CN104437640A - Pd/MIL-53(Al) catalyst, and preparation and application thereof - Google Patents
Pd/MIL-53(Al) catalyst, and preparation and application thereof Download PDFInfo
- Publication number
- CN104437640A CN104437640A CN201310416825.7A CN201310416825A CN104437640A CN 104437640 A CN104437640 A CN 104437640A CN 201310416825 A CN201310416825 A CN 201310416825A CN 104437640 A CN104437640 A CN 104437640A
- Authority
- CN
- China
- Prior art keywords
- mil
- catalyst
- catalytic
- deionized water
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 239000013206 MIL-53 Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 53
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 43
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003546 flue gas Substances 0.000 claims abstract description 14
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 4
- 230000004913 activation Effects 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000009467 reduction Effects 0.000 claims abstract description 4
- 230000000694 effects Effects 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 6
- 206010013786 Dry skin Diseases 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 239000007789 gas Substances 0.000 abstract description 12
- 229910000510 noble metal Inorganic materials 0.000 abstract description 8
- 230000008030 elimination Effects 0.000 abstract description 6
- 238000003379 elimination reaction Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000011068 loading method Methods 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 238000004523 catalytic cracking Methods 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 238000009827 uniform distribution Methods 0.000 abstract 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 39
- 239000012621 metal-organic framework Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000004231 fluid catalytic cracking Methods 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 239000000470 constituent Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000010718 Oxidation Activity Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 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
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 208000026106 cerebrovascular disease Diseases 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a Pd/MIL-53(Al) catalyst and a preparation method and application thereof; mixing the mass 1: 5: reacting 20-30 parts of terephthalic acid with aluminum nitrate and deionized water, naturally cooling to room temperature, filtering, and drying to obtain MIL-53 (Al); roasting to obtain carrier with high specific surface area, adding palladium nitrate, soaking in the same volume to obtain mixed solution, drying, introducing Ar/H2(0.1-0.2L/min) reduction activation; the loading amount of palladium is 1-8 wt%; the structural formula of MIL-53(Al) is [ Al (OH) (O)2C-C6H4-CO2)](ii) a The catalyst is suitable for catalytic elimination of CO in flue gas discharged by a catalytic cracking catalyst regeneration device and motor vehicle tail gas, and has the advantages of large specific surface area, uniform distribution of active components, high catalytic activity, high thermal stability, simple and convenient synthesis, capability of reducing CO catalytic conversion temperature, small consumption of noble metals and the like.
Description
Technical field
The present invention relates to petrochemical industry, be specifically related to a kind of Pd/MIL-53 (Al) catalyst and preparation thereof, the present invention has the purposes reducing the aspects such as CO in FCC regenerated flue gas and vehicle exhaust.
Background technology
Fluid catalytic cracking (FCC) is the main method that light-end products produced by oil plant.In the regenerative process of FCC catalyst, due to the imperfect combustion of coke, in the flue gas discharged, there is a large amount of carbon monoxide (CO).In addition, also there is a large amount of CO in vehicle exhaust.CO colorless and odorless, has a strong impact on the life health of people.Research shows, lives in for a long time in CO high concentration environment and can cause many cardiovascular and cerebrovascular diseases.Meanwhile, CO burns further and becomes CO
2time can release a large amount of heats, will a large amount of thermal waste be caused if do not made full use of.The use of combustion adjuvant not only can make the CO content in flue gas reduce, and reduces atmosphere pollution, and can the temperature of stable regeneration device, avoids regenerator to damage and catalyst failure, saves equipment investment, improve reproduction quality and the fume afterheat utilization ratio of catalyst.At present, the FCC regenerated flue gas of most of oil plant adopts the CO combustion adjuvant based on precious metals platinum catalyst, achieves remarkable result.Platinum catalyst is not only expensive, and the sulfide in flue gas and nitride catalyst can be converted into oxysulfide (SOx) and nitrogen oxide (NOx), thus causes the corrosion of regenerator and produce the new source of atmospheric pollution.Therefore, develop a kind of non-platinum catalysis material newly, eliminate regenerated flue gas to the pollution of environment, there is important Research Significance and application prospect.
