CN106582736A - Pillared layered zirconium phosphate loaded nickel-based catalyst, preparation method and application thereof - Google Patents
Pillared layered zirconium phosphate loaded nickel-based catalyst, preparation method and application thereof Download PDFInfo
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Abstract
Belonging to the technical field of chemical catalysis, the invention relates to a pillared layered zirconium phosphate loaded nickel-based catalyst, a preparation method and application thereof. The catalyst adopts a silicon pillared layered alpha-zirconium phosphate mesoporous material as the carrier, a transition metal is loaded on the carrier, the transition metal accounts for 0.1-30.0wt%, and the mesoporous carrier material accounts for 70.0-99.9wt%. The preparation method includes: firstly using organic alcohol amine to conduct colloidization modification on alpha-zirconium phosphate, then taking a long chain quaternary ammonium salt as the guiding agent and introducing organosilicon for self-assembly, and performing treatment to obtain a precursor of silicon pillared layered alpha-zirconium phosphate, then carrying out equivalent-volume impregnation of a soluble metal salt mixed solution on the precursor, and conducting drying, roasting and reduction activation to obtain a molded silicon pillared layered alpha-zirconium phosphate loaded nickel-based catalyst. The catalyst is used for hydrodeoxygenation reaction of an organic compound containing aromatic hydrocarbon C-O bond or alkyl C-O bond. The catalyst has the characteristics of large specific surface area, pore volume, high activity dispersion and good thermal stability, and is in favor of hydrodeoxygenation reaction o compounds containing aryl C-O bond or ether- oxygen bond.
Description
Technical field
The invention belongs to chemical industry catalysis technical field, and in particular to a kind of pillared layered zirconium phosphate load nickel base catalysis
Agent and its preparation method and application.
Background technology
Bedded zirconium phosphate (layered zirconium phosphate, α-ZrP) does not only have the general character of lamellar compound,
And the individual character being also equipped with not available for other lamellar compounds：(1) it is easy to prepare, good crystalline；(2) it is insoluble
In water and organic solvent, strong acidity and certain basicity is resistant to, heat stability and mechanical strength are very strong, chemistry
Stability is higher；(3) layer structure is stable, and after object introduces interlayer layer structure still can be kept；(4)
There is larger specific surface area, surface charge density is larger, be a kind of stronger solid acid, ion can occur
Exchange reaction；(5)-OH the groups of layer surface can be by the displacement of other groups (- OR or-R), so as to by phosphoric acid
The organic derivatization of zirconium, introduces various functional groups, thus can as needed select suitable group, while can
The arrangement of adjustment group and orientation, not only can so change the properties such as the hydrophilic-hydrophobic of interlayer surface, create
Be conducive in the layer that object inserts environment and the physical property of material of main part can be changed；(6) in certain condition
Under, delamination reaction can occur.
Because zirconium phosphate has good chemistry, heat stability and mechanical strength, and can provide quite big
Specific surface area, so having very big application prospect in effective catalyst direction.Zirconium phosphate itself has solid
Acid catalysiss function, and using inner layer space as reactor, because reactant or product shape are different, cause it
Pass in and out interlayer dynamic process it is different, so as to occur shape selective in catalytic reaction process.
(the A newmethod of immobilizing ionic liquids such as H.Y.Wang, D.X.Han
intolayeredzirconiumphosphates,Chinese Chemical Letters,2007,18:764-767.) in phosphorus
In the intercalation behavior of hydrochlorate and the research process of ion-exchange capacity, discovery polar micromolecules such as alkylamine,
Hydramine and alkyl amine base etc. can carry out colloidization process to it, and these small molecule insertion interlayers are made into interlamellar spacing
Reaction force attenuation between expansion, laminate, as presoma, other guest molecules easily enter interlayer shape
Into stable Pillared Comepound or intercalation compound.(the intercalation and photo such as R.A.Berm ú dez
physicalcharacterization of-pyrenemethylamine in zirconium phosphate
layeredmaterials,Langmuir,2005,21:890-895.) successfully by cetyl trimethyl quaternary ammonium sun from
The interlayer of the organic cations such as son insertion zirconium phosphate is prepared for Pillared Comepound.But the pillared chemical combination of existing zirconium phosphate
Thing is mostly quaternary ammonium cation, and its weak point is that temperature resistant capability is less than 200 DEG C, and the molding of general plastics adds
Work temperature limits its range of application all more than 200 DEG C.
Using ion exchange or the method with heterocycle organic amine complexation in layer, the metal with catalysis activity from
Son such as Rh3+、Pd2+、Pt2+Insertion main body interlayer.Dragone prepares the histidine intercalation compound of zirconium phosphate,
For being catalyzed H2O2Oxidation reaction；Phosphine rhodium is fixed on α-ZrP by Karlsson, for be catalyzed propylene and
The hydrogenation catalyst reaction of hexene.Porphyrin and the phthalein mountain valley with clumps of trees and bamboo are inserted α-ZrP interlayers, catalysis oxidation paraffin etc. by Nino
More metal ion Zirconium sulfuride intercalation compound is investigated, with catalytic hydrogenation, hydrolysis, polymerization and can be aoxidized
Etc. various reactions.
