the energy is not fully utilized in the traditional CLC technology is improved, and the iron-based oxygen carrier on the outer surface can also be subjected to high-efficiency catalytic reaction.
The invention has the beneficial effects that:
(1) the phase transition temperature of the core aluminum of the composite phase-change heat storage oxygen carrier is 660 ℃, the high-temperature resistance of the aluminum oxide and the like of the wrapping layer is good, the composite phase-change heat storage oxygen carrier can be used in an environment of 600-1400 ℃, and the industrial requirements of the CLC technology can be met more easily;
(2) the composite phase change heat storage oxygen carrier with the core-shell structure has a stable structure and uniform granularity, has a thick shell layer, enhances the sealing property, and can effectively prevent the leakage of core aluminum when the core aluminum is molten due to heat absorption, so that the thermal stability of the material is excellent;
(3) the composite phase change heat storage oxygen carrier with the core-shell structure has low price, and shows equivalent reaction activity under both normal pressure and pressurization conditions, namely Fe2O3/Fe3O4The conversion thermomechanical property is good;
(4) the aluminum oxide in the composite phase-change heat-storage oxygen carrier with the core-shell structure is used as an inert carrier, so that the performance of the Fe-based oxygen carrier can be improved, the oxygen storage capacity of the Fe-based oxygen carrier is improved, and the Fe-based oxygen carrier can be used as an adhesive, so that the Fe-based oxygen carrier is better and more uniformly attached to the surface of a heat storage material, and the performance of the heat-storage oxygen carrier is more stable and excellent;
(5) in the method, the ammonia water is adopted to precipitate iron and aluminum in the solution, so that the iron and the aluminum are promoted to be attached to the surface of the heat storage material, and the oxygen storage catalytic capacity of the heat storage oxygen carrier is improved;
(6) the composite phase-change heat storage oxygen carrier integrates heat storage and oxygen storage, greatly improves the problem that a fixed bed of the traditional CLC technology is easy to generate hot spots, and can effectively utilize intermediate heat in the reaction process, reduce energy consumption and improve energy utilization efficiency;
(7) the method has the advantages of cheap and easily-obtained raw materials, simple process flow and capability of realizing large-scale production.
Drawings
FIG. 1 shows Fe prepared in example 12O3-Al2O3(Al @ C) DSC heat absorption and release characteristic diagram of the composite heat storage type oxygen carrier;
FIG. 2 shows Fe prepared in example 12O3-Al2O3/(Al @ C) SEM image of composite heat storage type oxygen carrier.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: a preparation method of a core-shell structured composite phase-change heat-storage oxygen carrier for chemical-looping combustion comprises the following specific steps:
(1) respectively mixing aluminium powder and NiCl2、NH4F is added into water to prepare aluminum powder turbid liquid and NiCl2Solution and NH4F solution; wherein the aluminum powder and the NiCl2、NH4The molar ratio of F is 15:1.6:2, the concentration of the aluminum powder in the aluminum powder turbid liquid is 1.5mol/L, and NiCl2NiCl in solution2Is 0.16mol/L, NH4NH in solution F4The concentration of F is 0.2 mol/L;
(2) putting the turbid liquid of the aluminum powder in the step (1) into ultrasonic waves with the power of 70W for ultrasonic treatment for 10min to obtain a turbid liquid of the aluminum powder;
(3) adding gelatin to the NiCl of step (1)2In solution, gelatin and NiCl2The solid-liquid ratio g of the solution is 10:1, the solution is uniformly stirred at the temperature of 40 ℃, then the aluminum powder suspension liquid in the step (2) is added, and the solution A is obtained after the reaction is carried out for 10min at the temperature of 40 ℃ under the stirring condition;