Be no matter the CO contained in FCC flue gas or vehicle exhaust, cause high risks to environment and common people's health, exploitation effective catalyst becomes eliminates the strongest approach that CO reduces its discharge.Noble metal (Pt, Rh, Pd etc.) has excellent catalytic oxidation elimination activity to CO, but Pt, Rh relative rarity, cost intensive.Therefore, Pd catalyst gets more and more people's extensive concerning in recent years.
Metal organic framework compound (MOF) has regular, stable pore passage structure, the unsatuated metal site of high-ratio surface sum functionalization.Based on above advantage, using MOF as catalyst carrier, considerably increase dispersiveness and the uniformity of catalytic active center, make the contact of itself and reactant more extensive, greatly improve catalytic activity.In addition, MOF has good adsorption capacity to micro-molecular gas, when utilizing these Small molecular as reacting gas in catalytic reaction, selecting MOF as catalyst carrier, will be conducive to the carrying out of catalytic reaction.Therefore, the excellent activity of MOF and Pd is combined effectively, adopt specific preparation technology to be then expected to synthesize the catalyst of good activity accordingly.What the method loaded to by metal active constituent at present in metal organic framework compound was commonly used has chemical vapour deposition technique, coprecipitation, solid grinding method, infusion process.
Chinese patent CN1548368 reports at catalyst for selective oxidation of CO under hydrogen-enriched condition.This invention provides a kind of for catalyst for selective oxidation of CO under hydrogen-enriched condition, uses the noble metal of small amount, obtains the oxidation activity of higher low temperature carbon monoxide and selective.This catalyst is made up of the noble metal component be supported on porous inorganic thing carrier and other metal components.These catalyst noble metal content are low, effectively can be applied to the selective oxidation of carbon monoxide under hydrogen rich gas atmosphere.In addition, the activity starting temperature of this catalyst is low, serviceability temperature wide ranges, effectively can work between 80 DEG C-180 DEG C.But this invention depends on the use of hydrogen, process exists certain complexity.Therefore, the research and development of new catalyst system are still very important.
CN101143321 purifies the oxidation catalyst of CO under disclosing a kind of room temperature, adopt coprecipitation and deposition-precipitation method to prepare.This catalyst is made up of base metal active constituent and carrier, and active constituent load capacity is 5 ~ 80% of metallic element weight scaled value.Active constituent is from cobalt salt liquid, molysite liquid, nickel salt liquid, manganese saline solution, mantoquita liquid, zinc salt liquid, pink salt liquid, cerium saline solution.Carrier comes self-alumina, silica, molecular sieve, ceramic honey comb, wire netting, cobalt oxide, iron oxide, manganese oxide, cupric oxide, zinc oxide, tin oxide, cerium oxide.Precipitating reagent is Na
2cO
3, K
2cO
3, NaOH, urea, one in ammoniacal liquor.Catalyst preparing solution needs fully to stir 1 ~ 8 hour, aging 1 ~ 16 hour, after the drying need at air, oxygen, in hydrogen or nitrogen atmosphere, carries out in-situ treatment at 100 ~ 500 DEG C.But this technological process is comparatively complicated, and influence factor is more, limit its industrial application.
MIL-53(Al) be the terephthalate of the aluminium obtained under hydrothermal conditions.Octahedral aluminium atom is connected to form the pore passage structure of one dimension by terephthalic acid (TPA).At high temperature calcining can remove terephthaldehyde's acid molecule of disordered arrangements in duct.MIL-53(Al) can reversible adsorption polar molecule, as steam, methyl alcohol, ethanol, the structure of the process mesopore of reversible adsorption can expand and shrink, as breathing state.In addition, MIL-53 (Al) has high-specific surface area (BET is 1200m
2g
-1), still can stablize by holding structure in humidity and the aqueous solution, heat endurance is close to 500 DEG C.After the MIL-53 (Al) of synthesis heats a period of time under a high vacuum, these hydrones will be discharged from skeleton, the coordination of metal ion just becomes undersaturated condition, and organic ligand is also provided with the ability in conjunction with other molecule, and whole skeleton is just provided with alkalescence and acidic site.In sum, these features make MIL-53 (Al) as having unique superiority in the carrier of heterogeneous catalysis.