Duan Xue (catalysis journal, 1999,20 (5):High temperature solid-state ion exchange 510-514.) etc. is utilized, will
Copper/potassium polymerization introduces metal cation between zirconium phosphate layer, prepares the hybrid metal that aperture is 0.89nm and aoxidizes
Nitride layer post zirconium phosphate, the material shows good urging in methanol oxidation hydroxylating preparing dimethyl carbonate reaction
Change and select performance.But due to the restriction of poly hydroxy metal cation own vol, using it as column-supporting agent
To carry out the synthesis of zirconium phosphate layer column material, gained pillared material aperture it is less and exist rod structure it is wayward,
The drawbacks of laminate regularity is destroyed, makes the material that this kind of synthetic method is obtained urge in shape-selective absorption and selectivity
The application of change is restricted.
(chemical journals, 1998,56,1099-1105.) such as height tastes is leading using small molecule organic amines such as ethamine
It is inserted between zirconium phosphate layer, increases zirconium phosphate layer spacing, is inserted into the polymeric of zirconyl hydroxy and is prepared for aperture
In the pillared material of the pillared zirconium phosphate of single zirconium oxide of 2.5nm or so, by isopropanol dehydration and benzene first
Aldehyde reduction reaction is investigated, and is shown with good acid catalysiss and soda acid double-function catalyzing performance.Duan Xue is (inorganic
Chemical journal, 2002,18 (2)：Also using ethanolamine it is 166-170.) etc. colloidization reagent, slackens zirconium phosphate
Slab effect power, using aluminum/light Base Metal cation mixt of chromium polymerization specific surface area 310m2/g is prepared for,
Footpath is distributed in the mixed-metal oxides layer post zirconium phosphate of 2.3nm or so.Due to poly hydroxy metal cation
The restriction of volume, using it as column-supporting agent the synthesis of laminate zirconium phosphate micropore or mesoporous material is carried out, and is obtained
Plies of material aperture typically not over 2.5nm, be also faced with the synthesis of bigger mesopore size scope
Many difficulties.Due to the restriction of its ion volume, using it as column-supporting agent laminate zirconium phosphate micropore is carried out
Or the synthesis of mesoporous material, the aperture of the plies of material for obtaining typically not over 2.5nm, in bigger mesoporous chi
More difficulty is also faced in the synthesis of very little scope.Also, using polyhydroxy metal cation as column-supporting agent,
There is rod structure wayward, the drawback such as pore-size distribution is wider.
The content of the invention
It is an object of the present invention to provide a kind of catalyst supports laminar alpha zirconium phosphate mesoporous material as carrier with silicon column, nickel
Base Metal is equably supported on carrier surface,
A kind of pillared layered zirconium phosphate supported nickel based catalysts, described catalyst is with the pillared layered alpha-phosphate of silicon
Zirconium mesoporous material is carrier, and transition metal is supported on carrier；The catalyst constitutes mass percent
Cross metal and account for 0.1～30.0wt%, mesoporous supports material and account for 70.0～99.9wt%.
The transition metal active component using Ni as main catalytic active component, with other transition-metal Fes,
One kind is used as promoter active component, wherein Ni and another metal M in Mo, Cu, Re, Co, W
Atomic molar than 0.5～3.5.
The mesoporous supports material is bedded zirconium phosphate (α-ZrP), through the modified formation of organosilicon Intercalation reaction
Silicon pillared layered zirconium phosphate (SiO2-ZrP)。
Described catalyst composition mass percent accounts for 0.5～20.0wt%, mesoporous load for transition metal component total amount
Body material accounts for 80.0～99.5wt%.
A kind of preparation method of pillared layered zirconium phosphate supported nickel based catalysts, prepares according to following steps：
(1) weigh α-ZrP powder to be scattered in Amine Solutions, the organic amine-zirconium phosphate of colloidization is obtained after stirring
Solution；Long chain quaternary is added in above-mentioned solution, and adds organic silicon solution, mixed, adjust pH value
Between 9.0～11.0；Product centrifugation goes out solid phase, through washing, being separated by filtration, form of solid product is dry
To head product, as Silica pillared zirconium phosphate presoma；
(2) oxygen for obtaining the soluble transition metal salt solution impregnation that concentration is 0.5～10.0mol/L in (1)
On the presoma of SiClx layer post zirconium phosphate, then it is dried, roasting obtains catalyst precursors；
(3) by the catalyst precursors obtained in (2) at 550～700 DEG C, it is passed through the body of 100～200ml/min
Product percentage ratio carries out reduction activation process for 10% hydrogen (argon is balanced gas), and reduction switches after finishing
To lower the temperature and being passivated in the nitrogen of 50～100ml/min, the nickel of the silicon pillared layered zirconium phosphate load of molding is obtained
Base catalyst.
