CN110760360A - Method for preparing coal-fired chemical-looping combustion oxygen carrier by using isometric impregnation method - Google Patents
Method for preparing coal-fired chemical-looping combustion oxygen carrier by using isometric impregnation method Download PDFInfo
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- CN110760360A CN110760360A CN201911036076.9A CN201911036076A CN110760360A CN 110760360 A CN110760360 A CN 110760360A CN 201911036076 A CN201911036076 A CN 201911036076A CN 110760360 A CN110760360 A CN 110760360A
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- 238000000034 method Methods 0.000 title claims abstract description 58
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 48
- 239000001301 oxygen Substances 0.000 title claims abstract description 48
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 42
- 238000005470 impregnation Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000000843 powder Substances 0.000 claims abstract description 65
- 239000002002 slurry Substances 0.000 claims abstract description 55
- 238000010521 absorption reaction Methods 0.000 claims abstract description 37
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 15
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 229910016978 MnOx Inorganic materials 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 239000003245 coal Substances 0.000 abstract description 23
- 239000000463 material Substances 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 239000010419 fine particle Substances 0.000 abstract description 8
- 239000003607 modifier Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000005259 measurement Methods 0.000 abstract 1
- 239000006228 supernatant Substances 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000005431 greenhouse gas Substances 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 238000010248 power generation Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000004131 Bayer process Methods 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a method for preparing a coal-fired chemical-looping combustion oxygen carrier by using an isometric impregnation method, belonging to the technical field of energy environment. Repeatedly washing the red mud until the pH value is 7, drying the red mud for 12-24 hours at 110-150 ℃, roasting the red mud for 2-6 hours at 800-1000 ℃, grinding the roasted red mud into red mud powder, and measuring the saturated water absorption capacity of the red mud by taking a small part of the red mud powder; adding water into a carrier, an auxiliary agent and an active component to prepare a solution, wherein the volume of the solution is the volume corresponding to the saturated water absorption of the red mud addition obtained by measurement, slowly dripping the red mud powder obtained in the step (1) into the solution to form slurry, ultrasonically stirring for 20-30 min, placing in a constant-temperature water bath at 50-70 ℃ for 12h, drying at 110-150 ℃ for 12-24 h, and conventionally forming to obtain a formed mixture; and roasting the obtained molded mixture at 800-1000 ℃ for 2-6 h to obtain the coal-fired chemical-looping combustion oxygen carrier. The invention can make the modifier contact with the red mud fully to form a material with fine particles, porous inside and large specific surface area, and has better reaction activity with coal.
Description
Technical Field
The invention relates to a method for preparing a coal-fired chemical-looping combustion oxygen carrier by using an isometric impregnation method, belonging to the technical field of energy environment.
Background
In recent years, global warming has attracted widespread attention from countries and the public worldwide. Research shows that the increase of the concentration of greenhouse gases in the atmosphere is the main cause of global warming, and the CO2 gas in the greenhouse gases accounts for 77 percent of all greenhouse gas components, so that the CO is used for solving the problem of the global warming2Greenhouse gases contribute most to global warming. In China, CO2The industry with the largest discharge amount is the power generation industry, and the power generation industry CO using coal as main fuel2The emission of CO occupies domestic CO2About 50% of the total emission. Based on this, clean and efficient CO is developed2The emission reduction technology has important significance for sustainable development of energy and environment in China.
The chemical looping combustion is a novel combustion technology based on a zero emission concept, avoids direct contact between fuel and air through a process of obtaining oxygen loss by means of a solid oxygen carrier, and can realize CO in flue gas under the condition of near zero energy consumption2Internal separation of gases. Compared with the most promising oxygen-enriched combustion technology at present, the chemical looping combustion power generation system improves the net power generation efficiency by 6 percent only compared with the system without considering CO2The trapped supercritical fluid bed power station was 2 percentage points lower. On the basis, the chemical-looping combustion technology of the coal is to realize high-purity CO in the coal combustion process2The enrichment simultaneously maximizes the conversion efficiency of the coal. With Fe2O3Is a main active species oxygen carrier, and is considered to be an oxygen carrier with great industrial prospect due to the excellent performance of the oxygen carrier. However, for solid fuels, Fe-based oxygen carriers can suffer significant losses due to side reactions and friction with ash, which increases the need for low cost oxygen carrier materials to meet large-scale industrial applications.