In view of the above; incipient impregnation method is adopted to prepare Pd/MIL-53 (Al) catalyst; and be applied in the low temperature elimination of CO in FCC flue gas and vehicle exhaust; achieve the combination of carrier part and active component part; thus reduce the content of CO in flue gas and tail gas, there is very important basic research meaning and environmental protection meaning.
Summary of the invention
The object of this invention is to provide a kind of Pd/MIL-53 (Al) catalyst and Synthesis and applications thereof, utilize equi-volume impregnating, prepare granule-morphology homogeneous, there is Pd/MIL-53 (Al) catalyst of higher catalytic activity, low production cost, this catalyst is very high to the CO low temperature elimination activity in industrial smoke, the complete catalyzed conversion temperature of CO is significantly reduced, and the advantage such as this catalyst has high-specific surface area, high thermal stability, active component are uniformly distributed and preparation method is simple.
MIL-53 of the present invention (Al) loaded palladium catalyst is with MIL-53 (Al) for carrier, load active component Pd; The structural formula of MIL-53 (Al) is [Al (OH) (O
2c-C
6h
4-CO
2)], be the tridimensional network that transition metal aluminum and organic ligand bridging are formed.The load capacity of palladium is 1 ~ 5wt%(1wt%, 2wt%, 3wt%, 4wt%, 5wt%).
The invention provides the preparation method of above-mentioned metal organic framework compound MIL-53 (Al): by terephthalic acid (TPA) (H
2bDC) with aluminum nitrate (Al(NO
3)
39H
2o) put into the reactor of 100 ~ 200mL, add deionized water, stir 30 ~ 60min.Baking oven is put in reactor sealing, and react 72 ~ 80 hours under constant temperature 220 DEG C of conditions, heating rate is 0.9 ~ 1.1 DEG C per minute.Naturally cool to room temperature, deionized water is filtered, and 50 DEG C of dryings 12 ~ 18 hours, obtain MIL-53 (Al).
The present invention also provides the preparation method of Pd/MIL-53 (Al) catalyst: by MIL-53 (Al) roasting 72 ~ 80 hours under 330 DEG C of conditions, remove the hydrone in skeleton and unnecessary part, obtain the carrier of high-specific surface area.Add palladium nitrate, obtain mixed solution by incipient impregnation, 50 dryings 12 ~ 18 hours.Ar/H is passed under 250 DEG C of conditions
2(0.1 ~ 0.2L/min) reduction activation Pd/MIL-53 (Al), heating rate is 2 ~ 3 DEG C per minute.
Catalyst provided by the invention is a kind of support type, and precious metals pd is active component.Whole caltalyst architecture is homogeneous, has high chemical stability.Experimental result shows, and the pore distribution that metal organic framework compound MIL-53 (Al) is unique facilitates the dispersed of palladium, prevents its sintering at high temperature, thus substantially increases CO oxidation activity and stability.The complete catalysts oxidation temperature of CO is reduced within the scope of 100 ~ 150 DEG C, the elimination requirement causing a large amount of CO to pollute when meeting motor vehicle cold start (<200 DEG C).
Catalyst described in the present invention is used for CO catalytic removal and demonstrates excellent catalytic activity, and the complete conversion temperature of CO significantly reduces, how in the scope of 100 ~ 150 DEG C.Experimental result also shows, and after this caltalyst ties up to and is cycled to repeat 5 times, catalytic activity substantially remains unchanged and has superior stability.
