CN109304170A - A kind of three-dimensional ordered mesoporous NM-Al catalyst, preparation method and application - Google Patents
A kind of three-dimensional ordered mesoporous NM-Al catalyst, preparation method and application Download PDFInfo
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- CN109304170A CN109304170A CN201711133448.0A CN201711133448A CN109304170A CN 109304170 A CN109304170 A CN 109304170A CN 201711133448 A CN201711133448 A CN 201711133448A CN 109304170 A CN109304170 A CN 109304170A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 21
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical group [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 239000006193 liquid solution Substances 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 3
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 3
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 3
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- -1 polyethylene Polymers 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 229920000428 triblock copolymer Polymers 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 238000007084 catalytic combustion reaction Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical group O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 239000012855 volatile organic compound Substances 0.000 abstract description 14
- 238000009826 distribution Methods 0.000 abstract description 12
- 239000011148 porous material Substances 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 230000009257 reactivity Effects 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 239000000306 component Substances 0.000 abstract description 2
- 230000007812 deficiency Effects 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 239000002985 plastic film Substances 0.000 description 8
- 229920006255 plastic film Polymers 0.000 description 8
- 238000002336 sorption--desorption measurement Methods 0.000 description 6
- 238000001338 self-assembly Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 208000028659 discharge Diseases 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000002671 adjuvant Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 229910020639 Co-Al Inorganic materials 0.000 description 1
- 229910020675 Co—Al Inorganic materials 0.000 description 1
- 229910018657 Mn—Al Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 208000005392 Spasm Diseases 0.000 description 1
- 208000010513 Stupor Diseases 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 210000000750 endocrine system Anatomy 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000001537 neural effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 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
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
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- 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
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN A CARRIER GAS OR AIR
- F23C13/00—Apparatus in which combustion takes place in the presence of catalytic material
- F23C13/08—Apparatus in which combustion takes place in the presence of catalytic material characterised by the catalytic material
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of three-dimensional ordered mesoporous NM-Al catalyst, preparation method and application, belong to petrochemical industry.The technological deficiencies such as wide, hole link is poor, dead hole road is more, specific surface area is low, active component poor dispersion which solve noble metal catalyst pore size distribution$s in the prior art.The catalyst includes active component, auxiliary agent and catalyst carrier, and wherein active component is noble metal precursor liquid solution, and noble metal is selected from one of Pt, Pd, Rh, and content is selected from CeO in 0.05~0.5wt%, auxiliary agent2、La2O3、Ag2O, one or more of MnO, CoO, for content in 1~30wt%, catalyst carrier is aluminium isopropoxide.The activity of catalyst reaction prepared by the present invention is high, the service life is long.The catalyst has very high reactivity to volatile organic compounds in refined oil storage tank.
Description
Technical field
The invention belongs to petrochemical industry, it is related to a kind of catalyst, preparation method and application, and in particular to a kind of three-dimensional
Order mesoporous NM-Al catalyst, preparation method and application.
Background technique
The unordered discharge of volatile organic compounds (volatile organic compounds, referred to as VOCs) causes
People greatly pay close attention to, and generate harm to human body because VOCs is easily absorbed by skin, mucous membrane etc..Meanwhile being permitted in VOCs
Multicomponent, such as benzene, toluene etc. have carcinogenic, teratogenesis, mutagenicity, these substances interfere human endocrine system, have heredity
Toxicity, while the mankind are exposed in high concentration VOCs and are likely to result in the serious consequences such as neural spasm even stupor, death, to people
Class life and health, human survival procreation and Environmental security constitute a threat to.It is generated as a primary discharge source of VOCs, refinery
VOCs accounts for about three one-tenth of total amount or so.Therefore, China's revision implements new national standard, mainly GB 31571-2015 " stone
Oiling work emission of industrial pollutants standard " and GB 31570-2015 " petroleum refining enterprise emission of industrial pollutants standard ", it is desirable that
In the VOCs discharged in refinery, non-methane total hydrocarbons content is not higher than 120mg/m3。
In refinery, VOCs emission-reducing process common at this stage is based on adsorbents such as active carbon, silica gel, activated carbon fibre
" absorption " method recovery process.Since there are pore size distribution$, wider and randomness is poor, adsorption process temperature rise for above-mentioned adsorbent
High, weak to small molecule hydro carbons adsorption capacity, desorption is difficult to the disadvantages of thorough, it is difficult to reach GB 31571-2015 and GB 31570-
2015 emission request.Therefore, the feasible means of VOCs qualified discharge are to ensure that using catalytic combustion process.And in this technique
In, catalyst plays key effect.Common catalyst for catalytic combustion is divided into noble metal catalyst and non-precious metal catalyst.
