CN106582736B - A kind of pillared layered zirconium phosphate supported nickel based catalysts and its preparation method and application - Google Patents
A kind of pillared layered zirconium phosphate supported nickel based catalysts and its preparation method and application Download PDFInfo
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Abstract
A kind of pillared layered zirconium phosphate supported nickel based catalysts of the present invention and its preparation method and application, belong to chemical industry catalysis technical field.The catalyst is using silicon column support laminar alpha zirconium phosphate mesoporous material as carrier, and transition metal is supported on carrier, and transition metal accounts for 0.1~30.0wt%, mesoporous supports material accounts for 70.0~99.9wt%.The preparation method comprises the following steps: it is modified first to carry out colloidization to alpha zirconium phosphate with organic alcohol amine, then organosilicon is introduced as directed agents using long chain quaternary and carries out self assembly, the presoma of silicon pillared layered zirconium phosphate is obtained by processing, then by soluble metal mixed salt solution incipient impregnation on presoma, molding silicon pillared layered zirconium phosphate supported nickel based catalysts are prepared by drying, roasting and reduction activation.It is used to react containing the hydrogenation deoxidation of aromatic hydrocarbons C-O key or alkyl C-O key organic compound.The catalyst has biggish specific surface area, Kong Rong, high activity dispersion degree and good thermal stability, is advantageously used for reacting containing the hydrogenation deoxidation of aryl C-O key or ether oxygen key compound.
Description
Technical field
The invention belongs to chemical industry catalysis technical fields, and in particular to a kind of pillared layered zirconium phosphate supported nickel based catalysts and its
Preparation method and application.
Background technique
Bedded zirconium phosphate (layered zirconium phosphate, α-ZrP) not only has the general character of lamellar compound,
And be also equipped with individual character not available for other lamellar compounds: (1) preparation is easy, good crystalline；(2) not soluble in water and organic molten
Agent is resistant to strong acidity and certain basicity, and thermal stability and mechanical strength are very strong, and chemical stability is higher；(3) layer structure is steady
It is fixed, layer structure still can be kept after object introduces interlayer；(4) there is biggish specific surface area, surface charge density is larger,
It is a kind of stronger solid acid, ion-exchange reactions can occurs；(5)-OH the group of layer surface can be by other group (- OR
Or-R) displacement, so that the organic derivatization of basic zirconium phosphate is introduced various functional groups, thus it can according to need the suitable base of selection
Group, while the arrangement and orientation of adjustable group, not only can change the properties such as the hydrophilic-hydrophobic of interlayer surface, create
Be conducive to environment in the layer of object insertion and can change the physical property of material of main part；(6) under certain condition, can occur
Delamination reaction.
Since basic zirconium phosphate has good chemistry, thermal stability and mechanical strength, and it can provide and sizable compare table
Area, so there is very big application prospect in effective catalyst direction.Basic zirconium phosphate itself has the function of solid acid catalysis, and with
Inner layer space causes them to pass in and out the dynamic process of interlayer difference as reactor because reactant or product shape are different, from
And occurs 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 processing to it, expand interlamellar spacing these small molecules insertion interlayer, the active force between laminate
Weaken, as presoma, other guest molecules easily enter interlayer and form stable Pillared Comepound or intercalation compound.
(the intercalation and photo physicalcharacterization of- such as R.A.Berm ú dez
pyrenemethylamine in zirconium phosphate layeredmaterials,Langmuir,2005,21:
The interlayer of the organic cations such as cetyl trimethyl quaternary ammonium cation insertion basic zirconium phosphate successfully 890-895.) is prepared for column
Support compound.But existing basic zirconium phosphate Pillared Comepound is mostly quaternary ammonium cation, and shortcoming is temperature resistant capability lower than 200
DEG C, and the processing and forming temperature of general plastics is all at 200 DEG C or more, therefore limits its scope of application.
Using ion exchange or the method being complexed with heterocycle organic amine in layer, such as the metal ion with catalytic activity
Rh3+、Pd2+、Pt2+It is inserted into main body interlayer.Dragone prepares the histidine intercalation compound of basic zirconium phosphate, for being catalyzed H2O2Oxygen
Change reaction；Phosphine rhodium is fixed on α-ZrP by Karlsson, and the hydrogenation catalyst for being catalyzed propylene and hexene reacts.Nino is by porphin
Quinoline and the phthalein mountain valley with clumps of trees and bamboo are inserted into α-ZrP interlayer, and catalysis oxidation paraffin etc. is investigated more metal ion Zirconium sulfuride intercalation compound, can
With a variety of reactions such as catalytic hydrogenation, hydrolysis, polymerization and oxidation.