The invention provides a kind of Pd/MIL-53 (Al) catalyst in a word.Described catalyst prepares load type metal organic framework compounds catalyst by equi-volume impregnating.This catalyst is applicable to the catalytic removal of CO in motor-vehicle tail-gas and FCC flue gas, there is the advantage such as high-specific surface area, the free of losses of noble metal active uniform component distribution, catalytic activity is high, heat endurance is high, simple synthetic method, significantly can reduce the complete catalyzed conversion temperature of CO, save noble metal dosage, reduce production cost.Enforcement of the present invention has very important basic research meaning and actual environment protection significance to the low temperature elimination of CO in motor-vehicle tail-gas and industrial discharge flue gas.
Accompanying drawing explanation
Fig. 1 a is the PXRD spectrogram of metal organic framework compound MIL-53 (Al) prepared by the present invention.
Fig. 1 b is the PXRD spectrogram of carried noble metal Pd/MIL-53 (Al) catalyst prepared by the present invention.
Fig. 1 c is the PXRD spectrogram of Pd/MIL-53 (Al) catalyst after CO eliminative reaction.
Fig. 2 a is the TEM photo of 2.7wt%Pd/MIL-53 (Al) catalyst prepared by the present invention.
Fig. 2 b is the TEM photo of 2.7wt%Pd/MIL-53 (Al) catalyst after CO eliminative reaction.
Fig. 2 c is the HRTEM photo of 2.7wt%Pd/MIL-53 (Al) catalyst prepared by the present invention.
Fig. 2 d is the domain size distribution of 2.7wt%Pd/MIL-53 (Al) catalyst prepared by the present invention.
Fig. 3 is the N of 2.7wt%Pd/MIL-53 (Al) catalyst prepared by the present invention
2adsorption/desorption curve.
Fig. 4 a-d is the XPS spectrum figure of 2.7wt%Pd/MIL-53 (Al) catalyst prepared by the present invention.
Fig. 5 is the CO oxidation activity figure of different Pd loading Pd/MIL-53 (Al) (0.5wt%, 0.9wt%, 2.0wt%, 2.7wt%, 3.7wt%) catalyst.
Fig. 6 is 2.7wt%Pd/MIL-53 (Al) catalyst prepared by the present invention is cycled to repeat 5 times activity figure to CO oxidation reaction.
Detailed description of the invention
The evaluation method of embodiment 1 catalyst activity
Adopt atmospheric fixed bed microreactor laboratory evaluation device, evaluate the catalyst of the present invention's synthesis to the catalytic activity of CO oxidation reaction in FCC regenerated flue gas.Reactor adopts the quartz ampoule of internal diameter 6mm, and the temperature reaction of automatic temperature control instrument control program, programming rate is 5 DEG C/min.Take the catalyst of 100mg, be filled in the constant temperature zone of reaction tube, prepare reacting gas in advance on request, gas composition is: CO:1v%, O
2: 21v%, Ar are balanced gas; Gas flow is 50ml/min.The SP-3420 gas chromatograph that experimental result is produced through Beijing Analytical Instrument Factory detects, FID hydrogen flame ionization detector, and FID connects with methanator, and chromatographic column adopts 5A molecular sieve packed column (to be separated O
2, N
2, CO) and Porapak N packed column (separation of C O, CO
2and C
2h
2), methanator operating temperature is 380 DEG C.
The preparation method of embodiment 2Pd/MIL-53 (Al)
Take H respectively
2bDC(2.88g), Al(NO
3)
39H
2o(14.5g) put into the reactor of 100mL, add deionized water (65mL), stir 30 minutes.Baking oven is put in reactor sealing, and react 72 hours under constant temperature 220 DEG C of conditions, heating rate is 1 DEG C per minute.Naturally cool to room temperature, deionized water is filtered, and 50 DEG C of dryings 12 hours, obtain MIL-53 (Al).By MIL-53 (Al) roasting 72 hours under 330 DEG C of conditions, remove the hydrone in skeleton and unnecessary part, add palladium nitrate (0.5g), obtain mixed solution by incipient impregnation, 50 dry 12 hours.Ar/H is passed under 250 DEG C of conditions
2(0.1L/min) reduction activation Pd/MIL-53 (Al), heating rate is 3 DEG C per minute.
