CN105964258A - Transition metal nanoparticle catalyst with dual confinement structure as well as application thereof to catalysis of selective hydrogenation reaction of dimethyl terephthalate - Google Patents
Transition metal nanoparticle catalyst with dual confinement structure as well as application thereof to catalysis of selective hydrogenation reaction of dimethyl terephthalate Download PDFInfo
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- CN105964258A CN105964258A CN201610299467.XA CN201610299467A CN105964258A CN 105964258 A CN105964258 A CN 105964258A CN 201610299467 A CN201610299467 A CN 201610299467A CN 105964258 A CN105964258 A CN 105964258A
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- confinement structure
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 230000009977 dual effect Effects 0.000 title claims abstract description 50
- 229910021524 transition metal nanoparticle Inorganic materials 0.000 title claims abstract description 34
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 16
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002923 metal particle Substances 0.000 claims abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 11
- 150000003624 transition metals Chemical class 0.000 claims abstract description 11
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000012298 atmosphere Substances 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 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 description 12
- 229960001545 hydrotalcite Drugs 0.000 claims description 12
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000004702 methyl esters Chemical class 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- 230000009467 reduction Effects 0.000 abstract description 7
- 239000000376 reactant Substances 0.000 abstract description 5
- 239000004411 aluminium Substances 0.000 abstract description 3
- -1 aluminium ions Chemical class 0.000 abstract description 2
- LNGAGQAGYITKCW-UHFFFAOYSA-N dimethyl cyclohexane-1,4-dicarboxylate Chemical compound COC(=O)C1CCC(C(=O)OC)CC1 LNGAGQAGYITKCW-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229910017107 AlOx Inorganic materials 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000012266 salt solution Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000008187 granular material Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000010949 copper Substances 0.000 description 6
- 241000209094 Oryza Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 230000007850 degeneration Effects 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- 235000012222 talc Nutrition 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000002082 metal nanoparticle Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910000943 NiAl Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 150000001768 cations 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/72—Copper
-
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B01J35/396—
-
- B01J35/40—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C69/75—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a six-membered ring
Abstract
The invention discloses a method for preparing a transition metal nanoparticle catalyst with a dual confinement structure as well as an application thereof to catalysis of a selective hydrogenation reaction of dimethyl terephthalate. Firstly, a laminate of a hydrotalcite-like precursor containing transition metal and aluminium ions is synthesized, and then the transition metal nanoparticle catalyst with the dual confinement structure is prepared by reduction. The catalyst structure has the characteristics that transition metal nanoparticles are embedded in dual shells including an aluminium doped transition metal oxide shell and an amorphous aluminum oxide shell in order, and the dual confinement structure containing nanometer metal particles is formed. The structure with two oxide shells is used, so that transition metal is dispersed uniformly, mutual effects between the transition metal and a carrier are strong, sintering and loss of transition metal are prevented, and active sites of reaction are provided for reactants. The catalyst improves conversion rate of dimethyl terephthalate, and selectivity and reaction stability of dimethyl 1,4-cyclohexanedicarboxylate are substantially improved.
Description
Technical field
The invention belongs to catalyst preparation technical field, particularly to a kind of houghite precursor controlling reduction system
Within being embedded in metal-oxide and unformed aluminium oxide double housing successively with metal nanoparticle, formed
Transition metal nanoparticles catalyst and the catalysis dimethyl terephthalate (DMT) thereof of dual confinement structure select hydrogenation anti-
The application answered.
Background technology
Industrial dimethyl terephthalate (DMT) Hydrogenation mainly uses support type for 1,4 cyclohexanedicarboxylic acid dimethyl ester
Precious metals pd, Ru or Rh base catalyst.But noble metal catalyst has higher hydrogenation activity and selectivity,
But its process conditions are harsher, its price comparison is expensive in addition, and is unfavorable for industrialized further development.
