CN105921155A - High-dispersion supported ruthenium dioxide catalyst and preparing method thereof - Google Patents
High-dispersion supported ruthenium dioxide catalyst and preparing method thereof Download PDFInfo
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- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000006185 dispersion Substances 0.000 title claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 6
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 6
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 229910052599 brucite Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000002105 nanoparticle Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000012958 reprocessing Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 8
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 8
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- -1 deionized water compound Chemical class 0.000 claims description 3
- 230000036571 hydration Effects 0.000 claims description 3
- 238000006703 hydration reaction Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 2
- 239000013528 metallic particle Substances 0.000 claims description 2
- 239000011833 salt mixture Substances 0.000 claims description 2
- 239000010414 supernatant solution Substances 0.000 claims description 2
- 239000011265 semifinished product Substances 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 abstract description 12
- 230000009466 transformation Effects 0.000 abstract description 7
- 238000002425 crystallisation Methods 0.000 abstract description 6
- 230000008025 crystallization Effects 0.000 abstract description 6
- 238000005406 washing Methods 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004480 active ingredient Substances 0.000 abstract 2
- 239000010970 precious metal Substances 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000012704 polymeric precursor Substances 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 238000011268 retreatment Methods 0.000 abstract 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 18
- 235000019445 benzyl alcohol Nutrition 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910009112 xH2O Inorganic materials 0.000 description 7
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 208000035126 Facies Diseases 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 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
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 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
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000013462 industrial intermediate Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- 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
- B01J23/58—Platinum group metals with alkali- or alkaline earth 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
- 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
-
- B01J35/51—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
Abstract
The invention provides a high-dispersion supported ruthenium dioxide catalyst and a preparing method thereof. The preparing method comprises the steps that a precious metal polymeric precursor solution and a soluble salt solution composing the +2 and +3 valence metal ions of hydrotalcite are mixed, nucleating and growing are carried out in an alkali solution environment provided by a precipitating agent, and the RuO2/MAl-LDH catalyst is obtained through crystallization, washing, drying and further retreatment. According to the catalyst, the precious metal Ru serves as the active ingredient and is supported on the surface of hydrotalcite MAl-LDH as a supporter, and the supported RuO2 catalyst uniform in dispersion and size is formed; the supporting amount of the active ingredient Ru is within the range of 0.5-10%, formed RuO2 nanometer particles are highly dispersed on the surface of the supporter, the particle size of the RuO2 nanometer particles ranges from 1 nm to 5 nm, and the RuO2 nanometer particles are spherical or semispherical. The transformation frequency TOF of the catalyst is remarkably higher than that of a Ru-based catalyst reported in documents in alcohol selective oxidation reactions.
Description
Art
The present invention relates to brucite as carrier, active component is as RuO2Loaded noble metal catalyst and preparation method thereof, should
Catalyst can be applicable in the multiple oxidation reaction process in the field such as petrochemical industry, fine chemistry industry.
Background technology
Alcohols selectivity oxidation is functional group conversions's reaction that a class is important, and its product is the carbonyl compounds such as aldehyde ketone.Carbonyl compound
Thing has extensively in fields such as plastics, detergent, coating, cosmetics, food additive and medicines as industrial chemicals and intermediate
General application.At present, green alcohols selectivity oxidation reaction mainly selects molecular oxygen as oxidant.But, due to molecular oxygen
There is higher activation energy, slower oxidizing reaction rate, suitable catalyst stimulation molecular oxygen need to be added, to reduce activation energy
Promote its oxidizing reaction rate.Generally, the oxidation of alcohols reaction main employing carried noble metal with molecular oxygen as oxidant is urged
Agent.