Organic amine and the molar ratio of α-ZrP are 0.3～3.0 in step (1)：1, after organosilicon is added, body
The molar ratio of Si and Zr is 5.0～10.0 in system：1, wherein quaternary ammonium salt is with the molar ratio of α-ZrP
0.5～1.0:1.
In step (1) organic amine be ethanolamine, diethanolamine, isopropanolamine or butanolamine, preferred alcohol amine.
In step (1) organosilicon be APTES, 3- TSL 8330s,
N-butylamino propyl trimethoxy silicane, 3- (2- aminoethylaminos) propyl trimethoxy silicane, preferred 3-
Aminopropyltriethoxywerene werene or 3- TSL 8330s.
Add after organosilicon described in step (1), the temperature for being sufficiently mixed reaction is 30～60 DEG C.
Vacuum drying condition described in step (1) is 60～90 DEG C of 12～48h of drying, and vacuum is
40～90Pa.
Described long chain quaternary be Dodecyl trimethyl ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, ten
Six alkyl trimethyl ammonium bromides or Cetyltrimethylammonium bromide.
The soluble transition metal saline solution is：Soluble nickel salt, soluble ferric iron salt, soluble copper salt or
Solubility other transition metal salts；
Described soluble nickel salt is：Nickel nitrate, Nickel dichloride., nickel acetate, nickel sulfate, praseodynium nickel
In one or more, preferred nickel nitrate, nickel acetate, Nickel dichloride., nickel sulfate；
Described soluble ferric iron salt is：Ferric nitrate, ferrous chloride, ferrous acetate, iron sulfate, triacetyl third
Ketone ferrum, one or more, preferred ferric nitrate, ferrous chloride, ferrous acetate, iron sulfate；
Described soluble copper salt is：Copper nitrate, copper chloride, copper acetate, cupric oxalate, praseodynium copper,
One or more of sulfamic acid copper, copper stearate；
Described solubility other transition metal salts include：Ammonium molybdate, ammonium perrhenate, ammonium paratungstate, inclined tungsten
Sour ammonium, sodium tungstate, cobalt naphthenate, cobaltous octadecanate, new cobalt decanoate, cobalt nitrate, cobaltous chloride etc..
A kind of application of pillared layered zirconium phosphate supported nickel based catalysts, the catalyst is used to contain aromatic hydrocarbons C-O
The hydrogenation deoxidation reaction of key or alkyl C-O key organic compound.
Reactant feed used be phenol, methyl phenyl ethers anisole, cresol, tea phenol, guaiacol, diphenyl ether, two
Benzyl oxide, benzofuran；Or produce from biomass and/or waste plastic catalytic pyrolysis, waste oil thermal cracking
Thing.
Bedded zirconium phosphate itself interlamellar spacing is less, and interlayer charge density is big, can not be swelling in water, it is necessary to pre-
Organic amine is first embedded in increase interlamellar spacing or make Delamination (colloidization), guest molecule could be introduced.
The present invention, to press the micelle of salt formation interlayer long-chain season as template, is assembled using package technique is oriented to
Interlayer organo-silicon compound, form the silicon polymers cross-linked structure of ordered arrangement (such as Fig. 1 institutes between zirconium phosphate layer
Show), then metal active constituent is introduced by dipping method, organic amine and quaternary ammonium salt are removed finally by roasting,
Form silicon column support layer post zirconium phosphate loaded catalyst.Using the zirconium phosphate layer post material for being oriented to assemble method formation
Material, while keeping zirconium phosphate layer plate regularity, gives full play to the advantage of the adjustable change of phosphoric acid zircon-structure, makes institute
Obtain zirconium phosphate layer column material and possess more bigger serface and more preferable pore passage structure, and save laminate table well
The P-OH acidic sites in face, with metal active constituent double activity center is formed, and is conducive to improving associated catalytic reaction
Activity.
Because above-mentioned technical proposal is used, the present invention has compared with prior art following advantages:
1st, the regularity of zirconium phosphate veneer structure has obtained good holding, and silicon oxide is as pillared composite and carries
The high heat stability of structure.
2nd, the silicon pillared layered zirconium phosphate material prepared has bigger specific surface area, adjustable pore passage structure.
3rd, the P-OH acidic sites of zirconium phosphate layer plate surface have obtained good preservation, and and metal active constituent
Double activity center can be formed.
Of the invention the characteristics of：The nickel-base catalyst of the support type even particle distribution prepared by the present invention, silicon column
Support bedded zirconium phosphate carrier can strengthen catalytic performance.Dispersion is high during use, and active surface is big, catalysis
The specific surface and pore structure of agent is adjustable.The catalyst (contains suitable for all kinds of oxygen-containing organic compounds including hyperoxia
Amount) bio-oil hydrogenation deoxidation reaction, with very high activity and selectivity, while can substantially reduce
Catalyst cost, improves to a certain extent its heat stability, extends the service life of catalyst.