Duan Xue (catalysis journal, 1999,20 (5): 510-514.) etc. utilizes high temperature solid-state ion-exchange, and copper/potassium is gathered
It closes between metal cation introducing zirconium phosphate layer, prepares the mixed-metal oxides layer column basic zirconium phosphate that aperture is 0.89nm, it should
Material shows good catalysis and selection performance in methanol oxidation hydroxylating preparing dimethyl carbonate reaction.But due to poly hydroxyl
The limitation of Base Metal cation own vol carries out the synthesis of zirconium phosphate layer column material, gained layer column using it as column-supporting agent
The drawbacks of material aperture is smaller and there are rod structures to be difficult to control, laminate regularity is destroyed, obtains this kind of synthetic method
Material is restricted in shape-selective absorption and the application of selective catalysis.
(chemical journals, 1998,56,1099-1105.) such as height tastes is inserted into phosphorus using the small molecules organic amine such as ethamine in advance
Between sour zirconium layer, increase zirconium phosphate layer spacing, be inserted into the polymer of zirconyl hydroxy is prepared for aperture in the single oxygen of 2.5nm or so
The pillared material for changing the pillared basic zirconium phosphate of zirconium, by showing to have good to isopropanol dehydration and the investigation of benzaldehyde reduction reaction
Acid catalysis and soda acid double-function catalyzing performance.Duan Xue (Chinese Journal of Inorganic Chemistry, 2002,18 (2): 166-170.) etc. also utilizes ethyl alcohol
Amine is colloidization reagent, slackens basic zirconium phosphate laminate active force, polymerize light Base Metal cation mixt using aluminium/chromium and is prepared for comparing
Surface area 310m2/g, diameter are distributed in the mixed-metal oxides layer column basic zirconium phosphate of 2.3nm or so.Due to poly hydroxy metal sun
The limitation of ion volume carries out the synthesis of laminate basic zirconium phosphate micropore or mesoporous material, obtained laminate using it as column-supporting agent
The aperture of material does not exceed 2.5nm generally, also faces many difficulties in the synthesis of bigger mesopore size range.Due to it
The limitation of ion volume carries out the synthesis of laminate basic zirconium phosphate micropore or mesoporous material, obtained laminate using it as column-supporting agent
The aperture of material does not exceed 2.5nm generally, also faces more difficulty in the synthesis of bigger mesopore size range.Also,
Using polyhydroxy metal cation as column-supporting agent, it is not easy to control that there is rod structures, the drawbacks such as pore-size distribution is wider.
Summary of the invention
It is an object of the present invention to provide a kind of catalyst using silicon column support laminar alpha zirconium phosphate mesoporous material as carrier, nickel based metal
It is equably supported on carrier surface,
A kind of pillared layered zirconium phosphate supported nickel based catalysts, the catalyst are mesoporous with silicon column support laminar alpha zirconium phosphate
Material is carrier, and transition metal is supported on carrier；Catalyst composition mass percent be transition metal account for 0.1~
30.0wt%, mesoporous supports material account for 70.0~99.9wt%.
The transition metal active component using Ni as main catalytic active component, with other transition-metal Fes, Mo, Cu, Re,
A kind of in Co, W to be used as co-catalyst active component, wherein the atomic molar of Ni and another metal M is than 0.5~3.5.
The mesoporous supports material is bedded zirconium phosphate (α-ZrP), by the silicon of the modified formation of organosilicon Intercalation reaction
Pillared layered zirconium phosphate (SiO2-ZrP)。
The catalyst composition mass percent is that transition metal component total amount accounts for 0.5~20.0wt%, mesoporous supports
Material accounts for 80.0~99.5wt%.
A kind of preparation method of pillared layered zirconium phosphate supported nickel based catalysts, is prepared according to the following steps:
(1) it weighs α-ZrP powder to be scattered in Amine Solutions, organic amine-basic zirconium phosphate that colloidization is obtained after stirring is molten
Liquid；Long chain quaternary is added in above-mentioned solution, and organic silicon solution is added, is mixed, is adjusted between pH value 9.0~11.0；It produces
Object is centrifugated out solid phase, and by washing, being separated by filtration, form of solid product is dried to obtain head product, as silicon oxide layer column phosphorus
Sour zirconium precursor body；
(2) it is aoxidized obtained in the soluble transition metal salt solution impregnation to (1) by concentration for 0.5~10.0mol/L
On the presoma of silicon layer column basic zirconium phosphate, then dry, roasting obtains catalyst precursors；
(3) by catalyst precursors obtained in (2) at 550~700 DEG C, it is passed through the volume hundred of 100~200ml/min
Divide than being that 10% hydrogen (argon gas is balanced gas) carries out reduction activation processing, is switched to 50~100ml/min after reduction
Nitrogen in cool down and be passivated, obtain the nickel-base catalyst of molding silicon pillared layered zirconium phosphate load.
