CN109261201A - A kind of hud typed hydrogenation catalyst and preparation method thereof - Google Patents
A kind of hud typed hydrogenation catalyst and preparation method thereof Download PDFInfo
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
- C07C5/11—Partial hydrogenation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/54—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
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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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/14—All rings being cycloaliphatic
- C07C2602/26—All rings being cycloaliphatic the ring system containing ten carbon atoms
- C07C2602/28—Hydrogenated naphthalenes
Abstract
The invention discloses a kind of hud typed hydrogenation catalysts and preparation method thereof, the stratum nucleare structure of the hud typed hydrogenation catalyst is LTA type molecular sieve, and noble-metal-cluster is packaged in its hole cage, the noble-metal-cluster is introduced into noble metal precursor body in the synthetic system of LTA type molecular sieve, roasting reduction after Situ Hydrothermal crystallization, it is formed in the hole cage of LTA type molecular sieve, its shell structurre is ZSM-5 zeolite molecular sieve, it is the LTA type molecular sieve for being packaged with noble-metal-cluster described in addition in the gel rubber system of synthetic ZSM-5 zeolite molecular sieve, steam phase conversion reaction is carried out after drying, ZSM-5 zeolite molecular sieve shell is constructed in the LTA type molecular sieve surface for being packaged with noble-metal-cluster.Hud typed hydrogenation catalyst prepared by the present invention is applied in condensed-nuclei aromatics hydrogenation reaction, has high catalytic activity and good sulfur resistance.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst, especially a kind of catalyst for condensed-nuclei aromatics hydrogenation reaction, and
The preparation method of the catalyst.
Background technique
Crude oil heaviness and in poor quality degree are aggravated, and condensed-nuclei aromatics content is higher and higher in the diesel oil of catalytic cracking preparation,
It is not able to satisfy the requirement of environmental protection and automobile industry to indexs such as arene content in diesel oil and Cetane number.Therefore, to catalytic cracking
The quality of diesel oil is improved and is upgraded, and is the important topic that our times various countries PETROLEUM PROCESSING is faced.
Condensed-nuclei aromatics deep hydrogenation can not only reduce arene content, can also improve the Cetane number of diesel oil, be counterweight
Oil and poor quality FCC cracking gained diesel oil carry out an important channel of product up-gradation.
Ni-W, Ni-Mo, Co-Mo etc. of sulphided state are carried on manufactured catalyst on alumina catalyst support, are widely used
In the hydrogenation reaction of condensed-nuclei aromatics.But the reactivity of this kind of catalyst is lower, severe reaction conditions, high temperature, high pressure,
It is just carried out under low-speed.
Consider from thermodynamics, condensed-nuclei aromatics is hydrogenated to exothermic reaction, and favors low temperature is in the progress of hydrogenation reaction.Your gold
Metal catalyst can show high catalytic activity under cryogenic, but it is to sulfur-containing compound quite sensitive, need pair
Feedstock oil carry out deep desulfuration, thus considerably increase be handling and processed into this [A. Stanislaus, B.H.Cooper,Catal. Rev., 1994, 36, 75-123]。
Using zeolite molecular sieve carrier-supported precious metal as catalyst, not only deep hydrogenation can be carried out to condensed-nuclei aromatics,
Also there is certain sulfur resistance simultaneously.The sulfur resistive mechanism of this kind of catalyst mainly includes two classes: 1), the part of metallic electricity
Son can be transferred to the acidic site of zeolite molecular sieve carrier, reduce the electron density of metallic, to reduce and H2S's
Binding ability [B.H. Cooper, B.B.L. Donnis,Appl. Catal. A Gen, 1996, 137, 203-223]；
2), after metal active position is partially poisoned, the molecular sieve carrier acid centre of adjacent metal particle can use migration from gold
The hydrogen atom for belonging to particle makes it still keep preferable catalytic activity [L. J. Simon, J.G. van under suitable acid strength
Ommen, A. Jentys, J.A. Lercher, J. Phys. Chem. B, 2000, 104, 11644-11649；L.J.
Simon, J.G. van Ommen, A. Jentys, J.A. Lercher, J. Catal., 2001, 201, 60-69]。
However, noble-metal-supported only not can avoid noble metal component and sulfide still on zeolite molecular sieve carrier
Direct contact, may also suffer certain poison.