So, the focus of present research is using base metal mostly, and main use transition metal Ni substitutes expensive
Metal.On the other hand, tradition prepares loaded catalyst many employings infusion process, the method preparation simplicity and technique
Cost is relatively low, but infusion process is preparing loaded catalyst process owing to being affected by factors such as solvation effects,
Easily causing metallic particles reunion to grow up, prepared catalyst activity component dispersion is poor, causes catalyst
Reactivity and service life are poor.
LDHs is the compound formed by interlayer anion and positively charged laminate ordered fabrication, its chemical composition
Formula is as follows: [M2+ 1-xM3+ x(OH)2]x+[An-]x/n·yH2O, wherein M2+And M3+It is respectively bivalence and three
Valency metal cation, is positioned on main body laminate；An-For interlayer anion；X is M3+/(M2++M3+) mole
Ratio；Y is the number of intermediary water molecule.Due to LDHs have body layer sheetmetal ion form adjustable degeneration,
Main body laminate charge density and be distributed adjustable degeneration, intercalant anion guest species and the adjustable degeneration of quantity, layer
The construction features such as degeneration, the adjustable degeneration of host-guest interaction that interior space is adjustable so that LDHs is that we develop
The catalyst carrier of new catalyst, catalyst precarsor and adjustable structure changes and character provides highly significant
Platform.Using LDHs as presoma, can get through calcination process under certain condition (temperature, time)
Metal oxide-type catalysis material, the well-formed of this kind of material, catalytic active site dispersion ratio is more uniform.But
On based on this kind of material, by heat treatment under reducing atmosphere, the active metal nano-particle prepared is relatively
Greatly, the interaction force between metal and substrate is more weak, and reactivity is still restricted.And in reduction process
In, oxide reduction difficulty is big, and the reducing degree of Ni metal can reduce.
Summary of the invention
It is an object of the invention to provide a kind of simplicity and prepare the transition metal nanoparticles catalyst of dual confinement structure
Method and this catalyst is applied to be catalyzed dimethyl terephthalate (DMT) selective hydrogenation reaction.
First the present invention synthesizes laminate and contains transition metal and aluminum ions houghite presoma, then by also
The former transition metal nanoparticles catalyst preparing dual confinement structure.This catalyst structure feature is transition
Metal nanoparticle be embedded in successively aluminum doping transition metal oxide and unformed aluminium oxide double housing it
In, form dual confinement nano metal particles minor structure.This catalyst is applied to dimethyl terephthalate (DMT) select
In hydrogenation reaction, the conversion ratio of reaction, selectivity and stability can be effectively improved.
The transition metal nanoparticles catalyst of dual confinement structure of the present invention, its composition structure is: mistake
Crossing metal nanoparticle confinement in the transition metal oxide shell that aluminum adulterates, outermost is by unformed oxidation
The shell structurre of aluminum composition, forms dual confinement nano metal particles minor structure；This catalyst is black powder thing
Matter, individual particle particle diameter is at 4-8nm；On the basis of catalyst gross mass, the total load amount of transition metal is 60-66
Wt%.
The preparation method one of the transition metal nanoparticles catalyst of dual confinement structure of the present invention:
A. hydrotalcite precursor is dried at 60-100 DEG C 24-36h, then in Muffle furnace, under air atmosphere
300-700 DEG C of roasting 2-8h, heating rate is 2-10 DEG C/min, obtains the transition metal oxide of aluminum doping；
B. the transition metal oxide that aluminum adulterates is placed in atmosphere furnace, 300-700 DEG C of heat treatment in a hydrogen atmosphere
0.5-6h, heating rate is 2-10 DEG C/min；Hydrogen flow rate is 30-80mL/min, i.e. obtains dual after having reacted
The transition metal nanoparticles catalyst of confinement structure.
The preparation method two of the transition metal nanoparticles catalyst of dual confinement structure of the present invention: by water
Talcum precursor is placed in atmosphere furnace, in a hydrogen atmosphere 300-700 DEG C of heat treatment 0.5-6h, and heating rate is 2-10 DEG C
/min；Hydrogen flow rate is 30-80mL/min, i.e. obtains the transition metal nanoparticle of dual confinement structure after having reacted
Muonic catalysis agent.
