CN113351149A - Filler loaded with metal oxide/metal sulfide and preparation method thereof - Google Patents
Filler loaded with metal oxide/metal sulfide and preparation method thereof Download PDFInfo
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- CN113351149A CN113351149A CN202110728566.6A CN202110728566A CN113351149A CN 113351149 A CN113351149 A CN 113351149A CN 202110728566 A CN202110728566 A CN 202110728566A CN 113351149 A CN113351149 A CN 113351149A
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- 239000000945 filler Substances 0.000 title claims abstract description 182
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 107
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 107
- 229910052976 metal sulfide Inorganic materials 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000000919 ceramic Substances 0.000 claims abstract description 126
- 230000003197 catalytic effect Effects 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims description 96
- 238000005470 impregnation Methods 0.000 claims description 79
- 239000000243 solution Substances 0.000 claims description 68
- 239000012266 salt solution Substances 0.000 claims description 56
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 53
- 238000003795 desorption Methods 0.000 claims description 50
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 46
- 239000011261 inert gas Substances 0.000 claims description 43
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 239000008367 deionised water Substances 0.000 claims description 40
- 229910021641 deionized water Inorganic materials 0.000 claims description 40
- 150000001412 amines Chemical class 0.000 claims description 39
- 239000002184 metal Substances 0.000 claims description 34
- 238000001816 cooling Methods 0.000 claims description 33
- 238000005406 washing Methods 0.000 claims description 28
- 229910002651 NO3 Inorganic materials 0.000 claims description 26
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 26
- 239000001569 carbon dioxide Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 16
- 238000009835 boiling Methods 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 14
- 235000006408 oxalic acid Nutrition 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 6
- 238000004073 vulcanization Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000010521 absorption reaction Methods 0.000 abstract description 19
- 238000012856 packing Methods 0.000 abstract description 18
- 239000003054 catalyst Substances 0.000 abstract description 8
- 229910000831 Steel Inorganic materials 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 238000005265 energy consumption Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 238000005262 decarbonization Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/30—Loose or shaped packing elements, e.g. Raschig rings or Berl saddles, for pouring into the apparatus for mass or heat transfer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/80—Organic bases or salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
- B01D2255/2065—Cerium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20792—Zinc
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/209—Other metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/209—Other metals
- B01D2255/2092—Aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
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Abstract
The invention discloses a filler loaded with metal oxide/metal sulfide and a preparation method thereof, the filler comprises a porous ceramic filler and a catalytic active component attached to the porous ceramic filler, and the catalytic active component comprises metal oxide AmOnAnd metal sulfide BxSyThe packing can avoid various problems caused by respectively arranging the catalyst and the packing in the absorption tower.
Description
Technical Field
The invention belongs to the technical field of emission reduction of greenhouse gas carbon dioxide, and relates to a filler loaded with metal oxide/metal sulfide and a preparation method thereof.
Background
The decarbonization treatment of the flue gas is an effective measure for controlling the emission of greenhouse gases and preventing the harm of climate change. The flue gas decarbonization technology comprises a chemical absorption method, a temperature and pressure swing adsorption method and the like, wherein the chemical absorption method is a mature decarbonization technology at present, and generally adopts an amine solution to absorb carbon dioxide in flue gas, and then CO is desorbed by heat to ensure that CO is removed2Releasing to realize CO in the flue gas2Purification and separation. The chemical absorption method has the defects of high system energy consumption and the like, and the large-scale industrial application of the chemical absorption method is limited.
Patents CN109092020A and CN102350180B adopt a method of a carbon dioxide regeneration process system of a novel absorbent to reduce energy consumption of a carbon dioxide capture system; the method of using reaction phase change type absorption solvent in patent CN105536434B, CN110433611B, etc. utilizes specific solvent and CO2After the reaction, phase separation occurs, only for rich CO2The method for thermally regenerating the phase solution reduces the energy consumption of carbon dioxide desorption.
Patents CN110681410A, CN109433247A, CN109453801A, CN109316903A, CN108392950B and the like disclose methods for enriching CO2A method for preparing an amine solution catalyst; patent CN105749728B provides a method for carbon dioxide desorption based on catalytic reaction, in which a solid acid catalyst is used to promote the absorption of carbon dioxide by amine solution during the absorption process. These references catalyst in actual commercial CO2The process such as the mode of use in the desorber apparatus is not clear. Patent CN109351125A provides a method for reducing CO enrichment2The novel catalytic desorption tower with the energy consumption for regenerating the amine solution is characterized in that a catalytic reactor and a filler are arranged in a layered mode, and the height and the system resistance of the desorption tower are increased to a certain extent.
Amine solution chemical absorption of carbon dioxide usually employs a packed absorption tower, in which stainless steel, plastic or ceramic packing is arranged to increase gas-liquid contact area and mass transfer efficiency. If the catalyst and the packing are separately arranged in the absorption tower, problems such as insufficient space of the absorption tower, heavy weight of the internal parts, large gas-liquid flow resistance and the like may be caused.
Disclosure of Invention
The present invention has been made to overcome the above-mentioned drawbacks of the prior art, and an object of the present invention is to provide a metal oxide/metal sulfide-loaded packing and a method for preparing the same, which can avoid various problems associated with the arrangement of a catalyst and a packing in an absorption column, respectively.