The red mud is waste residue produced in the Bayer process for producing alumina. The red mud has great application potential as a low-cost oxygen carrier due to the unique chemical properties and compositions of the red mud. The main component of the red mud is Fe2O3、Al2O3、SiO2And TiO2Fe in different bauxites2O3The content of (a) is between 30 and 60 percent, and the Fe-based oxygen carrier is a very potential Fe-based oxygen carrier. In addition, the red mud yield is 1.2 million tons every year around the world, wherein, China is the fourth alumina producing country in the world, and the red mud discharged every year is up to millions of tons. A large amount of red mud cannot be fully and effectively utilized, and can only be stacked by a large-area yard, thereby not only occupying a large amount of land, but also causing serious pollution to the environment due to strong alkalinity. Therefore, the red mud is used as an oxygen carrier in the coal-fired chemical looping combustion technology, and the realization of the large-amount reclamation of the red mud becomes an effective solution.
Disclosure of Invention
Aiming at the problems and the defects in the prior art, the invention provides a method for preparing a coal-fired chemical looping combustion oxygen carrier by using an isometric impregnation method. The invention firstly pretreats the red mud and measures the saturated water absorption capacity, then prepares a modifier into a solution with a certain volume and adds the solution into the red mud powder drop by drop, and obtains the high-efficiency red mud-based oxygen carrier by molding and roasting. The invention is realized by the following technical scheme.
A method for preparing a coal-fired chemical looping combustion oxygen carrier by using an isometric impregnation method comprises the following steps:
step 1, repeatedly washing red mud until the pH value is 7, drying the red mud for 12-24 hours at 110-150 ℃, roasting the red mud for 2-4 hours at 800-1000 ℃, grinding the roasted red mud into red mud powder, and taking a small part of the red mud powder to measure the saturated water absorption capacity of the red mud;
step 2, adding water into the carrier, the auxiliary agent and the active component to prepare a solution, wherein the volume of the solution is the volume corresponding to the saturated water absorption of the red mud addition obtained by the determination in the step 1, slowly dropping the red mud powder obtained in the step 1 into the solution to form slurry, ultrasonically stirring for 20-30 min, standing in a constant-temperature water bath at 50-70 ℃ for 12h, drying at 110-150 ℃ for 12-24 h, and conventionally forming to obtain a formed mixture;
and 3, roasting the formed mixture obtained in the step 2 at 800-1000 ℃ for 1-6 h to obtain the coal-fired chemical-looping combustion oxygen carrier.
The specific process for measuring the saturated water absorption capacity of the red mud in the step 1 is as follows: and adding excessive deionized water into the red mud powder to obtain slurry, ultrasonically stirring the slurry for 20-30 min, and placing the slurry in a constant-temperature water bath at 60 ℃ for 12 h. And pouring out the supernatant in the placed slurry, measuring the volume, and subtracting the volume of the supernatant from the excessive deionized water to obtain the saturated water absorption corresponding to the added red mud powder.
In the step 2, the carrier is one or a mixture of several inert oxides in any proportion, and the carrier is 0-30% of the mass of the red mud powder.
The auxiliary agent in the step 2 is CaCO3、Na2CO3And K2CO3One or a mixture of a plurality of the red mud powder in any proportion, wherein the auxiliary agent accounts for 0-10% of the weight of the red mud powder.
In the step 2, the active components comprise perovskite oxides, CuO and MnOxAnd one or a mixture of more than one of NiO in any proportion, wherein the active component is 0-20% of the mass of the red mud powder.