Noble-metal-cluster is packaged in the cage of zeolite molecular sieve, your gold is the restriction effect of through hole cage can completely avoid
Belong to cluster directly to contact with sulfide, and inhibits its sintering in high-temperature process and reaction to assemble, while also using Hydrogen spillover
Effect is carried out to the molecule being located at outside cage plus hydrogen, is the most effectual way for preparing sulfur resistive type noble metal hydrogenation catalyst.
In view of organic sulfur compound can be changed into H under hydrogenation conditions2S, thoroughly to prevent sulfide to your gold
Belong to poisoning for component, the aperture of encapsulation noble-metal-cluster carrier should be less than H2The molecular dimension 0.36nm of S.According to this standard, often
With only sodalite (SOD) can satisfy this condition in zeolite, port size is 0.28nm × 0.28nm.But due to square sodium
The sial of stone is relatively low, and acid weaker, external surface area is smaller, cannot provide acidic site, the sodalite material of package metals cluster
It is not appropriate for the catalyst directly as hydrogenation reaction.
To reach the port size of other common zeolites to H2The restriction effect that S molecule enters, then need to its hole
Mouth is modified.Im etc. [J. Im, H. Shin, H. Jang, H. Kim, M. Choi,Nat Commun, 2014,
5,3370] it reports, the port size that LTA type molecular sieve is reduced in processing can be exchanged by ammonium, and the degree of ammonium exchange is different,
The size in aperture can be regulated and controled.The ammonium exchange that suitable degree is carried out to LTA type molecular sieve, can not only limit H2S points
Son enters, and does not influence H2Diffusion, can use Hydrogen spillover effect and the molecule being located at outside cage carried out plus hydrogen.
Hydrogen spillover is to provide migration path by surface hydroxyl for reactive hydrogen, is made outside active hydrogen migration to cage to aromatic hydrocarbon molecule
Add a kind of phenomenon of hydrogen.The concentration of surface hydroxyl groups of LTA type molecular sieve is low, even if being exchanged for H-type molecular sieve, concentration of surface hydroxyl groups
Also it is limited, adjustable extent is small, causes its catalytic activity lower.
Lee etc. [S. Lee, K. Lee, J. Im, H. Kim, M. Choi, J. Catal., 2015, 325,
26-34] the acid materials physical mixeds such as LTA type molecular sieve and amorphous silicon aluminium material or the HZSM-5 of noble metal, LTA will be encapsulated
The reactive hydrogen generated in type molecular sieve cage via LTA type molecular sieve surface migrate on the Lewis acid position of acid material with react
Object reacts, and compared with the LTA type molecular sieve for only encapsulating noble metal, catalytic activity has obtained certain raising.
The transmitting distance of active hydrogen migration to acid carrier is an important factor for influencing Hydrogen spillover effect.Your gold will be only encapsulated
The LTA type molecular sieve and acid material of category carry out simple physical mixed, transmitting distance tool of the reactive hydrogen on acid carrier
There is certain limitation.
Acid zeolite shell is constructed in LTA type molecular sieve surface, can effectively shorten the transmitting distance of Hydrogen spillover.However,
No matter certain compatibility is all lacked from structure or chemical composition between LTA type molecular sieve and common acid zeolite, meanwhile,
In conventional hydrothermal synthetic system, LTA type molecular sieve easily occurs to turn brilliant formation P type zeolite.
Therefore, one kind antitoxinization is developed, the hud typed hydrogenation catalyst of high activity is very necessary.
Summary of the invention
The object of the present invention is to provide a kind of hud typed hydrogenation catalysts with high catalytic activity and good sulfur resistance
Agent.There is high catalytic activity in condensed-nuclei aromatics hydrogenation reaction, also there is good sulfur resistance.
The preparation method of the hud typed hydrogenation catalyst is provided, is another goal of the invention of the invention.