In the laminate of described hydrotalcite precursor, bivalent metal ion is selected from transition metal ions, trivalent metal ion
For aluminium ion.
Described transition metal ions is Ni2+、Co2+、Cu2+、Fe2+In one or more.
The transition metal nanoparticles catalyst p-phthalic acid two of dual confinement structure prepared by said method
Methyl ester selects the application of hydrogenation.Its Catalytic processes condition is: dimethyl terephthalate (DMT) is 0.5-2.5g, dual limit
The transition metal nanoparticles catalyst amount of domain structure is 0.15-0.5g, solvent 80-100mL, and reaction temperature is
80-130 DEG C, Hydrogen Vapor Pressure is 2-8MPa, response time 3-6h.
One or more in isopropanol, ethanol, ethyl acetate of described solvent.
The method that the present invention uses hydrotalcite precursor to control reduction is prepared for the transition nanometer gold of dual confinement structure
Belonging to nano-particle catalyst, two oxide shell structures make the dispersion of transition metal evenly, transition metal
Interphase interaction with carrier is higher, it is therefore prevented that sintering runs off with transition metal, and provides instead for reactant
The avtive spot answered.This catalyst not only increases the conversion ratio of dimethyl terephthalate (DMT), and is greatly improved
The selectivity of Isosorbide-5-Nitrae-dimethyl hexahydrophthalate, and there is prominent reaction stability, and then improve hydrogenation
Reactivity worth.Its 90 DEG C, under the conditions of 6MPa hydrogen pressure, reactant/catalyst be 4:1, p-phthalic acid two
Methyl ester selective hydrogenation reaction conversion ratio is 99.9%, and selectivity is 93.3%.And this catalyst preparation process without
Using organic solvent or additive, method is easy, environmental friendliness.This catalyst can be additionally used in drippolene one section
Select hydrogenation, methane reforming and CO, CO2During Hydrogenation reacts for lower carbon number hydrocarbons and alcohol etc..
Accompanying drawing explanation
Fig. 1 is the Ni of embodiment 1 preparation2X-ray diffractogram of powder sample (a) of Al-LDHs, Fourier transform infrared
Pattern (b), TG-DT A spectrum pattern (c), scanning electron microscope diagram sheet (d).
Fig. 2 is R600 and the XRD figure of C400R600 sample of embodiment 2 preparation of embodiment 1 preparation.
Fig. 3 be embodiment 1 preparation R400 (a), R600 (b) and embodiment 2 preparation C400R400 (c),
The photo of the high-resolution-ration transmission electric-lens of C400R600 (d) and corresponding particle size distribution figure are (based on each sample
150 granules calculate).
Fig. 4 is the scanning of the transition metal nanoparticles catalyst R600 sample of dual confinement structure in embodiment 1
Light field figure (a) under transmission electron microscope, details in a play not acted out on stage, but told through dialogues figure (b), and add the details in a play not acted out on stage, but told through dialogues after energy dispersive power spectrum adnexa
Figure (c), Ni Elemental redistribution (d), aluminium element distribution (e), NiAl Elemental redistribution close figure (f).
Detailed description of the invention
Embodiment 1
A. by the Ni (NO of 19.2g3)2·6H2Al (the NO of O, 12.4g3)2·9H2O joins 150mL deionized water
In, ultrasonic dissolution obtains mixing salt solution；The sodium hydroxide of 6.3g and the sodium carbonate of 7.0g are joined 150mL
In ionized water, ultrasonic dissolution obtains mixed ammonium/alkali solutions；Take 150mL deionized water and put in 500mL there-necked flask,
The most progressively instilling mixed ammonium/alkali solutions is 10 to pH, then is simultaneously added dropwise mixing salt solution and makes pH be always held at 10；
After being added dropwise to complete, the serosity obtained is transferred in the Teflon autoclave of 250mL, crystallization 24h at 130 DEG C,
Filtering, being washed with deionized and filter to pH is 7, is finally dried 24h at 70 DEG C, obtains the water of high dispersive
Talcum precursor, is designated as Ni2Al-LDHs (XRD, FT-IR, TG-DTA spectrogram and SEM figure are shown in Fig. 1)；
B. by the high dispersive hydrotalcite precursor Ni of preparation in step A2Al-LDHs is positioned in high-temperature atmosphere furnace, logical
Enter the H that purity is 99.999%2, flow velocity is 60mL/min, raise in-furnace temperature respectively to 400 DEG C and 600 DEG C,
Heating rate is 5 DEG C/min, keeps 5h, then naturally cools to room temperature, obtains the transition gold of dual confinement structure
Belong to nano-particle catalyst and be designated as Ni/NiAlO respectivelyx/AlOxAnd Ni/NiAlO (R400)x/AlOx(R600) sample
(XRD figure is shown in Fig. 2).