The molar ratio of organic amine and α-ZrP are 0.3~3.0:1 in step (1), after organosilicon is added, in system Si with
The molar ratio of Zr is 5.0~10.0:1, and wherein the molar ratio of quaternary ammonium salt and α-ZrP are 0.5~1.0:1.
Organic amine is ethanol amine, diethanol amine, isopropanolamine or butanolamine, preferred alcohol amine in step (1).
Organosilicon is 3-aminopropyltriethoxysilane, 3- TSL 8330, normal-butyl in step (1)
TSL 8330,3- (2- aminoethylamino) propyl trimethoxy silicane, preferably three ethoxy of 3- aminopropyl
Base silane or 3- TSL 8330.
After addition 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 dry 12~48h, and vacuum degree is 40~90Pa.
The long chain quaternary is dodecyl trimethyl ammonium bromide, tetradecyltrimethylammonium bromide, cetyl
Trimethylammonium bromide or Cetyltrimethylammonium bromide.
The soluble transition metal salting liquid are as follows: soluble nickel salt, soluble ferric iron salt, soluble copper salt or it is soluble its
His transition metal salt；
The soluble nickel salt are as follows: one of nickel nitrate, nickel chloride, nickel acetate, nickel sulfate, praseodynium nickel or
It is a variety of, preferably nickel nitrate, nickel acetate, nickel chloride, nickel sulfate；
The soluble ferric iron salt are as follows: ferric nitrate, frerrous chloride, ferrous acetate, ferric sulfate, praseodynium iron, one of
Kind is a variety of, preferably ferric nitrate, frerrous chloride, ferrous acetate, ferric sulfate；
The soluble copper salt are as follows: copper nitrate, copper chloride, copper acetate, cupric oxalate, praseodynium copper, sulfamic acid
Copper, copper stearate it is one or more；
Other described soluble transition metal salts include: ammonium molybdate, ammonium perrhenate, ammonium paratungstate, ammonium metatungstate, wolframic acid
Sodium, cobalt naphthenate, cobaltous octadecanate, new cobalt decanoate, cobalt nitrate, cobalt chloride etc..
A kind of application of pillared layered zirconium phosphate supported nickel based catalysts, the catalyst be used for containing aromatic hydrocarbons C-O key or
The hydrogenation deoxidation of person's alkyl C-O key organic compound reacts.
Reactant feed used is phenol, methyl phenyl ethers anisole, cresols, tea phenol, guaiacol, diphenyl ether, benzyl ether, benzo furan
It mutters；Or derive from biomass and/or waste plastic catalytic pyrolysis, gutter oil thermal cracking products.
Bedded zirconium phosphate itself interlamellar spacing is smaller, and interlayer charge density is big, cannot be swollen in water, it is necessary to be pre-embedded with
Machine amine could introduce guest molecule to increase interlamellar spacing or make Delamination (colloidization).
The present invention is using guiding package technique, and as template, assemble interlayer has the micella formed using interlayer long-chain season by salt
Organic silicon compound forms the silicon polymers cross-linked structure (as shown in Figure 1) of ordered arrangement between zirconium phosphate layer, then passes through dipping side
Method introduces metal active constituent, removes organic amine and quaternary ammonium salt finally by roasting, forms silicon column and supports layer column basic zirconium phosphate support type
Catalyst.The zirconium phosphate layer column material formed using guiding assemble method while keeping zirconium phosphate layer plate regularity, is sufficiently sent out
The advantage for waving the adjustable change of phosphoric acid zircon-structure makes gained zirconium phosphate layer column material have more bigger serface and more preferable cellular structure,
And the P-OH acidic site of lamina surface is saved well, double activity center is formed with metal active constituent, is conducive to improve phase
Close the activity of catalysis reaction.
Due to the above technical solutions, the present invention has the following advantages over the prior art:
1, the regularity of basic zirconium phosphate veneer structure has obtained good holding, and silica is as pillared composite and raising finishes
The thermal stability of structure.
2, the silicon pillared layered zirconium phosphate material prepared has bigger specific surface area, adjustable cellular structure.
3, the P-OH acidic site of zirconium phosphate layer plate surface has obtained good preservation, and can be formed with metal active constituent
Double activity center.
The features of the present invention: the nickel-base catalyst of support type even particle distribution prepared by the present invention, silicon are pillared layered
Zirconium phosphate carrier can enhance catalytic performance.Dispersion degree is high in use process, and active surface is big, the specific surface and pore structure of catalyst
It is adjustable.The catalyst is suitable for the hydrogenation deoxidation reaction of the bio-oil of all kinds of oxygen-containing organic compounds (including elevated oxygen level),
It is highly active and selective, while catalyst cost can be substantially reduced, its thermal stability is improved to a certain extent,
Extend the service life of catalyst.
Detailed description of the invention
Fig. 1 silicon column supports zirconium phosphate material forming process schematic diagram.