Hud typed hydrogenation catalyst of the present invention has core-shell structure, and stratum nucleare structure is LTA type molecular sieve, and
Noble-metal-cluster is packaged in the hole cage of the LTA type molecular sieve, the noble-metal-cluster is that noble metal precursor body is introduced LTA type point
In the synthetic system of son sieve, roasting reduction after Situ Hydrothermal crystallization is formed, shell in the hole cage of LTA type molecular sieve
Structure is ZSM-5 zeolite molecular sieve, is to be packaged with noble metal described in addition in the gel rubber system of synthetic ZSM-5 zeolite molecular sieve
The LTA type molecular sieve of cluster carries out steam phase conversion reaction after dry, in the LTA type molecular sieve table for being packaged with noble-metal-cluster
ZSM-5 zeolite molecular sieve shell is constructed in face.
In hud typed hydrogenation catalyst of the present invention, it is preferable that the noble-metal-cluster is in hud typed hydrogenation catalyst
Encapsulation amount be 0.02~2.6wt%.
It is highly preferred that the encapsulation amount of the noble-metal-cluster is 0.1~1.2wt% in the hud typed hydrogenation catalyst.
In turn, further, in the hud typed hydrogenation catalyst, the stratum nucleare LTA type molecular sieve and shell ZSM-5
The mass ratio of zeolite molecular sieve is 1: 0.2~4.
In hud typed hydrogenation catalyst of the present invention, the noble metal is any one in Pt, Pd, Ir, Ru or Rh
Kind.
Hud typed hydrogenation catalyst of the present invention not only has high catalytic activity in condensed-nuclei aromatics hydrogenation reaction,
Also there is good sulfur resistance.
The present invention also provides the preparation methods of the hud typed hydrogenation catalyst, comprising:
Using silica, sodium metaaluminate, noble metal precursor body and sodium hydroxide as raw material, it is brilliant that Situ Hydrothermal is carried out in aqueous solution
Change reaction, roasting reduction prepares the LTA type molecular sieve for being packaged with noble-metal-cluster；
Using silicon source, tetrapropylammonium hydroxide and sodium metaaluminate as raw material, synthetic ZSM-5 zeolite molecular sieve is formed in aqueous solution
Sol system；
The synthetic ZSM-5 zeolite molecular sieve is added in the LTA type molecular sieve for being packaged with noble-metal-cluster or its dispersion liquid
Sol system, drying form dry glue；
Steam phase conversion reaction is carried out to the dry glue, in the LTA type molecular sieve surface synthesis for being packaged with noble-metal-cluster
ZSM-5 zeolite molecular sieve；
Thus the hud typed hydrogenation catalyst is prepared.
Synthesis of the present invention is packaged in the Situ Hydrothermal crystallization of LTA type molecular sieve of noble-metal-cluster, various originals
The dosage molar ratio of material meets Na2O∶Al2O3∶SiO2∶H2O=2~8: 1: 0.5~4: 80~160.
The Situ Hydrothermal crystallization preferably at 60~100 DEG C reaction 8~for 24 hours.
In turn, in the sol system of synthetic ZSM-5 zeolite molecular sieve of the present invention, the dosage molar ratio of various raw materials is full
Sufficient Na2O∶Al2O3∶SiO2: tetrapropylammonium hydroxide: H2O=1.4~10: 1: 20~100: 20~80: 850~3100.
Wherein, the silicon source is one of ethyl orthosilicate, silica solution, fumed silica.
Steam phase conversion reaction of the present invention is crystallization 1~8 day at 120~180 DEG C.It is highly preferred that be 140~
Crystallization 2~5 days at 180 DEG C.
Further, in the steam phase conversion reaction, the dosage solid-to-liquid ratio of the dry glue and distilled water is 1: 5~50
(g/mL)。
In the preparation method of hud typed hydrogenation catalyst of the present invention, the dispersion liquid of the LTA type molecular sieve is by institute
It states and is packaged with the LTA molecular sieve of noble-metal-cluster and is dispersed in ethyl alcohol and isometric mixed liquor of deionized water.
Wherein, the roasting reduction of the noble metal precursor body is 10% H at 300~500 DEG C21 is restored in/Ar atmosphere
~5h.
Specifically, the noble metal precursor body is any one in the complex salt of precious metals pt, Pd, Ir, Ru or Rh.