In order to achieve the above purpose, the filler loaded with metal oxide/metal sulfide of the invention comprises a porous ceramic filler and a catalytic active component attached to the porous ceramic filler, wherein the catalytic active component comprises metal oxide AmOnAnd metal sulfide BxSy。
The porous ceramic filler is in the form of pall ring, Raschig ring, ceramic ball or corrugated plate.
Metal oxide AmOnIs Al2O3、ZrO2Or CeO2；
Metal oxide BxSyIs ZnS or CdS.
The preparation method of the filler loaded with the metal oxide/metal sulfide comprises the following steps:
1) pretreating the porous ceramic filler;
2) adding the nitrate of the metal A into deionized water to obtain a salt solution A with the mass percentage concentration of 5-20%, and adding the nitrate of the metal B into deionized water to obtain a salt solution B with the mass percentage concentration of 5-20%;
3) immersing the porous ceramic filler in the B salt solution, then carrying out ultrasonic impregnation, drying and vulcanization treatment, and then naturally cooling to room temperature under the inert gas atmosphere;
4) immersing the porous ceramic filler treated in the step 3) in the salt solution A, then carrying out ultrasonic impregnation, drying and calcination, and naturally cooling to room temperature to obtain the filler loaded with the metal oxide/metal sulfide.
The specific operation of the step 1) is as follows:
removing impurities on the surface of the porous ceramic filler, cleaning the porous ceramic filler by adopting an oxalic acid solution with the mass percentage concentration of 50%, condensing, refluxing and boiling for 1h, cooling, washing by using deionized water until the pH value of a washing liquid is 7, and then drying for 12h in an oven at 110 ℃.
The specific operation of the step 3) is as follows:
immersing the porous ceramic filler in a B salt solution, performing ultrasonic impregnation and drying for 2-4 times, wherein the ultrasonic impregnation temperature is 35 ℃, the impregnation time is 1-3H, the drying temperature is 110 ℃, the drying time is 12H, then putting the porous ceramic filler into a vulcanizing device, and introducing H2S and N2Then sulfurizing the mixed gas at 300-500 ℃ for 0.3-1H, wherein H in the mixed gas2The volume percentage of S is 5-15%, and finally the product is naturally cooled to room temperature under the inert gas atmosphere.
The specific operation of the step 4) is as follows:
immersing the porous ceramic filler treated in the step 3) in the salt solution A, then carrying out ultrasonic impregnation and drying for 2-4 times, wherein the ultrasonic impregnation temperature is 35 ℃, the ultrasonic impregnation time is 1-3 h, the drying temperature is 110 ℃, the drying time is 12h, then calcining for 2-4 h at the temperature of 500-700 ℃ in an inert gas atmosphere, and then naturally cooling to room temperature in the inert gas atmosphere to obtain the filler loaded with the metal oxide/metal sulfide.
Filler loaded with metal oxide/metal sulfide and used for desorbing CO from amine solution in carbon dioxide capture device2In the desorption tower, the amine solution in the desorption tower desorbs CO2The operating temperature of (A) is 80-95 ℃.
The invention has the following beneficial effects:
when the filler loaded with the metal oxide/metal sulfide and the preparation method thereof are specifically operated, a catalytic active component is attached to the porous ceramic filler, and the catalytic active component comprises the metal oxide AmOnAnd metal sulfide BxSyArranged in amine solution for desorbing CO2In the desorption tower, while the gas-liquid distribution and the mass transfer function of the conventional packing are not influenced,can accelerate the desorption of CO from the amine solution2The desorption temperature is reduced, the consumption of desorption heat is reduced, and the problems of high energy consumption and the like of a carbon dioxide chemical absorption method trapping device are solved. In addition, the load metal oxide/metal sulfide provided by the invention has double functions of the traditional filler and the catalyst, has the characteristics of corrosion resistance, uniform gas-liquid distribution, good mass transfer performance and the like of the traditional ceramic filler, and also has the advantages of small through-flow resistance, low CO2The desorption temperature and the energy consumption are low, and the like, and the CO content of the amine solution in the carbon dioxide capturing and desorbing tower can be obviously reduced2Thereby reducing the CO desorption temperature2The trapping device consumes energy such as steam, electric power and the like of an amine solution system, and avoids various problems caused by respectively arranging a catalyst and a filler in an absorption tower.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the following will clearly and completely describe the technical solution of the present invention with reference to the embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments, and are not intended to limit the scope of the disclosure of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present disclosure. 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.
The filler loaded with the metal oxide/metal sulfide comprises a porous ceramic filler and a catalytic active component attached to the porous ceramic filler, wherein the catalytic active component comprises a metal oxide AmOnAnd metal sulfide BxSy。
The porous ceramic filler is in the form of pall ring, Raschig ring, ceramic ball or corrugated plate.
Metal oxide AmOnIs Al2O3、ZrO2Or CeO2；
Metal oxide BxSyIs ZnS or CdS.
