CN105709856B - A kind of preparation method for the catalyst that modulation metal is distributed over a molecular sieve - Google Patents
A kind of preparation method for the catalyst that modulation metal is distributed over a molecular sieve Download PDFInfo
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- CN105709856B CN105709856B CN201610236429.XA CN201610236429A CN105709856B CN 105709856 B CN105709856 B CN 105709856B CN 201610236429 A CN201610236429 A CN 201610236429A CN 105709856 B CN105709856 B CN 105709856B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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Abstract
A kind of preparation method for the catalyst that modulation metal is distributed over a molecular sieve, pass through the pH value of control blocking molecular sieve pore passage and solution, or the pH value by selecting appropriately sized metal complex and adjustment deposition sedimentation procedure parameter and solution, it can be by the "outside" surface specific site for being deposited on molecular sieve of catalytically-active metals element selectivity or preferential deposition in molecular sieve "inner" surface specific site.
Description
Technical field
The present invention relates to a kind of catalyst fields, specifically, being related to a kind of preparation method of catalyst, more particularly to a kind of
The method for preparing catalyst of modulation metal nanoparticle spatial distribution on molecular sieve carrier.
Background technique
90% process is all realized under the effect of the catalyst in modern chemical industry, and wherein load type metal is catalyzed
Agent is a kind of catalyst being most widely used.In many factors for influencing load type metal catalyst performance, metal and load
Interaction between body is an important factor for determining catalyst performance height.It can influence metal active constituent on carrier
Dispersion behavior and interaction mode to play chemical promotor action to metal active constituent finally influence catalytic performance.
Zeolite-type molecular sieve covers catalytic cracking in China's energy industry plus hydrogen as a kind of important catalysis material
Multiple important links such as cracking, isomerization, alkylation, aromatizing low-carbon paraffin.Molecule screens out may be used as acid catalyst in itself
Outside, it is also used as carrier metal catalytic center is introduced near sour position, forms bifunctional catalyst.Such as in hysomer
In Pt/ZSM-5 catalyst, dehydrogenation and hydrogenation reaction occur on Pt metal active position for reactant, and occur on ZSM-5 acid position
Isomerization reaction, the two function, which combines, to be made isomerization reaction rate and selectivity of product while improving.
Demand according to reaction system to catalyst structure, carrys out accuracy controlling noble metal nano particles on molecular sieve carrier
Deposition site, be the challenging research topic of current catalytic field.Iglesia etc. passes through hydrothermal synthesis method for noble metal
Nanocluster (such as Pt, Ir, Pd and Ag) is selectively wrapped in LTA molecular sieve, is limited using the narrow cellular structure of molecular sieve
The reunion of metallic particles processed improves the selectivity of hydrogenation of olefins and oxidation of alcohols dehydrogenation in combination with the shape-selective effect of molecular sieve
(Journal of Catalysis.2014,311:458-468).K.P.de jong etc. utilizes Al in molecular scale2O3Adhesive
Change Pt nano particle spatial position (at a distance from zeolite B acid position) on a catalyst, realize controllable modulation isomeric olefine,
The purpose (Nature.2015,528:245-254) of cracking olefin and coke content.
For molecular sieve carrier, distinguished from macro-scale its surface can be divided into "inner" surface (inside duct) and
"outside" surface, its surface is distinguished from molecular scale again can be divided into different metal framework sites (such as oxygen-octahedron, titanyl four sides
Body, aluminum-oxygen tetrahedron).When metal nanoparticle is deposited on the "inner" surface of molecular sieve, it is typically due to the limit of molecular sieve pore passage
Domain act on and keep certain granule-morphology, can use the Studies On The Shape-selective Catalysis of molecular sieve and improve portion of product selectivity or
Catalyst activity, but it is easy to happen rapid deactivation again simultaneously；When metal nanoparticle is deposited on the "outside" surface of molecular sieve, produce
The mass-transfer performance of object is dramatically improved, it is easier to which desorption improves catalysis to avoid some side reactions from occurring in time
The stability of agent, but the reunion for being easy to appear metallic particles again simultaneously is grown up.So distribution of the particle in molecular sieve surfaces externally and internally
There is important role for catalyst performance.In addition, metal particles deposition is in molecular sieve inner surface or outer surface different metal
Framework sites, it will usually influence the distance between metal and molecular sieve surface two types active sites, and then influence in reaction
The transmitting and diffusion of mesosome, and finally change reactivity worth.Currently, still lacking related accuracy controlling metal nanoparticle in molecule
The technology of space deposition site on sieve, it would be highly desirable to further it be studied.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of catalyst that modulation metal is distributed over a molecular sieve, using this
Preparation method can prepare the catalyst of different structure feature, for example: can be adapted for including selective oxidation of olefins (such as benzene second
Alkene epoxidation), CO oxidation, in many reaction systems such as hydrogenation deoxidation or F- T synthesis.