The invention has the beneficial effects that:
(1) the invention realizes the resource utilization of the hazardous waste red mud;
(2) the red mud is used as a raw material to prepare the oxygen carrier for chemical-looping combustion of the coal, so that the preparation cost of the oxygen carrier is greatly reduced, the problem that the oxygen carrier and coal ash are subjected to side reaction or friction to inactivate the coal carrier in the chemical-looping combustion of the coal is solved, and a foundation is laid for the industrialization of the chemical-looping technology of the coal;
(3) the invention can lead the modifier to be fully contacted with the red mud base to form a material with fine particles, porous inside and large specific surface area, and has better reaction activity with coal;
(4) the invention combines the coal chemical-looping combustion technology with red mud resource utilization, realizes the high-efficiency utilization of resources, improves the energy utilization efficiency, and provides technical support for carbon dioxide emission reduction while generating electricity.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention is further described with reference to the following drawings and detailed description.
Example 1
As shown in figure 1, the method for preparing the oxygen carrier for the chemical looping combustion of the coal by using the equal volume impregnation method comprises the following steps:
step 1, repeatedly washing red mud (red mud components are shown in table 1 below) until the pH value is 7, drying at 120 ℃ for 12h, roasting at 900 ℃ for 4h to prepare a material with fine particles, porous inside and large specific surface area, grinding the material into red mud powder after roasting, and taking a small part of the red mud powder to measure the saturated water absorption capacity of the red mud; the specific process for measuring the saturated water absorption capacity of the red mud comprises the following steps: adding excessive deionized water into red mud powder to obtain slurry, ultrasonically stirring the slurry (ultrasonic frequency is 53 kHz) for 25min, and placing the slurry in a constant-temperature water bath at 60 ℃ for 12 h; pouring out the supernatant in the placed slurry, measuring the volume, and subtracting the volume of the supernatant from the volume of the excessive deionized water to obtain the saturated water absorption corresponding to the added red mud powder;
TABLE 1
Step 2, adding water into a carrier (magnesium nitrate corresponding to MgO required to be added is calculated, and the carrier is 0.5% of the mass of red mud powder) to prepare a solution, wherein the volume of the solution is the volume corresponding to the saturated water absorption of the red mud obtained by the determination in the step 1, then slowly dripping the red mud powder in the step 1 into the solution to form slurry, ultrasonically stirring (ultrasonic frequency is 53 kHz) for 25min, then drying in a constant-temperature water bath at 50 ℃ for 12h, and conventionally forming after drying at 110 ℃ for 24h to obtain a formed mixture;
and 3, roasting the molded mixture obtained in the step 2 at 900 ℃ for 4 hours to obtain the coal-fired chemical-looping combustion oxygen carrier.
The coal-fired chemical-looping combustion oxygen carrier prepared by the embodiment is prepared by a precipitation method and a mechanical mixing method in the prior art, and the conversion rate of coal is improved by nearly 12%.
Example 2
As shown in figure 1, the method for preparing the oxygen carrier for the chemical looping combustion of the coal by using the equal volume impregnation method comprises the following steps:
step 1, repeatedly washing red mud (red mud components are shown in table 2 below) until the pH value is 7, drying at the temperature of 110 ℃ for 24 hours, roasting at the temperature of 800 ℃ for 2 hours to prepare a material with fine particles, porous inside and large specific surface area, grinding the material into red mud powder after roasting, and taking a small part of red mud powder to measure the saturated water absorption capacity of the red mud; the specific process for measuring the saturated water absorption capacity of the red mud comprises the following steps: adding excessive deionized water into red mud powder to obtain slurry, ultrasonically stirring the slurry (ultrasonic frequency is 53 kHz) for 20min, and placing the slurry in a constant-temperature water bath at 60 ℃ for 12 h; pouring out the supernatant in the placed slurry, measuring the volume, and subtracting the volume of the supernatant from the volume of the excessive deionized water to obtain the saturated water absorption corresponding to the added red mud powder;
TABLE 2
Step 2, adding water into active components (nickel nitrate corresponding to NiO to be added is calculated, and the active components are 0.5 percent of the mass of red mud powder) to prepare a solution, wherein the volume of the solution is the volume corresponding to the saturated water absorption of the red mud obtained by the determination in the step 1, then slowly dripping the red mud powder obtained in the step 1 into the solution to form slurry, ultrasonically stirring the slurry (ultrasonic frequency is 53 kHz) for 20min, then carrying out constant-temperature water bath at 60 ℃ for 12h, drying the slurry for 24h at 110 ℃, and then carrying out conventional forming to obtain a formed mixture;
and 3, roasting the formed mixture obtained in the step 2 at 800 ℃ for 2h to obtain the coal-fired chemical-looping combustion oxygen carrier.
