CN114505046A - Cerium dioxide nanocrystalline composite material and preparation method and application thereof - Google Patents
Cerium dioxide nanocrystalline composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims abstract description 45
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000001354 calcination Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000002159 nanocrystal Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 229910001868 water Inorganic materials 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- 239000011593 sulfur Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000002808 molecular sieve Substances 0.000 claims description 23
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000002707 nanocrystalline material Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 5
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 22
- 239000007789 gas Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003463 adsorbent Substances 0.000 description 9
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 6
- 230000023556 desulfurization Effects 0.000 description 6
- 239000011734 sodium Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000001741 organic sulfur group Chemical group 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N carbon disulfide Substances S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 238000012546 transfer 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
-
- 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
-
- 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
Abstract
The invention provides a cerium dioxide nanocrystalline composite material and a preparation method and application thereof, wherein the preparation method comprises the following steps: preparing a cerium nitrate solution; adding a nano-crystal material into the cerium nitrate solution, uniformly stirring and drying to obtain a cerium dioxide nano-crystal precursor; and calcining the cerium dioxide nanocrystalline precursor to obtain the cerium dioxide nanocrystalline composite material. The cerium dioxide nanocrystalline composite material provided by the invention has the advantages of regular shape, controllable size, large adsorption capacity, low regeneration condition, high sulfur removal rate of over 99 percent, strong water resistance and high hydrothermal stability, and is suitable for actual industrial production conditions.
Description
Technical Field
The invention relates to the technical field of fine desulfurization, and particularly relates to a cerium dioxide nanocrystalline composite material and a preparation method and application thereof.
Background
With the increasing demand of industrial development on fossil fuels and the increasing emission of sulfur dioxide, the harm to human health and ecological environment is great, and the enhancement of sulfur dioxide pollution prevention and control is an important subject to be solved urgently in air pollution control engineering.
Sulfur dioxide mainly comes from hydrogen sulfide and organic sulfur combustion such as carbonyl sulfide, carbon disulfide, methyl sulfide and the like, and treatment technologies can be divided into three types: the front desulfurization, the combustion process desulfurization and the rear desulfurization, and various desulfurization technologies have advantages and disadvantages and mainly depend on the performances of materials such as an absorbent, an adsorbent, a catalyst and the like.
At present, the desulfurization is mainly carried out by adsorbents or catalysts such as activated carbon, molecular sieves, transition metal oxides and the like at home and abroad. In the prior art, the organic sulfur hydrolysis catalyst has extremely high catalytic activity, but has short service life, and is easy to generate sulfur and deactivate. The active carbon adsorbent has excellent adsorption effect on sulfur dioxide and hydrogen sulfide, but is not high in temperature resistance, and the application condition is limited. The transition metal oxide has good effect of adsorbing hydrogen sulfide, but the temperature requirement is harsh. The molecular sieve has stable adsorption and catalytic properties, high temperature resistance, high hydrothermal stability and cheap and easily available raw materials, and is a research focus for removing sulfur-containing gas in recent years.
Disclosure of Invention
In view of the above, the invention provides a cerium dioxide nanocrystal composite material, and a preparation method and an application thereof, so as to promote the application of a molecular sieve desulfurizer.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a cerium dioxide nanocrystalline composite material comprises the following steps:
s1, preparing a cerous nitrate solution;
s2, adding a nanocrystalline material into the cerium nitrate solution, uniformly stirring, and drying to obtain a cerium dioxide nanocrystalline precursor;
and S3, calcining the cerium dioxide nanocrystal precursor to obtain the cerium dioxide nanocrystal composite material.
Optionally, in step S1, the concentration of the cerium nitrate solution is in the range of 0.1mol/L to 3 mol/L.
Optionally, ethanol, methanol, isopropanol or water is used as a solvent in the preparation of the cerium nitrate solution.
Optionally, in step S2, the nanocrystalline material is a molecular sieve, a mesoporous molecular sieve, or silica, the molecular sieve including at least one of MFI, FAU, Beta, and ZSM-5.
