CN109304172A - A kind of high dispersing microporous/mesoporous Ag-Al catalyst, preparation method and applications - Google Patents
A kind of high dispersing microporous/mesoporous Ag-Al catalyst, preparation method and applications Download PDFInfo
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- CN109304172A CN109304172A CN201711133476.2A CN201711133476A CN109304172A CN 109304172 A CN109304172 A CN 109304172A CN 201711133476 A CN201711133476 A CN 201711133476A CN 109304172 A CN109304172 A CN 109304172A
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- high dispersing
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 14
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000007084 catalytic combustion reaction Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 230000000694 effects Effects 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000006073 displacement reaction Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 6
- 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 description 5
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- -1 polyethylene Polymers 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920000428 triblock copolymer Polymers 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 229910000510 noble metal Inorganic materials 0.000 abstract description 10
- 239000012855 volatile organic compound Substances 0.000 abstract description 9
- 238000001338 self-assembly Methods 0.000 abstract description 5
- 230000009257 reactivity Effects 0.000 abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 239000002912 waste gas Substances 0.000 abstract description 2
- 238000002485 combustion reaction Methods 0.000 abstract 1
- 239000010970 precious metal Substances 0.000 abstract 1
- 229910002001 transition metal nitrate Inorganic materials 0.000 abstract 1
- 239000002985 plastic film Substances 0.000 description 8
- 229920006255 plastic film Polymers 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 2
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ISHFYECQSXFODS-UHFFFAOYSA-M 1,2-dimethyl-3-propylimidazol-1-ium;iodide Chemical compound [I-].CCCN1C=C[N+](C)=C1C ISHFYECQSXFODS-UHFFFAOYSA-M 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- OBROYCQXICMORW-UHFFFAOYSA-N tripropoxyalumane Chemical compound [Al+3].CCC[O-].CCC[O-].CCC[O-] OBROYCQXICMORW-UHFFFAOYSA-N 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of high dispersing microporous/mesoporous Ag-Al catalyst, preparation method and applications, belong to petrochemical industry.Which solve precious metal catalyst combustion catalyst load capacity existing in VOCs catalytic combustion process is low, cause effectively to contact in reaction process it is poor, while the defects of noble metal catalyst is at high cost, sulfur resistive is not malicious.The present invention is using silver nitrate and aluminium isopropoxide as raw material, transition metal nitrate is auxiliary agent, and P123 is template, introduces hydrochloric acid, nitric acid or phosphoric acid and adjusts acid-base property, synthetic reaction is carried out by " solvent volatilization-solute self assembly " method, the mesoporous Ag-Al catalyst being finally prepared by roasting.The Ag-Al catalyst that the present invention is prepared has high reactivity to waste gas containing benzene, is 35000h in air speed‑1Under conditions of, reaction temperature is lower than 280 DEG C when conversion ratio is not less than 99%, and alternative noble metal catalyst is in catalytic combustion process.
Description
Technical field
The invention belongs to petrochemical industry, it is related to a kind of volatile organic compounds catalyst for catalytic combustion and its preparation
Method, especially a kind of high dispersing microporous/mesoporous Ag-Al catalyst, preparation method and applications.
Background technique
With China start to push forward comprehensively implementation " petroleum refining industry pollutant emission standard " (GB31570-2015) and
" petro chemical industry pollutant emission standard " (GB31571-2015), volatile organic compounds (VOCs) and Partial Feature are dirty
The discharge needs of dye object reach harsher requirement.Required in above-mentioned two standard the treatment effeciency of non-methane total hydrocarbons >=
97%, non-methane hydrocarbon emission limit value≤120mg/m3, benzene≤4mg/m is required in organic properties pollutant emission limit3, toluene
≤15mg/m3, dimethylbenzene≤20mg/m3.Traditional oil-gas recovery method, including absorption method, absorption process, membrane separation process, condensation method
And combinations thereof technique, such as absorption-absorption process, condensation-absorption method be difficult to reach so low emission request.Therefore, it is catalyzed
The popularization and application of burning process are extremely urgent tasks.