To the Ni obtained2Al-LDHs precursor carries out XRD, FTIR, TG-DTA and SEM and characterizes, and result is shown in Fig. 1,
The layer structure of houghite, and material overall structure uniformity, Ni are obtained as seen from the figure2Al-LDHs
Precursor is the hexagonal flake structure of tens nanometers, and integral thickness only has ten several nanometers.
The transition metal nanoparticles catalyst of the dual confinement structure of above-mentioned preparation, its composition structure is: nickel is received
Rice corpuscles confinement in the nickel oxide shell that aluminum adulterates, the shell structurre that outermost is made up of unformed aluminium oxide,
Form dual confinement nano metal particles minor structure；This catalyst is black powder material, and individual particle particle diameter exists
4-8nm；On the basis of catalyst gross mass, the total load amount of nickel is 65wt%.
Embodiment 2
Hydrotalcite precursor prepared by step A in embodiment 1 is positioned in Muffle furnace, air roasting, rises in blast furnace
Temperature is to 400 DEG C, and heating rate is 5 DEG C/min, keeps 5h, then naturally cools to room temperature；Put again after taking-up
It is placed in high-temperature atmosphere furnace, is passed through the H that purity is 99.999%2, flow velocity is 60mL/min, rises in blast furnace respectively
Temperature is to 400 DEG C and 600 DEG C, and heating rate is 5 DEG C/min, keeps 5h, then naturally cools to room temperature,
Transition metal nanoparticles catalyst to dual confinement structure is designated as Ni/NiAlO respectivelyx/AlOx(C400R400)
And Ni/NiAlOx/AlOx(C400R600) sample (XRD figure is shown in Fig. 2).
The transition metal nanoparticles catalyst of the dual confinement structure of above-mentioned preparation, its composition structure is: nickel is received
Rice corpuscles confinement in the nickel oxide shell that aluminum adulterates, the shell structurre that outermost is made up of unformed aluminium oxide,
Form dual confinement nano metal particles minor structure；This catalyst is black powder material, and individual particle particle diameter exists
4-8nm；On the basis of catalyst gross mass, the total load amount of nickel is 65wt%.
The C400R600 specimen material that the R600 obtaining embodiment 1 and embodiment 2 obtain carries out XRD sign, knot
Fruit sees Fig. 2, and the R600 sample obtained as seen from Figure 2 is compared with C400R600 sample, and the characteristic peak of Ni is higher,
The reducing degree of Ni is higher, and the characteristic peak of NiO is the lowest flat.In C400R600 sample, NiO still accounts for always
The major part of phase composition.
C400R400 and the C400R600 sample that R400 and R600 obtaining embodiment 1 and embodiment 2 obtain
Material carries out HRETEM sign, and result is shown in Fig. 3, in the R400 sample obtained as seen from Figure 3, and 3.0-5.0nm
Particle size has accounted for 86%, and in C400R400 sample, the granule of 4.0-6.0nm accounts for 90%.In R600 sample
Account for 85% more than 5.5-7.5nm granule, and in C400R600 sample, the granule of 9.0-12.0nm has accounted for 83%.
