CN105709856A - Method for preparing catalyst used for modulating distribution of metal on molecular sieve - Google Patents
Method for preparing catalyst used for modulating distribution of metal on molecular sieve Download PDFInfo
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- CN105709856A CN105709856A CN201610236429.XA CN201610236429A CN105709856A CN 105709856 A CN105709856 A CN 105709856A CN 201610236429 A CN201610236429 A CN 201610236429A CN 105709856 A CN105709856 A CN 105709856A
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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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- 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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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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- 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
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- 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
Provided is a method for preparing a catalyst used for modulating distribution of metal on a molecular sieve.By control over the blockage of molecular sieve ducts and the pH of solution, or by selection of metal complexes of appropriate sizes and adjustment of deposition-precipitation process parameters and the pH of solution, catalytic activity metal elements can be selectively deposited on specific loci of the outer surface of the molecular sieve or deposited on specific loci of the inner surface of the molecular sieve as a priority.
Description
Technical field
The present invention relates to a kind of catalyst field, concrete, the preparation method that relates to a kind of catalyst, particularly relate to a kind of modulation metal nanoparticle method for preparing catalyst of spatial distribution on molecular sieve carrier.
Background technology
In modern chemical industry, the process of 90% is all realize under the effect of catalyst, and wherein load type metal catalyst is the class catalyst being most widely used.In many factors affecting load type metal catalyst performance, the interaction between metal and carrier is the key factor determining catalyst performance height.It can affect metal active constituent dispersion behavior on carrier and interaction mode, thus metal active constituent rises chemistry promotor action, finally affects catalytic performance.
Zeolite-type molecular sieve, as the important catalysis material of a class, covers multiple important steps such as catalytic cracking in China's energy industry, hydrogenation cracking, isomerization, alkylation, aromatizing low-carbon paraffin.Except molecular sieve can serve as acid catalyst except itself, it is also possible to as carrier, metal catalytic center is incorporated near acid position, forms bifunctional catalyst.As, in hysomer Pt/ZSM-5 catalyst, there is dehydrogenation and hydrogenation reaction in reactant, and isomerization reaction occurs on ZSM-5 acid position on Pt metal active position, and the two function combines and makes isomerization reaction speed and selectivity of product improve simultaneously.
According to the reaction system demand to catalyst structure, carry out accuracy controlling noble metal nano particles deposition site on molecular sieve carrier, be the challenging research topic of current catalytic field.Noble metal nano cluster (such as Pt, Ir, Pd and Ag) is optionally wrapped in LTA molecular sieve by hydrothermal synthesis method by Iglesia etc., utilize the reunion of the narrow pore passage structure restriction metallic particles of molecular sieve, shape effect of selecting in combination with molecular sieve improves the selectivity (JournalofCatalysis.2014,311:458-468) of hydrogenation of olefins and oxidation of alcohols dehydrogenation.K.P.dejong etc. utilize Al at molecular scale2O3Binding agent changes Pt nano-particle locus (distance with zeolite B-acid position) on a catalyst, it is achieved that the purpose (Nature.2015,528:245-254) of controlled modulation isomeric olefine, cracking olefin and coke content.
For molecular sieve carrier, from macro-scale distinguish its surface can be divided into " interior " surface (inside duct) and " " surface, distinguish its surface from molecular scale and can be divided into again different metal framework sites (such as silicon-oxy tetrahedron, titanyl tetrahedron, aluminum-oxygen tetrahedron).When metal nanoparticle is deposited on " interior " surface of molecular sieve, it is typically due to the confinement effect of molecular sieve pore passage and keeps certain granule-morphology, the Studies On The Shape-selective Catalysis of molecular sieve can be utilized to improve portion of product selectivity or catalyst activity, but be susceptible to again rapid deactivation simultaneously；When metal nanoparticle is deposited on " outward " surface of molecular sieve, the mass-transfer performance of product is improved dramatically, being easier to timely desorption thus avoiding some side reactions to occur, improving the stability of catalyst, but easily occurring that again the reunion of metallic particles is grown up simultaneously.So, granule has important effect in the distribution of molecular sieve surfaces externally and internally for catalyst performance.In addition; metal particles deposition is at molecular sieve inner surface or outer surface different metal framework sites; would generally have influence on the distance between metal and molecular sieve surface two types active sites, and then affect transmission and the diffusion of reaction intermediate, and finally change reactivity worth.At present, the technology about accuracy controlling metal nanoparticle spatial deposition site over a molecular sieve is still lacked, it would be highly desirable to further it is studied.
Summary of the invention
The preparation method that it is an object of the invention to provide the catalyst that a kind of modulation metal is distributed over a molecular sieve, adopt this preparation method can prepare the catalyst of different structure feature, such as: go for including in many reaction systems such as selective oxidation of olefins (such as epoxidation of styrene), CO oxidation, hydrogenation deoxidation or F-T synthesis.