Description of the drawings
Fig. 1. silicon column supports zirconium phosphate material forming process schematic diagram.
Specific embodiment
Embodiment of the present invention and produced effect, but this are further illustrated by embodiment and comparison example
The protection domain of invention is not limited to the content listed by embodiment.
Embodiment 1
Weigh 5.61g (0.02mo1) stratiform α-ZrP and be scattered in 300ml molar concentrations for 0.1mol/L ethanolamine
(ETA) in aqueous solution, stirring reaction 96h at 60 DEG C obtains ETA-ZrP solution after stirring.Then
By 100ml molar concentrations for 0.1mol/L Dodecyl trimethyl ammonium chloride (DTAB) aqueous solution and
The APTES ethanol solution of 445ml mass percentage concentration 10% is made into microemulsion, delays
Slowly in being added dropwise to ETA-ZrP solution, 6h is reacted in stirring at 25 DEG C, the ammonia spirit of Deca 25% is adjusted
PH value is 10.0, and centrifugation goes out solid phase dehydrated alcohol and deionized water is fully washed, filtered, by solid
Thing is washed with distilled water to and detects filtrate without bromide ion with silver nitrate solution, 90 DEG C of vacuum (vacuum 70Pa)
It is dried 24h and obtains head product, then superfine grinding is less than 5 microns to mean diameter, obtains the pillared layer of silane
Shape zirconium phosphate material, product is designated as DTAB-SiZrP-1.
Embodiment 2
Weigh 5.61g (0.02mo1) stratiform α-ZrP and be scattered in 80ml molar concentrations for 0.1mol/L isopropanolamines
(IPA) in aqueous solution, stirring reaction 72h at 40 DEG C obtains IPA-ZrP solution after stirring.Then by 160ml
Molar concentration is Tetradecyl Trimethyl Ammonium Bromide (TTAB) aqueous solution and 220ml mass of 0.1mol/L
The 3- TSL 8330 ethanol solution of percentage concentration 10% is made into microemulsion, be slowly added dropwise into
In IPA-ZrP solution, 3h is reacted in stirring at 40 DEG C, it is 10.0 that the ammonia spirit of Deca 25% adjusts pH value,
Centrifugation goes out solid phase dehydrated alcohol and deionized water is fully washed, filtered, by solid content distillation washing
Wash to silver nitrate solution and detect filtrate without bromide ion, 80 DEG C of vacuum (vacuum 70Pa) are dried 24h and obtain
Head product, then superfine grinding is less than 5 microns to mean diameter, obtains silane pillared layered zirconium phosphate material,
Product is designated as TTAB-SiZrP-2.
Embodiment 3
Weigh 5.61g (0.02mo1) stratiform α-ZrP and be scattered in 500ml molar concentrations for 0.1mol/L butanolamines
(BTA) in aqueous solution, stirring reaction 120h at 50 DEG C obtains BTA-ZrP solution after stirring.Then will
190ml molar concentrations are the cetyl trimethylammonium bromide aqueous solution and 355ml mass percentages of 0.1mol/L
The n-butylamino propyl trimethoxy silicane ethanol solution of concentration 10% is made into microemulsion, be slowly added dropwise into
In BTA-ZrP solution, 4h is reacted in stirring at 30 DEG C, it is 10.0 that the ammonia spirit of Deca 25% adjusts pH value,
Centrifugation goes out solid phase dehydrated alcohol and deionized water is fully washed, filtered, by solid content distillation washing
Wash to silver nitrate solution and detect filtrate without bromide ion, 60 DEG C of vacuum (vacuum 70Pa) are dried 24h and obtain
Head product, then superfine grinding is less than 5 microns to mean diameter, obtains silane pillared layered zirconium phosphate material,
Product is designated as CTAB-SiZrP-3.