Specific embodiment
Embodiment of the present invention and generated effect are further illustrated by embodiment and comparative example, but of the invention
Protection scope is not limited to content listed by embodiment.
Embodiment 1
Weighing 5.61g (0.02mo1) stratiform α-ZrP to be scattered in 300ml molar concentration is 0.1mol/L ethanol amine (ETA) water
In solution, it is stirred to react 96h at 60 DEG C, ETA-ZrP solution is obtained after stirring.It then is 0.1mol/ by 100ml molar concentration
Dodecyl trimethyl ammonium bromide (DTAB) aqueous solution of L and three ethoxy of 3- aminopropyl of 445ml mass percentage concentration 10%
Base silane ethanol solution is made into microemulsion, is slowly added dropwise in ETA-ZrP solution, stirring, reacts 6h at 25 DEG C, is added dropwise 25%
Ammonia spirit adjust pH value be 10.0, be centrifugated out solid phase dehydrated alcohol and deionized water and sufficiently wash, filter, will consolidate
Shape object is washed with distilled water to silver nitrate solution detection filtrate without bromide ion, and 90 DEG C of vacuum (vacuum degree 70Pa) are dry to be obtained for 24 hours
To head product, then ultra-fine grinding to average grain diameter obtains silane pillared layered zirconium phosphate material less than 5 microns, and product is denoted as
DTAB-SiZrP-1。
Embodiment 2
Weighing 5.61g (0.02mo1) stratiform α-ZrP to be scattered in 80ml molar concentration is 0.1mol/L isopropanolamine (IPA)
In aqueous solution, it is stirred to react 72h at 40 DEG C, IPA-ZrP solution is obtained after stirring.Then it is by 160ml molar concentration
Tetradecyltrimethylammonium bromide (TTAB) aqueous solution of 0.1mol/L and the 3- aminopropyl of 220ml mass percentage concentration 10%
Trimethoxy silane ethanol solution is made into microemulsion, is slowly added dropwise in IPA-ZrP solution, stirring, reacts 3h at 40 DEG C, drips
Add 25% ammonia spirit adjust pH value be 10.0, be centrifugated out solid phase dehydrated alcohol and deionized water sufficiently wash, mistake
Solid content is washed with distilled water to silver nitrate solution detection filtrate without bromide ion by filter, and 80 DEG C of vacuum (vacuum degree 70Pa) are dry
Dry to obtain head product for 24 hours, then ultra-fine grinding to average grain diameter obtains silane pillared layered zirconium phosphate material less than 5 microns, produces
Product are denoted as TTAB-SiZrP-2.
Embodiment 3
Weighing 5.61g (0.02mo1) stratiform α-ZrP to be scattered in 500ml molar concentration is 0.1mol/L butanolamine (BTA) water
In solution, it is stirred to react 120h at 50 DEG C, BTA-ZrP solution is obtained after stirring.Then it is by 190ml molar concentration
The cetyl trimethylammonium bromide aqueous solution of 0.1mol/L and the n-butylamino propyl three of 355ml mass percentage concentration 10%
Methoxy silane ethanol solution is made into microemulsion, is slowly added dropwise in BTA-ZrP solution, stirring, reacts 4h at 30 DEG C, is added dropwise
It is 10.0 that 25% ammonia spirit, which adjusts pH value, is centrifugated out solid phase dehydrated alcohol and deionized water and sufficiently washs, filters,
Solid content is washed with distilled water to silver nitrate solution detection filtrate without bromide ion, 60 DEG C of vacuum (vacuum degree 70Pa) are dry
Head product is obtained for 24 hours, and then ultra-fine grinding to average grain diameter obtains silane pillared layered zirconium phosphate material, product less than 5 microns
It is denoted as CTAB-SiZrP-3.