One aspect of the present invention, the preparation method of the catalyst that a kind of modulation metal is distributed over a molecular sieve, comprise the steps:
(1) hole-blocking agent is pre-mixed with molecular sieve I, obtains duct has been filled with the molecular sieve II of hole-blocking agent molecule；
(2) by metal front liquid solution and molecular sieve II mix and blend, mixed solution I is obtained；
(3) pH value of mixed solution I is regulated, and centrifugal after aging certain time, dry, obtain molecular sieve catalyst A.
In catalyst A, catalytically-active metals granule is only deposited on molecular sieve outer surface specific site.
Another aspect of the present invention, the preparation method of the catalyst that a kind of modulation metal is distributed over a molecular sieve, comprise the steps:
(i) regulate metal precursor solution I pH, obtain metal complex solution II, wherein metal complex be smaller in size than the aperture equal to molecular sieve I；
(ii) molecular sieve I is dried under vacuum；
(iii) by metal complex solution II and molecular sieve I mix and blend, maintaining the pH of step (i) simultaneously, obtain mixed solution I II, the cumulative volume of metal complex should be less than the pore volume of molecular sieve；
(iv) mixed solution I II is centrifugal, dry, prepare the molecular sieve catalyst B being loaded with metal nanoparticle,
In catalyst B, metal nanoparticle preferential deposition is in the catalyst of molecular sieve inner surface specific site.
The preparation method that the application provides is applicable to the preparation that be there is a need to adjust the catalyst of catalytic active component locus on carrier.
The preparation method of the catalyst that the modulation metal of the present invention is distributed over a molecular sieve, blocks the duct of molecular sieve by controlling employing hole-blocking agent, and metal can not enter in duct, can only in the outside deposition of molecular sieve；Or preparation is smaller in size than the metal complex in aperture of molecular sieve pore passage so that small size and have the metal complex species that carrier has relatively strong interaction to be easier to suck in the middle of the duct of molecular sieve, make metal preferential deposition at the inner surface of molecular sieve.Successfully by internal for metal nanoparticle deposition to molecular sieve surface or preferential deposition to molecular sieve particular space site, it is achieved the accuracy controlling of metal space position.
Accompanying drawing explanation
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 contrast
Fig. 5 is the HRTEM figure of Au/TS-1 in comparative example 6.
Detailed description of the invention
Below the method for preparing catalyst of the present invention is described in further detail.Not limiting the protection domain of the application, its protection domain defines with claims.Embodiment disclosed in each is provided by detail disclosed in some to be understood comprehensively.But, those skilled in the relevant art know, do not adopt these concrete details one or more, and adopt the situation of other material etc. also can realize embodiment.
Unless the context otherwise requires, in description and claims, term " includes ", " comprising " is interpreted as implication open, that include, is " including, but are not limited to ".
" embodiment ", " embodiment ", " another embodiment " or " some embodiment " mentioned in the description etc. refer to relevant to described embodiment described by the feature being specifically related to, structure or characteristic include at least one embodiment.Therefore, " embodiment ", " embodiment ", " another embodiment " or " some embodiment " there is no need to refer both to identical embodiment.And, concrete feature, structure or characteristic can combine in any manner in one or more embodiments.Each feature disclosed in description, it is possible to any alternative characteristics providing identical, impartial or similar purpose replaces.Therefore except having special instruction, disclosed feature to be only impartial or similar features general example.
The definition of isoelectric point, IP: in the solution, carrier (molecular sieve) surface cation and anion are equal, and in electric neutrality, now the pH of solution becomes the isoelectric point, IP of this carrier (molecular sieve).When pH is more than isoelectric point, IP, carrier surface is electronegative；When pH is less than isoelectric point, IP, carrier surface positively charged.
Molecular sieve in the application includes aperture and sieves or synthesis of molecular sieve between the mesopore natural molecule of 2-50nm less than the micropore of 2nm, aperture.Micro porous molecular sieve such as includes ZSM-5, titanium-silicon molecular sieve TS-1, TS-2, A type, SAPO-34, modenite；Mesoporous molecular sieve such as includes Ti-HMS, Ti-3D mesopore molecular sieve, MCM-41, MCM-48, SBA-15.
Metal in the application can be the catalytic active component that each field is conventional, and in some embodiments, described metal includes but not limited to one or more the mixing in gold, platinum, palladium, silver, iridium, rhenium, ruthenium, nickel, molybdenum, cobalt, ferrum etc..
Metal precursor in the application is 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.
Regulating the pH reagent used in the application is NaOH or ammonia.
In one embodiment, the hole-blocking agent in the application includes but not limited to one or more kinds of mixing in organic amine template, saccharide, alcohols material or hydrone.
Described organic amine template includes but not limited to tetraethyl ammonium hydroxide, TPAOH and/or 4-propyl bromide.
Described glucide includes but not limited to one or more mixing of the saccharides such as glucose, sucrose, fructose, lactose.
Described alcohols material includes but not limited to ethanol, methanol, propanol, propylene glycol, glycerol, butanol etc..
The metal complex of the application small-medium size is sterically hindered minimum metal complex, and generally chloride more many complex are sterically hindered more big, and chloride number be hydrolyzed adjustment by changing pH.