One aspect of the present invention, a kind of preparation method for the catalyst that modulation metal is distributed over a molecular sieve, including walk as follows
It is rapid:
(1) hole-blocking agent and molecular sieve I are pre-mixed, obtain the molecular sieve II for having been filled with plug-hole agent molecule in duct；
(2) metal front liquid solution and molecular sieve II are mixed, obtain mixed solution I；
(3) pH value of mixed solution I is adjusted, and aging is centrifuged after a certain period of time, is dry, obtains molecular sieve catalyst A.
In catalyst A, catalytically-active metals particle is only deposited on molecular sieve outer surface specific site.
Another aspect of the present invention, a kind of preparation method for the catalyst that modulation metal is distributed over a molecular sieve, including it is as follows
Step:
(i) pH for adjusting metal precursor solution I, obtains metal complex solution II, wherein the size of metal complex
Less than or equal to the aperture of molecular sieve I；
(ii) molecular sieve I is dried under vacuum conditions；
(iii) metal complex solution II and molecular sieve I is mixed, while maintains the pH of step (i), mixed
The total volume of solution III, metal complex should be less than the pore volume of molecular sieve；
It is (iv) obtained to load the molecular sieve catalyst B for having metal nanoparticle by mixed solution I II centrifugation, drying,
In catalyst B, metal nanoparticle preferential deposition is in the catalyst of molecular sieve inner surface specific site.
Preparation method provided by the present application is suitable for that institute is in need to adjust spatial position of the catalytic active component on carrier
Catalyst preparation.
The preparation method for the catalyst that modulation metal of the invention is distributed over a molecular sieve, will using hole-blocking agent by control
The duct of molecular sieve is blocked, and metal cannot enter in duct, can only be in the outside deposition of molecular sieve；Or preparation size is less than
The metal complex in the aperture of molecular sieve pore passage so that small size and have carrier have compared with strong interaction metal complex object
Kind is easier in the duct of sucking molecular sieve, makes metal preferential deposition in the inner surface of molecular sieve.Successfully by metal nano
Particle is deposited to particular space site inside molecular sieve surface or preferential deposition to molecular sieve, realizes the essence of metal space position
Really regulation.
Detailed description of the invention
Fig. 1 catalyst repeat performance
Fig. 2 catalyst repeat performance
The HRTEM figure of Au/TS-1 in Fig. 3 comparative example 4
Fig. 4 is catalyst activity comparison
The HRTEM figure that Fig. 5 is Au/TS-1 in comparative example 6.
Specific embodiment
Method for preparing catalyst of the invention is described in further detail below.The protection scope of the application is not limited,
Its protection scope is defined with claims.Certain disclosed details provide reason comprehensively to each disclosed embodiment
Solution.However, those skilled in the relevant art know, one or more of these concrete details are not used, and use other materials
The situation of material etc. can also realize embodiment.
Unless the context otherwise requires, in specification and claims, the terms "include", "comprise" are interpreted as
Meaning that is open, including, as " includes, but are not limited to ".
Mentioned " embodiment ", " embodiment ", " another embodiment " or " certain embodiment party in the description
Case " etc. refers to that described feature, the structure or characteristic being specifically related to relevant to the embodiment is included at least one
In embodiment.Therefore, " embodiment ", " embodiment ", " another embodiment " or " certain embodiments " must not
Refer both to identical embodiment.And specific feature, structure or characteristic can be in one or more embodiments to appoint
What mode combines.Each feature disclosed in specification any can provide replacing for identical, impartial or similar purpose
Replace for property feature.Therefore except there is special instruction, revealed feature is only impartial or similar features general examples.
The definition of isoelectric point: in the solution, carrier (molecular sieve) surface cation and anion are equal, are in electroneutral, this
When solution pH become the carrier (molecular sieve) isoelectric point.When pH is greater than isoelectric point, carrier surface is negatively charged；When pH is less than
When isoelectric point, carrier surface is positively charged.
Molecular sieve in the application includes that aperture is less than the micropore of 2nm, aperture is sieved between the mesoporous natural molecule of 2-50nm
Or synthesis of molecular sieve.Micro porous molecular sieve for example includes ZSM-5, titanium-silicon molecular sieve TS-1, TS-2, A type, SAPO-34, mercerising boiling
Stone；Mesoporous molecular sieve for example includes Ti-HMS, Ti-3D mesopore molecular sieve, MCM-41, MCM-48, SBA-15.
Metal in the application can be the common catalytic active component in each field, in some embodiments, described
Metal includes but is not limited to the mixing of one or more of gold, platinum, palladium, silver, iridium, rhenium, ruthenium, nickel, molybdenum, cobalt, iron etc..
Metal precursor in the application be often referred to the chloride of different metal, acetylacetonate, acetic acid compound or
Nitrate compound etc., such as gold chloride, acetic acid gold, chloroplatinic acid, chloro-iridic acid, perrhenic acid, nickel nitrate, ferric nitrate.
It is NaOH or ammonium hydroxide that reagent used in pH is adjusted in the application.
In one embodiment, the hole-blocking agent in the application includes but is not limited to organic amine template, carbohydrate, alcohols material
Or one or more kinds of mixing in hydrone.
The organic amine template includes but is not limited to tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide and/or 4 third
Base ammonium bromide.