The preparation method of the filler loaded with the metal oxide/metal sulfide comprises the following steps:
1) removing impurities on the surface of the porous ceramic filler, cleaning the porous ceramic filler by adopting an oxalic acid solution with the mass percentage concentration of 50%, condensing, refluxing and boiling for 1h, cooling, washing by using deionized water until the pH value of a washing solution is 7, and then drying for 12h in an oven at 110 ℃;
2) adding the nitrate of the metal A into deionized water to obtain a salt solution A with the mass percentage concentration of 5-20%, and adding the nitrate of the metal B into deionized water to obtain a salt solution B with the mass percentage concentration of 5-20%;
3) immersing the porous ceramic filler in a B salt solution, performing ultrasonic impregnation and drying for 2-4 times, wherein the ultrasonic impregnation temperature is 35 ℃, the impregnation time is 1-3H, the drying temperature is 110 ℃, the drying time is 12H, then putting the porous ceramic filler into a vulcanizing device, and introducing H2S and N2Then sulfurizing the mixed gas at 300-500 ℃ for 0.3-1H, wherein H in the mixed gas2The volume percentage of S is 5-15%, and finally, the steel is naturally cooled to room temperature under the atmosphere of inert gas;
4) immersing the porous ceramic filler treated in the step 3) in the salt solution A, then carrying out ultrasonic impregnation and drying for 2-4 times, wherein the ultrasonic impregnation temperature is 35 ℃, the ultrasonic impregnation time is 1-3 h, the drying temperature is 110 ℃, the drying time is 12h, then calcining for 2-4 h at the temperature of 500-700 ℃ in an inert gas atmosphere, and then naturally cooling to room temperature in the inert gas atmosphere to obtain the filler loaded with the metal oxide/metal sulfide.
Filler loaded with metal oxide/metal sulfide and used for desorbing CO from amine solution in carbon dioxide capture device2In the desorption tower, the amine solution in the desorption tower desorbs CO2The operating temperature of (A) is 80-95 ℃.
Example one
The filler loaded with the metal oxide/metal sulfide comprises a porous ceramic filler and a catalytic active component attached to the porous ceramic filler, wherein the catalytic active component comprisesMetal oxide AmOnAnd metal sulfide BxSy。
The porous ceramic packing is in the form of a pall ring.
Metal oxide AmOnIs Al2O3；
Metal oxide BxSyIs ZnS.
The preparation method of the filler loaded with the metal oxide/metal sulfide comprises the following steps:
1) removing impurities on the surface of the porous ceramic filler, cleaning the porous ceramic filler by adopting an oxalic acid solution with the mass percentage concentration of 50%, condensing, refluxing and boiling for 1h, cooling, washing by using deionized water until the pH value of a washing solution is 7, and then drying for 12h in an oven at 110 ℃;
2) adding the nitrate of the metal A into deionized water to obtain a salt solution A with the mass percentage concentration of 15%, and adding the nitrate of the metal B into deionized water to obtain a salt solution B with the mass percentage concentration of 15%;
3) immersing the porous ceramic filler in a B salt solution, performing ultrasonic impregnation and drying for 3 times, wherein the ultrasonic impregnation temperature is 35 ℃, the impregnation time is 2 hours, the drying temperature is 110 ℃, the drying time is 12 hours, then putting the porous ceramic filler into a vulcanizing device, and introducing H2S and N2And then sulfurizing at 400 ℃ for 0.3H, wherein H in the mixed gas2The volume percentage of S is 10 percent, and finally, the steel is naturally cooled to room temperature under the inert gas atmosphere;
4) immersing the porous ceramic filler treated in the step 3) in the salt solution A, performing ultrasonic impregnation and drying for 2 times, wherein the ultrasonic impregnation temperature is 35 ℃, the ultrasonic impregnation time is 3h, the drying temperature is 110 ℃, the drying time is 12h, calcining for 3h at 600 ℃ in an inert gas atmosphere, and naturally cooling to room temperature in the inert gas atmosphere to obtain the filler loaded with the metal oxide/metal sulfide.
Filler loaded with metal oxide/metal sulfide and used for desorbing CO from amine solution in carbon dioxide capture device2By desorption ofCO desorption of amine solution in tower or desorber2The operating temperature of (2) was 95 ℃.
Example two
The filler loaded with the metal oxide/metal sulfide comprises a porous ceramic filler and a catalytic active component attached to the porous ceramic filler, wherein the catalytic active component comprises a metal oxide AmOnAnd metal sulfide BxSy。
The porous ceramic packing is in the form of a pall ring.
Metal oxide AmOnIs ZrO2；
Metal oxide BxSyIs CdS.