Due to the advantages such as initiation temperature is low, reactivity is high, noble metal catalyst is using more.However, noble metal catalyst there is also
Some shortcomings.In common noble metal catalyst carrier be aluminium oxide (patent CN 103191733B), pore size distribution$ compared with
Wide, duct is not connected to and dead hole road is more, specific surface area is relatively small, and the defect of pore property will lead to the expensive gold of active component
Belong to and the dispersibility of auxiliary agent is poor.In addition, patent CN 104138756A is reported and molecular sieve is used to prepare precious metal catalyst for carrier
Agent, the pore size distribution$ of carrier molecule sieve is more concentrated, specific surface area is larger, but molecular sieve contains stronger acidity, is easy
Make VOCs coking raw carbon blocking duct, hinders catalysis reaction.
Summary of the invention
For some shortcomings of noble metal catalyst in the prior art, the invention proposes a kind of three-dimensional ordered mesoporous
NM-Al catalyst, preparation method and application are to prepare noble metal catalyst in " solvent volatilization-solute self assembly " method, can
To prepare the noble metal catalyst of three-dimensional ordered mesoporous, which has that three-dimensional ordered mesoporous, pore size distribution$ be narrow, duct connects
The general character is good, active component is uniformly dispersed, and has high catalytic reaction activity to VOCs.
One of task of the invention is to provide a kind of three-dimensional ordered mesoporous NM-Al catalyst.
A kind of three-dimensional ordered mesoporous NM-Al catalyst, the catalyst include active component, auxiliary agent and catalyst carrier；
The active component is noble metal precursor liquid solution, and the noble metal is selected from one of Pt, Pd, Rh；The auxiliary agent is selected from
CeO2、La2O3、Ag2O、MnO2, one or more of CoO；The catalyst carrier is aluminium isopropoxide；It is living in the catalyst
Property component content be 0.05~0.5wt%, the content of the auxiliary agent is 1~30wt%, and surplus is aluminium isopropoxide.
Further, the specific surface area of the three-dimensional ordered mesoporous NM-Al catalyst is 220~390m2/g。
The two of task of the invention are to provide the preparation method of above-mentioned NM-Al catalyst.
The preparation method of above-mentioned three-dimensional ordered mesoporous NM-Al catalyst, successively the following steps are included:
A weighs a certain amount of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and aluminium isopropoxide,
A certain amount of acid is measured, sequentially adds and is contained in the container of solvent, stirring is to being completely dissolved；
B weighs a certain amount of noble metal precursor liquid solution and auxiliary agent is added into step a container；
C is continuously stirred by the container closure, and at room temperature, and then open container mouth is when 45~75 DEG C one section dry
Between；
The solid taken out in container after d is dry is roasted, and three-dimensional ordered mesoporous NM-Al catalyst can be obtained.