The glucide includes but is not limited to the one or more of the carbohydrates such as glucose, sucrose, fructose, lactose
Mixing.
The alcohols material includes but is not limited to ethyl alcohol, methanol, propyl alcohol, propylene glycol, glycerine, butanol etc..
The metal complex of the application small-medium size is the smallest metal complex of steric hindrance, networks usually more containing chlorine
Close object space steric hindrance it is bigger, and containing chlorine number by change pH adjusting is hydrolyzed.
Inventor in the application is after extensive and in-depth study, it was found that a kind of accurate modulation metal is over a molecular sieve
The method in spatial deposition site is filled micro- that is, using the difference of different molecular sieve framework metal isoelectric point in conjunction with inertia hole-blocking agent
The method of hole duct and modulation metal precursor size, can effective modulation metal nanoparticle spatial deposition position over a molecular sieve
Point.On this basis, the present invention is completed.
Specific embodiment:
On the one hand, a kind of preparation method for the catalyst that modulation metal is distributed over a molecular sieve, the specific steps are as follows:
(1) hole-blocking agent and molecular sieve I are pre-mixed, obtain the molecular sieve II for having been filled with plug-hole agent molecule in duct；
(2) metal front liquid solution and molecular sieve II are mixed, obtain mixed solution I；
(3) pH value for adjusting mixed solution I is less than or equal to the isoelectric point of deposition position element on molecular sieve I, then always
Change, centrifugation, drying, obtains catalyst A.
In catalyst A, the duct of molecular sieve I is blocked by plug-hole agent molecule, metal front liquid solution and molecular sieve II
After mixing, metal species preferentially can be contacted and be reacted with molecular sieve in aperture so that aperture be blocked and Au species are difficult to enter
Duct.Adjust solution pH value be less than molecular sieve I in certain element-specific isoelectric point, metal precursor then can Preferential adsorption in
Near molecular sieve element-specific, i.e., metal nanoparticle is only deposited on molecular sieve outer surface specific site.
During metal active constituent is supported on molecular sieve, in the molecular sieve as catalyst activity component carrier
Each deposition site has specific isoelectric point, by adjusting the pH value in mixed solution, metal active constituent can be deposited to
The target position of molecular sieve.For example, it is carrier by presoma, Titanium Sieve Molecular Sieve of gold chloride, gold element is loaded to titanium silicon point
It on the titanium position of son sieve, needs to adjust the isoelectric point that pH value of solution is less than titanium, and is greater than the isoelectric point of silicon, is i.e. pH=3-7 i.e. will be active
In group parting deposition and titanium position.If being intended to need to adjust to Si by metal particles deposition pH less than 3；If preventing metal
Grain is deposited on certain position, then pH needs the isoelectric point greater than the position.
In some embodiments, as in step (3), the molecular sieve in metal front liquid solution and plug-hole road is mixed, and is mixed
Close solution I pH be less than molecular sieve be intended to deposition position backbone element isoelectric point and be greater than other backbone elements of molecular sieve etc.
Electric point, it is preferred that the pH of mixed solution I than molecular sieve be intended to deposition position backbone element isoelectric point difference less than 1, it is more excellent
Choosing, the pH of mixed solution I than molecular sieve be intended to deposition position backbone element isoelectric point difference less than 0.1.
In some embodiments, as in step (3), gold element precursor solution is mixed with Titanium Sieve Molecular Sieve, is mixed molten
Liquid pH is less than the isoelectric point of framework of molecular sieve titanium elements, and is greater than the isoelectric point of element silicon, it is preferable that mixed solution pH is controlled in 3-
7。
The dosage for the hole-blocking agent that blocking molecular sieve I is used can determine its specific dosage according to hole-blocking agent type.
For example, in some embodiments, in step (1), volume when hole-blocking agent hydrone or carbohydrate liquid is added
Hold greater than molecular sieve pores, it is preferable that the volume of addition hole-blocking agent hydrone or carbohydrate is 1-1000 times of Kong Rong；It is further preferred that being added
The volume of hole-blocking agent hydrone or carbohydrate is 10-1000 times of Kong Rong；Most preferably, the volume of hole-blocking agent hydrone or carbohydrate is added
It is 100-1000 times of Kong Rong.
In some embodiments, in step (1), hole-blocking agent hydrone or carbohydrate and molecular sieve I incorporation time are 10-
500 minutes；It is preferred that incorporation time is 100-500 minutes；It is further preferred that incorporation time is 300-500 minutes；
If it is template, dosage is 0.1-10 times of silicon mole in molecular sieve.
In some embodiments, in step (1), when hydrone and molecular sieve I are mixed, mixing temperature is less than 100 DEG C.
In some embodiments, in step (1), when carbohydrate is mixed with molecular sieve I, mixing temperature control is being higher than sugar
5-50 DEG C of the fusing point of class and the tolerable temperature for being less than molecular sieve I skeleton.Preferably, mixing temperature control is being higher than the molten of carbohydrate
5-25 DEG C of point and the tolerable temperature for being less than molecular sieve I skeleton.It is further preferred that mixing temperature control is in the fusing point 5-10 for being higher than carbohydrate
DEG C and be less than molecular sieve I skeleton tolerable temperature.