Nanometer metal particle catalyst Ni/NiAlO to the dual confinement structure obtainedx/AlOxCarry out
Cs-corrected STEM characterizes, and result is shown in Fig. 4, the nanoparticle size great majority obtained as seen from Figure 4
Between 4-7 nanometer, wherein Ni element is mainly distributed on the central area of nano-particle, and Al element mainly divides
It is distributed in the edge of granule and the junction in some spaces.Show that the nano-particle dispersion obtained is higher, granule
Size is less, and shape is uniform, particularly defines the nanometer metal particle catalyst of dual confinement structure
Ni/NiAlOx/AlOx。
Embodiment 3
A. by the Co (NO of 19.2g3)2·6H2Al (the NO of O, 12.4g3)2·9H2O joins 150mL deionized water
In, ultrasonic dissolution obtains mixing salt solution；The sodium hydroxide of 6.3g and the sodium carbonate of 7.0g are joined 150mL
In ionized water, ultrasonic dissolution obtains mixed ammonium/alkali solutions；Take 150mL deionized water and put in 500mL there-necked flask,
The most progressively instilling mixed ammonium/alkali solutions is 10 to pH, then is simultaneously added dropwise mixing salt solution and makes pH be always held at 10；
After being added dropwise to complete, the serosity obtained is transferred in the Teflon autoclave of 250mL, crystallization 24h at 130 DEG C,
Filtering, being washed with deionized and filter to pH is 7, is finally dried 24h at 70 DEG C, obtains the water of high dispersive
Talcum precursor, is designated as Co2Al-LDHs；
B. by the high dispersive hydrotalcite precursor Co of preparation in step A2Al-LDHs is positioned in high-temperature atmosphere furnace, logical
Enter the H that purity is 99.999%2, flow velocity is 60mL/min, and rising in-furnace temperature is to 300 DEG C, and heating rate is
5 DEG C/min, keep 5h, then naturally cool to room temperature, obtain the transition metal nanoparticles of dual confinement structure
Catalyst, is designated as Co/CoAlOx/AlOx。
The transition metal nanoparticles catalyst of the dual confinement structure of above-mentioned preparation, its composition structure is: cobalt is received
Rice corpuscles confinement in the cobalt oxide shell that aluminum adulterates, the shell structurre that outermost is made up of unformed aluminium oxide,
Form dual confinement nano metal particles minor structure；This catalyst is black powder material, and individual particle particle diameter exists
4-8nm；On the basis of catalyst gross mass, the total load amount of cobalt is 65wt%.
Embodiment 4
A. by the Cu (NO of 19.5g3)2·6H2Al (the NO of O, 12.4g3)2·9H2O joins 150mL deionized water
In, ultrasonic dissolution obtains mixing salt solution；The sodium hydroxide of 6.3g and the sodium carbonate of 7.0g are joined 150mL
In ionized water, ultrasonic dissolution obtains mixed ammonium/alkali solutions；Take 150mL deionized water and put in 500mL there-necked flask,
The most progressively instilling mixed ammonium/alkali solutions is 10 to pH, then is simultaneously added dropwise mixing salt solution and makes pH be always held at 10；
After being added dropwise to complete, the serosity obtained is transferred in the Teflon autoclave of 250mL, crystallization 24h at 130 DEG C,
Filtering, being washed with deionized and filter to pH is 7, is finally dried 24h at 70 DEG C, obtains the water of high dispersive
Talcum precursor, is designated as Cu2Al-LDHs；
B. by the high dispersive hydrotalcite precursor Cu of preparation in step A2Al-LDHs is positioned in high-temperature atmosphere furnace, logical
Enter the H that purity is 99.999%2, flow velocity is 60mL/min, and rising in-furnace temperature is to 700 DEG C, and heating rate is
5 DEG C/min, keep 5h, then naturally cool to room temperature, obtain the transition metal nanoparticles of dual confinement structure
Catalyst, is designated as Cu/CuAlOx/AlOx。
The transition metal nanoparticles catalyst of the dual confinement structure of above-mentioned preparation, its composition structure is: copper is received
Rice corpuscles confinement in the copper oxide shell that aluminum adulterates, the shell structurre that outermost is made up of unformed aluminium oxide,
Form dual confinement nano metal particles minor structure；This catalyst is black powder material, and individual particle particle diameter exists
4-8nm；On the basis of catalyst gross mass, the total load amount of copper is 65wt%.