Currently, being directed to the catalytic combustion process of VOCs, what industrially application was more is noble metal catalyst, such as platinum group, palladium
Series catalysts.The advantages of noble metal catalyst is that its catalytic reaction activity is higher, and initiation temperature is lower.But due to noble metal
Very rare, price is very expensive, and leading to entire catalytic combustion system, the cost is relatively high, answers to limit its popularization
With.Meanwhile common noble metal catalyst is prepared using infusion process, is limited to the low-down load capacity of active component, usually
No more than 0.5wt.%, cause on carrier (such as γ-Al2O3Or SiO2) overwhelming majority that exposes is non-catalytic reaction activity
Carrier surface, be unfavorable for effectively contacting and subsequent reaction between reaction raw materials and catalyst activity component, thus seriously
Affect catalytic reaction activity.In addition, being produced for refinery, oil depot etc. in discharged VOCs, it will usually containing having for some
Machine sulfide, and noble metal catalyst is very easy to sulfur poisoning and leads to not play reactivity.
Summary of the invention
In order to solve above-mentioned defect existing in the prior art, the present invention passes through " solvent volatilization-solute self assembly " method
It is prepared for a kind of mesoporous Ag-Al catalyst of active component high degree of dispersion, alternative noble metal catalyst is for being catalyzed burner
Skill.
One of task of the invention is to provide a kind of high dispersing microporous/mesoporous Ag-Al catalyst.
A kind of high dispersing microporous/mesoporous Ag-Al catalyst, required raw material include catalyst activity component, auxiliary agent, catalyst carrier,
Template and solvent；
The catalyst activity component is selected from silver nitrate, and the auxiliary agent is nitrate；
The catalyst carrier is aluminium isopropoxide, and the template is selected from polyethylene oxide-polypropylene oxide-polycyclic oxygen second
Alkane triblock copolymer, the solvent are Organic Alcohol；
The mass content of Ag is 1~30% in the Ag-Al catalyst, and the mass content of the auxiliary agent is 0.1~20%,
The specific surface area of the Ag-Al catalyst is 250~400m2/g。
The direct bring advantageous effects of above-mentioned technical proposal are as follows:
Active component A g and auxiliary agent are anchored in mesopore orbit, not only facilitate the high degree of dispersion of active component, while solely
The interaction of special mesopore orbit structure feature and active component and mesopore orbit wall aluminium oxide can be reasonably resistant to organic sulfur
Poisoning effect of the compound to active component.Meanwhile high dispersing microporous/mesoporous Ag-Al catalyst specific surface area with higher and relatively narrow
Pore distribution enhances reaction raw materials in the diffusion of catalyst, promotes catalyst reaction activity.
As a preferred solution of the present invention, the nitrate solution is selected from cerous nitrate, lanthanum nitrate, manganese nitrate, nitric acid
The mixture of one or both of cobalt or zirconium nitrate.
As another preferred embodiment of the invention, the organic alcohol solvent is selected from methanol, ethyl alcohol, 1- propyl alcohol or 2- third
Alcohol.
Another task of the invention is to provide the preparation method of above-mentioned high dispersing microporous/mesoporous Ag-Al catalyst, successively includes
Following steps:
A weighs a certain amount of template and aluminium isopropoxide respectively, measures a certain amount of acid, is added sequentially to stir in container
Until dissolution；
B weighs a certain amount of silver nitrate solution and auxiliary agent is added in the container of step a, and stirs；
Step b is equipped with the container closure of silver nitrate solution and auxiliary agent by c, is stirred at room temperature；
After d opens vessel port, it is placed in baking oven and controls in 50~70 DEG C of dry no less than 12h；
E takes out the solid after drying in an oven, then is roasted up to high dispersing microporous/mesoporous Ag-Al catalyst.
Further, the additional amount of the template and the quality proportioning of aluminium isopropoxide are 0.1~0.7:1.
Further, above-mentioned roasting process carries out in Muffle furnace, with 1~2 DEG C/min of heating rate in roasting process
It is warming up to 500 DEG C and maintains 4 hours, and Muffle furnace air is in displacement circulation status.
Further, above-mentioned acid is hydrochloric acid, nitric acid or phosphoric acid, above-mentioned acid and the quality proportioning of aluminium isopropoxide be 0.3~
1:1。
In above-mentioned preparation method, committed step is to adjust content, assistant types and the content of active component silver and above-mentioned
The type and dosage of acid, the adjusting of mixing time and calcination procedure is added in the material ratio of the two and aluminium isopropoxide, and roasts
Program includes the parameters such as heating rate, platform temperature, maturing temperature again.By the adjusting of above-mentioned key parameter, can effectively adjust
Control the physical-chemical parameters such as the active composition of high dispersing microporous/mesoporous Ag-Al catalyst, surface topography, microstructure, pore property.
Another task of the invention is to provide application of the above-mentioned Ag-Al catalyst in catalytic combustion process.