In the present invention, aging, centrifuge separation, drying of step (3) etc. are common using prior art preparation catalyst
Equipment, process conditions etc..
On the other hand, a kind of preparation method for the catalyst that modulation metal is distributed over a molecular sieve, the specific steps are as follows:
(i) pH for adjusting metal precursor solution I is less than the isoelectric point for being intended to deposition position backbone element, obtains metal complex
Object solution II, wherein the size of metal complex is less than or equal to the aperture of molecular sieve I；
(ii) molecular sieve I is dried into 12h or more under vacuum conditions；
(iii) the molecular sieve I after metal complex solution II and drying is mixed, while maintains the pH of step (i),
Obtain mixed solution I II；
(iv) by mixed solution I II centrifugation, drying, metal nanoparticle is made and is only deposited on molecular sieve inner surface certain bits
The catalyst B of point.
In preparing another embodiment, preferred dimension is less than the metal complex in the aperture molecular sieve I, and adjusts metal network
The pH value of polymer solution is less than the isoelectric point of the specific backbone element position molecular sieve I, and metal front liquid solution is mixed with molecular sieve I
Afterwards, due to capillary phenomenon and concentration difference effect, so that small size and having carrier that there are the metal complex species compared with strong interaction
It more easily sucks in the duct of molecular sieve, while by the adjusting of pH, making metal particles deposition in molecular sieve pore passage inner surface
Specific site can make in metal precursor solution catalyst B 97% or more metal (for example Au) particle by this method
It is distributed in inside molecular sieve.
For the isoelectric point of molecular sieve I, different types of molecular sieve isoelectric point is different.In some embodiments, in step
Suddenly in (i), the pH value for adjusting mixed solution I is smaller than the element isoelectric point for being intended to deposition position in molecular sieve I.
In some embodiments, pH needs are selected according to the isoelectric point of framework of molecular sieve element, i.e. pH needs small
In the isoelectric point of deposition site metal.
In some embodiments, as in step (i), 5-80 DEG C of the temperature of metal precursor solution I, preferably 5-50 DEG C,
More preferably 5-20 DEG C.
Control metal front liquid solution should be controlled at 5-80 DEG C in step (i), and especially control is at 5-20 DEG C.Because
Under hot conditions, metal complex is easy to be bound to each other to form polymerization state, and volume increases, causes to be difficult to more to enter duct
It is interior.
In some embodiments, when being mixed as in step (iii), adjusted precursor solution I with the molecular sieve I after drying
Between 1-25 hours；It is preferred that 8-15 hours.
In some embodiments, as in step (iii), any hole-blocking agent is not contained in molecular sieve I.
In the present invention, the centrifuge separation, drying of step (iv) use the common equipment of prior art preparation catalyst, work
Skill condition etc..
The present invention has the advantages that
For the prior art, the duct that metal nanoparticle is wrapped in molecular sieve usually may be implemented, hole wall is worked as
In, it can be difficult to metallic particles is only deposited near the special metal active sites of in molecular sieve or outer surface.And the application
More metal nanoparticle preferential deposition is intended to deposition site (for example site Ti or Si by accurate realize in the duct of molecular sieve
Site), and metal nanoparticle is deposited on the outer surface of molecular sieve and is intended to deposition site (for example site Ti or Si
Point), realize the space site accuracy controlling of particle.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip
Part or according to the normal condition proposed by manufacturer.Unless otherwise stated, otherwise all percentage, ratio, ratio or number is pressed
Poidometer.
The unit in percent weight in volume in the present invention is well-known to those skilled in the art, such as is referred to
The weight of solute in 100 milliliters of solution.
Unless otherwise defined, it anticipates known to all professional and scientific terms as used herein and one skilled in the art
Justice is identical.In addition, any method similar to or equal to what is recorded and material can be applied to the method for the present invention.Wen Zhong
The preferred implement methods and materials are for illustrative purposes only.
Catalyst test method, by taking epoxidation of styrene reacts as an example: operate under normal pressure, by 0.3g catalyst with
20mmol styrene, 50mmol hydrogen peroxide and a certain amount of solvent are set in a round bottom flask, are reacted at 60 DEG C and are carried out product
Analysis.
Embodiment 1
By Au nanoparticle deposition in the specific site Ti of molecular sieve outer surface
The titanium-silicon molecular sieve TS-1 for taking 0.5g to contain tetraethyl ammonium hydroxide is placed in a beaker, and 40g water is added and stirs 10 points
Clock, the chlorauric acid solution that 10mL0.1mol/L is then added form mixed solution I；Mixed solution I is stirred at room temperature 30 points
Clock and to maintain pH be 7, by the centrifugation of obtained mixed solution, washing, it is dry after obtain Au nano particle and be only deposited at titanium silicon molecule
Sieve the catalyst near the outer surface TS-1 Ti.