The direct bring advantageous effects of above-mentioned technical proposal are as follows:
In the preparation method of above-mentioned three-dimensional ordered mesoporous NM-Al catalyst, formation mechenism be may be summarized as follows: organic
In solvent, certain density surfactant P123 forms hexagonal phase arrangement, aluminium isopropoxide, noble metal precursor as template
Liquid solution and auxiliary agent nanoparticle are adhered to template polyethylene oxide-polycyclic oxygen by hydrogen bond, electrostatic interaction and molecular separating force
Around propane-polyethylene oxide triblock copolymer (P123), hexagonal phase arrangement is formed.Solvent is volatilized by dry, then
Template P123 is removed by Muffle furnace baking operation, and aluminium isopropoxide, noble metal precursor body and auxiliary agent presoma are decomposed,
Stable oxide is formed, while retaining its hexagonal phase structure, as three-dimensional ordered mesoporous NM-Al catalyst.
Preferably, in step a, the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and isopropyl
The quality proportioning of aluminium alcoholates is 0.1~0.7:1
Preferably, the quality proportioning of the acid and aluminium isopropoxide is 0.3~1:1.
Further, in step c, no less than 4h is continuously stirred at room temperature, in 45~75 DEG C of dry no less than 12h.
Further, in step d, solid is roasted in Muffle furnace, and calcining time is no less than 4h.
Further, solvent described in step a is ethyl alcohol, methanol, 1- propyl alcohol or 2- propyl alcohol.
Preferably, acid described in step a is hydrochloric acid, nitric acid or phosphoric acid.
The three of task of the invention are to provide above-mentioned three-dimensional ordered mesoporous NM-Al catalyst in catalytic combustion process
Using.
Three-dimensional ordered mesoporous NM-Al catalyst proposed by the present invention, preparation method and applications are novel, product it is physico
It learns nature parameters to be easy to regulate and control, catalytic reaction activity is preferable, while can facilitate product from experiment with large-scale production in factory
Room prepares the conversion to industrial application.
Compared with loaded noble metal catalyst in the prior art, the NM-Al catalyst used in the present invention is to use
Novel " solvent volatilization-solute self assembly " method is prepared, noble metal NM, adjuvant component and the evenly dispersed formation of aluminium oxide
Three-dimensional ordered mesoporous structure, has that specific surface area is high, pore size distribution$ is narrow, duct is that three-dimensional through hole, active component dispersion are equal
The even, advantages such as reactivity is high.
The present invention uses " solvent volatilization-solute self assembly " method, and it is equal to realize noble metal NM, adjuvant component and aluminium oxide
Even mixing forms three-dimensional ordered mesoporous structure.In NM-Al catalyst, the meso-hole structure that above-mentioned three is formed is three-dimensional perforation
, while pore size distribution$ is narrow, large specific surface area, Active components distribution is uniform, and reactivity is high, has wide industrial application
Prospect.The object phase and three-dimensional ordered mesoporous structure of three-dimensional ordered mesoporous NM-Al catalyst prepared by the present invention can pass through X-ray
Diffraction is analyzed, and specific surface area and pore-size distribution can be characterized using low temperature nitrogen adsorption desorption instrument.
Detailed description of the invention
The present invention will be further described with reference to the accompanying drawing:
Fig. 1 is the XRD diagram of three-dimensional ordered mesoporous Pd-Ce-Al catalyst of the present invention；
Fig. 2 is the small angle XRD diagram of three-dimensional ordered mesoporous Pd-Ce-Al catalyst of the present invention；
Fig. 3 is the low temperature nitrogen adsorption desorption curve graph of three-dimensional ordered mesoporous Pd-Ce-Al catalyst of the present invention；
Fig. 4 is three-dimensional ordered mesoporous Pd-Ce-Al catalyst graph of pore diameter distribution of the present invention.
Specific embodiment
Raw material needed for the present invention can be bought by commercial channel and be obtained.
It elaborates combined with specific embodiments below to the present invention.
Embodiment 1:
The preparation method of three-dimensional ordered mesoporous Pd-Ce-Al catalyst, specifically includes the following steps:
Firstly, 14g template P123 is dissolved in the beaker for filling 270mL dehydrated alcohol, add 21mL concentrated nitric acid and
27g aluminium isopropoxide is continuously vigorously stirred 30 minutes；
Secondly, 0.6g palladium nitrate and 1.8g cerous nitrate sequence to be added in above-mentioned solution and be 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.Taking-up when being down to room temperature, obtains three
Tie up order mesoporous Pd-Ce-Al catalyst.