The noble metal precursor body can be Pt (NH3)4Cl2, [Pd (NH3)4](NO3)2, [Pd (NH2CH2CH2NH2)2]
Cl2, [Rh (NH3)5Cl]Cl2, [Rh (NH2CH2CH2NH2)3]Cl3, [Ru (NH3)6]Cl3, [Ir (NH3)5Cl]Cl2。
For noble metal hydrogenation catalyst, guarantee that its metal position is not poisoned and still keeps higher catalytic activity
It is critical issue.In the preparation method of condensed-nuclei aromatics hydrogenation catalyst of the present invention, noble-metal-cluster is packaged in LTA type molecular sieve
In the cage of hole, its aperture is reduced in such a way that ammonium exchanges, is limited using aperture and sulfide is prevented to enter in its cage, made packaged
Noble-metal-cluster is protected, and there is high resistance sulfide to poison performance.The noble-metal-cluster being packaged in LTA type molecular sieve pores cage
Although cannot directly contact with reactant, the Hydrogen spillover effect between packaged noble-metal-cluster and shell acid zeolite can use
It answers, the condensed-nuclei aromatics molecule being located at outside the cage of hole is carried out to add hydrogen.
In turn, it is packaged with after the LTA type molecular sieve of noble-metal-cluster exchanges calcination process by ammonium, can not only reduce its hole
Mouthful sulfide is prevented to enter, and increases its density of surface hydroxyl, for Hydrogen spillover carry out provide more migration paths.
Meanwhile the present invention constructs acid zeolite shell in the LTA type molecular sieve surface for being packaged with noble-metal-cluster, shortens work
Migration distance of the property hydrogen on acid carrier, enhances Hydrogen spillover effect, compared to the LTA type molecular sieve for being packaged with noble-metal-cluster
The catalyst of preparation is simply mixed with acid material, the hud typed hydrogenation catalyst of the method for the present invention preparation can effectively improve thick
The hydrogenation activity of cycloaromatics.
The hud typed hydrogenation catalyst prepared in the process of the present invention effectively ties the shape selectivity of molecular sieve and Hydrogen spillover effect
Altogether, packaged metal cluster is protected using interception of the LTA type molecular sieve to sulfide, have antitoxinization,
The characteristic of resistance to sintering, while acid zeolite shell is constructed in LTA type molecular sieve surface to shorten reactive hydrogen migration path, it enhances
Hydrogen spillover effect shows excellent catalytic performance in the hydrogenation reaction of condensed-nuclei aromatics, deep hydrogenation product in reaction product
Selectivity dramatically increase.
Detailed description of the invention
Fig. 1 is the XRD diagram of the hud typed hydrogenation catalyst of Pt@LTA@ZSM-5 prepared by embodiment 1.
Fig. 2 is the SEM figure of the hud typed hydrogenation catalyst of Pt@LTA@ZSM-5 prepared by embodiment 1.
Specific embodiment
Following embodiments are only the preferred technical solution of the present invention, are not used to carry out any restrictions to the present invention.For
For those skilled in the art, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made
Any modification, equivalent substitution, improvement and etc., should all be included in the protection scope of the present invention.
Embodiment 1.
30.3mmol sodium metaaluminate, 24.6mmol sodium hydroxide are taken, 11mmol fumed silica sequentially adds 19.8mL
In deionized water, 3h is stirred at 60 DEG C, adds 0.24mmol Pt (NH3)4Cl2, continue to stir 1h.It is then charged into poly- four
In the stainless steel cauldron of vinyl fluoride liner, 100 DEG C of constant temperature Dynamic Hydrothermal crystallizations are for 24 hours.By obtained solid product wash to
Neutrality, dry, first 350 DEG C of roasting 2h in air atmosphere, through 10% H at 350 DEG C2/ Ar reductase 12 h, is prepared encapsulation
There is the Pt@LTA sample of Pt metal cluster.
The Pt@LTA sample of the above-mentioned preparation of 2g is taken, is added in 10mL ethyl alcohol and the mixed liquor (1: 1) of deionized water, ultrasonic 1h
After obtain dispersion liquid A.
Take 2.98mmol sodium metaaluminate, 1.22mmol sodium hydroxide, the 25wt% water with 33.6mmol tetrapropylammonium hydroxide
Solution is added in 32mL deionized water together and stirs to clarify, and adds 55.4mmol ethyl orthosilicate, stirs 12h at room temperature,
Obtain sol B.
