CN109999801A - M-B@Pd-B@Al2O3Catalyst and preparation method thereof, application - Google Patents
M-B@Pd-B@Al2O3Catalyst and preparation method thereof, application Download PDFInfo
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Abstract
The invention belongs to hydrogenation catalyst technical fields, and in particular to a kind of M-B@Pd-B@Al2O3Catalyst and preparation method thereof, application.M-B@Pd-B@Al of the invention2O3Catalyst includes active component kernel, the active component middle layer being wrapped in outside active component kernel and the auxiliary agent outer layer being wrapped in outside active component middle layer；The active component kernel is M-B amorphous alloy, and M is selected from one of Zn, Cu, Fe, Co, Ni；The active component middle layer is Pd-B amorphous alloy；The auxiliary agent outer layer is aluminium oxide.The present invention provides a kind of new catalyst, which prepares activity and selectivity with higher when gamma-valerolactone for the selection of levulic acid water phase plus hydrogen.
Description
Technical field
The invention belongs to hydrogenation catalyst technical fields, and in particular to a kind of M-B@Pd-B@Al2O3Catalyst and its preparation
Method, application.
Background technique
Fossil fuel is as the energy and fuel source, and not only reserves are increasingly reduced, but also the sulphur oxygen generated in consumption process
Compound and nitrogen oxides easily cause environmental pollution.The substitute of lignocellulose biomass and its derivative as fossil fuel,
Not only have sustainability, but also its production fine chemical product and fuel have the characteristics that it is environmental-friendly.
It is highly important reaction in biomass chemical process that levulic acid, which adds hydrogen to prepare gamma-valerolactone, is by cellulose
Or hemicellulose prepares the important intermediate reaction of liquid fuel.Formic acid prepares the common production of levulic acid as cellulose simultaneously
Object may be used as the hydrogen source of hydrogenation process, improve carbon atom utilization rate.In addition, using aqueous phase reactions process by wood fibre
Small molecule after element hydrolysis carries out Efficient Conversion and is of great significance: avoiding small organic molecule separation from water phase
Process reduces production cost；For pyrolytic reaction and gasification reaction, temperature reduces aqueous phase reactions, reduces energy
Loss.Therefore, the height that levulic acid and formic acid reaction prepare gamma-valerolactone can be catalyzed in water phase by developing in reaction system
Active and highly selective catalyst has important economy and society meaning.
《Co/γ-Al2O3Be catalyzed levulic acid hydrogenation synthesis gamma-valerolactone research " one be disclosed herein it is a kind of catalysis plus
The technique of hydrogen, the Co/ γ-Al which prepares equi-volume impregnating2O3Catalyst, 1.67g levulic acid and 40mL methanol add
Enter autoclave, lead to air in hydrogen displacement autoclave, then leads to hydrogen to reaction pressure, be to slowly warm up to reaction temperature, start
Reaction (beautiful jade etc., Industrial Catalysis, the 7th phase of volume 21,68~71).Hydrogen γ-penta is added using the catalyst levulic acid
When lactone, the selective highest of valerolactone is only capable of reaching 81.4%, and selectivity is poor.In addition, levulic acid adds in the prior art
Hydrogen gamma-valerolactone majority is carried out in organic phase, since raw material levulic acid generally utilizes biomass by hydrolyzation to generate, is adopted
The levulic acid generated to hydrolysis is needed to separate with when organic phase, and the polarity of product gamma-valerolactone is smaller, using having
Machine mutually also increases the difficulty that product is separated from system.
Summary of the invention
The first purpose of this invention is to provide a kind of M-B@Pd-B@Al2O3Catalyst adds hydrogen system for levulic acid
It can be improved the selectivity to gamma-valerolactone when gamma-valerolactone.
Second object of the present invention is to provide a kind of M-B@Pd-B@Al of simple process2O3The preparation side of catalyst
Method.
Third object of the present invention is to provide a kind of M-B@Pd-B@Al2O3Catalyst answering in hydrogenation reduction
With the catalyst has preferable hydrogenation activity.