Above-mentioned concrete application is embodied in: in catalytic combustion process, being handled the organic sulfur compound in VOCs.
Compared with prior art, high dispersing microporous/mesoporous Ag-Al method for preparing catalyst proposed by the present invention is novel, the object of product
Physicochemical nature parameters are easy to regulate and control, catalytic reaction activity and sulfur resistive poison better performances, while may be implemented extensive in factory
Metaplasia produces, and facilitates product and prepares conversion to industrial application from laboratory.
Compared with existing loaded noble metal catalyst, the Ag-Al catalyst used in the present invention is using novel
" solvent volatilization-solute self assembly " method is prepared, and active component can be highly dispersed in catalyst duct, to play
Higher reactivity；Meanwhile active component silver and auxiliary agent are anchored in mesopore orbit, it is mutual between cell walls aluminium oxide
Effect can effectively resist the poisoning effect of organic sulfur compound；Finally, novel is high dispersing microporous/mesoporous compared with noble metal catalyst
Ag-Al catalyst cost has to be declined more significantly, has more wide prospects for commercial application and economic benefit.
Ag-Al catalyst specific surface area with higher, reaches 250m prepared by the present invention2/ g or more, unique Jie
Hole pore distribution enhances the haptoreaction between VOCs and active component, lower to the initiation temperature of benzene, reaches 250 DEG C, complete
Full conversion temperature (conversion ratio >=99%) is not higher than 280 DEG C.Active component and the interaction of mesopore orbit wall inhibit simultaneously
Toxic action of the sulfide to catalyst.Therefore, the Ag-Al catalyst is in the zero-emission field that becomes of VOCs with wide application
Prospect and commercial value.
Detailed description of the invention
The present invention will be further described with reference to the accompanying drawing:
Fig. 1 is the high dispersing microporous/mesoporous Ag-Al catalyst electron scanning micrograph of the present invention；
Fig. 2 is the low temperature nitrogen adsorption desorption curve graph of high dispersing microporous/mesoporous Ag-Al catalyst；
Fig. 3 is high dispersing microporous/mesoporous Ag-Al catalyst graph of pore diameter distribution.
Specific embodiment
It is of the invention in order to make the invention proposes a kind of high dispersing microporous/mesoporous Ag-Al catalyst, preparation method and applications
Advantage, technical solution are clearer, clear, elaborate combined with specific embodiments below to the present invention.
Raw material needed for the present invention can be commercially available by commercial channel,
Template used dose of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer of the invention, it is real below
It applies and is referred to as P123 in example.
Embodiment 1:
In the present embodiment, being prepared for the Ag-Al catalyst that the mass ratio of Ag:Ce:Al is about 10:2:88, (Ce is to help
Agent).
It is specific the preparation method is as follows:
Firstly, 21g template P123 is dissolved in the beaker for filling 400mL1- propyl alcohol, 32mL concentrated nitric acid and 41g are added
Aluminium isopropoxide is continuously vigorously stirred 30 minutes；
Secondly, by 6.8g silver nitrate (AgNO3) and 1.2g cerous nitrate (Ce (NO3)3·6H2O it) is sequentially added in above-mentioned solution
And it is stirred continuously；
Then, beaker mouth is covered with PET plastic film and bound, continuously stir 12 hours；
PET plastic film is removed, and is placed the beaker in vacuum oven, it is 14 hours dry at 55 DEG C；
Finally, the plastic-like solid in beaker is taken out, it is placed in Muffle furnace, is warming up to 2 DEG C/min of heating rate
500 DEG C and maintenance 4 hours, during which Muffle furnace air is constantly in displacement circulation status.It takes out when being down to room temperature to get height
Disperse mesoporous Ag-Al catalyst.
The mass ratio of each component Ag:Ce:Al is about 10:2:88 in catalyst manufactured in the present embodiment (in terms of oxide).
Electron microscope analysis and performance test are done to the high dispersing microporous/mesoporous Ag-Al catalyst that the present embodiment is prepared.Electronic Speculum point
As shown in FIG. 1, FIG. 1 is the scanning electron microscope (SEM) of high dispersing microporous/mesoporous Ag-Al catalyst characterization, Fig. 1 shows by new for analysis
In the Ag-Al catalyst of " solvent volatilization-solute self assembly " the method preparation of type, active component is gathered in one in a manner of piling up
It rises.