The preparation method of the filler loaded with the metal oxide/metal sulfide comprises the following steps:
1) removing impurities on the surface of the porous ceramic filler, cleaning the porous ceramic filler by adopting an oxalic acid solution with the mass percentage concentration of 50%, condensing, refluxing and boiling for 1h, cooling, washing by using deionized water until the pH value of a washing solution is 7, and then drying for 12h in an oven at 110 ℃;
2) adding the nitrate of the metal A into deionized water to obtain a salt solution A with the mass percentage concentration of 10%, and adding the nitrate of the metal B into deionized water to obtain a salt solution B with the mass percentage concentration of 10%;
3) immersing the porous ceramic filler in a B salt solution, performing ultrasonic impregnation and drying for 2 times, wherein the ultrasonic impregnation temperature is 35 ℃, the impregnation time is 2 hours, the drying temperature is 110 ℃, the drying time is 12 hours, then putting the porous ceramic filler into a vulcanizing device, and introducing H2S and N2Then sulfurizing at 450 deg.C for 0.5H, wherein H is in the mixed gas2The volume percentage of S is 8 percent, and finally, the steel is naturally cooled to room temperature under the inert gas atmosphere;
4) immersing the porous ceramic filler treated in the step 3) in the salt solution A, performing ultrasonic impregnation and drying for 2 times, wherein the ultrasonic impregnation temperature is 35 ℃, the ultrasonic impregnation time is 2 hours, the drying temperature is 110 ℃, the drying time is 12 hours, calcining for 3 hours at the temperature of 600 ℃ in an inert gas atmosphere, and then naturally cooling to room temperature in the inert gas atmosphere to obtain the filler loaded with the metal oxide/metal sulfide.
Filler loaded with metal oxide/metal sulfide and used for desorbing CO from amine solution in carbon dioxide capture device2In the desorption tower, the amine solution in the desorption tower desorbs CO2The operating temperature of (2) was 90 ℃.
EXAMPLE III
The filler loaded with the metal oxide/metal sulfide comprises a porous ceramic filler and a catalytic active component attached to the porous ceramic filler, wherein the catalytic active component comprises a metal oxide AmOnAnd metal sulfide BxSy。
The porous ceramic packing is in the form of Raschig rings.
Metal oxide AmOnIs CeO2；
Metal oxide BxSyIs ZnS.
The preparation method of the filler loaded with the metal oxide/metal sulfide comprises the following steps:
1) removing impurities on the surface of the porous ceramic filler, cleaning the porous ceramic filler by adopting an oxalic acid solution with the mass percentage concentration of 50%, condensing, refluxing and boiling for 1h, cooling, washing by using deionized water until the pH value of a washing solution is 7, and then drying for 12h in an oven at 110 ℃;
2) adding nitrate of metal A into deionized water to obtain a salt solution A with the mass percentage concentration of 12%, and adding nitrate of metal B into deionized water to obtain a salt solution B with the mass percentage concentration of 8%;
3) immersing the porous ceramic filler in a B salt solution, performing ultrasonic impregnation and drying for 3 times, wherein the ultrasonic impregnation temperature is 35 ℃, the impregnation time is 2 hours, the drying temperature is 110 ℃, the drying time is 12 hours, then putting the porous ceramic filler into a vulcanizing device, and introducing H2S and N2Then sulfurizing at 380 deg.C for 0.3H, wherein H is in the mixed gas2S has a volume percentage of12 percent, and finally, naturally cooling to room temperature under the atmosphere of inert gas;
4) immersing the porous ceramic filler treated in the step 3) in the salt solution A, performing ultrasonic impregnation and drying for 2 times, wherein the ultrasonic impregnation temperature is 35 ℃, the ultrasonic impregnation time is 3h, the drying temperature is 110 ℃, the drying time is 12h, calcining for 3h at 600 ℃ in an inert gas atmosphere, and naturally cooling to room temperature in the inert gas atmosphere to obtain the filler loaded with the metal oxide/metal sulfide.
Filler loaded with metal oxide/metal sulfide and used for desorbing CO from amine solution in carbon dioxide capture device2In the desorption tower, the amine solution in the desorption tower desorbs CO2The operating temperature of (2) was 84 ℃.
Example four
The filler loaded with the metal oxide/metal sulfide comprises a porous ceramic filler and a catalytic active component attached to the porous ceramic filler, wherein the catalytic active component comprises a metal oxide AmOnAnd metal sulfide BxSy。
The porous ceramic packing is in the form of Raschig rings.
Metal oxide AmOnIs Al2O3；
Metal oxide BxSyIs CdS.
The preparation method of the filler loaded with the metal oxide/metal sulfide comprises the following steps:
1) removing impurities on the surface of the porous ceramic filler, cleaning the porous ceramic filler by adopting an oxalic acid solution with the mass percentage concentration of 50%, condensing, refluxing and boiling for 1h, cooling, washing by using deionized water until the pH value of a washing solution is 7, and then drying for 12h in an oven at 110 ℃;
2) adding nitrate of metal A into deionized water to obtain a salt solution A with the mass percentage concentration of 12%, and adding nitrate of metal B into deionized water to obtain a salt solution B with the mass percentage concentration of 10%;
3) immersing the porous ceramic filler inB, ultrasonic dipping and drying for 2 times in the salt solution, wherein the ultrasonic dipping temperature is 35 ℃, the dipping time is 2 hours, the drying temperature is 110 ℃, the drying time is 12 hours, then the obtained product is put into a vulcanizing device, and H is introduced into the vulcanizing device2S and N2Then sulfurizing at 450 deg.C for 0.5H, wherein H is in the mixed gas2The volume percentage of S is 8 percent, and finally, the steel is naturally cooled to room temperature under the inert gas atmosphere;
4) immersing the porous ceramic filler treated in the step 3) in the salt solution A, performing ultrasonic impregnation and drying for 3 times, wherein the ultrasonic impregnation temperature is 35 ℃, the ultrasonic impregnation time is 2h, the drying temperature is 110 ℃, the drying time is 12h, calcining for 2h at 600 ℃ in an inert gas atmosphere, and naturally cooling to room temperature in the inert gas atmosphere to obtain the filler loaded with the metal oxide/metal sulfide.