Inventor in the application is through extensive and deep research, a kind of method being found that accurate modulation metal spatial deposition site over a molecular sieve, namely the difference of different molecular sieve framework metal isoelectric point, IP is utilized, in conjunction with the method that inertia hole-blocking agent fills micropore canals and modulation metal precursor size, it is possible to effectively modulation metal nanoparticle spatial deposition site over a molecular sieve.On this basis, the present invention is completed.
Specific embodiments:
On the one hand, the preparation method of the catalyst that a kind of modulation metal is distributed over a molecular sieve, specifically comprise the following steps that
(1) hole-blocking agent is pre-mixed with molecular sieve I, obtains duct has been filled with the molecular sieve II of hole-blocking agent molecule；
(2) by metal front liquid solution and molecular sieve II mix and blend, mixed solution I is obtained；
(3) pH value of mixed solution I is regulated less than or equal to the isoelectric point, IP of deposition position element on molecular sieve I, then aging, centrifugal, dry, obtain catalyst A.
In catalyst A, the duct of molecular sieve I is blocked by plug-hole agent molecule, and after metal front liquid solution mixes with molecular sieve II, metal species preferential can contact with molecular sieve in aperture and react so that aperture is blocked and Au species are difficult to entrance duct.Adjust solution pH value less than the isoelectric point, IP of certain element-specific in molecular sieve I, metal precursor then can Preferential adsorption near molecular sieve element-specific, namely metal nanoparticle is only deposited on molecular sieve outer surface specific site.
In metal active constituent load in the process of molecular sieve, as each deposition site in the molecular sieve of catalyst activity component carrier, there is specific isoelectric point, IP, by regulating the pH value in mixed solution, it is possible to metal active constituent to be deposited to the target location of molecular sieve.Such as, with gold chloride be presoma, HTS for carrier, gold element is loaded on the titanium position of HTS, it is necessary to regulate pH value of solution less than the isoelectric point, IP of titanium, and more than the isoelectric point, IP of silicon, namely pH=3-7 by active component gold deposition with on titanium position.If be intended to metal particles deposition to Si position, then need to regulate pH less than 3；If preventing metal particles deposition in certain position, then pH needs the isoelectric point, IP more than this position.
In some embodiments, in step (3), the molecular sieve mixing in metal front liquid solution and plug-hole road, the pH of the mixed solution I isoelectric point, IP less than molecular sieve desire deposition position backbone element and the isoelectric point, IP more than other backbone elements of molecular sieve, preferably, the pH of mixed solution I is intended to the difference of the isoelectric point, IP of deposition position backbone element less than 1 than molecular sieve, it is further preferred that the pH of mixed solution I is intended to the difference of the isoelectric point, IP of deposition position backbone element less than 0.1 than molecular sieve.
In some embodiments, in step (3), gold element precursor solution mixes with HTS, and mixed solution pH is less than the isoelectric point, IP of framework of molecular sieve titanium elements, and more than the isoelectric point, IP of element silicon, it is preferable that mixed solution pH controls at 3-7.
The consumption of the hole-blocking agent that blocking molecular sieve I adopts can determine its concrete consumption according to hole-blocking agent kind.
Such as, in some embodiments, in step (1), volume when addition hole-blocking agent hydrone or saccharide liquid is more than molecular sieve pore volume, it is preferable that add 1-1000 times that volume is pore volume of hole-blocking agent hydrone or saccharide；It is further preferred that add 10-1000 times that volume is pore volume of hole-blocking agent hydrone or saccharide；Most preferably, 100-1000 times that volume is pore volume of hole-blocking agent hydrone or saccharide is added.
In some embodiments, in step (1), hole-blocking agent hydrone or saccharide and molecular sieve I incorporation time are 10-500 minute；Preferably, incorporation time is 100-500 minute；It is further preferred that incorporation time is 300-500 minute；
If template, its consumption is in molecular sieve 0.1-10 times of silicon mole.
In some embodiments, in step (1), when hydrone and molecular sieve I mixing, mixing temperature is less than 100 DEG C.
In some embodiments, in step (1), when saccharide mixes with molecular sieve I, mixing temperature controls at fusing point 5-50 DEG C higher than saccharide and the tolerable temperature less than molecular sieve I skeleton.Preferably, mixing temperature controls at fusing point 5-25 DEG C higher than saccharide and the tolerable temperature less than molecular sieve I skeleton.It is further preferred that mixing temperature controls at fusing point 5-10 DEG C higher than saccharide and the tolerable temperature less than molecular sieve I skeleton.
In the present invention, step (3) aging, centrifugation, dry etc. adopt prior art to prepare the conventional equipment of catalyst, process conditions etc..