The coal-fired chemical-looping combustion oxygen carrier prepared by the embodiment is prepared by a precipitation method and a mechanical mixing method in the prior art, and the conversion rate of coal is improved by nearly 19 percent.
Example 3
As shown in figure 1, the method for preparing the oxygen carrier for the chemical looping combustion of the coal by using the equal volume impregnation method comprises the following steps:
step 1, repeatedly washing red mud (red mud components are shown in table 3 below) until the pH value is 7, drying at the temperature of 130 ℃ for 12 hours, roasting at the temperature of 1000 ℃ for 2 hours to prepare a material with fine particles, porous inside and large specific surface area, grinding the material into red mud powder after roasting, and taking a small part of red mud powder to measure the saturated water absorption capacity of the red mud; the specific process for measuring the saturated water absorption capacity of the red mud comprises the following steps: adding excessive deionized water into red mud powder to obtain slurry, ultrasonically stirring the slurry (ultrasonic frequency is 53 kHz) for 30min, and placing the slurry in a constant-temperature water bath at 70 ℃ for 12 h; pouring out the supernatant in the placed slurry, measuring the volume, and subtracting the volume of the supernatant from the volume of the excessive deionized water to obtain the saturated water absorption corresponding to the added red mud powder;
TABLE 3
Step 2, adding an auxiliary agent (Na)2CO3Adding water into the auxiliary agent which accounts for 5 percent of the mass of the red mud powder to prepare a solution, wherein the volume of the solution is the volume corresponding to the saturated water absorption amount of the red mud obtained by the determination in the step 1, then slowly dripping the red mud powder obtained in the step 1 into the solution to form slurry, ultrasonically (the ultrasonic frequency is 53 kHz) stirring for 30min, then carrying out constant-temperature water bath at 70 ℃ for 12h, drying at 130 ℃ for 12h, and then carrying out conventional forming to obtain a formed mixture;
and 3, roasting the molded mixture obtained in the step 2 at 1000 ℃ for 2 hours to obtain the coal-fired chemical-looping combustion oxygen carrier.
The coal-fired chemical-looping combustion oxygen carrier prepared by the embodiment is prepared by a precipitation method and a mechanical mixing method in the prior art, and the conversion rate of coal is improved by nearly 15%.
Example 4
As shown in figure 1, the method for preparing the oxygen carrier for the chemical looping combustion of the coal by using the equal volume impregnation method comprises the following steps:
step 1, repeatedly washing red mud (red mud components are shown in table 1 below) until the pH value is 7, drying at 120 ℃ for 12h, roasting at 800 ℃ for 2h to prepare a material with fine particles, porous inside and large specific surface area, grinding the material into red mud powder after roasting, and taking a small part of the red mud powder to measure the saturated water absorption capacity of the red mud; the specific process for measuring the saturated water absorption capacity of the red mud comprises the following steps: adding excessive deionized water into red mud powder to obtain slurry, ultrasonically stirring the slurry (ultrasonic frequency is 53 kHz) for 30min, and placing the slurry in a constant-temperature water bath at 60 ℃ for 12 h; pouring out the supernatant in the placed slurry, measuring the volume, and subtracting the volume of the supernatant from the volume of the excessive deionized water to obtain the saturated water absorption corresponding to the added red mud powder;
step 2, adding a carrier (MgO, the mass ratio of the carrier to the red mud powder is 0.1: 4) and an auxiliary agent (Na)2CO3Adding water into an auxiliary agent which is 0.1 percent of the mass of the red mud powder and an active component (calculating nickel nitrate corresponding to NiO to be added, wherein the mass ratio of the active component to the red mud powder is 0.1: 4) to prepare a solution, wherein the volume of the solution is the volume corresponding to the saturated water absorption of the red mud obtained by the step 1, slowly dropping the red mud powder obtained by the step 1 into the solution to form slurry, ultrasonically stirring the slurry (the ultrasonic frequency is 53 kHz) for 30min, drying the slurry in a constant-temperature water bath at 50 ℃ for 12h, and conventionally forming the slurry after drying the slurry at 100 ℃ for 24h to obtain a formed mixture;
and 3, roasting the molded mixture obtained in the step 2 at 800 ℃ for 4 hours to obtain the coal-fired chemical-looping combustion oxygen carrier.