Dispersion liquid A is slowly added dropwise in sol B, 50 DEG C of stirred in water bath for 24 hours, are dried to obtain dry glue in 100 DEG C of baking ovens.
1.5g dry glue is taken, is placed on the bracket of polytetrafluoroethyllining lining, bottom is packed into 30mL deionized water, by polytetrafluoroethyl-ne
Alkene liner is transferred in stainless steel cauldron, 140 DEG C steam phase conversion reaction 3 days, obtained solid product wash drying, be prepared into
To hud typed hydrogenation catalyst Pt@LTA@ZSM-5, wherein the encapsulation amount of Pt metal cluster is 0.65wt%.
Fig. 1 gives prepared Pt@LTA and Pt@LTA@ZSM-5 sample and LTA type molecular sieve and ZSM-5 zeolite molecule
The XRD diagram of sieve.It can be seen from the figure that Pt@LTA shows the characteristic diffraction peak of LTA type molecular sieve, there is not Pt particle and spread out
Peak is penetrated, illustrates that Pt particle is uniformly distributed in the skeleton of LTA type molecular sieve, and do not destroy skeleton structure.Pt@LTA@ZSM-5
It shows two kinds of characteristic diffraction peaks of LTA type molecular sieve and ZSM-5 zeolite molecular sieve, shows to contain LTA type molecule in sample simultaneously
Sieve and two kinds of crystalline materials of ZSM-5 zeolite molecular sieve.
Fig. 2 gives the SEM figure of prepared sample, wherein a) is Pt@LTA, b) it is Pt@LTA@ZSM-5.It can be with from figure
Find out, Pt@LTA is bulk morphologies and shows smooth, and for Pt@LTA@ZSM-5, then can clearly be found out in Pt@LTA table
It looks unfamiliar and grows one layer of ZSM-5 zeolite sieve particle, be indicated above and successfully constructed ZSM-5 zeolite molecular sieve on the surface Pt@LTA
Shell.
Embodiment 2.
30.3mmol sodium metaaluminate, 101.2mmol sodium hydroxide are taken, 22mmol fumed silica sequentially adds
In 21.5mL deionized water, 3h is stirred at 60 DEG C, and 0.12mmol [Pd (NH is added2CH2CH2NH2)2]Cl2, continue to stir 1h.So
It is fitted into the stainless steel cauldron with polytetrafluoroethyllining lining afterwards, 100 DEG C of constant temperature Dynamic Hydrothermal crystallization 12h.By gained
Solid product is washed to neutrality, dry, first 350 DEG C of roasting 2h in air atmosphere, through 10% H at 300 DEG C2/ Ar reduction
The Pd@LTA sample for being packaged with Pd metal cluster is prepared in 3h.
The Pd@LTA sample of the above-mentioned preparation of 1.5g is taken, is added in 10mL ethyl alcohol and the mixed liquor (1: 1) of deionized water, ultrasound
Dispersion liquid A is obtained after 1h.
Take 2.98mmol sodium metaaluminate, 2.21mmol sodium hydroxide, the 25wt% water with 50.4mmol tetrapropylammonium hydroxide
Solution is added in 21mL deionized water together and stirs to clarify, and adds 72.6mmol ethyl orthosilicate, stirs 12h at room temperature,
Obtain sol B.
Dispersion liquid A is slowly added dropwise in sol B, 50 DEG C of stirred in water bath for 24 hours, are dried to obtain dry glue in 100 DEG C of baking ovens.
2g dry glue is taken, is placed on the bracket of polytetrafluoroethyllining lining, bottom is packed into 30mL deionized water, by polytetrafluoroethylene (PTFE)
Liner is transferred in stainless steel cauldron, 140 DEG C steam phase conversion reaction 2 days, obtained solid product wash drying, be prepared
Hud typed hydrogenation catalyst Pd@LTA@ZSM-5, wherein Pd metal cluster encapsulation amount is 0.3wt%.
Embodiment 3.
30.3mmol sodium metaaluminate, 63.4mmol sodium hydroxide are taken, 18.4mmol fumed silica sequentially adds
In 22.8mL deionized water, 3h is stirred at 60 DEG C, and 0.12mmol [Ir (NH is added3)5Cl]Cl2, continue to stir 1h.It is then charged into
In stainless steel cauldron with polytetrafluoroethyllining lining, 80 DEG C of constant temperature Dynamic Hydrothermal crystallizations are for 24 hours.By obtained solid product
It washs to neutrality, dry, first 350 DEG C of roasting 2h in air atmosphere, through 10% H at 370 DEG C2/ Ar reductase 12 h, is prepared into
To the Ir@LTA sample for being packaged with Ir nano-cluster.