To achieve the above object, the technical solution adopted by the present invention are as follows:
M-B@Pd-B@Al2O3Catalyst, including in active component kernel, the active component being wrapped in outside active component kernel
Interbed and the auxiliary agent outer layer being wrapped in outside active component middle layer；The active component kernel is M-B amorphous alloy, M choosing
From one of Zn, Cu, Fe, Co, Ni；The active component middle layer is Pd-B amorphous alloy；The auxiliary agent outer layer is oxygen
Change aluminium.
Catalyst of the invention makes using M-B amorphous alloy and Pd-B amorphous alloy as active component in outer layer
It is wrapped up with aluminium oxide, active component is avoided in aqueous phase reactions and is contacted with the direct of hydrone, it is relatively stable in water phase.This
The active component of the catalyst of invention is made of noble metal and base metal, not only ensure that the hydrogenation activity of catalyst but also certain
It is reduced costs in degree.Catalyst of the invention be used for levulic acid water phase selective hydrogenation gamma-valerolactone when have compared with
High selectivity and activity.
M atom in the M-B amorphous alloy, in Pd-B amorphous alloy in Pd atom and aluminium oxide Al atom object
The ratio between amount of matter is 1:(0.05~1.5): (0.05~1.5).The M-B@Pd-B@Al in aforementioned proportion2O3Catalyst show compared with
Good activity and selectivity.
To guarantee that catalyst comes into full contact with reactant, the M-B@Pd-B@Al2O3The average grain diameter of catalyst be 3~
8nm。
Above-mentioned M-B@Pd-B@Al2O3The preparation method of catalyst, comprising the following steps:
1) M-B amorphous alloy is mixed with Pd colloidal sol, and carries out gelation under protective atmosphere, Pd colloidal sol is made to become Pd
Gel is simultaneously coated on M-B amorphous alloy surface, and boron hydride is then added and is reacted, Pd gel is made to become Pd-B amorphous state
Alloy washs obtained precipitating after fully reacting, obtains the M-B amorphous alloy of Pd-B package；
2) the M-B amorphous alloy that Pd-B obtained is wrapped up is mixed with Al colloidal sol, and carries out gel under protective atmosphere
Change, Al colloidal sol is made to become Al gel and be coated on the M-B amorphous alloy surface of Pd-B package, is then separated by solid-liquid separation, by solid
Washed to get.
The present invention provides a kind of preparation methods of new catalyst, and this method is simple, can be used for preparing core-shell structure
Catalyst.
For the uniform cladding for realizing gel, it is 50~150 DEG C that gelation described in step 1) and step 2), which is in temperature, is protected
The pressure for protecting gas keeps 1~5h under the conditions of being 1~5MPa.
For the progress convenient for subsequent process, the preparation method of the M-B amorphous alloy, comprising: in the solubility of metal M
Boron hydride is added in saline solution to be reacted, after fully reacting by the precipitating of generation be washed till it is neutral to get.
To be reduced M atom completely, M atom and B atom in boron hydride in the soluble-salt aqueous solution of the metal M
The ratio between the amount of substance be 1:(5~50).
To be reduced Pd atom completely, the substance of Pd atom and B atom in boron hydride in step 1) the Pd colloidal sol
The ratio between amount be 1:(5~50).
M-B@Pd-B@Al2O3Application of the catalyst in hydrogenation reduction.Catalyst of the invention has preferable add
Hydrogen activity can be used in such as common hydrogenation reduction of furfural hydrogenation, benzene hydrogenation.
Above-mentioned hydrogenation reduction is that levulic acid is hydrogenated to gamma-valerolactone.M-B@Pd-B@Al of the invention2O3Catalysis
When agent adds hydrogen gamma-valerolactone for levulic acid, when using hydrogen as hydrogen source, when reacting 5h, the conversion ratio of levulic acid is
100%, gamma-valerolactone has selectively reached 99% or more, has important industrial application value.