Fig. 2 is the low temperature nitrogen adsorption desorption curve of high dispersing microporous/mesoporous Ag-Al catalyst, and display Ag-Al catalyst has allusion quotation
The Type IV type of type shows that the Ag-Al catalyst has mesopore orbit feature, while its BET method specific surface area reaches
325m2/ g, Kong Rong have also reached 0.47cm3/g；
Fig. 3 is the graph of pore diameter distribution of high dispersing microporous/mesoporous Ag-Al catalyst, display product pore-size distribution is concentrated mainly on 1~
Between 8nm, most probable pore size is 6nm or so.
Embodiment 2:
In the present embodiment, being prepared for the Ag-Al catalyst that the mass ratio of Ag:La:Al is about 20:5:75, (La is to help
Agent).
Specific preparation method the following steps are included:
Firstly, 12g template P123 is dissolved in the beaker for filling 400mL methanol, adds 21mL concentrated hydrochloric acid and 27g is different
Aluminium propoxide is continuously vigorously stirred 30 minutes；
Secondly, by 5.3g silver nitrate (AgNO3) and 2.4g lanthanum nitrate (La (NO3)3·6H2O it) is sequentially added in above-mentioned solution
And it is stirred continuously；
Then, beaker mouth is covered with PET plastic film and bound, continuously stir 12 hours；
PET plastic film is removed, and is placed the beaker in vacuum oven, it is 16 hours dry at 55 DEG C；
Finally, the plastic-like solid in beaker is taken out, it is placed in Muffle furnace, is warming up to 2 DEG C/min of heating rate
500 DEG C and maintenance 4 hours, during which Muffle furnace air is constantly in displacement circulation status.It takes out when being down to room temperature to get height
Disperse mesoporous Ag-Al catalyst.
The mass ratio of each component Ag:La:Al is about 20:5:75 in catalyst manufactured in the present embodiment (in terms of oxide).
Pass through the Ag-La-Al catalyst of this kind of novel " solvent volatilization-solute self assembly " method preparation, the SEM result of gained sample
It is similar with Fig. 1 result, it was demonstrated that the Ag-Al catalyst series with similar microstructure can be prepared by this kind of method.
Low temperature nitrogen adsorption desorption the experimental results showed that, improve the content of active component and introduced after auxiliary agent lanthanum simultaneously, BET
There is a little decline in specific surface area, is 295m2/ g, Kong Rong have been also reduced to 0.42cm3/ g, and its Type IV type meso pore characteristics
No change has taken place.
Embodiment 3:
In the present embodiment, the Ag-Al catalyst (not adding auxiliary agent) that the mass ratio for being prepared for Ag:Al is about 25:75.
Specific preparation method the following steps are included:
Firstly, 18g template P123 is dissolved in the beaker for filling 400mL dehydrated alcohol, add 28mL concentrated nitric acid and
23g aluminium isopropoxide is continuously vigorously stirred 30 minutes；
Secondly, by 5.6g silver nitrate (AgNO3) be sequentially added in above-mentioned solution and be stirred continuously；
Then, beaker mouth is covered with PET plastic film and bound, continuously stir 16 hours；
PET plastic film is removed, and is placed the beaker in vacuum oven, it is 15 hours dry at 65 DEG C；
Finally, the plastic-like solid in beaker is taken out, it is placed in Muffle furnace, is heated up with 1.5 DEG C/min of heating rate
It to 500 DEG C and maintains 5 hours, during which Muffle furnace air is constantly in displacement circulation status.Taking-up when being down to room temperature, obtains
High dispersing microporous/mesoporous Ag-Al catalyst,
The mass ratio of each component Ag:Al is about 25:75 in the catalyst (in terms of oxide).
Using waste gas containing benzene as raw material, the reactivity of catalyst in embodiment 1,2 and 3 is investigated, as shown in table 1.
Note: reaction velocity 35000h-1。
Embodiment 4:
In the present embodiment, be prepared for Ag-Al catalyst that the mass ratio of Ag:Ce:La:Al is about 15:5:5:75 (Ce,
La is auxiliary agent).