The mass ratio of each component Pd:Ce:Al is about 0.4:9.6:90 in the catalyst (in terms of oxide).
Fig. 1 is the X-ray diffractogram of three-dimensional ordered mesoporous Pd-Ce-Al catalyst, is the feature diffraction pattern of aluminium oxide, nothing
The characteristic diffraction peak of active component shows that the Pd-Ce-Al prepared by novel " solvent volatilization-solute self assembly " method is urged
In agent, active component is scattered；
Fig. 2 be three-dimensional ordered mesoporous Pd-Ce-Al catalyst small angle X-ray diffraction figure, while be labelled with (1 0 0) and
The XRD diffraction maximum of (1 1 0) crystal face shows that Pd-Ce-Al catalyst has three-dimensional ordered mesoporous structure.
Fig. 3 is the low temperature N of three-dimensional ordered mesoporous Pd-Ce-Al catalyst2Adsorption desorption curve shows Pd-Ce-Al catalyst
Adsorption desorption curve is Type IV type, i.e., Pd-Ce-Al catalyst has typical mesopore orbit feature, while its BET method ratio
Surface area has reached 328m2/ g, Kong Rong have also reached 0.50cm3/g。
Fig. 4 is the graph of pore diameter distribution of three-dimensional ordered mesoporous Pd-Ce-Al catalyst, and catalyst pore-size distribution is concentrated mainly on 3
Between~8nm, most probable pore size is 6nm or so.
Embodiment 2:
Firstly, 9g template P123 is dissolved in the beaker for filling 270mL 1- propyl alcohol, 15mL concentrated hydrochloric acid and 41g are added
Aluminium isopropoxide is continuously vigorously stirred 30 minutes；
Secondly, 0.3g platinum nitrate and 3.1g lanthanum nitrate sequence to be added in above-mentioned solution and be 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 50 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 6 hours, during which Muffle furnace air is constantly in displacement circulation status.Taking-up when being down to room temperature, obtains three
Tie up order mesoporous Pt-La-Al catalyst.
The mass ratio of each component Pt:La:Al is about 0.3:14.7:85 in the catalyst (in terms of oxide).
Pass through the Pt-La-Al catalyst of this kind of novel " solvent volatilization-solute self assembly " method preparation, gained sample
XRD result it is similar with Fig. 1 and Fig. 2 result in embodiment 1, it was demonstrated that the NM-Al of high degree of dispersion can be prepared by this kind of method
Catalyst.
Low temperature N2Adsorption desorption the experimental results showed that, using platinum as active component, lanthanum be auxiliary agent preparation Pt-La-Al catalyst,
BET specific surface area is 335m2/ g, Kong Rongwei 0.52cm3/ g, adsorption desorption curve are still the mesoporous curve of Type IV type.
Embodiment 3:
Firstly, 19g template P123 is dissolved in the beaker for filling 270mL methanol, adds 25mL concentrated phosphoric acid and 41g is different
Aluminium propoxide is continuously vigorously stirred 30 minutes；
Secondly, 0.01g rhodium nitrate and 4.6g cobalt nitrate sequence to be added in above-mentioned solution and be 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 65 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 5 hours, during which Muffle furnace air is constantly in displacement circulation status.Taking-up when being down to room temperature, obtains three
Tie up order mesoporous Rh-Co-Al catalyst.
The mass ratio of each component Rh:Co:Al is about 0.05:24.95:75 in the catalyst (in terms of oxide).
Embodiment 4:
Firstly, 24g template P123 is dissolved in the beaker for filling 270mL 2- propyl alcohol, add 21mL concentrated hydrochloric acid and
53g aluminium isopropoxide is continuously vigorously stirred 30 minutes；
Secondly, 0.14g palladium nitrate and 4.3g manganese nitrate sequence to be added in above-mentioned solution and be 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 12 hours dry at 75 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.Taking-up when being down to room temperature, obtains three
Tie up order mesoporous Pd-Mn-Al catalyst.