Detailed description of the invention
Fig. 1 is M-B@Pd-B@Al2O3Zn-B@Pd-B@Al in the embodiment 1 of catalyst2O3The TEM of catalyst schemes；
Fig. 2 is M-B@Pd-B@Al2O3Cu-B@Pd-B@Al in the embodiment 2 of catalyst2O3The TEM of catalyst schemes；
Fig. 3 is M-B@Pd-B@Al2O3Co-B@Pd-B@Al in the embodiment 3 of catalyst2O3The TEM of catalyst schemes；
Fig. 4 is M-B@Pd-B@Al2O3Ni-B@Pd-B@Al in the embodiment 4 of catalyst2O3The TEM of catalyst schemes；
Fig. 5 is M-B@Pd-B@Al2O3Fe-B@Pd-B@Al in the embodiment 5 of catalyst2O3The TEM of catalyst schemes.
Specific embodiment
M-B@Pd-B@Al of the invention2O3The work that catalyst includes active component kernel, is wrapped in outside active component kernel
Property component middle layer and the auxiliary agent outer layer being wrapped in outside active component middle layer；The active component kernel is M-B amorphous state
Alloy, M are selected from one of Zn, Cu, Fe, Co, Ni；The active component middle layer is Pd-B amorphous alloy；The auxiliary agent
Outer layer is aluminium oxide.Wherein the mass content of B is 0.02~0.04%.
Preferably, M atom in M-B amorphous alloy, Al atom in Pd atom and aluminium oxide in Pd-B amorphous alloy
The ratio between the amount of substance be 1:0.4:0.2.The M-B@Pd-B@Al in aforementioned proportion2O3The performance of catalyst is best.
M-B@Pd-B@Al of the invention2O3The preparation method of catalyst, comprising the following steps:
1) M-B amorphous alloy is mixed with Pd colloidal sol, and carries out gelation under protective atmosphere, Pd colloidal sol is made to become Pd
Gel is simultaneously coated on M-B amorphous alloy surface, and boron hydride is then added and is reacted, Pd gel is made to become Pd-B amorphous state
Alloy washs obtained precipitating after fully reacting, obtains the M-B amorphous alloy of Pd-B package；
2) the M-B amorphous alloy that Pd-B obtained is wrapped up is mixed with Al colloidal sol, and carries out gel under protective atmosphere
Change, Al colloidal sol is made to become Al gel and be coated on the M-B amorphous alloy surface of Pd-B package, is then separated by solid-liquid separation, by solid
Washed to get.
Preferably, the protective atmosphere is at least one of hydrogen, nitrogen, argon gas, helium.It is further preferred that protecting
Shield gas is hydrogen.
Wherein the preparation method of M-B amorphous alloy in the soluble-salt aqueous solution of metal M the following steps are included: be added
Boron hydride is reacted, after fully reacting by the precipitating of generation be washed till it is neutral to get.The temperature of the reaction is 0~50 DEG C.
The boron hydride is the aqueous solution of alkali metal borohydride.
The preparation method of step 1) the Pd colloidal sol is the following steps are included: add aqueous slkali extremely in the soluble salt solutions of Pd
No longer generate precipitating, then adding citric acid solution to precipitating be completely dissolved to get.
OH in the aqueous slkali-Concentration be 0.1~10mol/L；The concentration of citric acid is in the citric acid solution
0.01~5mol/L.The soluble-salt of the Pd is the+soluble-salt of divalent Pd.The aqueous slkali is sodium hydroxide, hydroxide
The solution of at least one of potassium, sodium carbonate, sodium bicarbonate.
In step 2), the preparation method of the Al colloidal sol, comprising: containing Al3+Solution in reinforce aqueous slkali generate precipitating,
Continue reinforce aqueous slkali to precipitating be completely dissolved to get.Being ultimately generated by Tyndall effect confirmation is Al colloidal sol.It is described strong
Alkali is at least one of sodium hydroxide, potassium hydroxide.
Combined with specific embodiments below and attached drawing the invention will be further described.