Optionally, in step S2, the volume of the nanocrystalline material and the volume of the cerium nitrate solution are equal.
Optionally, in step S2, the stirring time is in a range of 3h to 24 h.
Optionally, in step S2, the drying condition includes: the drying temperature is in the range of 60 ℃ to 150 ℃, and the drying time is in the range of 8h to 24 h.
Alternatively, in step S3, the calcining conditions include: the calcination temperature is within the range of 200 ℃ to 600 ℃, the calcination time is within the range of 0.5h to 10h, and the heating rate is within the range of 1 ℃/min to 10 ℃/min.
On the basis of the above scheme, the second objective of the present invention is to provide a ceria nano-crystalline composite material, which is prepared by the above method for preparing a ceria nano-crystalline composite material.
On the basis of the above scheme, the third objective of the present invention is to provide an application of the above ceria nano-crystal composite material in the field of sulfur-containing gas removal.
Compared with the prior art, the invention has the following advantages:
(1) the invention synthesizes the cerium dioxide nanocrystalline composite material by using the nanocrystalline material as the substrate, has simple preparation method, short synthesis period, low requirement on equipment, low cost and easy realization of industrialization.
(2) The cerium dioxide nanocrystalline composite material prepared by the invention has regular shape and controllable size, and compared with common molecular sieve adsorbents and metal oxide adsorbents, the cerium dioxide nanocrystalline composite material has the advantages of large adsorption capacity, low regeneration condition, removal rate of over 99 percent, extremely strong water resistance and high hydrothermal stability, and is suitable for actual industrial production conditions.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, specific embodiments thereof are described in detail below.
It should be noted that in the description of the embodiments herein, the description of the term "some embodiments" means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. Throughout this specification, the schematic representations of the terms used above do not necessarily refer to the same implementation or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. The term "in.. range" as used herein includes both ends, such as "in the range of 1 to 100" including both ends of 1 and 100.
Cerium oxide (CeO)2) Is a rare earth catalytic material and has wide application in the aspects of motor vehicle tail gas treatment, industrial flue gas denitration and catalytic combustion of volatile organic pollutants (VOCs). Compared with the prior molecular sieve adsorbents such as AgY, AgX, CuY, Z/Y and the like and metal oxide adsorbents, the method has the advantages of small adsorption capacity and low sulfur removal rate. The cerium dioxide and the nanocrystalline material are compounded to form a porous structure material with a large specific surface area, so that the removal rate of sulfur in sulfur-containing gas is improved, and certain feasibility is achieved.
Based on the above strategy, the embodiment of the present invention provides a method for preparing a cerium dioxide nanocrystal composite material, comprising the following steps:
s1, preparing a cerous nitrate solution;
s2, adding the nanocrystalline material into a cerium nitrate solution, uniformly stirring, and drying to obtain a cerium dioxide nanocrystalline precursor;
and S3, calcining the cerium dioxide nanocrystal precursor to obtain the cerium dioxide nanocrystal composite material.
Therefore, the embodiment of the invention synthesizes the cerium dioxide nanocrystalline composite material by using the nanocrystalline material as the substrate, the cerium dioxide nanocrystalline composite material has larger specific surface area and rich and regular and ordered pore channel structures, and the special pore channel network structures can provide better mass transfer effect and larger contact area for gas-solid phase reaction, thereby being very beneficial to the removal of sulfur.
Specifically, in step S1, ethanol, methanol, isopropanol or water is used as a solvent in the process of preparing the cerium nitrate solution. Due to Ce (NO) in each system3)3The solubility varies, and the concentration varies, and preferably, the concentration of the cerium nitrate solution is in the range of 0.1mol/L to 3 mol/L.
Specifically, in step S2, the nanocrystal material is a molecular sieve, a mesoporous molecular sieve, or silica, and the molecular sieve includes at least one of MFI, FAU, Beta, and ZSM-5.