Embodiment 4
0.21g nickel sulfate (NiSiO are weighed respectively according to ferronickel mol ratio nNi/nFe=0.64·6H2) and 3.65g O
Ferrous sulfate (FeSO4·7H2O) it is distributed in aqueous solution, is impregnated in embodiment 1 with incipient impregnation method
On DTAB-SiZrP-1 silane pillared layered zirconium phosphate materials (weighing 9.23g), dip time 12 hours,
First in vacuum drying oven 80 DEG C be dried 24h, then in an oven 110 DEG C be dried 24h, obtain dry sample
500 DEG C of roasting 3h under moving air in Muffle furnace.Obtain the sample after roasting and carry out compression molding being sieved into
20～40 mesh granules.Above-mentioned 5g particulate samples are obtained in the H that the percent by volume of 200ml/min is 10%2(argon
Gas is Balance Air) circulate lower 700 DEG C of reduction 3h, and reduction switches to the N of 100ml/min after finishing2Middle cooling
And be passivated, until it reaches the catalyst for molding is taken out after room temperature, ferrum nickel mass content is 7.72%, is designated as
0.6NiFe/SiZrP-1。
Embodiment 5
2.66g Ni (NO are weighed respectively according to ferronickel mol ratio nNi/nFe=1.03)2·6H2O and 3.67g
Fe(NO3)3·9H2O is distributed in aqueous solution, is impregnated in embodiment 1 with incipient impregnation method
On DTAB-SiZrP-1 silane pillared layered zirconium phosphate materials (weighing 8.98g), dip time 12 hours,
First in vacuum drying oven 60 DEG C be dried 12h, then in an oven 120 DEG C be dried 24h, obtain dry sample
500 DEG C of roasting 3h under moving air in Muffle furnace.Obtain the sample after roasting and carry out compression molding being sieved into
20～40 mesh granules.Above-mentioned 5g particulate samples are obtained in the H that the percent by volume of 150ml/min is 10%2(argon
Gas is Balance Air) circulate lower 650 DEG C of reduction 3h, and reduction switches to the N of 60ml/min after finishing2Middle cooling is simultaneously
Passivation, until it reaches the catalyst for molding is taken out after room temperature, ferrum nickel mass content is 10.25%, is designated as
NiFe/SiZrP-2。
Embodiment 6
6.25g nickel acetates (C4H6O4Ni4H2O) are weighed respectively according to ferronickel mol ratio nNi/nFe=2.0
With 3.48g ferrous chloride (FeCl24H2O) it is distributed in aqueous solution, is impregnated into incipient impregnation method
In embodiment 2 on TTAB-SiZrP-2 silane pillared layered zirconium phosphate material (weighing 17.00g), during dipping
Between 12 hours, first in vacuum drying oven 75 DEG C be dried 20h, then in an oven 120 DEG C be dried 24h, obtain
To dry sample in Muffle furnace 500 DEG C of roasting 3h under moving air.Obtain the sample after roasting to be pressed
Sheetmolding is sieved into 20～40 mesh granules.Obtain percent by volume of the above-mentioned 5g particulate samples in 150ml/min
For 10% H2(argon is Balance Air) circulates lower 600 DEG C and reduces 5h, and reduction switches to 60ml/min after finishing
N2Middle cooling is simultaneously passivated, until it reaches the catalyst for molding is taken out after room temperature, and ferrum nickel mass content is
15.0%, it is designated as 2NiFe/SiZrP-3.
Embodiment 7
3.10g Nickel dichloride. (NiCl are weighed respectively according to ferronickel mol ratio nNi/nFe=3.22·6H2) and 0.78g O
During ferrous acetate (2 (C2H3O2) Fe) is distributed to aqueous solution, it is impregnated in embodiment 3 with incipient impregnation method
On CTAB-SiZrP-3 silane pillared layered zirconium phosphate materials (weighing 4.03g), dip time 14 hours,
First in vacuum drying oven 65 DEG C be dried 48h, then in an oven 105 DEG C be dried 48h, obtain dry sample
550 DEG C of roasting 2h under moving air in Muffle furnace.Obtain the sample after roasting and carry out compression molding being sieved into
20～40 mesh granules.Above-mentioned 5g particulate samples are obtained in the H that the percent by volume of 100ml/min is 10%2(argon
Gas is Balance Air) circulate lower 600 DEG C of reduction 4h, and reduction switches to the N of 80ml/min after finishing2Middle cooling is simultaneously
Passivation, until it reaches the catalyst for molding is taken out after room temperature, ferrum nickel mass content is 19.49%, is designated as
3.2NiFe/SiZrP-4。
Embodiment 8
Weigh 3.79g Ni (NO3)2·6H2O is distributed in aqueous solution, and with incipient impregnation method reality is impregnated into
Apply in example 3 on CTAB-SiZrP-3 silane pillared layered zirconium phosphate material (weighing 4.25g), dip time
12 hours, first in vacuum drying oven 65 DEG C be dried 30h, then in an oven 120 DEG C be dried 24h, done
Dry sample 500 DEG C of roasting 3h under moving air in Muffle furnace.Obtain the sample after roasting carry out tabletting into
Type is sieved into 20～40 mesh granules.It is 10% that above-mentioned 5g particulate samples are obtained in the percent by volume of 150ml/min
H2(argon is Balance Air) circulates lower 600 DEG C and reduces 3h, and reduction switches to 60ml/min's after finishing
N2Middle cooling is simultaneously passivated, until it reaches the catalyst for molding is taken out after room temperature, and nickel mass content is 15.0%,
It is designated as Ni/SiZrP-5.