In recent years, RuO2Catalyst shows the catalysis activity and selectivity of excellence, has been widely used in all kinds of alcohol selectivity oxygen
Change in reaction.RuO2Produce stronger chemisorbed with reaction substrate coordination, and there is unsaturation coordination with oxidizer molecule oxygen,
Play the effect of excited oxygen.In 1981, document Masakatsu Matsumoto and Satoru Ito, J.C.S.Chem.Comm,
1981,907-908, find RuO the earliest2Capryl alcohol catalysis can be oxidized to octanal by catalyst in a mild condition, and its productivity reaches
92%.Subsequently, in 1989, document Gemma Morea, Luigia Sabbatini and Pier G.Zambonin, J.Chem.Soc.,
Faraday Trans.1989,85 (11), 3861-3870, find RuO2·xH2O is compared to RuO2It is more beneficial for catalyzing alcohols oxidation
Reaction, RuO is thought in research2·xH2In O, constitution water can promote the electron transfer between reactant and active component, thus carries
High catalytic activity.Document Kazuya Yamaguchi and Noritaka Mizuno, Angew.Chem.2002,114,
4720-4724, by RuO2·xH2O deposits to Al2O3RuO is prepared on carrier2·xH2O/Al2O3, test result indicate that,
In the oxidation reaction of benzyl alcohol, reaction temperature is 100 DEG C, during reaction 2h, and the conversion ratio of benzyl alcohol and the selectivity of benzaldehyde
Being all higher than 99%, transformation frequency TOF is 37h-1.RuO prepared by traditional method2·xH2O nano-particle general size is relatively big,
Interaction with carrier is more weak, easily occurs to migrate and reunite, and the activity of current Ru base catalyst is universal in course of reaction
The highest (TOF < 78h-1), it is therefore desirable to improve traditional preparation method or process means improve RuO2·xH2O nano-particle divides
Dissipate and catalysis activity, thus obtain high dispersive high performance support type RuO2·xH2O catalyst.
Complex metal hydroxide (being called for short LDHs) is a class two-dimensional layered anionic type clay material, and its construction features includes:
Laminate metal cation has Modulatory character and atomic level high degree of dispersion, and metallic element is mainly magnesium, cobalt, nickel, manganese, aluminum etc.;
Object interlayer anion and main body laminate exist weak chemical bond makes LDHs have interlayer anion interchangeability, common interlayer cloudy from
Son has CO3 2-、NO3 -、OH-、PO4 3-、SO4 2-、Cl-Deng;It is adjustable that surface has Acidity of Aikalinity;Nano-particle is had strong suction
Attached property and confinement effect.Owing to LDHs has the layer structure of uniqueness, Acidity of Aikalinity, strong adsorptivity feature, as high-performance
Catalysis material, adsorbing material, separation material, functional aid material etc. are applied to the multiple field of national economy, especially as urging
Agent material is widely used in alcohols selectivity oxidation reaction.
In sum, support type RuO2The traditional preparation methods of catalyst is complicated, nano-particle interacts more weak with carrier, leads
Cause particle migration and reunion in course of reaction, thus cause the problems such as the reduction of activity, selectivity and bad stability.Therefore, open
Send out a kind of with RuO2The support type RuO of high dispersive is prepared for the one-step synthesis that active component, brucite are auxiliary agent and carrier2Catalysis
Agent tool is of great significance.The present invention intends preparing the high-dispersion nano RuO with brucite as carrier with one-step synthesis2Catalysis
Agent.Such catalyst carrier has higher specific surface and pore structure, abundant basic site, can support size and spatial distribution
All than more uniform RuO2Nano-particle.
Summary of the invention
It is an object of the invention to provide a kind of with brucite as carrier, active component is stablized and the carried noble metal of high degree of dispersion
RuO2Catalyst and preparation method thereof, another object is to provide catalyst reprocessing means, and regulation and control reprocessing condition is to regulate and control RuO2
Water of crystallization, particle size, Lacking oxygen and active component valence state in catalyst thus obtain high performance Ru base catalyst.