(4) dropwise adding the solution A obtained in the step (3) into the solution A at the temperature of 40 ℃ under stirring(1) NH of (2)4Continuously reacting the solution F for 0.5h, wherein the dropping speed is 1 drop/s; washing for 3 times alternately according to the sequence of water-absolute ethyl alcohol-water, separating solid from liquid, and drying the solid at 100 ℃;
(5) uniformly heating the solid dried in the step (4) to 800 ℃ and roasting at high temperature for 2h to obtain a precursor Al @ Al2O3Wherein the rate of constant temperature rise is 10 ℃/min;
(6) leading the precursor Al @ Al in the step (5)2O3Placing the material in a fixed bed, introducing a methane-nitrogen mixed gas, and carrying out methane catalytic cracking reaction for 2 hours at the temperature of 650 ℃ to obtain the Al @ C composite phase-change heat storage material with the core-shell structure; wherein the volume fraction of methane in the methane-nitrogen mixed gas is 10 percent;
(7) dispersing the Al @ C composite phase-change heat storage material with the core-shell structure in the step (6) into deionized water to prepare an Al @ C composite phase-change heat storage material suspension with the core-shell structure; wherein the concentration of the Al @ C composite phase-change heat storage material suspension is 70 g/L;
(8) mixing Fe (NO)3)3·9H2O and Al (NO)3)3·9H2Adding O into deionized water to prepare solution B; wherein Fe3+And Al3+In a molar ratio of 1: 2; fe in solution B3+And Al3+The total concentration of (a) is 0.3 mol/L; with Fe3+And Al3+The total molar weight of the Al @ C composite phase change heat storage material is 10 g/mol;
(9) adding the Al @ C composite phase-change heat storage material suspension into the solution B to react for 0.5h under the conditions of stirring at the temperature of 70 ℃; dropwise adding ammonia water to adjust the pH value of the solution to 10, reacting for 2 hours, and then keeping the temperature at 70 ℃ for carrying out constant-temperature aging treatment for 12 hours; performing solid-liquid separation, alternately washing the solid for 3 times according to the sequence of water, absolute ethyl alcohol and water, and drying the solid for 3 hours at the temperature of 60 ℃;
(10) roasting the solid dried in the step (9) at the high temperature of 600 ℃ for 3h to obtain the core-shell structure Fe for chemical chain combustion2O3-Al2O3/(Al @ C) composite accumulatorA thermal-type oxygen carrier;
fe prepared in this example2O3-Al2O3The DSC heat absorption and release characteristic diagram of the (Al @ C) composite heat storage type oxygen carrier is shown in figure 1, and as can be seen from figure 1, the heat absorption and release of the heat storage oxygen carrier mainly occur at 660 ℃ and 630 ℃, and the heat absorption and release value is about 275J/g, which is slightly lower than that of the Al @ C heat storage material, namely 300J/g, which is slightly lower than that of the Al @ C heat storage material, so that the oxygen carrier successfully covers the surface of Al @ C, the proportion of the inner core aluminum is reduced, namely the corresponding heat absorption and release value is slightly reduced, but the heat absorption and release difference value of the oxygen carrier is smaller, and the heat storage performance is excellent;
fe prepared in this example2O3-Al2O3The SEM photograph of the composite heat storage type oxygen carrier is shown in FIG. 2, and it is understood from FIG. 2 that Fe2O3-Al2O3The Al @ C composite heat storage type oxygen carrier has rich surface and good wrapping performance, and the aluminum-iron-oxygen carrier is successfully attached to the surface of the Al @ C composite phase change heat storage material.
Example 2: a preparation method of a core-shell structured composite phase-change heat-storage oxygen carrier for chemical-looping combustion comprises the following specific steps:
(1) respectively mixing aluminium powder and NiCl2、NH4F is added into water to prepare aluminum powder turbid liquid and NiCl2Solution and NH4F solution; wherein the aluminum powder and the NiCl2、NH4The molar ratio of F is 5:0.5:1, the concentration of the aluminum powder in the aluminum powder turbid liquid is 0.5mol/L, and NiCl2NiCl in solution2Is 0.05mol/L, NH4NH in solution F4The concentration of F is 0.1 mol/L;