Activity rating
Evaluation method according to above-mentioned catalyst activity is evaluated Pd/MIL-53 (Pd), wherein (wherein ordinate is CO conversion ratio to the Activity evaluation of Pd/MIL-53 (Pd) as shown in Figure 5, abscissa is reaction temperature), the activity rating data of above-mentioned catalyst are in table 1.
The Activity evaluation of table 1Pd/MIL-53 (Al) catalyst
Claims (3)
1. a preparation method for Pd/MIL-53 (Al) catalyst, is characterized in that:
(1) terephthalic acid (TPA) and aluminum nitrate are put into the reactor of 100 ~ 200mL, add deionized water, stir 30min ~ 60min; Baking oven is put in reactor sealing, react 72 ~ 80 hours under constant temperature 220 DEG C of conditions, heating rate is 0.9 ~ 1.1 DEG C per minute, naturally cool to room temperature, deionized water is filtered, 50 DEG C of dryings 12 ~ 18 hours, obtain MIL-53 (Al), the mass ratio of aluminum nitrate, terephthalic acid (TPA) and deionized water is: 1:5:20 ~ 30;
(2) by MIL-53 (Al) roasting 72 ~ 80 hours under 330 DEG C of conditions, remove the hydrone in skeleton and unnecessary part, obtain the carrier of high-specific surface area, add palladium nitrate, mixed solution is obtained by incipient impregnation, 50 DEG C of dryings 12 ~ 18 hours, pass into Ar/H under 250 DEG C of conditions
2(0.1 ~ 0.2L/min) reduction activation Pd/MIL-53 (Al), heating rate is 2 ~ 3 DEG C per minute; The load capacity of palladium is 1 ~ 8wt%;
The structural formula of MIL-53 (Al) is [Al (OH) (O
2c-C
6h
4-CO
2)].
2. Pd/MIL-53 (Al) catalyst, is characterized in that: prepared by preparation method according to claim 1.
3. an application for Pd/MIL-53 according to claim 3 (Al) catalyst, is characterized in that: for reducing the complete catalyzed conversion temperature of CO in FCC flue gas and vehicle exhaust, under its effect, CO is oxidized to CO
2eliminate.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310416825.7A CN104437640A (en) | 2013-09-13 | 2013-09-13 | Pd/MIL-53(Al) catalyst, and preparation and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310416825.7A CN104437640A (en) | 2013-09-13 | 2013-09-13 | Pd/MIL-53(Al) catalyst, and preparation and application thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN104437640A true CN104437640A (en) | 2015-03-25 |
Family
ID=52884848
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201310416825.7A Pending CN104437640A (en) | 2013-09-13 | 2013-09-13 | Pd/MIL-53(Al) catalyst, and preparation and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104437640A (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105233878A (en) * | 2015-11-11 | 2016-01-13 | 北京林业大学 | Synthesis method for metal-loaded-type MIL-101 bio-oil hydrogenation catalyst |
CN105289735A (en) * | 2015-11-03 | 2016-02-03 | 浙江工业大学 | Pd/UiO-66-NH2 material having high stability as well as preparation method and application of Pd/UiO-66-NH2 material |
CN107349963A (en) * | 2017-07-05 | 2017-11-17 | 辽宁大学 | A kind of composites of Pt@MIL 101 and its preparation method and application |
CN108404987A (en) * | 2018-03-07 | 2018-08-17 | 南京工业大学 | Method for improving catalytic efficiency of nanoparticle @ MOFs material |
CN108654693A (en) * | 2017-04-01 | 2018-10-16 | 南京农业大学 | A kind of hydrophobic palladium/metal-organic framework material and preparation method thereof and the application for synthesizing 2,5- dimethyl furans |
CN108993556A (en) * | 2018-08-09 | 2018-12-14 | 贵州理工学院 | Silicon adulterates wolframic acid zinc/zinc oxide composite material, preparation method and applications |