The high-dispersion loading type RuO that the present invention provides2Catalyst, is a kind of noble metal RuO with brucite as carrier2Catalyst,
It is designated as RuO2/ MAl-LDH, wherein RuO2Comprise anhydrous RuO2With hydration RuO2Two kinds of forms, its particle diameter 1~5nm it
Between, pattern is spherical or hemispherical, and metallic particles is uniformly dispersed stably on brucite, complete crystal form, size uniformity;
MAl-LDH is brucite, and its chemical composition formula is: [M2+ 1-xAl3+ x(OH)2](An-)x/n·mH2O, wherein M2+For bivalence
Metal ions M g2+、Zn2+、Ni2+、Co2+、Cu2+Or Mn2+In one or more, An-It is Cl-、NO3-、SO4 2-Or
CO3 2-In one or more;X is Al3+/(M2++Al3+) molar ratio, 0.2≤x≤0.33;M is rubbing of intermediary water molecule
You measure, 2≤m≤4.5;The architectural feature of brucite is the growth of lamellar hydrotalcite nano piece vertical interlaced, presents outward opening horn-like
Bouquet structure, average diameter is between 300~600nm.
The preparation technology of this catalyst is, by solubility Ru precursor salt, M2+Salt and Al3+Saline solution is configured to mixed solution,
It is simultaneously added dropwise to reaction vessel with precipitant solution again, makes the generation of brucite and active component synchronize to carry out, at design temperature
Lower crystallization obtains RuO2/ MAl-LDH catalyst.Hereafter, the sample obtained is reprocessed under selected atmosphere, control
Reprocessing condition, the middle water of crystallization of regulating catalyst, particle size, Lacking oxygen and active component valence state.
Concrete preparation process is as follows:
A. solubility Ru salt is dissolved in the Ru saline solution A that compound concentration in deionized water is 0.01~0.1mmol/L;
Described solubility Ru salt is: Ru (NO) (NO3)3、Ru(NO3)3·2H2O、RuCl3、RuCl3·3H2O、RuBr3、RuBr3·3H2O
In one, be preferably RuCl3·3H2O;
B. by soluble divalent metal M salt and Al (NO3)3·9H2O is dissolved in deionized water preparation mixing salt solution, wherein M2+
Concentration be 0.02~0.08mol/L, M2+With Al3+Molar concentration rate is 2~10;Stir in solution A is joined this salt-mixture again
Mix and uniformly obtain mixed solution, and make M in mixed solution2+With Ru3+Molar concentration rate be 10~100:1;
Described M2+For bivalent metal ion Mg2+、Zn2+、Ni2+、Co2+、Cu2+Or Mn2+In one or more, mixing
Anion in solution is Cl-、NO3-、SO4 2-Or CO3 2-One or more.
C, use Na2CO3It is 0.05~5mol/L precipitant solution, wherein Na with NaOH and deionized water compound concentration2CO3
It is 4-2:1 with the mol ratio of NaOH;The mixed solution of step B and precipitant solution being simultaneously added dropwise to container, it is heavy to control
The addition of shallow lake agent solution makes the pH of solution be maintained at 8.5~10.5, and control rate of addition, between 0.8~1.5mL/min, is treated molten
After drop adds, at 60~100 DEG C, stir 6~36h, naturally cool to room temperature, filter, precipitate is washed with deionized
Centrifugal is repeatedly 7~8 to supernatant solution pH value, is dried 5~24h then at 40~80 DEG C, and one-step synthesis prepares RuO2Nano-particle
It is carried on MAl-LDH carrier, is designated as RuO2/MAl-LDH。
D, sample step C obtained carry out the reprocessing of 2~5 hours at a temperature of atmosphere and 100~600 DEG C, obtain
Finished catalyst;Described atmosphere is the one in air, oxygen, oxygen-nitrogen mixture, nitrogen;Preferably oxygen or
Oxygen-nitrogen mixture;In described oxygen-nitrogen mixture, oxygen is 10:10-90 with the volume ratio of nitrogen.