Embodiment 4
0.21g nickel sulfate (NiSiO is weighed respectively according to ferronickel molar ratio nNi/nFe=0.64·6H2) and 3.65g sulfuric acid O
Ferrous iron (FeSO4·7H2O it) is distributed in aqueous solution, is impregnated into DTAB-SiZrP-1 silicon in embodiment 1 with incipient impregnation method
On alkane pillared layered zirconium phosphate material (weighing 9.23g), dip time 12 hours, first in vacuum drying oven 80 DEG C of dryings for 24 hours, so
110 DEG C of dryings for 24 hours, obtain dry sample 500 DEG C of roasting 3h under moving air in Muffle furnace in an oven afterwards.It is roasted
Sample afterwards carries out compression molding and is sieved into 20~40 mesh particles.Above-mentioned 5g particulate samples are obtained in the volume hundred of 200ml/min
Divide the H than being 10%2The lower 700 DEG C of reduction 3h of (argon gas is Balance Air) circulation, is switched to the N of 100ml/min after reduction2In
Cool down and be passivated, until taking out after reaching room temperature is molding catalyst, iron nickel mass content is 7.72%, is denoted as 0.6NiFe/
SiZrP-1。
Embodiment 5
2.66g Ni (NO is weighed respectively according to ferronickel molar ratio nNi/nFe=1.03)2·6H2O and 3.67g Fe
(NO3)3·9H2O is distributed in aqueous solution, and it is pillared to be impregnated into DTAB-SiZrP-1 silane in embodiment 1 with incipient impregnation method
On layered zirconium phosphate material (weighing 8.98g), dip time 12 hours, first 60 DEG C of dry 12h in vacuum drying oven, were then drying
120 DEG C of dryings for 24 hours, obtain dry sample 500 DEG C of roasting 3h under moving air in Muffle furnace in case.Sample after being roasted
Product carry out compression molding and are sieved into 20~40 mesh particles.Above-mentioned 5g particulate samples, which are obtained, in the percent by volume of 150ml/min is
10% H2The lower 650 DEG C of reduction 3h of (argon gas is Balance Air) circulation, is switched to the N of 60ml/min after reduction2Middle cooling is simultaneously blunt
Change, until taking out after reaching room temperature is molding catalyst, iron nickel mass content is 10.25%, is denoted as NiFe/SiZrP-2.
Embodiment 6
6.25g nickel acetate (C4H6O4Ni4H2O) and 3.48g are weighed respectively according to ferronickel molar ratio nNi/nFe=2.0
Frerrous chloride (FeCl24H2O it) is distributed in aqueous solution, is impregnated into TTAB- in embodiment 2 with incipient impregnation method
On SiZrP-2 silane pillared layered zirconium phosphate material (weighing 17.00g), dip time 12 hours, first 75 DEG C in vacuum drying oven
Dry 20h, then 120 DEG C of dryings for 24 hours, obtain the 500 DEG C of roastings under moving air in Muffle furnace of dry sample in an oven
3h.Sample after being roasted carries out compression molding and is sieved into 20~40 mesh particles.Above-mentioned 5g particulate samples are obtained in 150ml/
The H that the percent by volume of min is 10%2The lower 600 DEG C of reduction 5h of (argon gas is Balance Air) circulation, is switched to after reduction
The N of 60ml/min2Middle cooling is simultaneously passivated, until taking out after reaching room temperature is molding catalyst, iron nickel mass content is
15.0%, it is denoted as 2NiFe/SiZrP-3.
Embodiment 7
3.10g nickel chloride (NiCl is weighed respectively according to ferronickel molar ratio nNi/nFe=3.22·6H2) and 0.78g acetic acid O
Ferrous (2 (C2H3O2) Fe) is distributed in aqueous solution, is impregnated into CTAB-SiZrP-3 in embodiment 3 with incipient impregnation method
On silane pillared layered zirconium phosphate material (weighing 4.03g), dip time 14 hours, first 65 DEG C of dry 48h in vacuum drying oven,
Then 105 DEG C of dry 48h in an oven obtain dry sample 550 DEG C of roasting 2h under moving air in Muffle furnace.It is roasted
Sample after burning carries out compression molding and is sieved into 20~40 mesh particles.Above-mentioned 5g particulate samples are obtained in the volume of 100ml/min
The H that percentage is 10%2The lower 600 DEG C of reduction 4h of (argon gas is Balance Air) circulation, is switched to the N of 80ml/min after reduction2In
Cool down and be passivated, until taking out after reaching room temperature is molding catalyst, iron nickel mass content is 19.49%, is denoted as
3.2NiFe/SiZrP-4。
Embodiment 8
Weigh 3.79g Ni (NO3)2·6H2O is distributed in aqueous solution, is impregnated into embodiment 3 with incipient impregnation method
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 of dry 30h, then 120 DEG C of dryings for 24 hours, obtain dry sample in Muffle furnace 500 DEG C under moving air in an oven
Roast 3h.Sample after being roasted carries out compression molding and is sieved into 20~40 mesh particles.Above-mentioned 5g particulate samples are obtained to exist
The H that the percent by volume of 150ml/min is 10%2The lower 600 DEG C of reduction 3h of (argon gas is Balance Air) circulation, switches after reduction
For the N of 60ml/min2Middle cooling is simultaneously passivated, until taking out after reaching room temperature is molding catalyst, nickel mass content is
15.0%, it is denoted as Ni/SiZrP-5.