Filler loaded with metal oxide/metal sulfide and used for desorbing CO from amine solution in carbon dioxide capture device2In the desorption tower, the amine solution in the desorption tower desorbs CO2The operating temperature of (2) was 85 ℃.
Comparative example 1
This comparative example provides a catalyst-free ceramic blank comprising the steps of:
1) selecting
Removing surface impurities from the porous ceramic filler of pall ring, pretreating the porous ceramic filler by adopting oxalic acid solution with the mass percentage concentration of 50%, and condensing, refluxing and boiling for 1 h; cooling, washing with deionized water until the pH value of the washing solution is 7, and then drying in an oven at 110 ℃ for 12 h;
2) and calcining the dried ceramic filler in a muffle furnace at 600 ℃ for 2h under the atmosphere of inert gas, and then naturally cooling to room temperature under the atmosphere of inert gas to obtain the hollow ceramic filler.
Small CO in laboratory for ceramic fillers prepared in examples one to comparative example one2Effect verification in a desorption apparatus, CO2Desorption for desorption apparatusThe tower is a stainless steel reactor with the inner diameter of 95mm, ceramic filler is filled, the length of the filler section is 1m, and a heat-insulating layer is arranged outside the absorption tower, and the measuring conditions adopted by the invention are as follows: the desorbed organic amine solution is used for absorbing CO2The subsequent organic amine solution consists of 15% MEA + 5% AMP aqueous solution, the organic amine liquid volume of the analytical tower is 80mL/min, and the desorption temperature is 95 ℃.
When the reaction conditions are stably achieved, continuously measuring the barren liquor CO at the bottom outlet of the desorption tower2Loaded, barren liquor CO2Load and CO2The formula for calculating the desorption rate is as follows:
absorption liquid CO2Absorption liquid CO2Molarity/molarity of solution absorbent
Absorption liquid CO2The molar concentration is obtained by a chemical analysis method of excessive acid reaction, and the molar concentration of the absorbent is obtained by an acid-base titration method;
CO2desorption rate (rich liquid CO)2Loading lean liquid CO2Load)/rich liquid CO2A load;
desorption energy consumption is the enthalpy of the reboiler inlet steam-the enthalpy of the reboiler outlet steam (or water).
Pall ring or raschig ring packing loaded in the desorption tower is the loaded ceramic packing prepared in the first embodiment to the first comparative embodiment in sequence, the packing amount and other conditions are the same, and the verification results are shown in table 1.
TABLE 1
| Serial number | Filler material | CO2Energy consumption for desorption (GJ. t)-1) | CO2Rate of desorption |
| Comparative example 1 | CP5 (blank) | 3.24 | 61.3％ |
| Example 1 | CP1(Al2O3-ZnS) | 3.65 | 54.7％ |
| Example 2 | CP2(Al2O3-ZnS) | 3.62 | 56.1％ |
| Example 3 | CP3(CeO2-ZnS) | 4.27 | 41.7％ |
| Example 4 | CP4(Al2O3-CdS) | 5.63 | 31.7％ |
As can be seen from Table 1, the ceramic fillers prepared in examples one through four reduced the CO of the amine solution as compared to the unsupported ceramic blank filler of comparative example one2Desorption temperature and desorption energy consumption.
EXAMPLE five
The filler loaded with metal oxide/metal sulfide comprises a porous ceramic filler and a catalytic active component attached to the porous ceramic filler, so thatThe catalytically active component comprises a metal oxide AmOnAnd metal sulfide BxSy。
The porous ceramic packing is in the form of a pall ring.
Metal oxide AmOnIs Al2O3；
Metal oxide BxSyIs ZnS.
The preparation method of the filler loaded with the metal oxide/metal sulfide comprises the following steps:
1) removing impurities on the surface of the porous ceramic filler, cleaning the porous ceramic filler by adopting an oxalic acid solution with the mass percentage concentration of 50%, condensing, refluxing and boiling for 1h, cooling, washing by using deionized water until the pH value of a washing solution is 7, and then drying for 12h in an oven at 110 ℃;
2) adding the nitrate of the metal A into deionized water to obtain a salt solution A with the mass percentage concentration of 5%, and adding the nitrate of the metal B into deionized water to obtain a salt solution B with the mass percentage concentration of 5%;
3) immersing the porous ceramic filler in a B salt solution, performing ultrasonic impregnation and drying for 2 times, wherein the ultrasonic impregnation temperature is 35 ℃, the impregnation time is 1H, the drying temperature is 110 ℃, the drying time is 12H, then putting the porous ceramic filler into a vulcanizing device, and introducing H2S and N2And then sulfurizing at 300 ℃ for 0.3H, wherein H in the mixed gas2The volume percentage of S is 5 percent, and finally, the steel is naturally cooled to room temperature under the inert gas atmosphere;
4) immersing the porous ceramic filler treated in the step 3) in the salt solution A, performing ultrasonic impregnation and drying for 2 times, wherein the ultrasonic impregnation temperature is 35 ℃, the ultrasonic impregnation time is 1h, the drying temperature is 110 ℃, the drying time is 12h, calcining for 2h at 500 ℃ in an inert gas atmosphere, and naturally cooling to room temperature in the inert gas atmosphere to obtain the filler loaded with the metal oxide/metal sulfide.