Based on said method, by the pH of regulation and control mixed solution and modulation crystallization temperature and time, obtain with brucite as carrier
Support type RuO2Catalyst.The method utilizes hydrotalcite supports to have strong adsorptivity to nano-particle and confinement effect can make
RuO2Nanoparticles stable is also dispersed in carrier surface, improves RuO2Nano-particle problem unstable, that easily reunite.
Additionally, the RuO to preparation2/ MAl-LDH reprocesses, and controls RuO by regulating and controlling temperature, condition2Catalyst crystallizes
Water, particle size, Lacking oxygen and active component valence state, to obtain high-performance Ru base catalyst.
Fig. 1 is the RuO of embodiment 1 preparation2/Co3The XRD spectra of Al-LDH catalyst.
Fig. 2 is the RuO of embodiment 1 preparation2/Co3The HRTEM photo of Al-LDH catalyst.Can from HRTEM photo
Go out the support type RuO of preparation2In catalyst, active metal component is evenly dispersed in carrier surface, and mean diameter is 1.69
nm。
Fig. 3 is the RuO of embodiment 1 preparation2/Co3The XPS spectrum figure of Al-LDH catalyst.Find from XPS spectrum figure
RuO2/Co3In Al-LDH catalyst, the 3p of Ru3/2Track occurs characteristic peak at 464.7eV and 462.7eV, and explanation is urged
Agent contains hydration RuO simultaneously2With anhydrous RuO2。
Fig. 4 is the RuO of embodiment 1 preparation2/Co3Al-LDH catalyst benzyl alcohol in benzyl alcohol selective oxidation reaction turns
Rate curve.Successive reaction 3h, the benzyl alcohol conversion ratio of catalyst reaches 99%.
Fig. 5 is the RuO of embodiment 3 preparation2/Mg3The HRTEM photo of Al-LDH catalyst.Can from HRTEM photo
Go out the support type RuO of preparation2In catalyst, active metal component is evenly dispersed in carrier surface, and mean diameter is 1.57
nm。
Fig. 6 is that embodiment 5,6,7 and 8 obtains RuO2/Co3Al-LDH-110℃、RuO2/Co3Al-LDH-200℃、
RuO2/Co3Al-LDH-300 DEG C and RuO2/Co3The transformation frequency TOF of Al-LDH-500 DEG C of catalyst is with the change of reprocessing temperature
Change curve.In benzyl alcohol selective oxidation reaction, the transformation frequency TOF of catalyst is respectively as follows: 51h-1、142h-1、100h-1、
23h-1.When reprocessing temperature is 200 DEG C, the highest (142h of transformation frequency TOF of catalyst-1), hence it is evident that higher than document Ru/HAP
Transformation frequency value (78h-1)。
The invention have the characteristics that by using one-step synthesis, by saline solution and the Ru precursor solution of composition hydrotalcite material
Mixing, one-step synthesis RuO2/ MAl-LDH catalyst, the method saves Ru precursor solution and the carrier impregnation of traditional method
Step, preparation method is simple, and enhances the interaction of active component and carrier.The active metal particles of this kind of catalyst
Be uniformly dispersed, grain size less, owing to the carrier of brucite is to the strong adsorptivity of nano-particle and confinement effect, make RuO2
Nanoparticles stable exists and carrier surface.Additionally, the catalyst of preparation is reprocessed under different atmosphere, control catalysis
The middle water of crystallization of agent, particle size, Lacking oxygen and active component valence state, be the another kind of means improving catalytic performance.
Accompanying drawing illustrates:
Fig. 1 is the RuO of embodiment 1 preparation2/Co3The XRD spectra of Al-LDH catalyst.
Fig. 2 is the RuO of embodiment 1 preparation2/Co3The HRTEM photo of Al-LDH catalyst.
Fig. 3 is the RuO of embodiment 1 preparation2/Co3The XPS spectrum figure of Al-LDH catalyst.