The Ir@LTA sample of the above-mentioned preparation of 2.3g is taken, is added in 10mL ethyl alcohol and the mixed liquor (1: 1) of deionized water, ultrasound
Dispersion liquid A is obtained after 1h.
Take 2.98mmol sodium metaaluminate, 2.9mmol sodium hydroxide, the 25wt% water with 60.1mmol tetrapropylammonium hydroxide
Solution is added in 44.3mL deionized water together and stirs to clarify, and adds 66.8mmol ethyl orthosilicate, stirs at room temperature
12h obtains sol B.
Dispersion liquid A is slowly added dropwise in sol B, 50 DEG C of stirred in water bath for 24 hours, are dried to obtain dry glue in 100 DEG C of baking ovens.
1g dry glue is taken, is placed on the bracket of polytetrafluoroethyllining lining, bottom is packed into 25mL deionized water, by polytetrafluoroethylene (PTFE)
Liner is transferred in stainless steel cauldron, 160 DEG C steam phase conversion reaction 3 days, obtained solid product wash drying, be prepared
Hud typed hydrogenation catalyst Ir@LTA@ZSM-5, wherein Ir metal cluster encapsulation amount is 0.27wt%.
Embodiment 4.
30.3mmol sodium metaaluminate, 52.1mmol sodium hydroxide are taken, 33.3mmol fumed silica sequentially adds
In 16.8mL deionized water, 3h is stirred at 60 DEG C, adds 0.2mmol Pt (NH3)4Cl2, continue to stir 1h.It is then charged into band
Have in the stainless steel cauldron of polytetrafluoroethyllining lining, 100 DEG C of constant temperature Dynamic Hydrothermal crystallization 12h.By obtained solid product
It washs to neutrality, dry, first 350 DEG C of roasting 2h in air atmosphere, through 10% H at 350 DEG C2/ Ar reductase 12 h, is prepared into
To the Pt@LTA sample for being packaged with Pt metal cluster.
The Pt@LTA sample of the above-mentioned preparation of 2.5g is taken, is added in 10mL ethyl alcohol and the mixed liquor (1: 1) of deionized water, ultrasound
Dispersion liquid A is obtained after 1h.
Take 2.98mmol sodium metaaluminate, 3.3mmol sodium hydroxide, the 25wt% water with 44.5mmol tetrapropylammonium hydroxide
Solution is added in 48.6mL deionized water together and stirs to clarify, and adds 80.2mmol fumed silica, stirs at room temperature
12h obtains sol B.
Dispersion liquid A is slowly added dropwise in sol B, 50 DEG C of stirred in water bath for 24 hours, are dried to obtain dry glue in 100 DEG C of baking ovens.
2g dry glue is taken, is placed on the bracket of polytetrafluoroethyllining lining, bottom is packed into 30mL deionized water, by polytetrafluoroethylene (PTFE)
Liner is transferred in stainless steel cauldron, 160 DEG C steam phase conversion reaction 2 days, obtained solid product wash drying, be prepared
Hud typed hydrogenation catalyst Pt@LTA@ZSM-5, wherein Pt metal cluster encapsulation amount is 0.51wt%.
Embodiment 5.
30mmol sodium metaaluminate, 126.5mmol sodium hydroxide are taken, 12.1mmol fumed silica sequentially adds
In 24.3mL deionized water, 3h is stirred at 60 DEG C, adds 0.36mmol Pt (NH3)4Cl2, continue to stir 1h.It is then charged into band
Have in the stainless steel cauldron of polytetrafluoroethyllining lining, 100 DEG C of constant temperature Dynamic Hydrothermal crystallizations are for 24 hours.By obtained solid product
It washs to neutrality, dry, first 350 DEG C of roasting 2h in air atmosphere, through 10% H at 350 DEG C2/ Ar reductase 12 h, is prepared into
To the Pt@LTA sample for being packaged with Pt nano-cluster.