On the other hand, the preparation method of the catalyst that a kind of modulation metal is distributed over a molecular sieve, specifically comprise the following steps that
(i) regulate metal precursor solution I pH less than be intended to deposition position backbone element isoelectric point, IP, obtain metal complex solution II, wherein metal complex be smaller in size than the aperture equal to molecular sieve I；
(ii) by molecular sieve I dry more than 12h under vacuum；
(iii) by metal complex solution II and dried molecular sieve I mix and blend, maintain the pH of step (i) simultaneously, obtain mixed solution I II；
(iv) mixed solution I II is centrifugal, dry, prepared metal nanoparticle is only deposited on the catalyst B of molecular sieve inner surface specific site.
In preparing another embodiment, preferred dimension is less than the metal complex in molecular sieve I aperture, and adjust the pH value isoelectric point, IP less than the specific skeleton element position of molecular sieve I of metal complex solution, after metal front liquid solution mixes with molecular sieve I, due to capillarity and concentration difference effect, make small size and have the metal complex species that carrier has relatively strong interaction to be easier to suck in the middle of the duct of molecular sieve, simultaneously by the adjustment of pH, make metal particles deposition in molecular sieve pore passage inner surface specific site, can so that metal (such as Au) distribution of particles of more than 97% be inside molecular sieve in metal precursor solution catalyst B by the method.
For the isoelectric point, IP of molecular sieve I, different types of molecular sieve isoelectric point, IP is different.In some embodiments, in step (i), the element isoelectric point, IP that the pH value of adjustment mixed solution I is intended to deposition position than in molecular sieve I is little.
In some embodiments, pH needs the isoelectric point, IP according to framework of molecular sieve element to select, and namely pH needs less than the isoelectric point, IP of deposition site metal.
In some embodiments, in step (i), temperature 5-80 DEG C of metal precursor solution I, it is preferable that 5-50 DEG C, more preferably 5-20 DEG C.
Step (i) controls metal front liquid solution should control, at 5-80 DEG C, especially to control at 5-20 DEG C.Because under the high temperature conditions, metal complex easily be combined with each other formation polymerization state, and volume increases, and causes being difficult in more entrance duct.
In some embodiments, in step (iii), regulate precursor solution I and dried molecular sieve I incorporation time 1-25 hour；Preferred 8-15 hour.
In some embodiments, in step (iii), molecular sieve I does not contain any hole-blocking agent.
In the present invention, the centrifugation of step (iv), dry employing prior art prepare the conventional equipment of catalyst, process conditions etc..
It is an advantage of the current invention that:
For prior art, generally can realize being wrapped in the middle of the duct of molecular sieve, hole wall metal nanoparticle, it can be difficult to be only deposited on by metallic particles in molecular sieve or near outer surface special metal active sites.And the application realizes metal nanoparticle preferential deposition is intended to deposition site (such as Ti site or Si site) in the duct of molecular sieve more accurately, and metal nanoparticle is deposited on the outer surface of molecular sieve and is intended to deposition site (such as Ti site or Si site), it is achieved site, the space accuracy controlling of granule.
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention rather than restriction the scope of the present invention.The experimental technique of unreceipted actual conditions in the following example, generally conventionally condition or according to manufacturer it is proposed that condition.Unless otherwise indicated, otherwise all of percent, ratio, ratio or number be by weight.
The unit in percent weight in volume in the present invention is well-known to those skilled in the art, for instance refer to the weight of solute in the solution of 100 milliliters.
Unless otherwise defined, the same meaning that all specialties used in literary composition are familiar with one skilled in the art with scientific words.Additionally, any method similar or impartial to described content and material all can be applicable in the inventive method.The use that preferably implementation described in literary composition and material only present a demonstration.
Catalyst test method, for epoxidation of styrene reaction: operate at ambient pressure, is placed in round-bottomed flask by 0.3g catalyst with 20mmol styrene, 50mmol hydrogen peroxide and a certain amount of solvent, reaction carry out product analysis at 60 DEG C.
Embodiment 1
By Au nanoparticle deposition in molecular sieve outer surface specific T i site
Taking the 0.5g titanium-silicon molecular sieve TS-1 containing tetraethyl ammonium hydroxide and be placed in beaker, add 40g water and stir 10 minutes, the chlorauric acid solution being subsequently added 10mL0.1mol/L forms mixed solution I；Mixed solution I at room temperature being stirred 30 minutes and maintaining pH is 7, by centrifugal for the mixed solution obtained, washing, obtains Au nano-particle after drying and is only deposited at the catalyst near titanium-silicon molecular sieve TS-1 outer surface Ti position.
Titanium-silicon molecular sieve TS-1 and the Au/TS-1 catalyst prepared are carried out N2Physical absorption, as shown in table 1.The pure Micropore volume of carrier TS-1 is compared with the Micropore volume of Au/TS-1 and is not almost become, and all only small, it was shown that template plugs micropore canals, and Au nano-particle is only deposited on molecular sieve outer surface.Additionally, due to the isoelectric point, IP of Ti slightly larger than 7, the isoelectric point, IP of silicon substantially 2, when pH is 7, HTS surface Ti bit strip positive electricity, silicon bit strip negative electricity, so electronegative gold chloride presoma is attracted near Ti position.
On this catalyst, the conversion ratio of epoxidation of styrene is with access times relation as shown in Figure 1.