Fig. 4 is the RuO of embodiment 1 preparation2/Co3Al-LDH catalyst benzyl alcohol in benzyl alcohol selective oxidation reaction turns
Rate curve.
Fig. 5 is the RuO of embodiment 3 preparation2/Mg3The HRTEM photo of Al-LDH catalyst.
Fig. 6 is the RuO of embodiment 5,6,7 and 82/Co3Al-LDH-110℃、RuO2/Co3Al-LDH-200℃、
RuO2/Co3Al-LDH-300 DEG C and RuO2/Co3The transformation frequency TOF of Al-LDH-500 DEG C of catalyst is with the change of reprocessing temperature
Change curve.
Detailed description of the invention:
Embodiment 1
A weighs 1g RuCl3·xH2O is also settled to 100mL with deionized water dissolving, is configured to RuO2Presoma RuCl3
Solution.
B is by 15mmol Co (NO3)2·6H2O and 5mmol Al (NO3)3·9H2O is 3 to 1 to be added to 100 with mol ratio
ML deionized water is configured to metal salt solution.
C adds the RuCl of the step A preparation of 4.4mL in the mixed solution that step B is prepared3Solution, is uniformly mixing to obtain
Mixed solution.
D is by 10.4mmol Na2CO3100mL deionized water is added with 32.3mmol NaOH, ultrasonic to dissolving completely, join
Make aqueous slkali.
Aqueous slkali prepared by the mixed solution that step C is prepared by E and step D is at the uniform velocity to drop in this four-hole boiling flask and in room temperature
Lower quickly stirring, during remain that solution ph is 9~10, after dropping completely, mixed solution is transferred to 85 DEG C of water-baths
Middle stirring 24h;After stirring terminates, it is down to room temperature, gained precipitate is centrifuged to neutrality, subsequently by precipitate through repeatedly washing
It is placed in 60 DEG C of baking ovens and is dried 10 hours, the sample obtained is ground, is labeled as RuO2/Co3Al-LDH。
The catalyst of preparation in embodiment 1 is used for benzyl alcohol selective oxidation reaction.Reaction condition: by 104 μ L benzyl alcohol and
The catalyst of respective quality is placed in six glass reactors of 50ml, is passed through high-purity O25min is in Ex-all reactor
Air.Course of reaction keeps the high-purity O of 0.1MPa2, 1000rpm stirs, is heated to 80 DEG C.During according to different reaction
Between sample, the sample of taking-up cools down rapidly, reduces reactant and the volatilization of product, by organic facies film, it is achieved catalyst and anti-
Answer the separation of thing, product.Reactant, the composition of product and content are analyzed by gas chromatogram, and data processing method is interior
Mark method.
Embodiment 2
Step A is with embodiment 1;
B is by 10mmol Co (NO3)2·6H2O and 5mmol Al (NO3)3·9H2O is 2 to 1 to be added to 100 with mol ratio
ML deionized water is configured to metal salt solution.
C adds the RuCl of the step A preparation of 2.9mL in the mixed solution that step B is prepared3Solution, is uniformly mixing to obtain
Mixed solution.
D is by 10.4mmol Na2CO3100mL deionized water is added with 24.2mmol NaOH, ultrasonic to dissolving completely, join
Make aqueous slkali.
Aqueous slkali prepared by the mixed solution that step C is prepared by E and step D is at the uniform velocity to drop in this four-hole boiling flask and in room temperature
Lower quickly stirring, during remain that solution ph is 9~10, after dropping completely, mixed solution is transferred to 85 DEG C of water-baths
Middle stirring 24h;After stirring terminates, it is down to room temperature, gained precipitate is centrifuged to neutrality, subsequently by precipitate through repeatedly washing
It is placed in 60 DEG C of baking ovens and is dried 10 hours, the sample obtained is ground, is labeled as RuO2/Co3Al-LDH。
Embodiment 3
Step A is with embodiment 1;
B is by 15mmol Mg (NO3)2·6H2O and 5mmol Al (NO3)3·9H2O is 3 to 1 to be added to 100 with mol ratio
ML deionized water is configured to metal salt solution.