(2) putting the turbid liquid of the aluminum powder in the step (1) into ultrasonic waves with the power of 40W for ultrasonic treatment for 5min to obtain a turbid liquid of the aluminum powder;
(3) adding gelatin to the NiCl of step (1)2In solution, gelatin and NiCl2The solid-liquid ratio g of the solution is 3:1, the solution is uniformly stirred at the temperature of 35 ℃, then the aluminum powder suspension liquid in the step (2) is added, and the solution A is obtained after the reaction for 5min at the temperature of 35 ℃ under the stirring condition;
(4) at a temperature of 35 ℃ under stirringDropwise adding NH in the step (1) into the solution A in the step (3)4Continuously reacting the solution F for 0.5h, wherein the dropping speed is 1 drop/s; washing for 3 times alternately according to the sequence of water-absolute ethyl alcohol-water, separating solid from liquid, and drying the solid at 50 ℃;
(5) uniformly heating the solid dried in the step (4) to 600 ℃ and roasting at high temperature for 2h to obtain a precursor Al @ Al2O3Wherein the rate of constant temperature rise is 1 ℃/min;
(6) leading the precursor Al @ Al in the step (5)2O3Placing the material in a fixed bed, introducing a methane-nitrogen mixed gas, and carrying out methane catalytic cracking reaction for 0.2h at the temperature of 500 ℃ to obtain the Al @ C composite phase change heat storage material with the core-shell structure; wherein the volume fraction of methane in the methane-nitrogen mixed gas is 1 percent;
(7) dispersing the Al @ C composite phase-change heat storage material with the core-shell structure in the step (6) into deionized water to prepare an Al @ C composite phase-change heat storage material suspension with the core-shell structure; wherein the concentration of the Al @ C composite phase-change heat storage material suspension is 70 g/L;
(8) mixing Fe (NO)3)3·9H2O and Al (NO)3)3·9H2Adding O into deionized water to prepare solution B; wherein Fe3+And Al3+In a molar ratio of 1: 1; fe in solution B3+And Al3+The total concentration of (a) is 0.1 mol/L; with Fe3+And Al3+The total molar weight of the Al @ C composite phase change heat storage material is 3 g/mol;
(9) adding the Al @ C composite phase-change heat storage material suspension into the solution B to react for 0.1h under the conditions of stirring and 40 ℃; dropwise adding ammonia water to adjust the pH value of the solution to 9, reacting for 3 hours, and then keeping the temperature at 40 ℃ for carrying out constant-temperature aging treatment for 12 hours; performing solid-liquid separation, alternately washing the solid for 3 times according to the sequence of water, absolute ethyl alcohol and water, and drying the solid for 24 hours at the temperature of 50 ℃;
(10) roasting the solid dried in the step (9) at the high temperature of 600 ℃ for 5 hours to obtain the core-shell structure Fe for chemical chain combustion2O3-Al2O3V (Al @ C) composite heat storage type oxygen carrier;
fe prepared in this example2O3-Al2O3The DSC heat absorption and release characteristic diagram of the (Al @ C) composite heat storage type oxygen carrier shows that the heat absorption and release of the heat storage oxygen carrier mainly occur at 660 ℃ and 630 ℃, the heat absorption and release value is about 275J/g, and is slightly reduced compared with the heat absorption and release value of 300J/g of Al @ C heat storage material, which indicates that the oxygen carrier successfully covers the surface of Al @ C, so that the proportion of the inner core aluminum is reduced, namely the corresponding heat absorption and release value is slightly reduced, but the heat absorption and release difference value of the oxygen carrier is smaller, and the heat storage performance is excellent;
fe prepared in this example2O3-Al2O3The SEM photograph of the composite heat storage type oxygen carrier revealed that Fe was contained in the carrier2O3-Al2O3The Al @ C composite heat storage type oxygen carrier has rich surface and good wrapping performance, and the aluminum-iron-oxygen carrier is successfully attached to the surface of the Al @ C composite phase change heat storage material.