Embodiment 9
1.39g Ni (NO are weighed respectively according to nickel molybdenum mol ratio nNi/nMo=2.03)2·6H2O and 2.93g
(NH4)6Mo7O24·4H2O is distributed in aqueous solution, is impregnated in embodiment 1 with incipient impregnation method
On DTAB-SiZrP-1 silane pillared layered zirconium phosphate materials (weighing 4.50g), dip time 12 hours,
First in vacuum drying oven 60 DEG C be dried 36h, then in an oven 120 DEG C be dried 24h, obtain dry sample
550 DEG C of roasting 3h under moving air in Muffle furnace.Obtain the sample after roasting and carry out compression molding being sieved into
20～40 mesh granules.Above-mentioned 5g particulate samples are obtained in the H that the percent by volume of 150ml/min is 10%2(argon
Gas is Balance Air) circulate lower 600 DEG C of reduction 3h, and reduction switches to the N of 60ml/min after finishing2Middle cooling is simultaneously
Passivation, until it reaches the catalyst for molding is taken out after room temperature, nickel molybdenum mass content is 15.0%, is designated as
2NiMo/SiZrP-1。
Embodiment 10
3.28g Ni (NO are weighed respectively according to ambrose alloy mol ratio nNi/nCu=2.03)2·6H2O and 1.05g
Cu (NO3) 23H2O is distributed in aqueous solution, is impregnated in embodiment 2 with incipient impregnation method
On TTAB-SiZrP-2 silane pillared layered zirconium phosphate materials (weighing 9.00g), dip time 12 hours,
First in vacuum drying oven 65 DEG C be dried 24h, then in an oven 120 DEG C be dried 24h, obtain dry sample
550 DEG C of roasting 3h under moving air in Muffle furnace.Obtain the sample after roasting and carry out compression molding being sieved into
20～40 mesh granules.Above-mentioned 5g particulate samples are obtained in the H that the percent by volume of 150ml/min is 10%2(argon
Gas is Balance Air) circulate lower 650 DEG C of reduction 3h, and reduction switches to the N of 60ml/min after finishing2Middle cooling is simultaneously
Passivation, until it reaches the catalyst for molding is taken out after room temperature, ambrose alloy mass content is 15.0%, is designated as
2NiCu/SiZrP-2。
Embodiment 11
3.91g Ni (NO are weighed respectively according to nickel rhenium mol ratio nNi/nRe=2.03)2·6H2O and
1.79g NH4ReO4In being distributed to aqueous solution, it is impregnated in embodiment 3 with incipient impregnation method
On CTAB-SiZrP-3 silane pillared layered zirconium phosphate materials (weighing 18.00g), dip time 12 hours,
First in vacuum drying oven 85 DEG C be dried 12h, then in an oven 120 DEG C be dried 24h, obtain dry sample
550 DEG C of roasting 3h under moving air in Muffle furnace.Obtain the sample after roasting and carry out compression molding being sieved into
20～40 mesh granules.Above-mentioned 5g particulate samples are obtained in the H that the percent by volume of 150ml/min is 10%2(argon
Gas is Balance Air) circulate lower 650 DEG C of reduction 3h, and reduction switches to the N of 60ml/min after finishing2Middle cooling is simultaneously
Passivation, until it reaches the catalyst for molding is taken out after room temperature, nickel rhenium mass content is 15.0%, is designated as
2NiRe/SiZrP-3。
Comparative example 1
By 14.55g Ni (NO3)2·6H2O and 10.5g carbamide is dissolved in 560m1 water and forms aqueous solution and in water-bath
In be heated to 30 DEG C holding constant temperature, its pH value is adjusted to 2.5 using nitric acid.Under conditions of stirring, will
The solution that 56m1 tetraethyl orthosilicates (TEOS) and 50m1 ethanol are prepared is added drop-wise in above-mentioned aqueous solution and forms molten
Glue.Continue to stir 4h after completion of dropping, then colloidal sol is heated to into 95 DEG C, carbamide generation hydrolysis makes molten
The pH of glue is raised, and colloidal sol forms gel, while nickel is deposited on gel.When the pH value of colloidal sol reaches 8.0
When, room temperature is cooled to, and Jing vacuum filters obtain filter cake, filter cake is obtained successively Jing after ethanol and water washing
To hydrogel.50 DEG C of hydrogel Jing is dried 48h, and 120 DEG C are dried after 12h and 550 DEG C of roasting 4h and obtain two
Silica supported nickel presoma.Take 0.44g NH4H2PO4Water is dissolved in, 9m1 mass concentration ratios is configured to for 4.7%
Aqueous solution, then silicon dioxide carried nickel presomas of incipient impregnation 5g, after standing 12h, 120 DEG C of Jing
It is dried 12h and 550 DEG C of roasting 5h and obtains the catalyst precursor that nickel phosphorus mol ratio is 3.Take 2.0g catalyst
Presoma is placed in quartz ampoule fixed bed reactors, in the H that 200m1/min percents by volume are 10%2(argon
Gas is Balance Air) in air-flow first with the heating rate of 10 DEG C/min from room temperature to 250 DEG C, then with 10
DEG C/heating rate of min is warming up to 650 DEG C of final reduction temperature from 250 DEG C, and in 650 DEG C of constant temperature reduction 3h,
Obtain support type Ni2P catalyst, nickel mass content is 15.0%, is designated as Ni2P-C1。
Comparative example 2
Using preparation catalyst presoma, again Jing temperature programmed reductions prepare iron phosphide Raney nickel
Process is as follows：6.08g Fe(NO3)3·9H2O、4.40g Ni(NO3)2·6H2O and 1.73g NH4H2PO4It is molten
8m1 aqueous solutions are prepared in water, with aqueous impregnation 5.0g SiO2, stand 12h and be dried 12h after 120 DEG C
Silicon dioxide carried iron phosphate nickel presoma is prepared with 550 DEG C of roasting 4h, nickel phosphorus ratio is 1.0 in presoma.