Embodiment 2
By Au nanoparticle deposition in molecular sieve outer surface specific T i site
Take the 0.5g titanium-silicon molecular sieve TS-1 contained in micropore without hole-blocking agent and be placed in beaker, at 60 DEG C, add 40g water stir 100 minutes, be subsequently added the chlorauric acid solution formation mixed solution I of 10mL0.1mol/L；Mixed solution I at room temperature being stirred 50 minutes and maintaining pH is 7, will obtain mixed solution and be centrifuged, and takes out washing after solid, obtains Au nano-particle after drying and be only deposited at the catalyst near titanium-silicon molecular sieve TS-1 outer surface Ti position.
N is carried out without the titanium-silicon molecular sieve TS-1 of hole-blocking agent and Au/TS-1 catalyst in micropore2Physical absorption, as shown in table 1.Although the pure Micropore volume of carrier TS-1 is compared all relatively big with the Micropore volume of Au/TS-1, but almost do not become, it was shown that Au nano-particle is also introduced into the duct of molecular sieve.Additionally, due to the isoelectric point, IP of Ti slightly larger than 7, the isoelectric point, IP of silicon substantially 2, when pH is 7, HTS surface Ti bit strip positive electricity, silicon bit strip negative electricity, so electronegative gold chloride presoma is attracted near Ti position.The Au/TS-1 catalyst using template blocking microporous in Au/TS-1 catalyst and embodiment 1 being carried out ICP-AES and XPS characterize, summarized results is as shown in table 2.Wherein ICP-AES can analyze whole caltalyst phase Au/Si mol ratio, and XPS analysis catalyst external surface Au/Si mol ratio, the two is almost consistent, and the numerical approximation of sample in the Au/Si mol ratio that in the present embodiment 2, XPS determines and embodiment 1, it was shown that Au nano-particle integrated distribution is in molecular sieve outer surface.
On this catalyst, the conversion ratio of epoxidation of styrene is with access times relation as shown in Figure 1.
Embodiment 3
By Au nanoparticle deposition in molecular sieve outer surface specific T i site
Take the 0.5g titanium-silicon molecular sieve TS-1 contained in micropore without hole-blocking agent and be placed in beaker, under 170 DEG C of conditions, add 20g glucose stir 120 minutes, be subsequently added the chlorauric acid solution formation mixed solution I of 10mL0.1mol/L；Mixed solution I at room temperature being stirred 60 minutes and maintaining pH is 7, will obtain mixed solution and be centrifuged, and takes out washing after solid, obtains Au nano-particle after drying and be only deposited at the catalyst near titanium-silicon molecular sieve TS-1 outer surface Ti position.
TS-1 catalyst after processing without the titanium-silicon molecular sieve TS-1 of hole-blocking agent and glucose in micropore is carried out N2Physical absorption, as shown in table 1.It is relatively big that the Micropore volume of pure carrier TS-1 compares gap with the Micropore volume of the TS-1 after glucose process, is mainly glucose molecule and plugs duct.Additionally, due to the isoelectric point, IP of Ti slightly larger than 7, the isoelectric point, IP of silicon substantially 2, when pH is 7, HTS surface Ti bit strip positive electricity, silicon bit strip negative electricity, so electronegative gold chloride presoma is attracted near Ti position.The Au/TS-1 catalyst using template blocking microporous in Au/TS-1 catalyst and embodiment 1 being carried out ICP-AES and XPS characterize, summarized results is as shown in table 2.Wherein ICP-AES can analyze whole caltalyst phase Au/Si mol ratio, and XPS analysis catalyst external surface Au/Si mol ratio, the two is almost consistent, and the numerical approximation of sample in the Au/Si mol ratio that in the present embodiment 2, XPS determines and embodiment 1, it was shown that Au nano-particle integrated distribution is in molecular sieve outer surface.On this catalyst, the conversion ratio of epoxidation of styrene relation in time is as shown in Figure 1.
On this catalyst, the conversion ratio of epoxidation of styrene is with access times relation as shown in Figure 1.
Embodiment 4
By Au nanoparticle deposition in molecular sieve inner surface specific T i site
The chlorauric acid solution taking 10mL0.1mol/L is placed in beaker, regulates pH and is 7 and maintains 30 minutes, obtain complex solution II, the aperture being smaller in size than molecular sieve TS-1 of complex under 28 DEG C of conditions；To carry out vacuum pumping 12 hours under room temperature without the titanium-silicon molecular sieve TS-1 of hole-blocking agent in micropore, and take stirring 500 minutes in the 0.5g above-mentioned solution of addition, form mixed solution, wherein, the volume of gold complex is less than molecular sieve pore passage volume；Mixed solution will be obtained be centrifuged, and wash after taking out solid, obtain Au nanoparticle deposition catalyst near titanium-silicon molecular sieve TS-1 inner surface Ti position after drying.