The coal-fired chemical-looping combustion oxygen carrier prepared by the embodiment is prepared by a precipitation method and a mechanical mixing method in the prior art, and the conversion rate of coal is improved by nearly 18%.
Example 5
As shown in figure 1, the method for preparing the oxygen carrier for the chemical looping combustion of the coal by using the equal volume impregnation method comprises the following steps:
step 1, repeatedly washing red mud (red mud components are shown in table 2 below) until the pH value is 7, drying at the temperature of 300 ℃ for 2h, grinding into red mud powder, drying, roasting at the temperature of 1000 ℃ for 2h to prepare a material with fine particles, porous inside and large specific surface area, grinding into red mud powder after roasting, and taking a small part of red mud powder to measure the saturated water absorption capacity of the red mud; the specific process for measuring the saturated water absorption capacity of the red mud comprises the following steps: adding excessive deionized water into red mud powder to obtain slurry, ultrasonically stirring the slurry (ultrasonic frequency is 53 kHz) for 30min, placing the slurry in a constant-temperature water bath at 50 ℃ for 12h, and measuring the saturated water absorption capacity of the slurry. Pouring out the supernatant in the placed slurry, measuring the volume, and subtracting the volume of the supernatant from the excessive deionized water to obtain the saturated water absorption corresponding to the added red mud powder;
step 2, adding a carrier (MgO, the mass ratio of the carrier to the red mud powder is 0.5: 4) and an auxiliary agent (Na with the mass ratio of 1: 1)2Adding water into a mixture of O and CaO, wherein the auxiliary agent is 5% of the mass of red mud powder, and an active component (nickel nitrate corresponding to NiO required to be added is calculated, the mass ratio of the active component to the red mud powder is 0.5: 4) to prepare a solution, wherein the volume of the solution is the volume corresponding to the saturated water absorption amount of the red mud obtained in the step 1, slowly dropping the red mud powder in the step 1 into the solution to form slurry, ultrasonically stirring (the ultrasonic frequency is 53 kHz) for 30min, then carrying out constant-temperature water bath at 50 ℃ for 12h, drying at 300 ℃ for 2h, and then carrying out conventional forming to obtain a formed mixture;
and 3, roasting the molded mixture obtained in the step 2 at 1000 ℃ for 2 hours to obtain the coal-fired chemical-looping combustion oxygen carrier.
The coal-fired chemical-looping combustion oxygen carrier prepared by the embodiment is prepared by a precipitation method and a mechanical mixing method in the prior art, and the conversion rate of coal is improved by nearly 21%.