Embodiment 5
A. by the Fe (NO of 26.7g3)2·9H2Al (the NO of O, 12.4g3)2·9H2O joins 150mL deionization
In water, ultrasonic dissolution obtains mixing salt solution；The sodium hydroxide of 6.3g and the sodium carbonate of 7.0g are joined 150mL
In deionized water, ultrasonic dissolution obtains mixed ammonium/alkali solutions；Take 150mL deionized water and put into 500mL tri-mouthfuls burning
In Ping, the most progressively instilling mixed ammonium/alkali solutions is 10 to pH, then is simultaneously added dropwise mixing salt solution and makes pH protect always
Hold 10；After being added dropwise to complete, the serosity obtained is transferred in the Teflon autoclave of 250mL, 130 DEG C
Lower crystallization 24h, filters, and being washed with deionized and filter to pH is 7, is finally dried 24h at 70 DEG C,
Obtain the hydrotalcite precursor of high dispersive, be designated as Fe2Al-LDHs；
B. by the high dispersive hydrotalcite precursor Fe of preparation in step A2Al-LDHs is positioned in high-temperature atmosphere furnace, logical
Enter the H that purity is 99.999%2, flow velocity is 60mL/min, raise in-furnace temperature respectively to 500 DEG C, heating rate
It is 5 DEG C/min, keeps 5h, then naturally cool to room temperature, obtain the transition metal nanoparticle of dual confinement structure
Muonic catalysis agent, is designated as Fe/FeAlOx/AlOx。
The transition metal nanoparticles catalyst of the dual confinement structure of above-mentioned preparation, its composition structure is: ferrum is received
Rice corpuscles confinement in the ferrum oxide shell that aluminum adulterates, the shell structurre that outermost is made up of unformed aluminium oxide,
Form dual confinement nano metal particles minor structure；This catalyst is black powder material, and individual particle particle diameter exists
4-8nm；On the basis of catalyst gross mass, the total load amount of ferrum is 65wt%.
Application examples 1
Catalyst sample 0.25g prepared by embodiment 1 and embodiment 2 is positioned over 300mL high-temperature high-pressure reaction kettle
In, add 1.0g dimethyl terephthalate (DMT) reactant, add 80mL isopropanol as solvent；The first row of being filled with
Go out 3 N2, it is re-filled with discharging 3 H2, finally Hydrogen Vapor Pressure is maintained at 6MPa, arranging reaction temperature is 90 DEG C,
Open stirring and record the time.During to response time 4h, stop stirring and heater, wait and be cooled to room temperature
After take still in liquid obtain product.Use gas chromatogram that product is analyzed (reaction result is shown in Table 1).
Table 1 is R400 in embodiment 1, R600, C400R400, C400R600 and business 65%Ni base catalyst sample
Product are to the conversion ratio of catalytic hydrogenation dimethyl terephthalate (DMT) and selective data table.
Table 1
Preparation method provided by the present invention, the nanometer metal particle catalyst of the dual confinement structure prepared
Ni/NiAlOx/AlOx, it is particularly suitable for dimethyl terephthalate (DMT) selective hydrogenation reaction.With R400 and
C400R400, C400R600 and Commercial Ni catalyst sample compares, and result is as shown in table 1:
1) from table 1 it follows that the nanometer metal particle catalyst R600 sample of dual confinement structure has
It is 99.9% to the conversion ratio that dimethyl terephthalate (DMT) reactant is the highest.
2) from table 1 it follows that with direct-reduction sample compared with, prior to the conversion of roasting sample in air
Rate is relatively low, and C400R400 only has 30.3%, and C400R600 only has 79.8%.And from figure 3, it can be seen that
R400 has less particle diameter compared with C400R400, R600 with C400R600 particle diameter differs bigger.This explanation is straight
Connecing catalyst prepared by reducing process has metal higher with the interaction of substrate, metal active site more temperature,
Activity under identical reduction degree is improved.