M-B@Pd-B@Al2O3The embodiment 1 of catalyst
The M-B@Pd-B@Al of the present embodiment2O3Catalyst is Zn-B@Pd-B@Al2O3Catalyst, including active component kernel
Zn-B amorphous alloy, the active component middle layer Pd-B amorphous alloy being wrapped in outside active component kernel and is wrapped in work
Auxiliary agent outer layer Al outside property component middle layer2O3；In catalyst, the ratio between amount of substance of Zn, Pd, Al element is 1:0.4:0.2.
The mass content that ICP measures B in the catalyst of the present embodiment is 0.03%.The Zn-B@Pd-B@Al of the present embodiment2O3Catalyst
Pattern is as shown in Figure 1, the average grain diameter of catalyst granules is 5nm or so as shown in Figure 1.
M-B@Pd-B@Al2O3The embodiment 2 of catalyst
The M-B@Pd-B@Al of the present embodiment2O3Catalyst is Cu-B@Pd-B@Al2O3Catalyst, including active component kernel
Cu-B amorphous alloy, the active component middle layer Pd-B amorphous alloy being wrapped in outside active component kernel and is wrapped in work
Auxiliary agent outer layer Al outside property component middle layer2O3；In catalyst, the ratio between amount of substance of Cu, Pd, Al element is 1:0.4:0.2.
The mass content that ICP measures B in the catalyst of the present embodiment is 0.04%.The Cu-B@Pd-B@Al of the present embodiment2O3Catalyst
Pattern is as shown in Fig. 2, the average grain diameter of catalyst granules is 5nm or so as shown in Figure 2.
M-B@Pd-B@Al2O3The embodiment 3 of catalyst
The M-B@Pd-B@Al of the present embodiment2O3Catalyst is Co-B@Pd-B@Al2O3Catalyst, including active component kernel
Co-B amorphous alloy, the active component middle layer Pd-B amorphous alloy being wrapped in outside active component kernel and is wrapped in work
Auxiliary agent outer layer Al outside property component middle layer2O3；In catalyst, the ratio between amount of substance of Co, Pd, Al element is 1:0.4:0.2.
The mass content that ICP measures B in the catalyst of the present embodiment is 0.03%.The Co-B@Pd-B@Al of the present embodiment2O3Catalyst
Pattern is as shown in figure 3, the average grain diameter of catalyst granules is 5nm or so as shown in Figure 3.
M-B@Pd-B@Al2O3The embodiment 4 of catalyst
The M-B@Pd-B@Al of the present embodiment2O3Catalyst is Ni-B@Pd-B@Al2O3Catalyst, including active component kernel
Ni-B amorphous alloy, the active component middle layer Pd-B amorphous alloy being wrapped in outside active component kernel and is wrapped in work
Auxiliary agent outer layer Al outside property component middle layer2O3；In catalyst, the ratio between amount of substance of Ni, Pd, Al element is 1:0.4:0.2.
The Ni-B@Pd-B@Al of the present embodiment2O3The pattern of catalyst is as shown in figure 4, the average grain diameter of catalyst granules is as shown in Figure 4
5nm or so.
M-B@Pd-B@Al2O3The embodiment 5 of catalyst
The M-B@Pd-B@Al of the present embodiment2O3Catalyst is Fe-B@Pd-B@Al2O3Catalyst, including active component kernel
Fe-B amorphous alloy, the active component middle layer Pd-B amorphous alloy being wrapped in outside active component kernel and is wrapped in work
Auxiliary agent outer layer Al outside property component middle layer2O3；In catalyst, the ratio between amount of substance of Fe, Pd, Al element is 1:0.4:0.2.
The Fe-B@Pd-B@Al of the present embodiment2O3The pattern of catalyst is as shown in figure 5, the average grain diameter of catalyst granules is as shown in Figure 5
5nm or so.