C adds the RuCl of the step A preparation of 2.4mL in the mixed solution that step B is prepared3Solution, is uniformly mixing to obtain
Mixed solution.
D is by 10.4mmol Na2CO3100mL deionized water is added with 32.3mmol NaOH, ultrasonic to dissolving completely, join
Make aqueous slkali.
Aqueous slkali prepared by the mixed solution that step C is prepared by E and step D is at the uniform velocity to drop in this four-hole boiling flask and in room temperature
Lower quickly stirring, during remain that solution ph is 9~10, after dropping completely, mixed solution is transferred to 85 DEG C of water-baths
Middle stirring 24h;After stirring terminates, it is down to room temperature, gained precipitate is centrifuged to neutrality, subsequently by precipitate through repeatedly washing
It is placed in 60 DEG C of baking ovens and is dried 10 hours, the sample obtained is ground, is labeled as RuO2/Mg3Al-LDH。
Embodiment 4
Step A is with embodiment 1;
B is by 15mmol Mn (NO3)2·6H2O and 5mmol Al (NO3)3·9H2O is 3 to 1 to be added to 100 with mol ratio
ML deionized water is configured to metal salt solution.
C adds the RuCl of the step A preparation of 2.4mL in the mixed solution that step B is prepared3Solution, is uniformly mixing to obtain
Mixed solution.
D is by 10.4mmol Na2CO3100mL deionized water is added with 32.3mmol NaOH, ultrasonic to dissolving completely, join
Make aqueous slkali.
Aqueous slkali prepared by the mixed solution that step C is prepared by E and step D is at the uniform velocity to drop in this four-hole boiling flask and in room temperature
Lower quickly stirring, during remain that solution ph is 9~10, after dropping completely, mixed solution is transferred to 85 DEG C of water-baths
Middle stirring 24h;After stirring terminates, it is down to room temperature, gained precipitate is centrifuged to neutrality, subsequently by precipitate through repeatedly washing
It is placed in 60 DEG C of baking ovens and is dried 10 hours, the sample obtained is ground, is labeled as RuO2/Mn3Al-LDH。
Embodiment 5
Step A, B, C, D and E are with embodiment 1;
The catalyst sample that step E is obtained by F is placed in tube furnace under air atmosphere, and 110 DEG C process 3 hours, obtain
RuO2/Co3Al-LDH-110 DEG C of catalyst.
Embodiment 6
Step A, B, C, D and E are with embodiment 1;
The catalyst sample that step E is obtained by F is placed in tube furnace under air atmosphere, and 200 DEG C process 3 hours, obtain
RuO2/Co3Al-LDH-200 DEG C of catalyst.
Embodiment 7
Step A, B, C, D and E are with embodiment 1;
The catalyst sample that step E is obtained by F is placed in tube furnace under air atmosphere, and 300 DEG C process 3 hours, obtain
RuO2/Co3Al-LDH-300 DEG C of catalyst.
Embodiment 8
Step A, B, C, D and E are with embodiment 1;
The catalyst sample that step E is obtained by F is placed in tube furnace under air atmosphere, and 500 DEG C process 3 hours, obtain
RuO2/Co3Al-LDH-500 DEG C of catalyst..
Embodiment 9
Step A, B, C, D and E are with embodiment 1;
The catalyst sample that step E is obtained by F is placed in tube furnace under oxygen atmosphere, and 200 DEG C process 3 hours, obtain
RuO2/Co3Al-LDH-200℃(O2) catalyst.