3) from table 1 it follows that the sample R400 of lower temperature reduction has less granule than R600 sample
Size (Fig. 3), but conversion ratio is significantly lower than the latter, it is known that higher reduction degree that dual confinement structure has and gold
Belong to the interaction between substrate and bring higher catalysis activity.
4) as it can be seen from table 1 the nanometer metal particle catalyst of the dual confinement structure obtained is right for hydrogenation
The activity of dimethyl phthalate is far above commercial catalyst, and commercial catalyst conversion ratio is only 32.2%.
5) as it can be seen from table 1 each sample is inconspicuous, for reactivity for the conversion ratio impact of reaction
Obvious effect.
Claims (8)
1. the transition metal nanoparticles catalyst of a dual confinement structure, it is characterised in that it forms structure
For: transition metal nanoparticles confinement is in the transition metal oxide shell that aluminum adulterates, and outermost is by without fixed
The shell structurre of type aluminium oxide composition, forms dual confinement nano metal particles minor structure；This catalyst is black powder
Powder material, individual particle particle diameter is at 4-8nm；On the basis of catalyst gross mass, the total load amount of transition metal
For 60-66wt%.
2. the preparation method of the transition metal nanoparticles catalyst of a dual confinement structure, it is characterised in that
Its concrete operation step is:
A. hydrotalcite precursor is dried at 60-100 DEG C 24-36h, then in Muffle furnace, under air atmosphere
300-700 DEG C of roasting 2-8h, heating rate is 2-10 DEG C/min, obtains the transition metal oxide of aluminum doping；
B. the transition metal oxide that aluminum adulterates is placed in atmosphere furnace, 300-700 DEG C of heat treatment in a hydrogen atmosphere
0.5-6h, heating rate is 2-10 DEG C/min；Hydrogen flow rate is 30-80mL/min, i.e. obtains dual after having reacted
The transition metal nanoparticles catalyst of confinement structure.
3. the preparation method of the transition metal nanoparticles catalyst of a dual confinement structure, it is characterised in that
Its concrete operations condition is: be placed in atmosphere furnace by hydrotalcite precursor, in a hydrogen atmosphere 300-700 DEG C of heat treatment
0.5-6h, heating rate is 2-10 DEG C/min；Hydrogen flow rate is 30-80mL/min, i.e. obtains dual after having reacted
The transition metal nanoparticles catalyst of confinement structure.
4. according to the preparation method described in Claims 2 or 3, it is characterised in that the layer of described hydrotalcite precursor
In plate, bivalent metal ion is selected from transition metal ions, and trivalent metal ion is aluminium ion.
Preparation method the most according to claim 4, it is characterised in that described transition metal ions is Ni2+、
Co2+、Cu2+、Fe2+In one or more.
The transition metal nanoparticle of the dual confinement structure prepared the most according to the method in claim 2 or 3
Muonic catalysis agent catalysis dimethyl terephthalate (DMT) selects the application of hydrogenation.
Application the most according to claim 6, it is characterised in that the transition gold of described dual confinement structure
The reaction condition belonging to nano-particle catalyst catalysis dimethyl terephthalate (DMT) selection hydrogenation is: p-phthalic acid two
Methyl ester is 0.5-2.5g, and the transition metal nanoparticles catalyst amount of dual confinement structure is 0.15-0.5g, solvent
80-100mL, reaction temperature is 80-130 DEG C, and Hydrogen Vapor Pressure is 2-8MPa, response time 3-6h.
Application the most according to claim 7, it is characterised in that described solvent selected from isopropanol, ethanol,
One or more in ethyl acetate.
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| CN103962140B (en) * | 2014-05-12 | 2016-05-11 | 北京化工大学 | A kind of microspheroidal hollow structure nickel-base hydrogenation catalyst and preparation method thereof |
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