M-B@Pd-B@Al2O3The embodiment 6 of catalyst
The M-B@Pd-B@Al of the present embodiment2O3Catalyst is Zn-B@Pd-B@Al2O3Catalyst, including active component kernel
Zn-B amorphous alloy, the active component middle layer Pd-B amorphous alloy being wrapped in outside active component kernel and is wrapped in work
Auxiliary agent outer layer Al outside property component middle layer2O3；In catalyst, the ratio between amount of substance of Zn, Pd, Al element is 1:0.07:1.3.
M-B@Pd-B@Al2O3The embodiment 7 of catalyst
The M-B@Pd-B@Al of the present embodiment2O3Catalyst is Zn-B@Pd-B@Al2O3Catalyst, including active component kernel
Zn-B amorphous alloy, the active component middle layer Pd-B amorphous alloy being wrapped in outside active component kernel and is wrapped in work
Auxiliary agent outer layer Al outside property component middle layer2O3；In catalyst, the ratio between amount of substance of Zn, Pd, Al element is 1:1.5:1.
M-B@Pd-B@Al2O3The embodiment 8 of catalyst
The M-B@Pd-B@Al of the present embodiment2O3Catalyst is Zn-B@Pd-B@Al2O3Catalyst, including active component kernel
Zn-B amorphous alloy, the active component middle layer Pd-B amorphous alloy being wrapped in outside active component kernel and is wrapped in work
Auxiliary agent outer layer Al outside property component middle layer2O3；In catalyst, the ratio between amount of substance of Zn, Pd, Al element is 1:1:0.08.
M-B@Pd-B@Al2O3The embodiment 1 of the preparation method of catalyst
The catalyst of the present embodiment is Zn-B@Pd-B@Al2O3, preparation method specifically uses following steps:
1) 2.1g ZnCl is taken2It is dissolved in 50mL distilled water and is made into ZnCl2Solution takes 5.8g NaBH4It is dissolved in 50mL distilled water
In be made into NaBH4Solution, NaBH4With ZnCl2The mass ratio of the material be 10:1, by NaBH under 30 DEG C, stirring condition4Solution drop
It is added to ZnCl2In solution, it is stirred to react until there is no black solid generation, black solid is washed with distilled water to by filtering
Filtrate is neutrality to get Zn-B amorphous alloy.
2) 1.1g PdCl is taken2It is dissolved in 50mL distilled water and is made into PdCl2The NaOH solution of 4mol/L is added drop-wise to by solution
PdCl2In solution, until there is no precipitating generate, add the citric acid solution of 1mol/L, until precipitating be completely dissolved to get
Pd colloidal sol；Zn-B amorphous alloy is added in Pd colloidal sol, temperature is 150 DEG C, Hydrogen Vapor Pressure 1MPa, mixing speed are
3h is kept under conditions of 800r/min, so that Pd colloidal sol becomes Pd gel and is wrapped in M-B amorphous alloy surface, is mixed
Liquid；In mixed liquor, the ratio between amount of substance of Zn and Pd is 1:0.4；
Take 3.5g NaBH4It is dissolved in 50mL distilled water and is made into NaBH4Solution, by NaBH under 30 DEG C, stirring condition4Solution
(the ratio between amount of substance of B and Pd is 15:1 in system) is added drop-wise in mixed liquor, continuing stirring 30min keeps reduction reaction complete,
There is no black solid generations in system at this time, and filtering, it is neutrality to get Pd-B that black solid, which is washed with distilled water to filtrate,
The Zn-B amorphous alloy of package.
3) 0.41g AlCl is taken3It is dissolved in 50mL distilled water and is made into AlCl3The NaOH solution of 4mol/L is added drop-wise to by solution
AlCl3In solution, until generating there is no precipitating, the NaOH solution of 4mol/L is added, until precipitating is completely dissolved, i.e.,
Obtain Al colloidal sol；By (in system, the ratio between Zn and the amount of substance of Al are in the Zn-B amorphous alloy addition Al colloidal sol of Pd-B package
1:0.2), 3h is kept under conditions of temperature is 150 DEG C, Hydrogen Vapor Pressure 1MPa, mixing speed are 800r/min, makes Al colloidal sol
Become Al gel and be coated on the M-B amorphous alloy surface of Pd-B package, gained black solid is washed with distilled water by filtering
To filtrate be it is neutral to get.