Filler loaded with metal oxide/metal sulfide and used for desorbing amine solution in carbon dioxide capture deviceCO2In the desorption tower, the amine solution in the desorption tower desorbs CO2The operating temperature of (2) was 88 ℃.
EXAMPLE six
The filler loaded with the metal oxide/metal sulfide comprises a porous ceramic filler and a catalytic active component attached to the porous ceramic filler, wherein the catalytic active component comprises a metal oxide AmOnAnd metal sulfide BxSy。
The porous ceramic packing is in the form of Raschig rings.
Metal oxide AmOnIs ZrO2；
Metal oxide BxSyIs CdS.
The preparation method of the filler loaded with the metal oxide/metal sulfide comprises the following steps:
1) removing impurities on the surface of the porous ceramic filler, cleaning the porous ceramic filler by adopting an oxalic acid solution with the mass percentage concentration of 50%, condensing, refluxing and boiling for 1h, cooling, washing by using deionized water until the pH value of a washing solution is 7, and then drying for 12h in an oven at 110 ℃;
2) adding the nitrate of the metal A into deionized water to obtain a salt solution A with the mass percentage concentration of 20%, and adding the nitrate of the metal B into deionized water to obtain a salt solution B with the mass percentage concentration of 20%;
3) immersing the porous ceramic filler in a B salt solution, performing ultrasonic impregnation and drying for 4 times, wherein the ultrasonic impregnation temperature is 35 ℃, the impregnation time is 3 hours, the drying temperature is 110 ℃, the drying time is 12 hours, then putting the porous ceramic filler into a vulcanizing device, and introducing H2S and N2And then sulfurizing at 500 deg.C for 1H, wherein H is in the mixed gas2The volume percentage of S is 15 percent, and finally, the steel is naturally cooled to room temperature under the inert gas atmosphere;
4) immersing the porous ceramic filler treated in the step 3) in the salt solution A, performing ultrasonic impregnation and drying for 4 times, wherein the ultrasonic impregnation temperature is 35 ℃, the ultrasonic impregnation time is 3 hours, the drying temperature is 110 ℃, the drying time is 12 hours, calcining for 4 hours at 700 ℃ in an inert gas atmosphere, and naturally cooling to room temperature in the inert gas atmosphere to obtain the filler loaded with the metal oxide/metal sulfide.
Filler loaded with metal oxide/metal sulfide and used for desorbing CO from amine solution in carbon dioxide capture device2In the desorption tower, the amine solution in the desorption tower desorbs CO2The operating temperature of (2) was 92 ℃.
EXAMPLE seven
The filler loaded with the metal oxide/metal sulfide comprises a porous ceramic filler and a catalytic active component attached to the porous ceramic filler, wherein the catalytic active component comprises a metal oxide AmOnAnd metal sulfide BxSy。
The porous ceramic filler is in the form of ceramic balls.
Metal oxide AmOnIs CeO2；
Metal oxide BxSyIs CdS.
The preparation method of the filler loaded with the metal oxide/metal sulfide comprises the following steps:
1) removing impurities on the surface of the porous ceramic filler, cleaning the porous ceramic filler by adopting an oxalic acid solution with the mass percentage concentration of 50%, condensing, refluxing and boiling for 1h, cooling, washing by using deionized water until the pH value of a washing solution is 7, and then drying for 12h in an oven at 110 ℃;
2) adding nitrate of metal A into deionized water to obtain a salt solution A with the mass percentage concentration of 12%, and adding nitrate of metal B into deionized water to obtain a salt solution B with the mass percentage concentration of 12%;
3) immersing the porous ceramic filler in a B salt solution, performing ultrasonic impregnation and drying for 3 times, wherein the ultrasonic impregnation temperature is 35 ℃, the impregnation time is 2 hours, the drying temperature is 110 ℃, the drying time is 12 hours, then putting the porous ceramic filler into a vulcanizing device, and introducing H2S and N2And then sulfurizing at 400 ℃ for 0.7H, wherein H in the mixed gas2The volume percentage of S is 10 percent, and finally, the steel is naturally cooled to room temperature under the inert gas atmosphere;
4) immersing the porous ceramic filler treated in the step 3) in the salt solution A, performing ultrasonic impregnation and drying for 3 times, wherein the ultrasonic impregnation temperature is 35 ℃, the ultrasonic impregnation time is 2 hours, the drying temperature is 110 ℃, the drying time is 12 hours, calcining for 3 hours at the temperature of 600 ℃ in an inert gas atmosphere, and then naturally cooling to room temperature in the inert gas atmosphere to obtain the filler loaded with the metal oxide/metal sulfide.
Filler loaded with metal oxide/metal sulfide and used for desorbing CO from amine solution in carbon dioxide capture device2In the desorption tower, the amine solution in the desorption tower desorbs CO2The operating temperature of (2) was 90 ℃.