Embodiment 9
1.39g Ni (NO is weighed respectively according to nickel molybdenum molar ratio nNi/nMo=2.03)2·6H2O and 2.93g (NH4)6Mo7O24·4H2O is distributed in aqueous solution, and it is pillared to be impregnated into DTAB-SiZrP-1 silane in embodiment 1 with incipient impregnation method
On layered zirconium phosphate material (weighing 4.50g), dip time 12 hours, first 60 DEG C of dry 36h in vacuum drying oven, were then drying
120 DEG C of dryings for 24 hours, obtain dry sample 550 DEG C of roasting 3h under moving air in Muffle furnace in case.Sample after being roasted
Product carry out compression molding and are sieved into 20~40 mesh particles.Above-mentioned 5g particulate samples, which are obtained, in the percent by volume of 150ml/min is
10% H2The lower 600 DEG C of reduction 3h of (argon gas is Balance Air) circulation, is switched to the N of 60ml/min after reduction2Middle cooling is simultaneously blunt
Change, until taking out after reaching room temperature is molding catalyst, nickel molybdenum mass content is 15.0%, is denoted as 2NiMo/SiZrP-1.
Embodiment 10
3.28g Ni (NO is weighed respectively according to ambrose alloy molar ratio nNi/nCu=2.03)2·6H2O and 1.05g Cu (NO3)
23H2O is distributed in aqueous solution, and it is pillared layered to be impregnated into TTAB-SiZrP-2 silane in embodiment 2 with incipient impregnation method
On zirconium phosphate material (weighing 9.00g), dip time 12 hours, first in vacuum drying oven 65 DEG C of dryings for 24 hours, then in an oven
120 DEG C of dryings for 24 hours, obtain dry sample 550 DEG C of roasting 3h under moving air in Muffle furnace.Sample after being roasted into
Row compression molding is sieved into 20~40 mesh particles.It is 10% that above-mentioned 5g particulate samples, which are obtained, in the percent by volume of 150ml/min
H2The lower 650 DEG C of reduction 3h of (argon gas is Balance Air) circulation, is switched to the N of 60ml/min after reduction2Middle cooling is simultaneously passivated,
Until taking out after reaching room temperature is molding catalyst, ambrose alloy mass content is 15.0%, is denoted as 2NiCu/SiZrP-2.
Embodiment 11
3.91g Ni (NO is weighed respectively according to nickel rhenium molar ratio nNi/nRe=2.03)2·6H2O and 1.79g NH4ReO4Point
It is scattered in aqueous solution, is impregnated into CTAB-SiZrP-3 silane pillared layered zirconium phosphate material in embodiment 3 with incipient impregnation method
Expect (weighing 18.00g) on, dip time 12 hours, first in vacuum drying oven 85 DEG C of dry 12h, then in an oven 120 DEG C do
It is dry for 24 hours, obtain dry sample 550 DEG C of roasting 3h under moving air in Muffle furnace.Sample after being roasted carries out tabletting
Molding is sieved into 20~40 mesh particles.Obtain the H that above-mentioned 5g particulate samples are 10% in the percent by volume of 150ml/min2(argon
Gas is Balance Air) the lower 650 DEG C of reduction 3h of circulation, the N of 60ml/min is switched to after reduction2Middle cooling is simultaneously passivated, until reaching
Taking out after to room temperature is molding catalyst, and nickel rhenium mass content is 15.0%, is denoted as 2NiRe/SiZrP-3.
Comparative example 1
By 14.55g Ni (NO3)2·6H2O and 10.5g urea is dissolved in 560m1 water and forms aqueous solution and heat in a water bath
To 30 DEG C of holding constant temperature, its pH value is adjusted to 2.5 using nitric acid.Under stirring conditions, by 56m1 ethyl orthosilicate (TEOS)
The solution prepared with 50m1 ethyl alcohol, which is added drop-wise in above-mentioned aqueous solution, forms colloidal sol.Continue to stir 4h after being added dropwise, it then will be molten
Glue is heated to 95 DEG C, and hydrolysis, which occurs, for urea increases the pH of colloidal sol, and colloidal sol forms gel, while nickel is deposited on gel.