The Pt@LTA sample of the above-mentioned preparation of 2g is taken, is added in 10mL ethyl alcohol and the mixed liquor (1: 1) of deionized water, ultrasonic 1h
After obtain dispersion liquid A.
Take 2.98mmol sodium metaaluminate, 4.3mmol sodium hydroxide, the 25wt% water with 39.7mmol tetrapropylammonium hydroxide
Solution is added in 51.2mL deionized water together and stirs to clarify, and adds 44.3mmol fumed silica, stirs at room temperature
12h obtains sol B.
Dispersion liquid A is slowly added dropwise in sol B, 50 DEG C of stirred in water bath for 24 hours, are dried to obtain dry glue in 100 DEG C of baking ovens.
1.5g dry glue is taken, is placed on the bracket of polytetrafluoroethyllining lining, bottom is packed into 15mL deionized water, by polytetrafluoroethyl-ne
Alkene liner is transferred in stainless steel cauldron, 180 DEG C steam phase conversion reaction 1 day, obtained solid product wash drying, be prepared into
To hud typed hydrogenation catalyst Pt@LTA@ZSM-5, wherein Pt metal cluster encapsulation amount is 0.93wt%.
Comparative example 1.
30mmol sodium metaaluminate, 24.6mmol sodium hydroxide are taken, 14.6mmol fumed silica sequentially adds 19.8mL
In deionized water, 3h is stirred at 60 DEG C, adds 0.24mmol Pt (NH3)4Cl2, continue to stir 1h.It is then charged into poly- four
In the stainless steel cauldron of vinyl fluoride liner, 100 DEG C of constant temperature Dynamic Hydrothermal crystallizations are for 24 hours.Obtained solid is washed to neutrality,
It is dry, first 350 DEG C of roasting 2h in air atmosphere, through 10% H at 350 DEG C2/ Ar reductase 12 h, is prepared and is packaged with Pt
The Pt@LTA sample of nano-cluster.
By the Pt LTA sample of above-mentioned preparation and HZSM-5 zeolite molecular sieve according to 1: 1 quality than mechanical mixture, grinding
Tabletting after uniformly, sieving, takes 40~60 mesh particles, in H2400 DEG C of activation 2h, are prepared condensed-nuclei aromatics hydrogenation catalyst in atmosphere
Agent Pt@LTA+HZSM-5.
Application examples 1.
According to solid-to-liquid ratio 1: 20 (g/mL), Pt@LTA@ZSM-5 catalyst prepared by embodiment 1 is placed in 0.5mol/L
NH4In Cl solution, 2h is stirred under room temperature.After repeated exchanged 3 times, 4h is roasted at 550 DEG C, the Pt@LTA@of Hydrogen is prepared
HZSM-5 catalyst.
The Pt@LTA+HZSM-5 catalyst for simultaneously preparing Pt@LTA and comparative example 1 makees same processing, as control
Example.
Hydrogenation reaction is carried out using naphthalene as condensed-nuclei aromatics model, evaluates the catalytic performance of catalyst.Naphthalene hydrogenation reaction is solid
It is carried out on fixed bed micro-reactor, the H of reaction is set2With feed liquor volume ratio 800, mass space velocity 0.63h-1, pressure 4MPa, reaction temperature
350 DEG C of degree.
Catalytic performance test of the different catalysts in naphthalene hydrogenation reaction is as shown in table 1.It is hud typed to urge compared to Pt@LTA
Agent Pt@LTA@HZSM-5 and Pt@LTA+HZSM-5 catalyst has shown higher catalytic activity, and the choosing of decahydronaphthalene
Selecting property significantly improves, and shows either can lead in Pt@LTA surface construction HZSM-5 shell or mechanical mixture HZSM-5
Cross Hydrogen spillover effect enhancing catalytic performance.
In turn, when core-shell catalyst Pt@LTA@HZSM-5 catalysis reaction, the selectivity of decahydronaphthalene is up to 82.6%, and
Pt@LTA+HZSM-5 is only 49.5% to the selectivity of decahydronaphthalene, shows to shorten in Pt@LTA surface construction HZSM-5 shell
The migration path of reactive hydrogen effectively enhances Hydrogen spillover effect, so that the further deep hydrogenation of naphthalene.