To increase the reaction degree, further, the volume of the nanocrystalline material and the cerium nitrate solution are equal. Wherein the stirring time is in the range of 3h to 24h, so as to avoid uneven mixing or precipitate formation.
After stirring, placing the solution in an oven for drying, wherein the drying conditions comprise: the drying temperature is in the range of 60 ℃ to 150 ℃, and the drying time is in the range of 8h to 24 h.
Specifically, in step S3, the conditions for the calcination of the ceria nanocrystal precursor include: the calcination temperature is within the range of 200 ℃ to 600 ℃, the calcination time is within the range of 0.5h to 10h, and the heating rate is within the range of 1 ℃/min to 10 ℃/min.
Therefore, the preparation method provided by the embodiment of the invention is simple, short in synthesis period, low in equipment requirement, low in cost and easy to realize industrialization.
On the basis of the above scheme, another embodiment of the present invention provides a ceria nanocrystal composite material, which is prepared by the above method for preparing a ceria nanocrystal composite material.
On the basis of the above scheme, another embodiment of the present invention provides an application of the above ceria nano-crystalline composite material in the field of sulfur-containing gas removal.
The cerium dioxide nanocrystalline composite material provided by the embodiment of the invention has regular shape and controllable size, and compared with a common molecular sieve adsorbent and a metal oxide adsorbent, the cerium dioxide nanocrystalline composite material has the advantages of large adsorption capacity, low regeneration condition, removal rate of over 99 percent, extremely strong water resistance and high hydrothermal stability, and is suitable for actual industrial production conditions.
On the basis of the above embodiments, the present invention is further illustrated by the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are examples of experimental procedures not specified under specific conditions, generally according to the conditions recommended by the manufacturer. Unless otherwise indicated, percentages and parts are by mass.
Example 1
The embodiment provides a preparation method of a cerium dioxide nanocrystalline composite material, which comprises the following steps:
1) synthesis of Y molecular sieve
a. Preparation of directing agent
According to Na2O:S/O2:Al2O3:H2O16: 15: 1: feeding in 320 proportion, wherein the feeding sequence is as follows: adding sodium hydroxide, sodium metaaluminate and a certain amount of water, stirring and dissolving, then adding a certain amount of water glass, stirring for 60min at room temperature, and then aging for 24h at 30 ℃ to obtain the guiding agent.
b. Preparing a master batch liquid:
according to Na2O:S/O2:Al2O3:H2O ═ 0.34: 10: 1: 144 proportion feeding, and the feeding sequence: adding sodium hydroxide, sodium metaaluminate and a certain amount of water, stirring and dissolving, and then adding a certain amount of water glass chamberStirring for 10min, adding guiding agent 10% of the total mother liquor, aging at 50 deg.C for 1 hr, and crystallizing at 95 + -5 deg.C for 24 hr; and after crystallization is finished, filtering and washing until the pH value is 8-9, drying in a drying oven at 110 ℃ and calcining in a muffle furnace at 550 ℃ for 5 hours to obtain the NaY molecular sieve.
2)CeO2Preparation of the-Y composite
S1, configuration 0.5M concentration Ce (NO)3)3A solution;
s2, weighing NaY molecular sieve, adding equal volume of Ce (NO) into the NaY molecular sieve3)3Stirring the solution for 12 ℃, and drying the turbid solution at 100 ℃ to obtain CeO2-a Y composite precursor;
s3, mixing CeO2Placing the Y composite material precursor in a muffle furnace for calcining and dehydrating, wherein the calcining temperature is as follows: 500 ℃, heating rate: the temperature is 2 ℃/min, the time is 5h, and CeO is obtained2-Y composite material.