When the pH value of colloidal sol reaches 8.0, it is cooled to room temperature, and obtain filter cake through vacuum filter, filter cake is successively through second alcohol and water
Hydrogel is obtained after washing.Hydrogel obtains titanium dioxide through 50 DEG C of dry 48h after 12h and 550 DEG C of roasting 4h of 120 DEG C of dryings
Silicon nickel-loaded presoma.Take 0.44g NH4H2PO4It is dissolved in water, is configured to the aqueous solution that 9m1 mass concentration ratio is 4.7%, then
The silicon dioxide carried nickel presoma of incipient impregnation 5g obtains nickel through 120 DEG C of dry 12h and 550 DEG C of roasting 5h after standing 12h
The catalyst precursor that phosphorus molar ratio is 3.2.0g catalyst precursor is taken to be placed in quartz ampoule fixed bed reactors, in 200m1/
The H that min percent by volume is 10%2In (argon gas is Balance Air) air-flow first with the heating rate of 10 DEG C/min from room temperature to
250 DEG C, 650 DEG C of final reduction temperature is then warming up to from 250 DEG C with the heating rate of 10 DEG C/min, and 650 DEG C of constant temperature also
Former 3h obtains support type Ni2P catalyst, nickel mass content are 15.0%, are denoted as Ni2P-C1。
Comparative example 2
The process of iron phosphide Raney nickel is prepared such as using preparation catalyst presoma, again through temperature programmed reduction
Under: 6.08g Fe (NO3)3·9H2O、4.40g Ni(NO3)2·6H2O and 1.73g NH4H2PO4It is dissolved in water and prepares 8m1 aqueous solution,
5.0g SiO is impregnated with the aqueous solution2, in 120 DEG C of dry 12h and 550 DEG C of roasting 4h silica is prepared after standing 12h
Ferric phosphate nickel presoma is loaded, nickel phosphorus ratio is 1.0 in presoma.2.0g presoma is taken to be placed in quartz ampoule fixed bed reactors,
The H for being 10% in 200ml/min percent by volume2First with the heating rate of 10 DEG C/min from room in (argon gas is Balance Air) air-flow
Temperature is warming up to 250 DEG C, 650 DEG C of final reduction temperature is then warming up to from 250 DEG C with the heating rate of 1 DEG C/min, and constant temperature is also
Former 3h obtains support type NiFeP catalyst, wherein iron nickel mass content is 15.0%, and obtained catalyst is denoted as NiFeP-
C2。
Table 1
Embodiment 12~21
Application of the catalyst provided by the invention in the reaction of methyl phenyl ethers anisole hydrogenation deoxidation.
Obtained each 2.0g of catalyst is placed in perseverance in fixed bed reactors in Example 4~11 and in comparative example 1~2
Temperature section, 5wt% methyl phenyl ethers anisole (n-dodecane is solvent) are reaction feed and H2Mixing, reaction pressure 4.0MPa, hydrogen-oil ratio are
500,360 DEG C of reaction temperature, liquid air speed (WHSV) 0.7min-1, obtained product carry out condensation and gas-liquid separation after obtain liquid
Body sample carries out gas-chromatography Agilent7890 analysis, and catalyst is carried out BET materialization phenetic analysis, the data obtained result
As shown in table 1.
Table 2
Embodiment 22~26
Application of the catalyst provided by the invention in the compound hydrogenation deoxidation reaction containing aromatic hydrocarbons C-O key.
(n-dodecane is molten to the guaiacol, benzofuran, cresols, phenol and diphenyl ether of preparation 10wt% concentration respectively
Agent) it is reaction solution, it obtains permanent in obtained 2.0g catalyst 2NiFe/SiZrP-3 merging fixed bed reactors in embodiment 6
Temperature section, reaction condition be pressure 4.0MPa, hydrogen-oil ratio (v/v) 800,400 DEG C of reaction temperature, liquid air speed (WHSV) 5.2min-1。
Obtained product obtains the online gas chromatographic analysis of fluid sample progress after carrying out condensation and gas-liquid separation, and the data obtained result is such as
Shown in table 3.
Table 3
The embodiment only technical concepts and features to illustrate the invention, its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (15)
1. a kind of pillared layered zirconium phosphate supported nickel based catalysts, it is characterised in that: the catalyst is with pillared layered phosphoric acid
Zirconium mesoporous material is carrier, and transition metal is supported on carrier；The catalyst composition mass percent is that transition metal accounts for 0.1
~30.0wt%, mesoporous material account for 70.0~99.9wt%；
The transition metal active component is using Ni as main catalytic active component, with other transition-metal Fes, Mo, Cu, Re, Co, W
Middle a kind of as co-catalyst active component, wherein the atomic molar of Ni and other transition metal is than 0.5~3.5:1.
2. a kind of pillared layered zirconium phosphate supported nickel based catalysts according to claim 1, it is characterised in that: described mesoporous
Material is pillared layered zirconium phosphate, by the silicon pillared layered zirconium phosphate of the modified formation of organosilicon Intercalation reaction.
3. a kind of pillared layered zirconium phosphate supported nickel based catalysts according to claim 1, it is characterised in that described urges
Transition metal component accounts for 0.5~20.0wt% in agent, mesoporous supports material accounts for 80.0~99.5wt%.
4. the preparation method of pillared layered zirconium phosphate supported nickel based catalysts according to claim 1, it is characterised in that institute
The catalyst stated is prepared according to the following steps:
(1) it weighs bedded zirconium phosphate powder to be scattered in Amine Solutions, organic amine-basic zirconium phosphate that colloidization is obtained after stirring is molten
Liquid；Long chain quaternary is added in above-mentioned solution and is reacted, forms pillared layered zirconium phosphate presoma, and organic silicon solution is added,
Mixing is adjusted between pH value 9.0~11.0；Product is centrifugated out solid phase, and by washing, being separated by filtration, form of solid product is done
It is dry to obtain head product, as silicon pillared layered zirconium phosphate presoma；
(2) silicon column obtained in the soluble transition metal salt solution impregnation to (1) by concentration for 0.5~10.0mol/L supports layer
On shape basic zirconium phosphate presoma, then dry, roasting obtains catalyst precursors；
(3) by catalyst precursors obtained in (2) at 550~700 DEG C, it is passed through the percent by volume of 100~200ml/min
Reduction activation processing is carried out for 10% hydrogen, wherein argon gas is balanced gas, is switched to 50~100ml/min after reduction
Nitrogen in cool down and be passivated, obtain the nickel-base catalyst of molding pillared layered zirconium phosphate load.