Embodiment 10
Step A, B, C, D and E are with embodiment 1;
The catalyst sample that step E is obtained by F is placed in tube furnace under nitrogen atmosphere, and 200 DEG C process 3 hours, obtain
RuO2/Co3Al-LDH-200℃(N2) catalyst.
Claims (3)
1. a preparation method for the high-dispersion loading type ruthenic oxide catalyst described in claim 1, specifically comprises the following steps that
A. solubility Ru salt is dissolved in the Ru saline solution A that compound concentration in deionized water is 0.01~0.1mmol/L;Described
Solubility Ru salt be: Ru (NO) (NO3)3、Ru(NO3)3·2H2O、RuCl3、RuCl3·3H2O、RuBr3、RuBr3·3H2O
In one;
B. by soluble divalent metal M salt and Al (NO3)3·9H2O is dissolved in deionized water preparation mixing salt solution, wherein M2+
Concentration be 0.02~0.08mol/L, M2+With Al3+Molar concentration rate is 2~10;Stir in solution A is joined this salt-mixture again
Mix and uniformly obtain mixed solution, and make M in mixed solution2+With Ru3+Molar concentration rate be 10~100:1;
Described M2+For bivalent metal ion Mg2+、Zn2+、Ni2+、Co2+、Cu2+Or Mn2+In one or more, mixing
Anion in solution is Cl-、NO3-、SO4 2-Or CO3 2-In one or more;
C, use Na2CO3It is 0.05~5mol/L precipitant solution, wherein Na with NaOH and deionized water compound concentration2CO3
It is 4-2:1 with the mol ratio of NaOH;The mixed solution of step B and precipitant solution being simultaneously added dropwise to container, it is heavy to control
The addition of shallow lake agent solution makes the pH of solution be maintained at 8.5~10.5, and control rate of addition, between 0.8~1.5mL/min, is treated molten
After drop adds, at 60~100 DEG C, stir 6~36h, naturally cool to room temperature, filter, precipitate is washed with deionized
Centrifugal is repeatedly 7~8 to supernatant solution pH value, is dried 5~24h then at 40~80 DEG C, and one-step synthesis prepares RuO2Nano-particle
It is carried on MAl-LDH supported catalyst semi-finished product, is designated as RuO2/MAl-LDH;
D, sample step C obtained carry out the reprocessing of 2~5 hours at a temperature of atmosphere and 100~600 DEG C, obtain
Finished catalyst;
Described atmosphere is the one in air, oxygen, oxygen-nitrogen mixture, nitrogen environment;In described oxygen-nitrogen mixture
Oxygen is 10:10-90 with the volume ratio of nitrogen.
The preparation method of high-dispersion loading type ruthenic oxide catalyst the most according to claim 1, is characterized in that: described in step A
Solubility Ru salt be RuCl3·3H2O;The atmosphere of the reprocessing described in step D is the ring at oxygen or oxygen-nitrogen mixture
Under border.
3. the high-dispersion loading type ruthenic oxide catalyst that prepared by method according to claim 1, is designated as
RuO2/ MAl-LDH, wherein RuO2Comprise anhydrous RuO2With hydration RuO2Two kinds of forms, its particle diameter between 1~5nm,
And metallic particles is uniformly dispersed stably on brucite, complete crystal form, size uniformity;MAl-LDH is brucite, and it is changed
Learn composition formula as follows: [M2+ 1-xAl3+ x(OH)2](An-)x/n·mH2O, wherein M2+For bivalent metal ion Mg2+、Zn2+、Ni2+、
Co2+、Cu2+、Mn2+In one or more, An-It is Cl-、NO3-、SO4 2-、CO3 2-In one or more;X is
Al3+/(M2++Al3+) molar ratio, 0.2≤x≤0.33;M is the mole of intermediary water molecule, 2≤m≤4.5;Brucite
Architectural feature is the growth of lamellar hydrotalcite nano piece vertical interlaced, presents outward opening trumpet-shaped bouquet structure, and average diameter is
Between 300~600nm.
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