CN109847740A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院大连化学物理研究所 | A kind of preparation method of the metallic catalyst based on MIL-53 support type |
CN114106343A (en) * | 2020-08-28 | 2022-03-01 | 中国石油化工股份有限公司 | Preparation method of metal organic framework material |
CN114160208A (en) * | 2021-12-16 | 2022-03-11 | 中国船舶重工集团公司第七一九研究所 | For CO2Preparation method of Pd/MOF catalyst for catalytic hydrogenation |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007131948A2 (en) * | 2006-05-16 | 2007-11-22 | Basf Se | Process for preparing porous metal organic frameworks |
CN101269317A (en) * | 2007-03-23 | 2008-09-24 | 中国科学院大连化学物理研究所 | Load type stephanoporate metal organic compound hydrogen storing material |
CN102744105A (en) * | 2011-04-18 | 2012-10-24 | 韩国化学研究院 | Method for functionalizing porous metal-organic framework materials, solid acid catalyst using same, and method for evaporating alcohol using the solid acid catalyst |
-
2013
- 2013-09-13 CN CN201310416825.7A patent/CN104437640A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007131948A2 (en) * | 2006-05-16 | 2007-11-22 | Basf Se | Process for preparing porous metal organic frameworks |
CN101269317A (en) * | 2007-03-23 | 2008-09-24 | 中国科学院大连化学物理研究所 | Load type stephanoporate metal organic compound hydrogen storing material |
CN102744105A (en) * | 2011-04-18 | 2012-10-24 | 韩国化学研究院 | Method for functionalizing porous metal-organic framework materials, solid acid catalyst using same, and method for evaporating alcohol using the solid acid catalyst |
Non-Patent Citations (2)
Title |
---|
HAI-LONG JIANG ET AL.: "Au@ZIF-8: CO Oxidation over Gold Nanoparticles Deposited to Metal-Organic Framework", 《J. AM. CHEM. SOC.》 * |
THIERRY LOISEAU ET AL.,: "A Rationale for the Large Breathing of the Porous Aluminum Terephthalate (MIL-53) Upon Hydration", 《CHEM. EUR. J.》 * |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105289735A (en) * | 2015-11-03 | 2016-02-03 | 浙江工业大学 | Pd/UiO-66-NH2 material having high stability as well as preparation method and application of Pd/UiO-66-NH2 material |
CN105233878A (en) * | 2015-11-11 | 2016-01-13 | 北京林业大学 | Synthesis method for metal-loaded-type MIL-101 bio-oil hydrogenation catalyst |
CN108654693B (en) * | 2017-04-01 | 2021-06-08 | 南京农业大学 | Hydrophobic palladium/metal organic framework material, preparation method thereof and application of hydrophobic palladium/metal organic framework material in synthesis of 2, 5-dimethylfuran |
CN108654693A (en) * | 2017-04-01 | 2018-10-16 | 南京农业大学 | A kind of hydrophobic palladium/metal-organic framework material and preparation method thereof and the application for synthesizing 2,5- dimethyl furans |
CN107349963A (en) * | 2017-07-05 | 2017-11-17 | 辽宁大学 | A kind of composites of Pt@MIL 101 and its preparation method and application |
CN109847740A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院大连化学物理研究所 | A kind of preparation method of the metallic catalyst based on MIL-53 support type |
CN109847740B (en) * | 2017-11-30 | 2021-06-11 | 中国科学院大连化学物理研究所 | Preparation method of MIL-53-based supported metal catalyst |
CN108404987B (en) * | 2018-03-07 | 2021-05-14 | 南京工业大学 | Method for improving catalytic efficiency of nanoparticle @ MOFs material |
CN108404987A (en) * | 2018-03-07 | 2018-08-17 | 南京工业大学 | Method for improving catalytic efficiency of nanoparticle @ MOFs material |
CN108993556A (en) * | 2018-08-09 | 2018-12-14 | 贵州理工学院 | Silicon adulterates wolframic acid zinc/zinc oxide composite material, preparation method and applications |
CN108993556B (en) * | 2018-08-09 | 2021-01-19 | 贵州理工学院 | Silicon-doped zinc tungstate/zinc oxide composite material, preparation method and application thereof |