5. the preparation method of pillared layered zirconium phosphate supported nickel based catalysts according to claim 4, it is characterised in that: step
Suddenly the molar ratio of organic amine and bedded zirconium phosphate is 0.3~3.0:1 in (1), and after organosilicon is added, Si's and Zr rubs in system
Your ratio is 5.0~10.0:1, and wherein the molar ratio of long chain quaternary and bedded zirconium phosphate is 0.5~1.0:1.
6. the preparation method of pillared layered zirconium phosphate supported nickel based catalysts according to claim 4, it is characterised in that: step
Suddenly organic amine is ethanol amine, diethanol amine, isopropanolamine or butanolamine in (1).
7. the preparation method of pillared layered zirconium phosphate supported nickel based catalysts according to claim 4, it is characterised in that: step
Suddenly organosilicon is 3-aminopropyltriethoxysilane, 3- TSL 8330, n-butylamino propyl three in (1)
Methoxy silane or 3- (2- aminoethylamino) propyl trimethoxy silicane.
8. the preparation method of pillared layered zirconium phosphate supported nickel based catalysts according to claim 4, it is characterised in that: step
Suddenly after addition organic silicon solution described in (1), the temperature for being sufficiently mixed reaction is 30~60 DEG C.
9. the preparation method of pillared layered zirconium phosphate supported nickel based catalysts according to claim 4, it is characterised in that: step
Suddenly drying described in (1) is vacuum drying, and condition is 60~90 DEG C of dry 12~48h, and vacuum degree is 40~90Pa.
10. the preparation method of pillared layered zirconium phosphate supported nickel based catalysts according to claim 4, it is characterised in that:
The long chain quaternary is dodecyl trimethyl ammonium bromide, tetradecyltrimethylammonium bromide, cetyl trimethyl bromine
Change ammonium or Cetyltrimethylammonium bromide.
11. the preparation method of pillared layered zirconium phosphate supported nickel based catalysts according to claim 4, which is characterized in that
Soluble transition metal salting liquid are as follows: soluble nickel salt, soluble ferric iron salt, soluble copper salt or other soluble transition metal
Salt；
The soluble nickel salt are as follows: one of nickel nitrate, nickel chloride, nickel acetate, nickel sulfate are a variety of；
The soluble ferric iron salt are as follows: one of ferric nitrate, frerrous chloride, ferrous acetate, ferric sulfate are a variety of；
The soluble copper salt are as follows: copper nitrate, copper chloride, copper acetate, one or more in cupric oxalate；
Other described soluble transition metal salts include: ammonium molybdate, ammonium perrhenate, ammonium paratungstate, ammonium metatungstate, sodium tungstate,
Cobalt nitrate or cobalt chloride.
12. the preparation method of pillared layered zirconium phosphate supported nickel based catalysts according to claim 4, it is characterised in that:
Organic amine is ethanol amine in step (1)；Organosilicon is 3-aminopropyltriethoxysilane or 3- aminopropyl three in step (1)
Methoxy silane.
13. the preparation method of pillared layered zirconium phosphate supported nickel based catalysts according to claim 11, it is characterised in that:
The soluble nickel salt is nickel nitrate, nickel acetate, nickel chloride or nickel sulfate；
The soluble ferric iron salt is ferric nitrate, frerrous chloride, ferrous acetate or ferric sulfate.
14. a kind of application of pillared layered zirconium phosphate supported nickel based catalysts as described in claim 1, it is characterised in that: described
Catalyst is for the hydrogenation deoxidation reaction containing C-O key organic compound.
15. according to the application of pillared layered zirconium phosphate supported nickel based catalysts described in claim 14, it is characterised in that: used anti-
Answering raw material is phenol, methyl phenyl ethers anisole, cresols, tea phenol, guaiacol, diphenyl ether, benzyl ether, benzofuran.
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| CN102430431A (en) * | 2012-01-12 | 2012-05-02 | 北京化工大学 | Supported organic rhenium catalyst and preparation method thereof |
| CN104119943A (en) * | 2013-04-26 | 2014-10-29 | 中国科学院大连化学物理研究所 | Method for preparing aviation kerosene from furyl oxygen-containing organic compounds by hydrogenation deoxidation |
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