N is carried out without the titanium-silicon molecular sieve TS-1 of hole-blocking agent and the Au/TS-1 catalyst made in micropore2Physical absorption, as shown in table 1.Compared to the Micropore volume of pure carrier TS-1, the Micropore volume of Au/TS-1 substantially reduces, it was shown that Au nano-particle enters the duct of molecular sieve.Additionally, due to the isoelectric point, IP of Ti slightly larger than 7, the isoelectric point, IP of silicon substantially 2, when pH is 7, HTS surface Ti bit strip positive electricity, silicon bit strip negative electricity, so electronegative gold chloride presoma is attracted near Ti position.The Au/TS-1 catalyst using template blocking microporous in Au/TS-1 catalyst and embodiment 1 is carried out XPS sign, as shown in table 2.Result show Au/Si mol ratio that in the present embodiment, XPS obtains much smaller than Au particulate load in the catalyst of outer surface, illustrate that Au nano-particle integrated distribution is in molecular sieve inner surface.On this catalyst, the conversion ratio of epoxidation of styrene relation in time is as shown in Figure 4.
Embodiment 5
By Au nanoparticle deposition in molecular sieve inner surface specific T i site
The chlorauric acid solution taking 10mL0.1mol/L is placed in beaker, regulates pH and is 7 and maintains 30 minutes, obtain complex solution II under 40 DEG C of conditions；Adding 0.5g and contain the interior titanium-silicon molecular sieve TS-1 without hole-blocking agent of micropore, stir 60 minutes, form mixed solution, wherein, the volume of gold complex is less than molecular sieve pore passage volume；Mixed solution will be obtained be centrifuged, and wash after taking out solid, obtain Au nanoparticle deposition catalyst near titanium-silicon molecular sieve TS-1 inner surface Ti position after drying.
It is shown that under proper temperature and mixing time, Au granule can be distributed in specific site in molecular sieve pore passage.On this catalyst, the conversion ratio of epoxidation of styrene relation in time is as shown in Figure 4.
Embodiment 6
By Au nanoparticle deposition in molecular sieve inner surface specific T i site
The chlorauric acid solution taking 10mL0.1mol/L is placed in beaker, regulates pH and is 7 and maintains 30 minutes, obtain complex solution II under 5 DEG C of conditions；Adding 0.5g and contain the interior titanium-silicon molecular sieve TS-1 without hole-blocking agent of micropore, stir 800 minutes, form mixed solution at 70 DEG C, wherein, the volume of gold complex is less than molecular sieve pore passage volume；Mixed solution will be obtained be centrifuged, and wash after taking out solid, obtain Au nanoparticle deposition catalyst near titanium-silicon molecular sieve TS-1 inner surface Ti position after drying.
It is shown that under proper temperature and mixing time, Au granule can be distributed in specific site in molecular sieve pore passage.On this catalyst, the conversion ratio of epoxidation of styrene relation in time is as shown in Figure 4.
Comparative example 1
Common Au/TS-1 catalyst preparing
Take the 0.5g titanium-silicon molecular sieve TS-1 contained in micropore without hole-blocking agent and be placed in beaker, add the chlorauric acid solution formation mixed solution I of 50mL0.1mol/L；Mixed solution I at room temperature being stirred 30 minutes and maintaining pH is 7, will obtain mixed solution and be centrifuged, and washs, obtains Au nanoparticle deposition catalyst in titanium-silicon molecular sieve TS-1 and near outer surface Ti position after drying after taking out solid.
It is shown that common Au/TS-1 catalyst, it is inside and outside that Au granule is randomly distributed in molecular sieve pore passage.On this catalyst, the conversion ratio of epoxidation of styrene is with access times relation as shown in Figure 2.
Comparative example 2
Au/TS-1 catalyst preparing
Take the 0.5g titanium-silicon molecular sieve TS-1 contained in micropore without hole-blocking agent and be placed in beaker, add 40g water and stir 5 minutes, be subsequently added the chlorauric acid solution formation mixed solution I of 10mL0.1mol/L；Mixed solution I at room temperature being stirred 30 minutes and maintaining pH is 7.5, will obtain mixed solution and be centrifuged, and washs, obtains Au nanoparticle deposition catalyst in titanium-silicon molecular sieve TS-1 and near outer surface Ti position after drying after taking out solid.
It is shown that when hydrone time of contacting with molecular sieve is shorter, it is impossible to play hole-blocking agent effect, and make Au granule cannot only be deposited on molecular sieve outer surface.On this catalyst, the conversion ratio of epoxidation of styrene is with access times relation as shown in Figure 2.
Comparative example 3
Au/TS-1 catalyst preparing
Take the 0.5g titanium-silicon molecular sieve TS-1 contained in micropore without hole-blocking agent and be placed in beaker, add 0.2g water and stir 100 minutes, be subsequently added the gold chloride of 10mL0.1mol/L and the mixed solution formation solution I of 40g water；Mixed solution I at room temperature being stirred 30 minutes and maintaining pH is 7.5, will obtain mixed solution and be centrifuged, and takes out washing after solid, obtains Au nano-particle after drying and be only deposited at the catalyst near titanium-silicon molecular sieve TS-1 outer surface Ti position.