Example 3: a preparation method of a core-shell structured composite phase-change heat-storage oxygen carrier for chemical-looping combustion comprises the following specific steps:
(1) respectively mixing aluminium powder and NiCl2、NH4F is added into water to prepare aluminum powder turbid liquid and NiCl2Solution and NH4F solution; wherein the aluminum powder and the NiCl2、NH4The molar ratio of F is 20:2:3, the concentration of the aluminum powder in the aluminum powder turbid liquid is 2mol/L, and NiCl2NiCl in solution2Is 0.2mol/L, NH4NH in solution F4The concentration of F is 0.3 mol/L;
(2) putting the turbid liquid of the aluminum powder in the step (1) into ultrasonic waves with the power of 80W for ultrasonic treatment for 30min to obtain a turbid liquid of the aluminum powder;
(3) adding gelatin to the NiCl of step (1)2In solution, gelatin and NiCl2The solid-liquid ratio g of the solution is 15:1, the solution is uniformly stirred at the temperature of 55 ℃, then the aluminum powder suspension liquid in the step (2) is added, and the solution A is obtained after the reaction for 20min at the temperature of 55 ℃ under the stirring condition;
(4) at a temperature of 55 ℃ under stirring conditions, in step (b)(3) Solution A of (2) to which NH of step (1) is added dropwise4Continuously reacting the solution F for 3 hours, wherein the dropping speed is 5 drops/s; washing for 5 times alternately according to the sequence of water, absolute ethyl alcohol and water, carrying out solid-liquid separation, and drying the solid at the temperature of 100 ℃;
(5) uniformly heating the solid dried in the step (4) to 800 ℃ and roasting at high temperature for 16h to obtain a precursor Al @ Al2O3Wherein the rate of constant temperature rise is 10 ℃/min;
(6) leading the precursor Al @ Al in the step (5)2O3Placing the material in a fixed bed, introducing a methane-nitrogen mixed gas, and carrying out methane catalytic cracking reaction for 5 hours at the temperature of 750 ℃ to obtain the Al @ C composite phase change heat storage material with the core-shell structure; wherein the volume fraction of methane in the methane-nitrogen mixed gas is 100 percent;
(7) dispersing the Al @ C composite phase-change heat storage material with the core-shell structure in the step (6) into deionized water to prepare an Al @ C composite phase-change heat storage material suspension with the core-shell structure; wherein the concentration of the Al @ C composite phase-change heat storage material suspension is 90 g/L;
(8) mixing Fe (NO)3)3·9H2O and Al (NO)3)3·9H2Adding O into deionized water to prepare solution B; wherein Fe3+And Al3+In a molar ratio of 1: 3; fe in solution B3+And Al3+The total concentration of (a) is 0.6 mol/L; with Fe3+And Al3+The total molar weight of the Al @ C composite phase change heat storage material is 12 g/mol;
(9) adding the Al @ C composite phase-change heat storage material suspension into the solution B to react for 1h under the stirring condition at the temperature of 90 ℃; dropwise adding ammonia water to adjust the pH value of the solution to 10, reacting for 0.5h, and keeping the temperature at 90 ℃ to perform constant-temperature aging treatment for 1 h; performing solid-liquid separation, alternately washing the solid for 5 times according to the sequence of water, absolute ethyl alcohol and water, and drying the solid for 3 hours at the temperature of 100 ℃;
(10) placing the solid dried in the step (9) at the temperature of 800 ℃ for high-temperature roasting for 1h to obtain the core-shell structure Fe for chemical-looping combustion2O3-Al2O3V (Al @ C) composite heat storage type oxygen carrier;
fe prepared in this example2O3-Al2O3The DSC heat absorption and release characteristic diagram of the (Al @ C) composite heat storage type oxygen carrier shows that the heat absorption and release of the heat storage oxygen carrier mainly occur at 660 ℃ and 630 ℃, the heat absorption and release value is about 275J/g, and is slightly reduced compared with the heat absorption and release value of 300J/g of Al @ C heat storage material, which indicates that the oxygen carrier successfully covers the surface of Al @ C, so that the proportion of the inner core aluminum is reduced, namely the corresponding heat absorption and release value is slightly reduced, but the heat absorption and release difference value of the oxygen carrier is smaller, and the heat storage performance is excellent;
fe prepared in this example2O3-Al2O3The SEM photograph of the composite heat storage type oxygen carrier revealed that Fe was contained in the carrier2O3-Al2O3The Al @ C composite heat storage type oxygen carrier has rich surface and good wrapping performance, and the aluminum-iron-oxygen carrier is successfully attached to the surface of the Al @ C composite phase change heat storage material.