It is 0.02% by the mass content that ICP measures B in catalyst manufactured in the present embodiment, this reality is confirmed by XRD
Apply example preparation catalyst in Al with Al2O3Form exist.
M-B@Pd-B@Al2O3The embodiment 2 of the preparation method of catalyst
The present embodiment is M-B@Pd-B@Al2O3Catalyst Cu-B@Pd-B@Al in the embodiment 2 of catalyst2O3Preparation side
Method, essentially identical with the operating procedure of the embodiment 1 of the preparation method of catalyst, difference is only that, in step 1), by 2.1g
ZnCl2It is changed to 2.1g CuCl2, the catalyst that active component kernel is Cu-B amorphous alloy is finally prepared.
M-B@Pd-B@Al2O3The embodiment 3 of the preparation method of catalyst
The present embodiment is M-B@Pd-B@Al2O3Catalyst Co-B@Pd-B@Al in the embodiment 3 of catalyst2O3Preparation side
Method, essentially identical with the operating procedure of the preparation method embodiment 1 of catalyst, difference is only that, in step 1), by 2.1g
ZnCl2It is changed to 2.0g CoCl2, the catalyst that active component kernel is Co-B amorphous alloy is finally prepared.
M-B@Pd-B@Al2O3The embodiment 4 of the preparation method of catalyst
The present embodiment is M-B@Pd-B@Al2O3Catalyst n i-B@Pd-B@Al in the embodiment 4 of catalyst2O3Preparation side
Method, essentially identical with the operating procedure of the preparation method embodiment 1 of catalyst, difference is only that, in step 1), by 2.1g
ZnCl2It is changed to 2.0g NiCl2, the catalyst that active component kernel is Ni-B amorphous alloy is finally prepared.It is surveyed by ICP
The mass content for obtaining B in catalyst manufactured in the present embodiment is 0.03%.
M-B@Pd-B@Al2O3The embodiment 5 of the preparation method of catalyst
The present embodiment is M-B@Pd-B@Al2O3Catalyst Fe-B@Pd-B@Al in the embodiment 5 of catalyst2O3Preparation side
Method, essentially identical with the operating procedure of the preparation method embodiment 1 of catalyst, difference is only that, in step 1), by 2.1g
ZnCl2It is changed to 2.0g FeCl2, the catalyst that active component kernel is Fe-B amorphous alloy is finally prepared.ICP is crossed to measure
The mass content of B is 0.03% in catalyst manufactured in the present embodiment.
M-B@Pd-B@Al2O3The embodiment 6 of the preparation method of catalyst
The present embodiment is M-B@Pd-B@Al2O3Catalyst Z n-B@Pd-B@Al in the embodiment 6 of catalyst2O3Preparation side
Method, essentially identical with the operating procedure of the preparation method embodiment 1 of catalyst, difference is, in step 1), preparation M-B is non-
When crystal alloy, ZnCl2Middle Zn and NaBH4The ratio between amount of substance of middle B is 1:7, and the temperature of reaction is room temperature；It, will in step 2)
Zn-B amorphous alloy is added in Pd colloidal sol, in temperature is 100 DEG C, Hydrogen Vapor Pressure 3MPa, mixing speed are 800r/min's
Under the conditions of keep 5h；NaBH is added4The temperature reacted after solution is room temperature；Pd and NaBH in Pd colloidal sol4The amount of the substance of middle B
The ratio between be 1:25；In step 3), Pd-B package Zn-B amorphous alloy be added Al colloidal sol in, in temperature be 100 DEG C, hydrogen pressure
Power is 3MPa, mixing speed keeps 5h under conditions of being 800r/min.