It is shown that when the hydrone that contacts with molecular sieve is less, it is impossible to play hole-blocking agent effect, and make Au granule cannot only be deposited on molecular sieve outer surface.On this catalyst, the conversion ratio of epoxidation of styrene is with access times relation as shown in Figure 2.
Comparative example 4
Au/TS-1 catalyst preparing
Take the 0.5g titanium-silicon molecular sieve TS-1 contained in micropore without hole-blocking agent and be placed in beaker, under 600 DEG C of conditions, add 20g glucose stir 120 minutes, be subsequently added the chlorauric acid solution formation mixed solution I of 10mL0.1mol/L；Mixed solution I at room temperature being stirred 30 minutes and maintaining pH is 7.5, will obtain mixed solution and be centrifuged, and takes out washing after solid, obtains Au nano-particle after drying and be only deposited at the catalyst near titanium-silicon molecular sieve TS-1 outer surface Ti position.
It is shown that when saccharide is too high with molecular sieve Contact Temperature, high temperature makes molecular sieve crystallinity reduce, its HRTEM schemes as shown in Figure 3.On this catalyst, the conversion ratio of epoxidation of styrene is with access times relation as shown in Figure 2.
Comparative example 5
By Au nanoparticle deposition in molecular sieve inner surface specific T i site
The chlorauric acid solution taking 10mL0.1mol/L is placed in beaker, regulates pH and is 2 and maintains 30 minutes, obtain complex solution II under 28 DEG C of conditions；Add 0.5g and contain the interior titanium-silicon molecular sieve TS-1 without hole-blocking agent of micropore, stir 50 minutes, form mixed solution；Mixed solution will be obtained be centrifuged, and wash after taking out solid, obtain Au/TS-1 catalyst after drying.
The result of contrast illustrates that when pH is relatively low, Au granule cannot be deposited on molecular sieve Ti location proximate, and only deposits to Si location proximate.On this catalyst, the conversion ratio of epoxidation of styrene relation in time is as shown in Figure 4.
Comparative example 6
By Au nanoparticle deposition in molecular sieve inner surface specific T i site
The chlorauric acid solution taking 10mL0.1mol/L is placed in beaker, regulates pH and is 7 and maintains 30 minutes, obtain complex solution II under 90 DEG C of conditions；Add 0.5g and contain the interior titanium-silicon molecular sieve TS-1 without hole-blocking agent of micropore, stir 50 minutes, form mixed solution；Mixed solution will be obtained be centrifuged, and wash after taking out solid, obtain Au/TS-1 catalyst after drying.
The result of contrast illustrates when whipping temp is too high, and substantially reuniting occurs in Au granule so that entering in duct less, its pore volume changes in Table 1, and its Au granule HRTEM schemes as shown in Figure 5.On this catalyst, the conversion ratio of epoxidation of styrene relation in time is as shown in Figure 4.
Comparative example 7
By Au nanoparticle deposition in molecular sieve inner surface specific T i site
The chlorauric acid solution taking 10mL0.1mol/L is placed in beaker, regulates pH and is 7 and maintains 30 minutes, obtain complex solution II under 30 DEG C of conditions；Add 0.5g and contain the interior titanium-silicon molecular sieve TS-1 without hole-blocking agent of micropore, stir 30 hours, form mixed solution；Mixed solution will be obtained be centrifuged, and wash after taking out solid, obtain Au/TS-1 catalyst after drying.
The result of contrast illustrates that when mixing time is long, Au granule migrates out on the contrary from duct, and its pore volume changes in Table 1.On this catalyst, the conversion ratio of epoxidation of styrene relation in time is as shown in Figure 4.
The different sample well structural property of table 1
| Sample | Micropore volume (cm3/g) | Specific surface area (cm2/g) |
| TS-1 without hole-blocking agent | 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 |
| Hole-blocking agent TS-1 is made containing template | 0.03 | 40 |
| Hole-blocking agent Au/TS-1 (embodiment 1) is made 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 phase of table 2 and surface A u/Si molar ratio
aRecorded by ICP-AES；
bRecorded by XPS.
Claims (10)
1. a preparation method for the catalyst that modulation metal is distributed over a molecular sieve, comprises the steps:
(1) hole-blocking agent is pre-mixed with molecular sieve I, obtains duct has been filled with the molecular sieve II of hole-blocking agent molecule；
Preferably, described hole-blocking agent includes one or more kinds of mixing in organic amine template, saccharide, alcohols material or hydrone；
It is furthermore preferred that described organic amine template includes tetraethyl ammonium hydroxide, TPAOH and/or 4-propyl bromide；
It is furthermore preferred that described glucide includes one or more mixing of the saccharides such as glucose, sucrose, fructose, lactose；
It is furthermore preferred that described alcohols material includes one or more mixing of ethanol, methanol, propanol, propylene glycol, glycerol, butanol；
(2) by metal front liquid solution and molecular sieve II mix and blend, mixed solution I is obtained, it is preferable that described metal includes one or more the mixing in gold, platinum, palladium, silver, iridium, rhenium, ruthenium, nickel, molybdenum, cobalt, ferrum etc.；
(3) pH value of mixed solution I is regulated, centrifugal after aging, dry, obtain catalyst A；Preferably, the pH value regulating mixed solution I is not more than the isoelectric point, IP of molecular sieve I metallic element, then aging, centrifugal, dry, obtains catalyst A.