Take 2.0g presomas to be placed in quartz ampoule fixed bed reactors, be 10% in 200ml/min percents by volume
H2First with the heating rate of 10 DEG C/min from room temperature to 250 DEG C in (argon is Balance Air) air-flow, so
Afterwards 650 DEG C of final reduction temperature, and constant temperature reduction 3h are warming up to from 250 DEG C with the heating rate of 1 DEG C/min
Support type NiFeP catalyst is obtained, wherein, ferrum nickel mass content is 15.0%, and resulting catalyst is designated as
NiFeP-C2。
Table 1
Embodiment 12～21
Application of the catalyst that the present invention is provided in the reaction of methyl phenyl ethers anisole hydrogenation deoxidation.
The resulting each 2.0g of catalyst inserts fixed bed reactors in Example 4～11 and in comparative example 1～2
Middle constant temperature zone, 5wt% methyl phenyl ethers anisoles (n-dodecane is solvent) are reaction feed and H2Mixing, reaction pressure
4.0MPa, hydrogen-oil ratio is 500,360 DEG C of reaction temperature, liquid air speed (WHSV) 0.7min-1, obtain
Product carry out obtaining fluid sample and carrying out the analysis of gas chromatogram Agilent7890 after condensation and gas-liquid separation, and
Catalyst is carried out into BET materialization phenetic analysis, the data obtained result is as shown in table 1.
Table 2
Embodiment 22～26
Application of the catalyst that the present invention is provided in the reaction of the compound hydrogenation deoxidation containing aromatic hydrocarbons C-O keys.
Guaiacol, benzofuran, cresol, phenol and the diphenyl ether (positive ten of 10wt% concentration are prepared respectively
Dioxane is solvent) it is reactant liquor, obtain 2.0g catalyst 2NiFe/SiZrP-3 resulting in embodiment 6 and put
Enter constant temperature zone in fixed bed reactors, reaction condition is pressure 4.0MPa, and hydrogen-oil ratio (v/v) 800 reacts
400 DEG C of temperature, liquid air speed (WHSV) 5.2min-1.The product for obtaining is carried out after condensation and gas-liquid separation
Obtaining fluid sample carries out online gas chromatographic analysiss, and the data obtained result is as shown in table 3.
Table 3
Embodiment technology design only to illustrate the invention and feature, its object is to allow and are familiar with this skill
The personage of art will appreciate that present disclosure and implements according to this, can not limit the protection model of the present invention with this
Enclose.All equivalence changes made according to spirit of the invention or modification, should all cover the protection in the present invention
Within the scope of.
Claims (16)
1. a kind of pillared layered zirconium phosphate supported nickel based catalysts, it is characterised in that：Described catalyst is with silicon column support
Laminar alpha zirconium phosphate mesoporous material is carrier, and transition metal is supported on carrier；The catalyst constitutes quality
Percentage ratio accounts for 0.1～30.0wt%, mesoporous supports material and accounts for 70.0～99.9wt% for transition metal.
2. a kind of pillared layered zirconium phosphate supported nickel based catalysts according to claim 1, it is characterised in that：
The transition metal active component using Ni as main catalytic active component, with other transition-metal Fes, Mo,
A kind of original as promoter active component, wherein Ni and another metal M in Cu, Re, Co, W
Sub- mol ratio 0.5～3.5：1.
3. a kind of pillared layered zirconium phosphate supported nickel based catalysts according to claim 1, it is characterised in that：
The mesoporous supports material is bedded zirconium phosphate α-ZrP, through the silicon column of the modified formation of organosilicon Intercalation reaction
Support bedded zirconium phosphate.
4. a kind of pillared layered zirconium phosphate supported nickel based catalysts according to claim 1, it is characterised in that institute
Mass percent transition metal component total amount is constituted in the catalyst stated and accounts for 0.5～20.0wt%, mesoporous supports material
Account for 80.0～99.5wt%.