Example 4: a preparation method of a core-shell structured composite phase-change heat-storage oxygen carrier for chemical-looping combustion comprises the following specific steps:
(1) respectively mixing aluminium powder and NiCl2、NH4F is added into water to prepare aluminum powder turbid liquid and NiCl2Solution and NH4F solution; wherein the aluminum powder and the NiCl2、NH4The molar ratio of F is 10:0.8:1.2, the concentration of the aluminum powder in the aluminum powder turbid liquid is 1mol/L, and NiCl2NiCl in solution2Is 0.08mol/L, NH4NH in solution F4The concentration of F is 0.12 mol/L;
(2) putting the turbid liquid of the aluminum powder in the step (1) into ultrasonic waves with the power of 70W for ultrasonic treatment for 15min to obtain a turbid liquid of the aluminum powder;
(3) adding gelatin to the NiCl of step (1)2In solution, gelatin and NiCl2The solid-liquid ratio g of the solution is 8:1, the solution is uniformly stirred at the temperature of 45 ℃, then the aluminum powder suspension liquid in the step (2) is added, and the solution A is obtained after the reaction for 20min at the temperature of 45 ℃ under the stirring condition;
(4) under the condition of stirring at the temperature of 45 ℃,dropwise adding NH in the step (1) into the solution A in the step (3)4Continuously reacting the solution F for 1.8h, wherein the dropping speed is 4 drops/s; washing for 3 times alternately according to the sequence of water, absolute ethyl alcohol and water, carrying out solid-liquid separation, and drying the solid at the temperature of 95 ℃;
(5) uniformly heating the solid dried in the step (4) to 750 ℃ and roasting at high temperature for 4h to obtain a precursor Al @ Al2O3Wherein the rate of constant temperature rise is 6 ℃/min;
(6) leading the precursor Al @ Al in the step (5)2O3Placing the material in a fixed bed, introducing a methane-nitrogen mixed gas, and carrying out methane catalytic cracking reaction for 1.8h at the temperature of 650 ℃ to obtain the Al @ C composite phase change heat storage material with the core-shell structure; wherein the volume fraction of methane in the methane-nitrogen mixed gas is 25 percent;
(7) dispersing the Al @ C composite phase-change heat storage material with the core-shell structure in the step (6) into deionized water to prepare an Al @ C composite phase-change heat storage material suspension with the core-shell structure; wherein the concentration of the Al @ C composite phase-change heat storage material suspension is 80 g/L;
(8) mixing Fe (NO)3)3·9H2O and Al (NO)3)3·9H2Adding O into deionized water to prepare solution B; wherein Fe3+And Al3+In a molar ratio of 1: 1.5; fe in solution B3+And Al3+The total concentration of (a) is 0.4 mol/L; with Fe3+And Al3+The total molar weight of the Al @ C composite phase change heat storage material is 8 g/mol;
(9) adding the Al @ C composite phase-change heat storage material suspension into the solution B to react for 0.5h under the conditions of stirring and the temperature of 80 ℃; then ammonia water is dripped to adjust the pH value of the solution to 9.5 and react for 2 hours, and then constant temperature aging treatment is carried out for 6 hours at the temperature of 80 ℃; performing solid-liquid separation, alternately washing the solid for 4 times according to the sequence of water, absolute ethyl alcohol and water, and drying the solid for 20 hours at the temperature of 60 ℃;
(10) placing the solid dried in the step (9) at the high temperature of 700 ℃ for roasting for 3h to obtain the core-shell structure Fe for chemical chain combustion2O3-Al2O3V (Al @ C) composite heat storage type oxygen carrier;
fe prepared in this example2O3-Al2O3The DSC heat absorption and release characteristic diagram of the (Al @ C) composite heat storage type oxygen carrier shows that the heat absorption and release of the heat storage oxygen carrier mainly occur at 660 ℃ and 630 ℃, the heat absorption and release value is about 275J/g, and is slightly reduced compared with the heat absorption and release value of 300J/g of Al @ C heat storage material, which indicates that the oxygen carrier successfully covers the surface of Al @ C, so that the proportion of the inner core aluminum is reduced, namely the corresponding heat absorption and release value is slightly reduced, but the heat absorption and release difference value of the oxygen carrier is smaller, and the heat storage performance is excellent;
fe prepared in this example2O3-Al2O3The SEM photograph of the composite heat storage type oxygen carrier revealed that Fe was contained in the carrier2O3-Al2O3The Al @ C composite heat storage type oxygen carrier has rich surface and good wrapping performance, and the aluminum-iron-oxygen carrier is successfully attached to the surface of the Al @ C composite phase change heat storage material.