Example 2
The embodiment provides a preparation method of a cerium dioxide nanocrystalline composite material, which comprises the following steps:
1) beta molecular sieve synthesis
According to Na2O:(TEA)2O:S/O2:Al2O3:H2O ═ 1.4: 18: 100: 1: 1180 proportional addition, the order of addition: firstly adding tetraethyl ammonium hydroxide, aluminum isopropoxide, sodium hydroxide and a certain amount of water, stirring and dissolving, then adding a certain amount of silica sol, stirring for 2 hours at room temperature, then carrying out crystal sublimation for 72 hours at 100 ℃, centrifuging and washing until the pH value is neutral after crystallization is finished, drying in a 100 ℃ oven, and calcining for 4 hours at 550 ℃ in a muffle furnace to obtain the Na beta molecular sieve.
2)CeO2Preparation of beta-composite materials
S1, configuration 0.5M concentration Ce (NO)3)3A solution;
s2, weighing Na beta molecular sieve, adding equal volume of Ce (NO) into the Na beta molecular sieve3)3Stirring the solution for 6h, and drying the turbid solution at 100 ℃ to obtain CeO2-a beta composite precursor;
s3, mixing CeO2Placing the beta composite material precursor in a muffle furnace for calcining and dehydrating, wherein the calcining temperature is as follows: 500 ℃, heating rate: the temperature is 2 ℃/min, the time is 5h, and CeO is obtained2-beta composite material.
Example 3
The embodiment provides a preparation method of a cerium dioxide nanocrystalline composite material, which comprises the following steps:
1) SBA-15 Synthesis
Respectively weighing 36g of surfactant P123 and 36g of glycerol, dissolving the surfactant P123 and the glycerol in 1380g of dilute hydrochloric acid with the concentration of 1.5mol/L, then placing the solution in a water bath at 35 ℃ for stirring, dropwise adding 77.4g of Tetraethoxysilane (TEOS) under the condition of vigorous stirring after the P123 is completely dissolved to be transparent, stopping stirring for 5min continuously, then sealing the mixed solution and the water bath kettle with a preservative film, and standing the solution in the water bath at 35 ℃ for 24 h; and then transferring the mixture into a reaction kettle, aging for 24h at 120 ℃, cooling, filtering, repeatedly washing with deionized water to neutrality, finally washing with ethanol for several times, then putting the product into a drying oven at 100 ℃, finally putting the product into a muffle furnace, heating to 550 ℃ at the speed of 2 ℃/min, treating for 5h, removing the residual surfactant, and finally obtaining the ordered mesoporous silica template SBA-15.
2) Preparation of CeO2-SBA-15 composite material
S1, configuration 1M concentration Ce (NO)3)3A solution;
s2, weighing SBA-15, adding equal volume of Ce (NO) into the SBA-153)3Stirring the solution for 6h, and drying the turbid solution at 100 ℃ to obtain CeO2-an SBA-15 composite precursor;
s3, mixing CeO2Placing the SBA-15 composite material precursor in a muffle furnace for calcining and dehydrating, wherein the calcining temperature is as follows: 500 ℃, heating rate: the temperature is 2 ℃/min, the time is 5h, and then the CeO is obtained2-SBA-15 composite material.
The cerium oxide nanocrystalline composites prepared in examples 1-3 were tested:
and (3) activity test: the test is carried out by using a normal pressure fixed bed reactor, and 1g of dry catalyst CeO is added2-nanocrystalline composite material (40-60 mesh)Placed in the center of the reactor, the reaction gas is composed of 100ppm COS and 500ppm H2S、100ppm CS2N2, at 25-80 deg.C, setting the total flow rate at 10-50mL min-1The reaction gas entered the reactor and was continuously measured by a gas phase analyzer. The test results are shown in table 1.
TABLE 1 CeO described in examples 1-32Table of results of sulfur-containing gas adsorption of nanocrystalline composite
As can be seen from Table 1, CeO prepared according to the present invention2The nanocrystalline composite material has high sulfur-containing gas removal rate and good water performance under the simulated gas condition of 25-80 ℃, does not need to greatly modify the original tail gas discharge system in practical application, is simple to operate, easy to control, conforms to the actual national conditions of China, is easy to popularize and use, and has high application value.