5. the preparation method of pillared layered zirconium phosphate supported nickel based catalysts according to claim 1, its feature
It is that described catalyst is prepared according to following steps：
(1) weigh α-ZrP powder to be scattered in Amine Solutions, the organic amine-zirconium phosphate of colloidization is obtained after stirring
Solution；Long chain quaternary is added in above-mentioned solution, and adds organic silicon solution, mixed, adjust pH value
Between 9.0～11.0；Product centrifugation goes out solid phase, through washing, being separated by filtration, form of solid product is dry
To head product, as Silica pillared zirconium phosphate presoma；
(2) oxygen for obtaining the soluble transition metal salt solution impregnation that concentration is 0.5～10.0mol/L in (1)
On the presoma of SiClx layer post zirconium phosphate, then it is dried, roasting obtains catalyst precursors；
(3) by the catalyst precursors obtained in (2) at 550～700 DEG C, it is passed through the body of 100～200ml/min
Product percentage ratio carries out reduction activation process for 10% hydrogen (argon is balanced gas), and reduction switches after finishing
To lower the temperature and being passivated in the nitrogen of 50～100ml/min, the nickel of the silicon pillared layered zirconium phosphate load of molding is obtained
Base catalyst.
6. the preparation method of pillared layered zirconium phosphate supported nickel based catalysts according to claim 5, its feature
It is：Organic amine and the molar ratio of α-ZrP are 0.3～3.0 in step (1)：1, after organosilicon is added,
The molar ratio of Si and Zr is 5.0～10.0 in system：1, wherein quaternary ammonium salt is with the molar ratio of α-ZrP
0.5～1.0:1.
7. the preparation method of pillared layered zirconium phosphate supported nickel based catalysts according to claim 5, its feature
It is：Organic amine is ethanolamine, diethanolamine, isopropanolamine or butanolamine in step (1).
8. the preparation method of pillared layered zirconium phosphate supported nickel based catalysts according to claim 5, its feature
It is：Organosilicon is APTES, 3- aminopropyl trimethoxy silicon in step (1)
Alkane, n-butylamino propyl trimethoxy silicane or 3- (2- aminoethylaminos) propyl trimethoxy silicane.
9. the preparation method of pillared layered zirconium phosphate supported nickel based catalysts according to claim 5, its feature
It is：Add after organosilicon described in step (1), the temperature for being sufficiently mixed reaction is 30～60 DEG C.
10. the preparation method of pillared layered zirconium phosphate supported nickel based catalysts according to claim 5, it is special
Levy and be：Vacuum drying condition described in step (1) is 60～90 DEG C of 12～48h of drying, and vacuum is
40～90Pa.
The preparation method of 11. pillared layered zirconium phosphate supported nickel based catalysts according to claim 5, it is special
Levy and be, described long chain quaternary be Dodecyl trimethyl ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide,
Cetyl trimethylammonium bromide or Cetyltrimethylammonium bromide.
The preparation method of 12. pillared layered zirconium phosphate supported nickel based catalysts according to claim 5, it is special
Levy and be, soluble transition metal saline solution is：Soluble nickel salt, soluble ferric iron salt, soluble copper salt or
Solubility other transition metal salts；
Described soluble nickel salt is：Nickel nitrate, Nickel dichloride., nickel acetate, nickel sulfate, praseodynium nickel
In one or more；
Described soluble ferric iron salt is：Ferric nitrate, ferrous chloride, ferrous acetate, iron sulfate, triacetyl third
One or more in ketone ferrum；
Described soluble copper salt is：Copper nitrate, copper chloride, copper acetate, cupric oxalate, praseodynium copper,
One or more of sulfamic acid copper, copper stearate；
Described solubility other transition metal salts include：Ammonium molybdate, ammonium perrhenate, ammonium paratungstate, inclined tungsten
Sour ammonium, sodium tungstate, cobalt naphthenate, cobaltous octadecanate, new cobalt decanoate, cobalt nitrate or cobaltous chloride.
The preparation method of 13. pillared layered zirconium phosphate supported nickel based catalysts according to claim 5, it is special
Levy and be：Organic amine preferred alcohol amine in step (1)；The preferred 3- aminopropyls of organosilicon in step (1)
Triethoxysilane or 3- TSL 8330s.
The preparation method of 14. pillared layered zirconium phosphate supported nickel based catalysts according to claim 5, it is special
Levy and be：The preferred nickel nitrate of described soluble nickel salt, nickel acetate, Nickel dichloride., nickel sulfate；Described can
The preferred ferric nitrate of dissolubility iron salt, ferrous chloride, ferrous acetate, iron sulfate.
15. a kind of application of pillared layered zirconium phosphate supported nickel based catalysts as claimed in claim 1, its feature exists
In：It is anti-that the catalyst is used for the hydrogenation deoxidation containing aromatic hydrocarbons C-O keys or alkyl C-O key organic compound
Should.
16. according to pillared layered zirconium phosphate supported nickel based catalysts described in claim 15 application, it is characterised in that：
Reactant feed used be phenol, methyl phenyl ethers anisole, cresol, tea phenol, guaiacol, diphenyl ether, benzyl ether,
Benzofuran；Or from biomass and/or waste plastic catalytic pyrolysis, waste oil thermal cracking products.
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