M-B@Pd-B@Al2O3The embodiment 7 of the preparation method of catalyst
The present embodiment is M-B@Pd-B@Al2O3Catalyst Z n-B@Pd-B@Al in the embodiment 7 of catalyst2O3Preparation side
Method, essentially identical with the operating procedure of the preparation method embodiment 1 of catalyst, difference is, in step 1), preparation M-B is non-
When crystal alloy, ZnCl2Middle Zn and NaBH4The ratio between amount of substance of middle B is 1:20, and the temperature of reaction is 15 DEG C；In step 2),
Zn-B amorphous alloy is added in Pd colloidal sol, in temperature is 80 DEG C, Hydrogen Vapor Pressure 5MPa, mixing speed are 800r/min's
Under the conditions of keep 2h；NaBH is added4The temperature reacted after solution is 15 DEG C；Pd and NaBH4The ratio between amount of substance of middle B is 1:8；
In step 3), the Zn-B amorphous alloy of Pd-B package is added in Al colloidal sol, is 80 DEG C, Hydrogen Vapor Pressure 5MPa, is stirred in temperature
It mixes under conditions of speed is 800r/min and keeps 2h.
M-B@Pd-B@Al2O3The embodiment 8 of the preparation method of catalyst
The present embodiment is M-B@Pd-B@Al2O3Catalyst Z n-B@Pd-B@Al in the embodiment 8 of catalyst2O3Preparation side
Method, essentially identical with the operating procedure of the preparation method embodiment 1 of catalyst, difference is, in step 1), preparation M-B is non-
When crystal alloy, ZnCl2Middle Zn and NaBH4The ratio between amount of substance of middle B is 1:15, and the temperature of reaction is 35 DEG C；In step 2),
By Zn-B amorphous alloy be added Pd colloidal sol in, in temperature be 150 DEG C, Hydrogen Vapor Pressure 2MPa, mixing speed 800r/min
Under conditions of keep 4h；NaBH is added4The temperature reacted after solution is 35 DEG C；Pd and NaBH in Pd colloidal sol4The substance of middle B
The ratio between amount is 1:12；In step 3), Pd-B package Zn-B amorphous alloy be added Al colloidal sol in, in temperature be 150 DEG C, hydrogen
Pressure is 2MPa, mixing speed keeps 4h under conditions of being 800r/min.
In M-B@Pd-B@Al of the invention2O3In the other embodiments of the preparation method of catalyst, preparation M-B amorphous state is closed
Other soluble M salt, such as ZnSO can be used in Jin Shi4Deng；When preparing Pt colloidal sol, other solubility Pd salt, such as Pd can be used
(NO3)2The model that can be limited according to the factors such as capacity of reaction condition, reaction kit in the present invention Deng the concentration of, each reaction raw materials
Enclose it is interior be adaptively adjusted, can obtain and the comparable test effect of embodiment.
M-B@Pd-B@Al2O3The embodiment of the application of catalyst
The present embodiment investigates M-B@Pd-B@Al using hydrogen and formic acid as hydrogen source respectively2O3The Examples 1 to 8 of catalyst
Catalyst adds hydrogen to prepare the catalytic effect in gamma-valerolactone reaction in levulic acid.
When using hydrogen as hydrogen source, reaction process are as follows: 0.5g catalyst and 12.5g levulic acid are added in reaction kettle,
250mL distilled water is added, with air in nitrogen replacement reaction kettle, it is 1.0MPa that hydrogen to pressure is then passed through into reaction kettle,
150 DEG C are warming up to the heating rate of 1 DEG C/min, control mixing speed is 800r/min.
When using formic acid as hydrogen source, reaction process are as follows: be added to 0.5g catalyst, 10.4g levulic acid and 1.4g formic acid
In reaction kettle, 250mL distilled water is added, is warming up to 150 DEG C with the heating rate of 1 DEG C/min, control mixing speed is 800r/
min。
After reaction, using using the chromatographic product of fid detector to form, area correction method meter is utilized
Production concentration is calculated, and then calculates the conversion ratio and gamma-valerolactone selectivity of levulic acid, the results are shown in Table 1.