Example eight
The filler loaded with the metal oxide/metal sulfide comprises a porous ceramic filler and a catalytic active component attached to the porous ceramic filler, wherein the catalytic active component comprises a metal oxide AmOnAnd metal sulfide BxSy。
The porous ceramic filler is in the form of corrugated plate.
Metal oxide AmOnIs CeO2；
Metal oxide BxSyIs CdS.
The preparation method of the filler loaded with the metal oxide/metal sulfide comprises the following steps:
1) removing impurities on the surface of the porous ceramic filler, cleaning the porous ceramic filler by adopting an oxalic acid solution with the mass percentage concentration of 50%, condensing, refluxing and boiling for 1h, cooling, washing by using deionized water until the pH value of a washing solution is 7, and then drying for 12h in an oven at 110 ℃;
2) adding the nitrate of the metal A into deionized water to obtain a salt solution A with the mass percentage concentration of 6%, and adding the nitrate of the metal B into deionized water to obtain a salt solution B with the mass percentage concentration of 6%;
3) filling porous ceramicImmersing the materials in a B salt solution, performing ultrasonic impregnation and drying for 2.5 times, wherein the ultrasonic impregnation temperature is 35 ℃, the impregnation time is 1.2H, the drying temperature is 110 ℃, the drying time is 12H, then putting the materials into a vulcanizing device, and introducing H2S and N2Then sulfurizing at 350 deg.C for 0.3-1H, wherein H is contained in the mixed gas2The volume percentage of S is 8 percent, and finally, the steel is naturally cooled to room temperature under the inert gas atmosphere;
4) immersing the porous ceramic filler treated in the step 3) in the salt solution A, performing ultrasonic impregnation and drying for 2 times, wherein the ultrasonic impregnation temperature is 35 ℃, the ultrasonic impregnation time is 1.5h, the drying temperature is 110 ℃, the drying time is 12h, calcining for 2.5h at 550 ℃ in an inert gas atmosphere, and naturally cooling to room temperature in the inert gas atmosphere to obtain the filler loaded with the metal oxide/metal sulfide.
Filler loaded with metal oxide/metal sulfide and used for desorbing CO from amine solution in carbon dioxide capture device2In the desorption tower, the amine solution in the desorption tower desorbs CO2The operating temperature of (2) was 85 ℃.
Example nine
The filler loaded with the metal oxide/metal sulfide comprises a porous ceramic filler and a catalytic active component attached to the porous ceramic filler, wherein the catalytic active component comprises a metal oxide AmOnAnd metal sulfide BxSy。
The porous ceramic packing is in the form of Raschig rings.
Metal oxide AmOnIs ZrO2；
Metal oxide BxSyIs ZnS.
The preparation method of the filler loaded with the metal oxide/metal sulfide comprises the following steps:
1) removing impurities on the surface of the porous ceramic filler, cleaning the porous ceramic filler by adopting an oxalic acid solution with the mass percentage concentration of 50%, condensing, refluxing and boiling for 1h, cooling, washing by using deionized water until the pH value of a washing solution is 7, and then drying for 12h in an oven at 110 ℃;
2) adding the nitrate of the metal A into deionized water to obtain a salt solution A with the mass percentage concentration of 15%, and adding the nitrate of the metal B into deionized water to obtain a salt solution B with the mass percentage concentration of 15%;
3) immersing the porous ceramic filler in a B salt solution, performing ultrasonic impregnation and drying for 3 times, wherein the ultrasonic impregnation temperature is 35 ℃, the impregnation time is 2.5H, the drying temperature is 110 ℃, the drying time is 12H, then putting the porous ceramic filler into a vulcanizing device, and introducing H2S and N2Then sulfurizing at 450 deg.C for 0.8H, wherein H is in the mixed gas2The volume percentage of S is 12 percent, and finally, the steel is naturally cooled to room temperature under the inert gas atmosphere;
4) immersing the porous ceramic filler treated in the step 3) in the salt solution A, performing ultrasonic impregnation and drying for 3 times, wherein the ultrasonic impregnation temperature is 35 ℃, the ultrasonic impregnation time is 2.5h, the drying temperature is 110 ℃, the drying time is 12h, calcining for 3.5h at 650 ℃ in an inert gas atmosphere, and naturally cooling to room temperature in the inert gas atmosphere to obtain the filler loaded with the metal oxide/metal sulfide.
Filler loaded with metal oxide/metal sulfide and used for desorbing CO from amine solution in carbon dioxide capture device2In the desorption tower, the amine solution in the desorption tower desorbs CO2The operating temperature of (2) was 95 ℃.
Example ten
The filler loaded with the metal oxide/metal sulfide comprises a porous ceramic filler and a catalytic active component attached to the porous ceramic filler, wherein the catalytic active component comprises a metal oxide AmOnAnd metal sulfide BxSy。
The porous ceramic packing is in the form of a pall ring.
Metal oxide AmOnIs Al2O3；
Metal oxide BxSyIs CdS.