Claims (9)

1. A preparation method of a core-shell structured composite phase-change heat-storage oxygen carrier for chemical-looping combustion is characterized by comprising the following specific steps:
(1) dispersing the Al @ C composite phase-change heat storage material with the core-shell structure into deionized water or ultrapure water to prepare an Al @ C composite phase-change heat storage material turbid liquid with the core-shell structure;
the preparation method of the Al @ C composite phase change heat storage material with the core-shell structure comprises the following specific steps:
1) respectively mixing aluminium powder and NiCl2、NH4F is added into deionized water or ultrapure water to prepare aluminum powder turbid liquid and NiCl2Solution and NH4F solution;
2) placing the aluminum powder turbid liquid obtained in the step 1) in ultrasonic waves for ultrasonic treatment for 5-30 min to obtain an aluminum powder turbid liquid;
3) adding gelatin to the NiCl of step 1)2Uniformly stirring the solution at the temperature of 35-55 ℃, then adding the aluminum powder suspension obtained in the step 2), and reacting for 5-20 min at the temperature of 35-55 ℃ under stirring to obtain a solution A;
4) dropwise adding the NH of the step 1) into the solution A of the step 3) at the temperature of 35-55 ℃ under the stirring condition4Continuously reacting the solution F for 0.5-3 h; washing for 3-5 times alternately according to the sequence of water, absolute ethyl alcohol and water, carrying out solid-liquid separation, and drying the solid at the temperature of 50-100 ℃;
5) uniformly heating the solid dried in the step 4) to 600-800 ℃ and roasting at high temperature for 2-16 h to obtain a precursor Al @ Al2O3；
6) The precursor Al @ Al in the step 5) is added2O3Placing the material in a fixed bed, introducing a methane-inert gas mixed gas, and carrying out methane catalytic cracking reaction for 0.2-5 h at the temperature of 500-750 ℃ to obtain the Al @ C composite phase change heat storage material with the core-shell structure;
(2) mixing Fe (NO)3)3·9H2O and Al (NO)3)3·9H2Adding O into deionized water or ultrapure water to prepare a solution B;
(3) adding the Al @ C composite phase change heat storage material suspension into the solution B to react for 0.1-1 h under the stirring condition at the temperature of 40-90 ℃; dropwise adding ammonia water to adjust the pH value of the solution to 9-10, reacting for 0.5-3 h, and then carrying out constant-temperature aging treatment for 1-12 h; carrying out solid-liquid separation, alternately washing the solid for 3-5 times according to the sequence of water-absolute ethyl alcohol-water, and drying the solid for 3-24 h at the temperature of 50-100 ℃;
(4) roasting the solid dried in the step (3) at a high temperature of 600-800 ℃ for 1-5 h to obtain the core-shell structure Fe for chemical-looping combustion2O3-Al2O3/(Al @ C) composite heat storage type oxygen carrier.
2. The preparation method of the composite phase-change heat-storage oxygen carrier with the core-shell structure for chemical-looping combustion according to claim 1 is characterized by comprising the following steps: preparation method of Al @ C composite phase change heat storage material with core-shell structure, in step 1), aluminum powder and NiCl2、NH4The molar ratio of F is (5-20): (0.5-2): 1-3), the concentration of aluminum powder in the aluminum powder turbid liquid is 0.5-2 mol/L, and NiCl2NiCl in solution2The concentration of (A) is 0.05-0.2 mol/L, NH4In solution FNH4The concentration of F is 0.1-0.3 mol/L; the ultrasonic power is 40-80W.
3. The preparation method of the composite phase-change heat-storage oxygen carrier with the core-shell structure for chemical-looping combustion according to claim 1 is characterized by comprising the following steps: preparation method of Al @ C composite phase change heat storage material with core-shell structure in step 3) of gelatin and NiCl2The solid-liquid ratio g of the solution to L is (3-15) to 1.
4. The preparation method of the composite phase-change heat-storage oxygen carrier with the core-shell structure for chemical-looping combustion according to claim 1 is characterized by comprising the following steps: the preparation method of the Al @ C composite phase change heat storage material with the core-shell structure has the advantage that the dripping speed in the step 4) is 1-5 drops/s.
5. The preparation method of the composite phase-change heat-storage oxygen carrier with the core-shell structure for chemical-looping combustion according to claim 1 is characterized by comprising the following steps: the preparation method of the Al @ C composite phase-change heat storage material with the core-shell structure has the advantage that in the step 5), the constant-speed heating rate is 1-10 ℃/min.
6. The preparation method of the composite phase-change heat-storage oxygen carrier with the core-shell structure for chemical-looping combustion according to claim 2 is characterized by comprising the following steps: in the step 6) of the preparation method of the Al @ C composite phase change heat storage material with the core-shell structure, the volume fraction of methane in the methane-inert gas mixed gas is 1-100%, and the inert gas is argon.
7. The preparation method of the composite phase-change heat-storage oxygen carrier with the core-shell structure for chemical-looping combustion according to claim 1 is characterized by comprising the following steps: fe3+And Al3+The molar ratio of (1) to (3); fe in solution B3+And Al3+The total concentration of (a) is 0.1-0.6 mol/L; the concentration of the Al @ C composite phase-change heat storage material suspension is 70-90 g/L; with Fe3+And Al3+The total molar weight of the Al @ C composite phase change heat storage material is 3-12 g/mol.