The catalytic performance test of 1 catalyst of table
As can be seen from Table 1, Zn-B@Pd-B@Al2O3Catalyst, Cu-B@Pd-B@Al2O3Catalyst, Fe-B@Pd-
B@Al2O3Catalyst, Co-B@Pd-B@Al2O3Catalyst and Ni-B@Pd-B@Al2O3Catalyst is using hydrogen as hydrogen source, levulinic
The conversion ratio of acid has all reached 100%, and the selectivity of gamma-valerolactone has all reached 99% or more when the reaction time is 5h.This table
Bright prepared by the method catalyst has important industrial application value.Formic acid is hydrogen source, Zn-B@Pd-B@Al2O3Catalysis
Agent conversion ratio of levulic acid when reacting for 24 hours still can reach 100%, and the selectivity of gamma-valerolactone selectively reaches
99.5%, illustrate that catalyst has preferable stability.
Claims (10)
1.M-B@Pd-B@Al2O3Catalyst, which is characterized in that the catalyst includes active component kernel, is wrapped in active group
The active component middle layer divided outside kernel and the auxiliary agent outer layer being wrapped in outside active component middle layer；The active component kernel
For M-B amorphous alloy, M is selected from one of Zn, Cu, Fe, Co, Ni；The active component middle layer is the conjunction of Pd-B amorphous state
Gold；The auxiliary agent outer layer is aluminium oxide.
2. M-B@Pd-B@Al according to claim 12O3Catalyst, which is characterized in that M in the M-B amorphous alloy
The ratio between amount of substance of Al atom is 1:(0.05~1.5 in Pd atom and aluminium oxide in atom, Pd-B amorphous alloy):
(0.05~1.5).
3. M-B@Pd-B@Al according to claim 12O3Catalyst, which is characterized in that the M-B@Pd-B@Al2O3Catalysis
The average grain diameter of agent is 3~8nm.
4. M-B@Pd-B@Al as described in claim 12O3The preparation method of catalyst, which comprises the following steps:
1) M-B amorphous alloy is mixed with Pd colloidal sol, and carries out gelation under protective atmosphere, Pd colloidal sol is made to become Pd gel
And it is coated on M-B amorphous alloy surface, boron hydride is then added and is reacted, Pd gel is made to become the conjunction of Pd-B amorphous state
Gold washs obtained precipitating after fully reacting, obtains the M-B amorphous alloy of Pd-B package；
2) the M-B amorphous alloy that Pd-B obtained is wrapped up is mixed with Al colloidal sol, and carries out gelation under protective atmosphere, made
Al colloidal sol becomes Al gel and is coated on the M-B amorphous alloy surface of Pd-B package, is then separated by solid-liquid separation, solid is washed
Wash to get.
5. M-B@Pd-B@Al according to claim 42O3The preparation method of catalyst, which is characterized in that step 1) and step
It is rapid 2) described in gelation be in temperature be 50~150 DEG C, the pressure of protective gas keeps 1~5h under the conditions of being 1~5MPa.
6. M-B@Pd-B@Al according to claim 42O3The preparation method of catalyst, which is characterized in that the M-B amorphous
The preparation method of state alloy, comprising: boron hydride is added in the soluble-salt aqueous solution of metal M and is reacted, fully reacting
Afterwards by the precipitating of generation be washed till it is neutral to get.
7. M-B@Pd-B@Al according to claim 62O3The preparation method of catalyst, which is characterized in that the metal M's
The ratio between M atom and the amount of substance of B atom in boron hydride are 1:(5~50 in soluble-salt aqueous solution).
8. M-B@Pd-B@Al according to claim 42O3The preparation method of catalyst, which is characterized in that step 1) is described
The ratio between Pd atom and the amount of substance of B atom in boron hydride are 1:(5~50 in Pd colloidal sol).
9. M-B@Pd-B@Al as described in claim 12O3Application of the catalyst in hydrogenation reduction.
10. M-B@Pd-B@Al according to claim 92O3Application of the catalyst in hydrogenation reduction, feature exist
In the hydrogenation reduction is that levulic acid is hydrogenated to gamma-valerolactone.
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