Example 6
As shown in figure 1, the method for preparing the oxygen carrier for the chemical looping combustion of the coal by using the equal volume impregnation method comprises the following steps:
step 1, repeatedly washing red mud (red mud components are shown in table 3 below) until the pH value is 7, drying at the temperature of 200 ℃ for 12 hours, grinding into red mud powder, drying, roasting at the temperature of 900 ℃ for 3 hours to prepare a material with fine particles, porous inside and large specific surface area, grinding into red mud powder after roasting, and taking a small part of red mud powder to measure the saturated water absorption capacity of the red mud; the specific process for measuring the saturated water absorption capacity of the red mud comprises the following steps: adding excessive deionized water into red mud powder to obtain slurry, ultrasonically stirring the slurry (ultrasonic frequency is 53 kHz) for 30min, placing the slurry in a constant-temperature water bath at 50 ℃ for 12h, and measuring the saturated water absorption capacity of the slurry. Pouring out the supernatant in the placed slurry, measuring the volume, and subtracting the volume of the supernatant from the excessive deionized water to obtain the saturated water absorption corresponding to the added red mud powder;
step 2, adding a carrier (MgO, the mass ratio of the carrier to the red mud powder is 1: 4) and an auxiliary agent (CaO and K in the mass ratio of 1: 1)2CO3Adding water into a mixture, wherein the auxiliary agent accounts for 10% of the mass of the red mud powder, and an active component (nickel nitrate corresponding to NiO required to be added is calculated, the mass ratio of the active component to the red mud powder is 1: 4) to prepare a solution, wherein the volume of the solution is the volume corresponding to the saturated water absorption amount of the red mud obtained in the step 1, slowly dripping the red mud powder in the step 1 into the solution to form slurry, ultrasonically stirring the slurry (the ultrasonic frequency is 53 kHz) for 30min, drying the slurry in a constant-temperature water bath at 50 ℃ for 12h, and conventionally forming the slurry after drying the slurry at 200 ℃ for 12h to obtain a formed mixture;
and 3, roasting the molded mixture obtained in the step 2 at 900 ℃ for 3 hours to obtain the coal-fired chemical-looping combustion oxygen carrier.
The coal-fired chemical-looping combustion oxygen carrier prepared by the embodiment is prepared by a precipitation method and a mechanical mixing method in the prior art, and the conversion rate of coal is improved by nearly 14%.
While the present invention has been described in detail with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit and scope of the present invention.
Claims (5)
1. A method for preparing a coal-fired chemical looping combustion oxygen carrier by using an isometric impregnation method is characterized by comprising the following steps:
step 1, repeatedly washing red mud until the pH value is 7, drying the red mud for 12-24 hours at 110-150 ℃, roasting the red mud for 2-4 hours at 800-1000 ℃, grinding the roasted red mud into red mud powder, and taking a small part of the red mud powder to measure the saturated water absorption capacity of the red mud;
step 2, adding water into the carrier, the auxiliary agent and the active component to prepare a solution, wherein the volume of the solution is the volume corresponding to the saturated water absorption of the red mud addition obtained by the determination in the step 1, slowly dropping the red mud powder obtained in the step 1 into the solution to form slurry, ultrasonically stirring for 20-30 min, placing the slurry in a constant-temperature water bath at 50-70 ℃ for 12h, drying the slurry at 110-150 ℃ for 12-24 h, and conventionally forming to obtain a formed mixture;
and 3, roasting the formed mixture obtained in the step 2 at 800-1000 ℃ for 1-6 h to obtain the coal-fired chemical-looping combustion oxygen carrier.
2. The method for preparing the coal-fired chemical looping combustion oxygen carrier by using the equal-volume impregnation method according to claim 1, which is characterized in that: the specific process for measuring the saturated water absorption capacity of the red mud in the step 1 is as follows: and adding excessive deionized water into the red mud powder to obtain slurry, ultrasonically stirring the slurry for 20-30 min, placing the slurry in a constant-temperature water bath at 50-70 ℃ for 12h, and measuring the saturated water absorption capacity of the slurry.
3. The method for preparing the coal-fired chemical looping combustion oxygen carrier by using the equal-volume impregnation method according to claim 1, which is characterized in that: in the step 2, the carrier is one or a mixture of several inert oxides in any proportion, and the carrier is 0-30% of the mass of the red mud powder.
4. The method for preparing a coal-fired chemical looping combustion oxygen carrier by using an equal-volume impregnation method according to claim 1, wherein the method comprises the following steps: the auxiliary agent in the step 2 is Na2O、CaO、Na2CO3And K2CO3One or a mixture of a plurality of the red mud powder in any proportion, wherein the auxiliary agent accounts for 0-10% of the weight of the red mud powder.
5. The method for preparing a coal-fired chemical looping combustion oxygen carrier by using an equal-volume impregnation method according to claim 1, wherein the method comprises the following steps: in the step 2, the active components comprise perovskite oxides, CuO and MnOxAnd one or a mixture of more than one of NiO in any proportion, wherein the active component accounts for 0-20% of the mass of the red mud powder。
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