N is carried out to titanium-silicon molecular sieve TS-1 and the Au/TS-1 catalyst prepared2Physical absorption, as shown in table 1.Pure load
The Micropore volume of body TS-1 is compared with the Micropore volume of Au/TS-1 almost not to be become, and equal very little, shows that template plugs micropore
Duct, and Au nano particle is only deposited on molecular sieve outer surface.Further, since isoelectric point of the isoelectric point of Ti slightly larger than 7, silicon
Substantially 2, when pH is 7, Ti, Titanium Sieve Molecular Sieve surface is positively charged, and silicon position is negatively charged, so electronegative gold chloride forerunner
Body is attracted near Ti.
The conversion ratio of epoxidation of styrene is as shown in Figure 1 with access times relationship on the catalyst.
Embodiment 2
By Au nanoparticle deposition in the specific site Ti of molecular sieve outer surface
It takes 0.5g to contain the titanium-silicon molecular sieve TS-1 without hole-blocking agent in micropore to be placed in a beaker, 40g water is added at 60 DEG C
Stirring 100 minutes, the chlorauric acid solution that 10mL0.1mol/L is then added form mixed solution I；At room temperature by mixed solution I
Stirring 50 minutes and maintaining pH is 7, will obtain mixed solution centrifugation, obtains Au nano particle after washing, drying after taking-up solid
The catalyst being only deposited near titanium-silicon molecular sieve TS-1 outer surface Ti.
To the titanium-silicon molecular sieve TS-1 and Au/TS-1 catalyst progress N in micropore without hole-blocking agent2Physical absorption, such as 1 institute of table
Show.Although the Micropore volume of pure carrier TS-1 compared with the Micropore volume of Au/TS-1 it is larger, almost do not become, show Au
Nano particle and the duct for not entering molecular sieve.Further, since isoelectric point substantially 2 of the isoelectric point of Ti slightly larger than 7, silicon, when
When pH is 7, Ti, Titanium Sieve Molecular Sieve surface is positively charged, and silicon position is negatively charged, so electronegative gold chloride presoma is attracted to Ti
Near position.ICP-AES is carried out to the Au/TS-1 catalyst for using template blocking microporous in Au/TS-1 catalyst and embodiment 1
It is characterized with XPS, summarized results is as shown in table 2.Wherein ICP-AES can analyze entire caltalyst phase Au/Si molar ratio, and
XPS analysis catalyst external surface Au/Si molar ratio, the two is almost consistent, and the Au/Si molar ratio that XPS is determined in the present embodiment 2
With the numerical approximation of sample in embodiment 1, show Au nano particle integrated distribution in molecular sieve outer surface.
The conversion ratio of epoxidation of styrene is as shown in Figure 1 with access times relationship on the catalyst.
Embodiment 3
By Au nanoparticle deposition in the specific site Ti of molecular sieve outer surface
It takes 0.5g to contain the titanium-silicon molecular sieve TS-1 without hole-blocking agent in micropore to be placed in a beaker, be added under the conditions of 170 DEG C
20g glucose stirs 120 minutes, and the chlorauric acid solution that 10mL0.1mol/L is then added forms mixed solution I；By mixed solution
It is 7 that I, which is stirred at room temperature 60 minutes and maintains pH, will obtain mixed solution centrifugation, obtains Au after washing, drying after taking-up solid
Nano particle is only deposited at the catalyst near titanium-silicon molecular sieve TS-1 outer surface Ti.
To in micropore without hole-blocking agent titanium-silicon molecular sieve TS-1 and glucose treated TS-1 catalyst carry out N2Physics
Absorption, as shown in table 1.The Micropore volume of the Micropore volume of pure carrier TS-1 and glucose treated TS-1 compare gap compared with
Greatly, predominantly glucose molecule plugs duct.Further, since isoelectric point substantially 2 of the isoelectric point of Ti slightly larger than 7, silicon, when
When pH is 7, Ti, Titanium Sieve Molecular Sieve surface is positively charged, and silicon position is negatively charged, so electronegative gold chloride presoma is attracted to Ti
Near position.ICP-AES is carried out to the Au/TS-1 catalyst for using template blocking microporous in Au/TS-1 catalyst and embodiment 1
It is characterized with XPS, summarized results is as shown in table 2.Wherein ICP-AES can analyze entire caltalyst phase Au/Si molar ratio, and
XPS analysis catalyst external surface Au/Si molar ratio, the two is almost consistent, and the Au/Si molar ratio that XPS is determined in the present embodiment 2
With the numerical approximation of sample in embodiment 1, show Au nano particle integrated distribution in molecular sieve outer surface.Benzene second on the catalyst
Relationship is as shown in Figure 1 at any time for the epoxidised conversion ratio of alkene.
The conversion ratio of epoxidation of styrene is as shown in Figure 1 with access times relationship on the catalyst.