The mass ratio of each component Pd:Mn:Al is about 0.5:11.5:88 in the catalyst (in terms of oxide).
Using refined oil storage tank head space gas as raw material, the reactivity of each catalyst in above-described embodiment is investigated, such as 1 institute of table
Show:
Processing result table of the catalyst to abhiseca exhaust gas in 1 Examples 1 and 2 of table
Note: reaction velocity 18000m3/h。
As can be known from Table 1, under the conditions of reaction temperature is 320 DEG C, embodiment 1, embodiment 2, embodiment 3 and embodiment 4
In catalyst 99.0%, 97.9%, 97.1% and 98.9% has been respectively reached to refined oil storage tank abhiseca exhaust-gas treatment rate, it is full
The requirement of sufficient new national standard GB 30570-2015 and GB 30571-2015, be it is a kind of with broad prospect of application catalysis burning urge
Agent.
Claims (10)
1. a kind of three-dimensional ordered mesoporous NM-Al catalyst, it is characterised in that: the catalyst includes active component, auxiliary agent and urges
Agent carrier；
The active component is noble metal precursor liquid solution, and the noble metal is selected from one of Pt, Pd, Rh；
The auxiliary agent is selected from CeO2、La2O3、Ag2O, one or more of MnO, CoO；
The catalyst carrier is aluminium isopropoxide；
In the catalyst, the content of active component is 0.05~0.5wt%, and the content of the auxiliary agent is 1~30wt%, surplus
For aluminium isopropoxide.
2. three-dimensional ordered mesoporous NM-Al catalyst according to claim 1, it is characterised in that: the three-dimensional ordered mesoporous
The specific surface area of NM-Al catalyst is 220~390m2/g。
3. the preparation method of three-dimensional ordered mesoporous NM-Al catalyst according to claim 1 or 2, which is characterized in that successively
The following steps are included:
A weighs a certain amount of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and aluminium isopropoxide, measures
A certain amount of acid, sequentially adds and holds in the container of organic solvent, and stirring is to being completely dissolved；
B weighs a certain amount of noble metal precursor liquid solution and auxiliary agent is added into step a container；
C is continuously stirred by the container closure, and at room temperature, and then open container mouth is in 45~75 DEG C of dry a period of times；
The solid taken out in container after d is dry is roasted, and three-dimensional ordered mesoporous NM-Al catalyst can be obtained.
4. the preparation method of three-dimensional ordered mesoporous NM-Al catalyst according to claim 3, it is characterised in that: step a
In, the quality proportioning of the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and aluminium isopropoxide is 0.1
~0.7:1.
5. the preparation method of three-dimensional ordered mesoporous NM-Al catalyst according to claim 3, it is characterised in that: the acid
Quality proportioning with aluminium isopropoxide is 0.3~1:1.
6. the preparation method of three-dimensional ordered mesoporous NM-Al catalyst according to claim 3, it is characterised in that: step c
In, no less than 4h is continuously stirred at room temperature, in 45~75 DEG C of dry no less than 12h.
7. the preparation method of three-dimensional ordered mesoporous NM-Al catalyst according to claim 3, it is characterised in that: step d
In, solid is roasted in Muffle furnace, and calcining time is no less than 4h.
8. the preparation method of three-dimensional ordered mesoporous NM-Al catalyst according to claim 3, it is characterised in that: in step a
The solvent is ethyl alcohol, methanol, 1- propyl alcohol or 2- propyl alcohol.
9. the preparation method of three-dimensional ordered mesoporous NM-Al catalyst according to claim 3, it is characterised in that: in step a
The acid is hydrochloric acid, nitric acid or phosphoric acid.
10. application of the three-dimensional ordered mesoporous NM-Al catalyst according to claim 1 in catalytic combustion process.
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