Specific preparation method the following steps are included:
Firstly, 32g template P123 is dissolved in the beaker for filling 400mL methanol, 42mL phosphoric acid and 49g isopropyl are added
Aluminium alcoholates is continuously vigorously stirred 30 minutes；
Secondly, by 9.6g silver nitrate (AgNO3), 2.0g cerous nitrate (Ce (NO3)3·6H2) and 2.2g lanthanum nitrate (La O
(NO3)3·6H2O it) is sequentially added in above-mentioned solution and is stirred continuously；
Then, beaker mouth is covered with PET plastic film and bound, continuously stir 18 hours；
PET plastic film is removed, and is placed the beaker in vacuum oven, it is 12 hours dry at 70 DEG C；
Finally, the plastic-like solid in beaker is taken out, it is placed in Muffle furnace, is warming up to 1 DEG C/min of heating rate
500 DEG C and maintenance 4 hours, during which Muffle furnace air is constantly in displacement circulation status.Taking-up when being down to room temperature, obtains height
Disperse mesoporous Ag-Al catalyst,
The mass ratio of each component Ag:Ce:La:Al is about 15:5:5:75 (with oxide in catalyst manufactured in the present embodiment
Meter).
Auxiliary agent selected by the present invention is cerous nitrate (Ce (NO3)3·6H2O), lanthanum nitrate (La (NO3)3·6H2O), manganese nitrate (Mn
(NO3)2), cobalt nitrate (Co (NO3)2·6H2O), zirconium nitrate (Zr (NO3)4·5H2O), under the guide of above-described embodiment 1-4,
Its unlisted auxiliary agent embodiment and combinations thereof can be realized obviously.
In addition, above-described embodiment 1-4 is not limitation of the invention, in the actual production process, technological parameter and
Proportion can be met needed for production by multiple amplification.
It should be understood that any equivalent way that those skilled in the art are made under the introduction of this specification, or
Obvious variant should all be within the scope of the present invention.
Claims (9)
1. a kind of high dispersing microporous/mesoporous Ag-Al catalyst, it is characterised in that: required raw material includes catalyst activity component, auxiliary agent, urges
Agent carrier, template and solvent；
The catalyst activity component is selected from silver nitrate, and the auxiliary agent is nitrate；
The catalyst carrier is aluminium isopropoxide, and the template is selected from polyethylene oxide-polypropylene oxide-polyethylene oxide three
Block copolymer, the solvent are Organic Alcohol；
The mass content of Ag is 1~30% in the Ag-Al catalyst, and the mass content of the auxiliary agent is 0.1~20%, described
The specific surface area of Ag-Al catalyst is 250~400m2/g。
2. high dispersing microporous/mesoporous Ag-Al catalyst according to claim 1, it is characterised in that: the nitrate solution is selected from
The mixture of one or both of cerous nitrate, lanthanum nitrate, manganese nitrate, cobalt nitrate or zirconium nitrate.
3. high dispersing microporous/mesoporous Ag-Al catalyst according to claim 1, it is characterised in that: the solvent Organic Alcohol is selected from
Ethyl alcohol, methanol, 1- propyl alcohol or 2- propyl alcohol.
4. the preparation method of high dispersing microporous/mesoporous Ag-Al catalyst according to claim 1, which is characterized in that successively include
Following steps:
A weighs a certain amount of template and aluminium isopropoxide respectively, measures a certain amount of acid, be added sequentially in container stirring until
Dissolution；
B weighs a certain amount of silver nitrate solution and auxiliary agent is added in the container of step a, and stirs；
Step b is equipped with the container closure of silver nitrate solution and auxiliary agent by c, is stirred at room temperature；
After d opens vessel port, it is placed in baking oven controlled at 50~70 DEG C of dry no less than 12h；
E takes out the solid after drying in an oven, then is roasted up to high dispersing microporous/mesoporous Ag-Al catalyst.
5. the preparation method of high dispersing microporous/mesoporous Ag-Al catalyst according to claim 4, it is characterised in that: the template
The quality proportioning of the additional amount aluminium isopropoxide of agent is 0.1~0.7:1.
6. the preparation method of high dispersing microporous/mesoporous Ag-Al catalyst according to claim 4, it is characterised in that: roasting process
It carries out, be warming up to 500 DEG C in the roasting process with 1~2 DEG C/min of heating rate and maintain 4 hours in Muffle furnace, and
Muffle furnace air is in displacement circulation status.
7. the preparation method of high dispersing microporous/mesoporous Ag-Al catalyst according to claim 4, it is characterised in that: in step c
12~18h is stirred at room temperature.
8. the preparation method of high dispersing microporous/mesoporous Ag-Al catalyst according to claim 4, it is characterised in that: the acid
For hydrochloric acid, nitric acid or phosphoric acid, the quality proportioning of the acid and aluminium isopropoxide is 0.3~1:1.
9. application of the high dispersing microporous/mesoporous Ag-Al catalyst according to claim 1 in catalytic combustion process.
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