Embodiment 4
By Au nanoparticle deposition in the specific site Ti of molecular sieve inner surface
It takes the chlorauric acid solution of 10mL 0.1mol/L to be placed in a beaker, pH is adjusted under the conditions of 28 DEG C and is 7 and maintains 30 points
Clock, obtains complex solution II, and the size of complex compound is less than the aperture of molecular sieve TS-1；By the titanium silicon in micropore without hole-blocking agent point
Son sieve TS-1 carries out vacuum pumping 12 hours at room temperature, and takes 0.5g to be added in above-mentioned solution and stir 500 minutes, forms mixing
Solution, wherein the volume of gold complex is less than molecular sieve pore passage volume；Mixed solution centrifugation will be obtained, washed after taking-up solid,
Catalyst of the Au nanoparticle deposition near titanium-silicon molecular sieve TS-1 inner surface Ti is obtained after drying.
N is carried out to the titanium-silicon molecular sieve TS-1 in micropore without hole-blocking agent and the Au/TS-1 catalyst made2Physics is inhaled
It is attached, as shown in table 1.Compared to the Micropore volume of pure carrier TS-1, the Micropore volume of Au/TS-1 is substantially reduced, and shows Au nanometers
Particle enters the duct of molecular sieve.Further, since isoelectric point substantially 2 of the isoelectric point of Ti slightly larger than 7, silicon, when pH is 7,
Ti, Titanium Sieve Molecular Sieve surface is positively charged, and silicon position is negatively charged, so electronegative gold chloride presoma is attracted near Ti.It is right
XPS characterization is carried out using the blocking microporous Au/TS-1 catalyst of template in Au/TS-1 catalyst and embodiment 1, such as 2 institute of table
Show.The result shows that the Au/Si molar ratio that XPS is obtained in the present embodiment is much smaller than Au particulate load in the catalyst of outer surface, say
Bright Au nano particle integrated distribution is in molecular sieve inner surface.Relationship is such as at any time for the conversion ratio of epoxidation of styrene on the catalyst
Shown in Fig. 4.
Embodiment 5
By Au nanoparticle deposition in the specific site Ti of molecular sieve inner surface
It takes the chlorauric acid solution of 10mL 0.1mol/L to be placed in a beaker, pH is adjusted under the conditions of 40 DEG C and is 7 and maintains 30 points
Clock obtains complex solution II；0.5g is added and contains the titanium-silicon molecular sieve TS-1 without hole-blocking agent in micropore, stirs 60 minutes, shape
At mixed solution, wherein the volume of gold complex is less than molecular sieve pore passage volume；Mixed solution centrifugation will be obtained, solid is taken out
It washs afterwards, obtain catalyst of the Au nanoparticle deposition near titanium-silicon molecular sieve TS-1 inner surface Ti after drying.
The result shows that Au particle can be distributed in specific site in molecular sieve pore passage under proper temperature and mixing time.
Relationship is as shown in Figure 4 at any time for the conversion ratio of epoxidation of styrene on the catalyst.
Embodiment 6
By Au nanoparticle deposition in the specific site Ti of molecular sieve inner surface
It takes the chlorauric acid solution of 10mL 0.1mol/L to be placed in a beaker, pH is adjusted under the conditions of 5 DEG C and is 7 and maintains 30 points
Clock obtains complex solution II；0.5g is added and contains the titanium-silicon molecular sieve TS-1 without hole-blocking agent in micropore, is stirred at 70 DEG C
800 minutes, form mixed solution, wherein the volume of gold complex is less than molecular sieve pore passage volume；To obtain mixed solution from
The heart, take out washing after solid, it is dry after obtain Au nanoparticle deposition urging near titanium-silicon molecular sieve TS-1 inner surface Ti
Agent.
The result shows that Au particle can be distributed in specific site in molecular sieve pore passage under proper temperature and mixing time.
Relationship is as shown in Figure 4 at any time for the conversion ratio of epoxidation of styrene on the catalyst.
Comparative example 1
Common Au/TS-1 catalyst preparation
It takes 0.5g to contain the titanium-silicon molecular sieve TS-1 without hole-blocking agent in micropore to be placed in a beaker, is added 50mL0.1mol/L's
Chlorauric acid solution forms mixed solution I；It is 7 that mixed solution I, which is stirred at room temperature 30 minutes, and maintains pH, will obtain mixing molten
Liquid centrifugation, take out washing after solid, it is dry after obtain Au nanoparticle deposition in titanium-silicon molecular sieve TS-1 and outer surface Ti
Neighbouring catalyst.
The result shows that common Au/TS-1 catalyst, it is inside and outside that Au particle is randomly distributed in molecular sieve pore passage.It should
The conversion ratio of epoxidation of styrene is as shown in Figure 2 with access times relationship on catalyst.
Comparative example 2
Au/TS-1 catalyst preparation
It takes 0.5g to contain the titanium-silicon molecular sieve TS-1 without hole-blocking agent in micropore to be placed in a beaker, 40g water is added and stirs 5 points
Clock, the chlorauric acid solution that 10mL0.1mol/L is then added form mixed solution I；Mixed solution I is stirred at room temperature 30 points
Clock and to maintain pH be 7.5, will obtain mixed solution centrifugation, take out washing after solid, it is dry after obtain Au nanoparticle deposition and exist
Catalyst in titanium-silicon molecular sieve TS-1 and near outer surface Ti.