2. preparation method according to claim 1, it is characterized in that, in step (3), the molecular sieve mixing in metal front liquid solution and plug-hole road, the pH of the mixed solution I isoelectric point, IP less than molecular sieve desire deposition position backbone element and the isoelectric point, IP more than other backbone elements of molecular sieve；
Preferably, the pH of mixed solution I is intended to the difference of the isoelectric point, IP of deposition position backbone element less than 1 than molecular sieve；
It is further preferred that the pH of mixed solution I is intended to the difference of the isoelectric point, IP of deposition position backbone element less than 0.1 than molecular sieve.
It is further preferred that in step (3), gold element precursor solution mixes with HTS, mixed solution pH is less than the isoelectric point, IP of framework of molecular sieve titanium elements, and more than the isoelectric point, IP of element silicon, it is most preferred that, the mixed solution pH that gold element precursor solution mixes with HTS controls at 3-7.
3. preparation method according to claim 1 and 2, it is characterised in that in step (1), adds the volume of hole-blocking agent hydrone or saccharide more than molecular sieve pore volume；Preferably, 1-1000 times that volume is pore volume of hole-blocking agent hydrone or saccharide is added；It is further preferred that add 10-1000 times that volume is pore volume of hole-blocking agent hydrone or saccharide；Most preferably, 100-1000 times that volume is pore volume of hole-blocking agent hydrone or saccharide is added；
Preferably, the consumption of template is in molecular sieve 0.1-10 times of silicon mole.
4. the preparation method according to any one of claim 1-3, it is characterised in that in step (1), hole-blocking agent hydrone or saccharide and molecular sieve I incorporation time are 10-500 minute；Preferably, incorporation time is 100-500 minute；It is further preferred that incorporation time is 300-500 minute.
5., when the preparation method according to any one of claim 1-3, it is characterised in that in step (1), hydrone and molecular sieve I mixing, mixing temperature is less than 100 DEG C；
In step (1), when saccharide mixes with molecular sieve I, mixing temperature controls at fusing point 5-50 DEG C higher than saccharide and the tolerable temperature less than molecular sieve I skeleton；Preferably, mixing temperature controls at fusing point 5-25 DEG C higher than saccharide and the tolerable temperature less than molecular sieve I skeleton；It is further preferred that mixing temperature controls at fusing point 5-10 DEG C higher than saccharide and the tolerable temperature less than molecular sieve I skeleton.
6. a preparation method for the catalyst that modulation metal is distributed over a molecular sieve, comprises the steps:
(i) regulate metal precursor solution I pH less than be intended to deposition position backbone element isoelectric point, IP, obtain metal complex solution II, wherein metal complex be smaller in size than the aperture equal to molecular sieve I；
Preferably, metal precursor includes the chloride of metal, acetylacetonate, acetic acid compound or nitrate compound；
It is further preferred that metal precursor include as gold chloride, acetic acid gold, chloroplatinic acid, monoxone, perrhenic acid, nickel nitrate one or more mixing；
(ii) molecular sieve I is dried more than 12 hours under vacuum；
(iii) by metal complex solution II and molecular sieve I mix and blend, maintaining pH in step (i) simultaneously, obtain mixed solution I II, wherein, metal complex volume is less than molecular sieve I pore volume；
(iv) mixed solution I II is centrifugal, dry, prepare catalyst B.
7. preparation method according to claim 6, it is characterised in that in step (i), temperature 5-80 DEG C of metal precursor solution I, it is preferable that 5-50 DEG C, more preferably 5-20 DEG C.
8. the preparation method according to claim 6 or 7, it is characterised in that in step (iii), regulates precursor solution I and molecular sieve I incorporation time 1-25 hour；Preferred 8-15 hour.
9. the preparation method according to claim 6 or 8, it is characterised in that the pH of metal precursor solution I is intended to the difference of the isoelectric point, IP of deposition position backbone element less than 1 than molecular sieve I；
Preferably, the pH of mixed solution I is intended to the difference of the isoelectric point, IP of deposition position backbone element less than 0.1 than molecular sieve.
10. the preparation method according to claim 1 or 6, it is characterized in that, described molecular sieve includes aperture and sieves or synthesis of molecular sieve between the mesopore natural molecule of 2-50nm less than the micropore of 2nm, aperture, described micro porous molecular sieve includes ZSM-5, titanium-silicon molecular sieve TS-1, TS-2, A type, SAPO-34, modenite；Described mesoporous molecular sieve includes Ti-HMS, Ti-3D mesopore molecular sieve, MCM-41, MCM-48, SBA-15；
Described metal includes one or more the mixing in gold, platinum, palladium, silver, iridium, rhenium, ruthenium, nickel, ferrum etc..
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