Although the present disclosure has been described with reference to the above embodiments, the scope of the present disclosure is not limited thereto. Various changes and modifications may be effected therein by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present disclosure, and these changes and modifications are intended to be within the scope of the present disclosure.
Claims (10)
1. A preparation method of a cerium dioxide nanocrystalline composite material is characterized by comprising the following steps:
s1, preparing a cerous nitrate solution;
s2, adding a nanocrystalline material into the cerium nitrate solution, uniformly stirring, and drying to obtain a cerium dioxide nanocrystalline precursor;
and S3, calcining the cerium dioxide nanocrystal precursor to obtain the cerium dioxide nanocrystal composite material.
2. The method according to claim 1, wherein in step S1, the concentration of the cerium nitrate solution is in the range of 0.1 to 3 mol/L.
3. The method according to claim 1 or 2, wherein ethanol, methanol, isopropanol or water is used as a solvent in the preparation of the cerium nitrate solution.
4. The method of claim 3, wherein in step S2, the nanocrystal material is a molecular sieve, a mesoporous molecular sieve, or silica, and the molecular sieve includes at least one of MFI, FAU, Beta, and ZSM-5.
5. The method according to claim 3, wherein in step S2, the volume of the nanocrystalline material and the volume of the cerium nitrate solution are equal.
6. The method according to claim 5, wherein in step S2, the stirring time is in the range of 3h to 24 h.
7. The method according to claim 6, wherein in step S2, the drying conditions include: the drying temperature is in the range of 60 ℃ to 150 ℃, and the drying time is in the range of 8h to 24 h.
8. The method according to claim 1, wherein in step S3, the calcining conditions include: the calcination temperature is within the range of 200 ℃ to 600 ℃, the calcination time is within the range of 0.5h to 10h, and the heating rate is within the range of 1 ℃/min to 10 ℃/min.
9. A cerium oxide nanocrystal composite material characterized by being produced by the method for producing a cerium oxide nanocrystal composite material according to any one of claims 1 to 8.
10. The use of the ceria nanocrystalline composite according to claim 9 in the field of sulfur-containing gas removal.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005007383A (en) * | 2003-05-28 | 2005-01-13 | Idemitsu Kosan Co Ltd | Adsorbent for removing sulfur compound and method for producing hydrogen for fuel cell |
US20080241054A1 (en) * | 2007-03-30 | 2008-10-02 | Tsinghua University | Method for making metal oxide nanocrystal |
CN101584981A (en) * | 2009-06-12 | 2009-11-25 | 华中师范大学 | Low-temperature preparation method of ceria nano-crystalline microsphere of graduation structure |
US20190055126A1 (en) * | 2015-09-22 | 2019-02-21 | Suzhou Xingshou Nanotech Co., Ltd. | Nanocrystal preparation method, nanocrystals, and apparatus for preparing and storing dissolved gas |
CN112844444A (en) * | 2021-01-25 | 2021-05-28 | 清华大学 | Method for preparing cerium dioxide catalytic material by utilizing carrier pore channel self-adsorption principle |
-
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- 2022-02-28 CN CN202210185056.3A patent/CN114505046A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005007383A (en) * | 2003-05-28 | 2005-01-13 | Idemitsu Kosan Co Ltd | Adsorbent for removing sulfur compound and method for producing hydrogen for fuel cell |
US20080241054A1 (en) * | 2007-03-30 | 2008-10-02 | Tsinghua University | Method for making metal oxide nanocrystal |
CN101584981A (en) * | 2009-06-12 | 2009-11-25 | 华中师范大学 | Low-temperature preparation method of ceria nano-crystalline microsphere of graduation structure |
US20190055126A1 (en) * | 2015-09-22 | 2019-02-21 | Suzhou Xingshou Nanotech Co., Ltd. | Nanocrystal preparation method, nanocrystals, and apparatus for preparing and storing dissolved gas |
CN112844444A (en) * | 2021-01-25 | 2021-05-28 | 清华大学 | Method for preparing cerium dioxide catalytic material by utilizing carrier pore channel self-adsorption principle |
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