The result shows that hole-blocking agent can not be played the role of when the hydrone time contacted with molecular sieve is shorter, and make Au particle
Molecular sieve outer surface can not be only deposited on.The conversion ratio of epoxidation of styrene is with access times relationship such as Fig. 2 institute on the catalyst
Show.
Comparative example 3
Au/TS-1 catalyst preparation
It takes 0.5g to contain the titanium-silicon molecular sieve TS-1 without hole-blocking agent in micropore to be placed in a beaker, 0.2g water stirring 100 is added
Minute, the mixed solution of gold chloride and 40g water that 10mL0.1mol/L is then added forms solution I；By mixed solution I in room temperature
Lower stirring 30 minutes and to maintain pH be 7.5, will obtain mixed solution centrifugation, take out washing after solid, it is dry after obtain Au nanometers
Particle is only deposited at the catalyst near titanium-silicon molecular sieve TS-1 outer surface Ti.
The result shows that hole-blocking agent can not be played the role of when the hydrone contacted with molecular sieve is less, and make Au particle can not
Only it is deposited on molecular sieve outer surface.The conversion ratio of epoxidation of styrene is as shown in Figure 2 with access times relationship on the catalyst.
Comparative example 4
Au/TS-1 catalyst preparation
It takes 0.5g to contain the titanium-silicon molecular sieve TS-1 without hole-blocking agent in micropore to be placed in a beaker, be added under the conditions of 600 DEG C
20g glucose stirs 120 minutes, and the chlorauric acid solution that 10mL 0.1mol/L is then added forms mixed solution I；It will mix molten
It is 7.5 that liquid I, which is stirred at room temperature 30 minutes and maintains pH, will obtain mixed solution centrifugation, after taking-up solid after washing, drying
The catalyst near titanium-silicon molecular sieve TS-1 outer surface Ti is only deposited to Au nano particle.
The result shows that high temperature reduces molecular sieve crystallinity when carbohydrate and molecular sieve Contact Temperature are excessively high, HRTEM figure
As shown in Figure 3.The conversion ratio of epoxidation of styrene is as shown in Figure 2 with access times relationship on the catalyst.
Comparative example 5
By Au nanoparticle deposition in the specific site Ti of molecular sieve inner surface
It takes the chlorauric acid solution of 10mL 0.1mol/L to be placed in a beaker, pH is adjusted under the conditions of 28 DEG C and is 2 and maintains 30 points
Clock obtains complex solution II；0.5g is added and contains the titanium-silicon molecular sieve TS-1 without hole-blocking agent in micropore, stirs 50 minutes, shape
At mixed solution；Mixed solution centrifugation will be obtained, obtains Au/TS-1 catalyst after washing, drying after taking-up solid.
When the result of comparison illustrates that pH is lower, Au particle can not be deposited on molecular sieve Ti location proximate, and only deposit to Si
Location proximate.Relationship is as shown in Figure 4 at any time for the conversion ratio of epoxidation of styrene on the catalyst.
Comparative example 6
By Au nanoparticle deposition in the specific site Ti of molecular sieve inner surface
It takes the chlorauric acid solution of 10mL 0.1mol/L to be placed in a beaker, pH is adjusted under the conditions of 90 DEG C and is 7 and maintains 30 points
Clock obtains complex solution II；0.5g is added and contains the titanium-silicon molecular sieve TS-1 without hole-blocking agent in micropore, stirs 50 minutes, shape
At mixed solution；Mixed solution centrifugation will be obtained, obtains Au/TS-1 catalyst after washing, drying after taking-up solid.
When the result of comparison illustrates that whipping temp is excessively high, there is obvious reunion in Au particle, so that into less in duct,
Hole holds variation and is shown in Table 1, Au particle HRTEM figure as shown in Figure 5.The conversion ratio of epoxidation of styrene closes at any time on the catalyst
System is as shown in Figure 4.
Comparative example 7
By Au nanoparticle deposition in the specific site Ti of molecular sieve inner surface
It takes the chlorauric acid solution of 10mL 0.1mol/L to be placed in a beaker, pH is adjusted under the conditions of 30 DEG C and is 7 and maintains 30 points
Clock obtains complex solution II；0.5g is added and contains the titanium-silicon molecular sieve TS-1 without hole-blocking agent in micropore, stirs 30 hours, shape
At mixed solution；Mixed solution centrifugation will be obtained, obtains Au/TS-1 catalyst after washing, drying after taking-up solid.
When the result of comparison illustrates that mixing time is too long, Au particle is migrated out from duct instead, and hole holds variation and is shown in Table
1.Relationship is as shown in Figure 4 at any time for the conversion ratio of epoxidation of styrene on the catalyst.