8. The composite phase-change heat-storage oxygen carrier prepared by the preparation method of the core-shell structure composite phase-change heat-storage oxygen carrier for chemical-looping combustion as claimed in any one of claims 1 to 7.
9. Use of the composite phase change thermal storage oxygen carrier of claim 8 as a chemical looping combustion catalyst.
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101824353A (en) * 2010-05-04 2010-09-08 昆明理工大学 Composite oxygen carrier for heat accumulating type chemical chain burning technology and preparation method thereof
CN102618349A (en) * 2012-03-31 2012-08-01 昆明理工大学 Oxygen carrier for methane chemical looping combustion and preparation method for oxygen carrier
CN102925117A (en) * 2012-11-08 2013-02-13 昆明理工大学 Preparation method of Al/Al2O3 composite heat storage material
CN103551156A (en) * 2013-11-05 2014-02-05 中国科学院山西煤炭化学研究所 Oxygen carrier for methane to prepare synthesis gas as well as preparation method and application of oxygen carrier
CN105056955A (en) * 2015-07-16 2015-11-18 西北大学 Oxygen carrier for chemical cycle dry gas reforming, and preparation method and application of oxygen carrier
CN106518125A (en) * 2016-12-08 2017-03-22 赵岩 Composite phase-change heat storage brick coated by refractory material
CN106622313A (en) * 2015-11-02 2017-05-10 中国石油化工股份有限公司 Oxygen carrier used for chemical-looping hydrogen production, and preparation method and application thereof
CN107539948A (en) * 2016-06-23 2018-01-05 中国石油化工股份有限公司 Oxygen carrier of recycle chemistry chain hydrogen production and its preparation method and application
CN108084973A (en) * 2018-02-05 2018-05-29 天津天爱环保技术开发有限公司 A kind of heat accumulation phase change composite material, preparation method and applications

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101824353A (en) * 2010-05-04 2010-09-08 昆明理工大学 Composite oxygen carrier for heat accumulating type chemical chain burning technology and preparation method thereof
CN102618349A (en) * 2012-03-31 2012-08-01 昆明理工大学 Oxygen carrier for methane chemical looping combustion and preparation method for oxygen carrier
CN102925117A (en) * 2012-11-08 2013-02-13 昆明理工大学 Preparation method of Al/Al2O3 composite heat storage material
CN103551156A (en) * 2013-11-05 2014-02-05 中国科学院山西煤炭化学研究所 Oxygen carrier for methane to prepare synthesis gas as well as preparation method and application of oxygen carrier
CN105056955A (en) * 2015-07-16 2015-11-18 西北大学 Oxygen carrier for chemical cycle dry gas reforming, and preparation method and application of oxygen carrier
CN106622313A (en) * 2015-11-02 2017-05-10 中国石油化工股份有限公司 Oxygen carrier used for chemical-looping hydrogen production, and preparation method and application thereof
CN107539948A (en) * 2016-06-23 2018-01-05 中国石油化工股份有限公司 Oxygen carrier of recycle chemistry chain hydrogen production and its preparation method and application
CN106518125A (en) * 2016-12-08 2017-03-22 赵岩 Composite phase-change heat storage brick coated by refractory material
CN108084973A (en) * 2018-02-05 2018-05-29 天津天爱环保技术开发有限公司 A kind of heat accumulation phase change composite material, preparation method and applications

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Performance of a Cu–Fe‐based oxygen carrier combined with a Ni‐based oxygen carrier in a chemical‐looping combustion process based on fixed‐bed reactors;Qiang Tian et al.;《GREENHOUSE GASES-SCIENCE AND TECHNOLOGY》;20180207;第8卷(第3期);第542-556页 *
Surface functionalized core/shell structured CuO/Al nanothermite with long-term storage stability and steady combustion performance;Ke Xiang et al.;《MATERIALS & DESIGN》;20180215;第140卷;第179-187页 *
氧化铁基蓄热型氧载体制备及其化学链燃烧性能;刘自松;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20140215(第2期);第2.2.3节、摘要第2段 *
煤灰对载氧体的煤焦化学链气化反应特性及形貌结构影响研究;万奇顺;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20180115;B017-25 *

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