Application examples 2.
Using benzothiophene as organic sulphur source, it is added in the hydrogenation reaction system of application examples 1, is examined with the concentration of 500ppm
Examine the sulfur resistance of various catalyst.
The sulfur resistance evaluation of different catalysts is equally listed in Table 1 below.When sulphur concentration reaches 500ppm in reactant, to the greatest extent
The catalytic activity for managing various catalyst is declined, but core-shell catalyst Pt@LTA@HZSM-5 decahydronaphthalene selectivity according to
66.9% can so be reached, compared to the 13.9% of Pt@LTA+HZSM-5, core-shell catalyst Pt@LTA@HZSM-5 has shown good
Good sulfur resistance.
Claims (10)
1. a kind of hud typed hydrogenation catalyst has core-shell structure, stratum nucleare structure is LTA type molecular sieve, and in the LTA type
Noble-metal-cluster is packaged in the hole cage of molecular sieve, the noble-metal-cluster is the conjunction that noble metal precursor body is introduced to LTA type molecular sieve
In architectonical, roasting reduction after Situ Hydrothermal crystallization is formed in the hole cage of LTA type molecular sieve, and shell structurre is
ZSM-5 zeolite molecular sieve is to be packaged with noble-metal-cluster described in addition in the gel rubber system of synthetic ZSM-5 zeolite molecular sieve
LTA type molecular sieve carries out steam phase conversion reaction after dry, in the LTA type molecular sieve surface structure for being packaged with noble-metal-cluster
Build ZSM-5 zeolite molecular sieve shell.
2. hud typed hydrogenation catalyst according to claim 1, it is characterized in that the noble-metal-cluster is urged in hud typed plus hydrogen
Encapsulation amount in agent is 0.02~2.6wt%.
3. hud typed hydrogenation catalyst according to claim 1, it is characterized in that the stratum nucleare LTA type molecular sieve and shell
The mass ratio of ZSM-5 zeolite molecular sieve is 1: 0.2~4.
4. hud typed hydrogenation catalyst according to claim 1, it is characterized in that the noble metal is Pt, Pd, Ir, Ru or Rh
In any one.
5. the preparation method of hud typed hydrogenation catalyst described in claim 1, comprising:
Using silica, sodium metaaluminate, noble metal precursor body and sodium hydroxide as raw material, it is brilliant that Situ Hydrothermal is carried out in aqueous solution
Change reaction, roasting reduction prepares the LTA type molecular sieve for being packaged with noble-metal-cluster；
Using silicon source, tetrapropylammonium hydroxide and sodium metaaluminate as raw material, synthetic ZSM-5 zeolite molecular sieve is formed in aqueous solution
Sol system；
The synthetic ZSM-5 zeolite molecular sieve is added in the LTA type molecular sieve for being packaged with noble-metal-cluster or its dispersion liquid
Sol system, drying form dry glue；
Steam phase conversion reaction is carried out to the dry glue, in the LTA type molecular sieve surface synthesis for being packaged with noble-metal-cluster
ZSM-5 zeolite molecular sieve；
Thus the hud typed hydrogenation catalyst is prepared.
6. preparation method according to claim 5, it is characterized in that in the Situ Hydrothermal crystallization, the use of various raw materials
Amount molar ratio meets Na2O∶Al2O3∶SiO2∶H2O=2~8: 1: 0.5~4: 80~160.
7. preparation method according to claim 5, it is characterized in that the sol system of the synthetic ZSM-5 zeolite molecular sieve
In, the dosage molar ratio of various raw materials meets Na2O∶Al2O3∶SiO2: tetrapropylammonium hydroxide: H2O=1.4~10: 1: 20~100
: 20~80: 850~3100.
8. preparation method according to claim 5, it is characterized in that the silicon source is ethyl orthosilicate, silica solution, gas phase two
One of silica.
9. preparation method according to claim 5, it is characterized in that the dispersion liquid of the LTA type molecular sieve is by the encapsulation
There is the LTA molecular sieve of noble-metal-cluster to be dispersed in ethyl alcohol and isometric mixed liquor of deionized water.
10. preparation method according to claim 5, it is characterized in that the noble metal precursor body be precious metals pt, Pd, Ir,
Any one in the complex salt of Ru or Rh.
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