The preparation method of the filler loaded with the metal oxide/metal sulfide comprises the following steps:
1) removing impurities on the surface of the porous ceramic filler, cleaning the porous ceramic filler by adopting an oxalic acid solution with the mass percentage concentration of 50%, condensing, refluxing and boiling for 1h, cooling, washing by using deionized water until the pH value of a washing solution is 7, and then drying for 12h in an oven at 110 ℃;
2) adding the nitrate of the metal A into deionized water to obtain a salt solution A with the mass percentage concentration of 5%, and adding the nitrate of the metal B into deionized water to obtain a salt solution B with the mass percentage concentration of 20%;
3) immersing the porous ceramic filler in a B salt solution, performing ultrasonic impregnation and drying for 2 times, wherein the ultrasonic impregnation temperature is 35 ℃, the impregnation time is 3 hours, the drying temperature is 110 ℃, the drying time is 12 hours, then putting the porous ceramic filler into a vulcanizing device, and introducing H2S and N2And then sulfurizing at 500 deg.C for 0.3H, wherein H is in the mixed gas2The volume percentage of S is 15 percent, and finally, the steel is naturally cooled to room temperature under the inert gas atmosphere;
4) immersing the porous ceramic filler treated in the step 3) in the salt solution A, performing ultrasonic impregnation and drying for 2 times, wherein the ultrasonic impregnation temperature is 35 ℃, the ultrasonic impregnation time is 3 hours, the drying temperature is 110 ℃, the drying time is 12 hours, calcining for 4 hours at 500 ℃ in an inert gas atmosphere, and naturally cooling to room temperature in the inert gas atmosphere to obtain the filler loaded with the metal oxide/metal sulfide.
Filler loaded with metal oxide/metal sulfide and used for desorbing CO from amine solution in carbon dioxide capture device2In the desorption tower, the amine solution in the desorption tower desorbs CO2The operating temperature of (2) was 80 ℃.
Claims (8)
1. The filler loaded with the metal oxide/metal sulfide is characterized by comprising a porous ceramic filler and a catalytic active component attached to the porous ceramic filler, wherein the catalytic active component comprises a metal oxide AmOnAnd metal sulfide BxSy。
2. The metal oxide/metal sulfide-supporting filler according to claim 1, wherein the porous ceramic filler is in the form of pall rings, raschig rings, ceramic balls, or corrugated plates.
3. The metal oxide/metal sulfide-supporting filler according to claim 1, wherein the metal oxide A ismOnIs Al2O3、ZrO2Or CeO2；
Metal oxide BxSyIs ZnS or CdS.
4. A method for producing a metal oxide/metal sulfide-supporting filler according to claim 1, comprising the steps of:
1) pretreating the porous ceramic filler;
2) adding the nitrate of the metal A into deionized water to obtain a salt solution A with the mass percentage concentration of 5-20%, and adding the nitrate of the metal B into deionized water to obtain a salt solution B with the mass percentage concentration of 5-20%;
3) immersing the porous ceramic filler in the B salt solution, then carrying out ultrasonic impregnation, drying and vulcanization treatment, and then naturally cooling to room temperature under the inert gas atmosphere;
4) immersing the porous ceramic filler treated in the step 3) in the salt solution A, then carrying out ultrasonic impregnation, drying and calcination, and naturally cooling to room temperature to obtain the filler loaded with the metal oxide/metal sulfide.
5. The method for preparing a metal oxide/metal sulfide-supporting filler according to claim 4, wherein the specific operation of step 1) is:
removing impurities on the surface of the porous ceramic filler, cleaning the porous ceramic filler by adopting an oxalic acid solution with the mass percentage concentration of 50%, condensing, refluxing and boiling for 1h, cooling, washing by using deionized water until the pH value of a washing liquid is 7, and then drying for 12h in an oven at 110 ℃.
6. The method for producing a metal oxide/metal sulfide-supporting filler according to claim 4, wherein the specific operation of step 3) is:
immersing the porous ceramic filler in a B salt solution, performing ultrasonic impregnation and drying for 2-4 times, wherein the ultrasonic impregnation temperature is 35 ℃, the impregnation time is 1-3H, the drying temperature is 110 ℃, the drying time is 12H, then putting the porous ceramic filler into a vulcanizing device, and introducing H2S and N2Then sulfurizing the mixed gas at 300-500 ℃ for 0.3-1H, wherein H in the mixed gas2The volume percentage of S is 5-15%, and finally the product is naturally cooled to room temperature under the inert gas atmosphere.
7. The method for preparing a metal oxide/metal sulfide-supporting filler according to claim 4, wherein the specific operation of step 4) is:
immersing the porous ceramic filler treated in the step 3) in the salt solution A, then carrying out ultrasonic impregnation and drying for 2-4 times, wherein the ultrasonic impregnation temperature is 35 ℃, the ultrasonic impregnation time is 1-3 h, the drying temperature is 110 ℃, the drying time is 12h, then calcining for 2-4 h at the temperature of 500-700 ℃ in an inert gas atmosphere, and then naturally cooling to room temperature in the inert gas atmosphere to obtain the filler loaded with the metal oxide/metal sulfide.
8. The method for producing a metal oxide/metal sulfide-supporting filler according to claim 4, wherein the metal oxide/metal sulfide-supporting filler is used for desorption of CO from an amine solution in a carbon dioxide capturing apparatus2In the desorption tower, the amine solution in the desorption tower desorbs CO2The operating temperature of (A) is 80-95 ℃.
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