CN114106343A (en) * | 2020-08-28 | 2022-03-01 | 中国石油化工股份有限公司 | Preparation method of metal organic framework material |
CN114160208A (en) * | 2021-12-16 | 2022-03-11 | 中国船舶重工集团公司第七一九研究所 | For CO2Preparation method of Pd/MOF catalyst for catalytic hydrogenation |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104437640A (en) | Pd/MIL-53(Al) catalyst, and preparation and application thereof | |
CN102365124B (en) | Age-resistant catalyst for oxidation of no to no2 in exhaust streams | |
Wyrwalski et al. | Synergistic coupling of the redox properties of supports and cobalt oxide Co 3 O 4 for the complete oxidation of volatile organic compounds | |
CN103495418B (en) | A kind of foramen magnum-mesoporous cerium zirconium sosoloid carries silver catalyst and preparation method and application | |
CN109759035B (en) | NOxAdsorbent and preparation method and application thereof | |
CN113769738B (en) | High-stability cerium oxide supported palladium nanocluster catalytic material and preparation method and application thereof | |
CN103464152A (en) | Catalyst for tail gas purification and preparation method thereof | |
CN110180582A (en) | A kind of diesel vehicle oxidation catalyst and preparation method thereof | |
CN105080538A (en) | Catalyst for purifying and dehydrogenating CO raw material gas and preparation method for catalyst | |
JP2007252989A (en) | Catalyst for carbon monoxide methanation and methanation method of carbon monoxide using the catalyst | |
JP5531212B2 (en) | Low temperature oxidation catalyst, method for producing the same, and oxidation method using the catalyst | |
Wang et al. | One-pot synthesis of hierarchical MnCu-SSZ-13 catalyst with excellent NH3-SCR activity at low temperatures | |
Lee et al. | HC-SCR system combining Ag/Al2O3 and Pd/Al2O3 catalysts with resistance to hydrothermal aging for simultaneous removal of NO, HC, and CO | |
CN111151247A (en) | Supported catalyst and preparation method and application thereof | |
CN110026175B (en) | Cerium-zirconium composite oxide and application thereof in catalyzing CO oxidation reaction | |
CN104014353B (en) | Palladous chloride. copper chloride catalyst and preparation for carbon monoxide room-temperature catalytic oxidation | |
CN115041218A (en) | Hierarchical zeolite core-shell catalyst, preparation method thereof and application thereof in purification of organic sulfur in blast furnace gas | |
CN102658137A (en) | Cerium-zirconium-palladium nano powder catalyst and preparation and application thereof | |
Wang et al. | Selective catalytic reduction of NO by CO over MOF-based CuOx@ ZIF-67 catalysts and reaction mechanism | |
JP2024501748A (en) | Three-way catalyst supporting noble metal in single atomic state, preparation method and use thereof | |
Lou et al. | Study on the catalytic characteristics of precious metal catalysts with different Pt/Pd ratios for soot combustion | |
CN112108145A (en) | Alumina-supported iridium cluster catalyst and preparation and application thereof | |
CN111111656A (en) | High-temperature-resistant catalytic combustion catalyst for normal-temperature catalytic ignition of VOCs self-sustaining combustion and preparation method and application thereof | |
JP6107487B2 (en) | N2O decomposition catalyst and N2O-containing gas decomposition method using the same | |
Bai et al. | Unveiling the effect of SO2 on CO selective catalytic reduction of NOx in the presence of O2 over IrRb@ SBA-15 catalyst |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150325 |
|
RJ01 | Rejection of invention patent application after publication |