The different sample well structural properties of table 1
| Sample | Micropore volume (cm3/g) | Specific surface area (cm2/g) |
| Without hole-blocking agent TS-1 | 0.22 | 420 |
| Common preparation Au/TS-1 (comparative example 1) | 0.15 | 390 |
| Au/TS-1 (comparative example 2) | 0.18 | 398 |
| Au/TS-1 (comparative example 3) | 0.19 | 402 |
| Make hole-blocking agent TS-1 containing template | 0.03 | 40 |
| Make hole-blocking agent Au/TS-1 (embodiment 1) containing template | 0.03 | 42 |
| Au/TS-1 (embodiment 2) containing hydrone hole-blocking agent | 0.21 | 432 |
| TS-1 (embodiment 3) containing glucose hole-blocking agent | 0.02 | 38 |
| Au/TS-1 (embodiment 4) | 0.08 | 291 |
| Au/TS-1 (comparative example 6) | 0.18 | 398 |
| Au/TS-1 (comparative example 7) | 0.20 | 405 |
The different sample body phases of table 2 and surface A u/Si molar ratio
aIt is measured by ICP-AES；
bIt is measured by XPS.
Claims (12)
1. a kind of preparation method for the catalyst that modulation metal is distributed on TS-1 molecular sieve, includes the following steps:
(1) hole-blocking agent and molecular sieve I are pre-mixed, obtain the molecular sieve II for having been filled with plug-hole agent molecule in duct；
(2) metal front liquid solution and molecular sieve II are mixed, obtain mixed solution I；
(3) pH value for adjusting mixed solution I is less than the isoelectric point that molecular sieve is intended to deposition position backbone element, and difference between the two
Value is centrifuged after aging less than 1, is dry, obtaining catalyst A；
The hole-blocking agent includes mixing one or two kinds of in carbohydrate or hydrone；
The glucide includes one or more kinds of mixing of glucose, sucrose, fructose, lactose,
In step (1), the volume that hole-blocking agent hydrone or carbohydrate is added is held greater than molecular sieve pores；
In step (1), hole-blocking agent hydrone or carbohydrate and molecular sieve I incorporation time are 10-500 minutes；
In step (1), when hydrone and molecular sieve I are mixed, mixing temperature is less than 100 DEG C；
In step (1), when carbohydrate is mixed with molecular sieve I, mixing temperature control is being higher than 5-50 DEG C of the fusing point of carbohydrate and is being less than
The tolerable temperature of molecular sieve I skeleton.
2. preparation method according to claim 1, which is characterized in that the metal include gold, platinum, palladium, silver, iridium, rhenium,
The mixing of one or more of ruthenium, nickel, molybdenum, cobalt, iron.
3. preparation method according to claim 1, which is characterized in that the pH of mixed solution I is less than molecular sieve position to be deposited
The isoelectric point of backbone element is set, and difference between the two is less than 0.1.
4. preparation method according to claim 1, which is characterized in that in step (3), gold element precursor solution and titanium silicon
Molecular sieve mixing, mixed solution pH is less than the isoelectric point of framework of molecular sieve titanium elements, and is greater than the isoelectric point of element silicon.
5. the preparation method according to claim 4, which is characterized in that gold element precursor solution is mixed with Titanium Sieve Molecular Sieve
Mixed solution pH control in 3-7.
6. preparation method according to claim 1, which is characterized in that the volume that hole-blocking agent hydrone or carbohydrate is added is hole
1-1000 times of appearance.
7. preparation method according to claim 1, which is characterized in that the volume that hole-blocking agent hydrone or carbohydrate is added is hole
10-1000 times of appearance.
8. preparation method according to claim 1, which is characterized in that the volume that hole-blocking agent hydrone or carbohydrate is added is hole
100-1000 times of appearance.
9. preparation method according to claim 1-8, which is characterized in that in step (1), carbohydrate and molecular sieve
When I is mixed, mixing temperature control is in 5-25 DEG C of the fusing point higher than carbohydrate and less than the tolerable temperature of molecular sieve I skeleton.
10. preparation method according to claim 1-8, which is characterized in that in step (1), carbohydrate and molecule
When sieving I mixing, mixing temperature control is in 5-10 DEG C of the fusing point higher than carbohydrate and less than the tolerable temperature of molecular sieve I skeleton.
11. a kind of preparation method for the catalyst that modulation metal is distributed on TS-1 molecular sieve, includes the following steps:
(1) hole-blocking agent and molecular sieve I are pre-mixed, obtain the molecular sieve II for having been filled with plug-hole agent molecule in duct；
(2) metal front liquid solution and molecular sieve II are mixed, obtain mixed solution I；
(3) pH value for adjusting mixed solution I is less than the isoelectric point that molecular sieve is intended to deposition position backbone element, and difference between the two
Value is centrifuged after aging less than 1, is dry, obtaining catalyst A；
The hole-blocking agent includes mixing one or two kinds of in carbohydrate or hydrone；
The glucide includes one or more kinds of mixing of glucose, sucrose, fructose, lactose, in step (1)
In, the volume that hole-blocking agent hydrone or carbohydrate is added is held greater than molecular sieve pores；
In step (1), incorporation time is 100-500 minutes；
In step (1), when hydrone and molecular sieve I are mixed, mixing temperature is less than 100 DEG C；
In step (1), when carbohydrate is mixed with molecular sieve I, mixing temperature control is being higher than 5-50 DEG C of the fusing point of carbohydrate and is being less than
The tolerable temperature of molecular sieve I skeleton.
12. preparation method according to claim 11, which is characterized in that in step (1), incorporation time is 300-500 points
Clock.
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