CN109806910A - A kind of molecular sieve carried high-dispersion metal catalyst of H-type EUO and preparation method thereof - Google Patents
A kind of molecular sieve carried high-dispersion metal catalyst of H-type EUO and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of molecular sieve carried high-dispersion metal catalysts of H-type EUO, it is characterised in that: catalyst activity component group VIII metal nanoparticle high-dispersion load is in H-type EUO molecular sieve pore passage, and tenor is 0.01~2.0wt% in the catalyst；H-type EUO molecular sieve silica alumina ratio is 10~200, is gathered into oval spherical in nanocrystal.The present invention is prepared using one kettle way crystallization synthetic reaction, specific method is that organic thiol ligand, metal precursor, NaOH solution hybrid reaction are formed M-S complex, it is added in sial mixed gel and is mixed into colloidal sol, add EUO molecular sieve seed, then first low temperature maturation is carried out, high temperature dynamic crystallization reacts to obtain metalliferous EUO molecular screen primary powder again, prepares finished catalyst followed by ammonium ion exchange, reduction reaction.Catalyst of the present invention shows good activity and selectivity in C8 aronmatic hydroisomerization reaction, and shows excellent anticoking capability, has good prospects for commercial application.
Description
Technical field
The present invention relates to a kind of carried molecular sieve noble metal catalysts and preparation method thereof, and in particular to arrives a kind of H-type
Molecular sieve carried high dispersion metal Pt nano-particle catalyst of EUO and preparation method thereof, belongs to catalysis material technical field.
Background technique
High-dispersion nano grade metal-supported catalyst is since (partial size is small, large specific surface area, has very for its unique property
High catalytic activity etc.) and receive much attention.Wherein, the molecular sieve supported body catalyst of high dispersion metal has both high-dispersion metal catalyst
The features such as metal center dispersion degree height and excellent molecular sieve catalyst structure is a kind of ideal high performance catalyst material.This
The preparation method of class catalyst mainly includes coprecipitation, infusion process, in-situ synthesis, ion-exchange, chemical grafting.Altogether
The precipitation method are that metallic salt co-precipitation is deposited on carrier surface, and catalyst sample then is made through high-temperature roasting and activation.
Infusion process is to prepare the commonly used method of conventional load type metallic catalyst, and process is main are as follows: impregnates porous carrier
In the salting liquid containing metal active constituent, makes moisture evaporation evolution by modes such as drying, heating, adhere to active component
On the inner surface of carrier, then the post-processings such as is calcined, restored and obtaining catalyst sample.Infusion process is easy to operate, but with dampening
Due to being influenced by solvation effect and maceration extract surface tension, metal active constituent is often assembled, is heavy for the evaporation divided
Product is in carrier surface；Active metal species after dipping be easy to cause the migration of metallic through high-temperature roasting, assemble to shape
At big metal grain, the dispersion degree and catalytic performance and reusability of active component are directly affected.In-situ synthesis is
Metal complex is first dispersed in organic media, the hydrophobic end in template micella is then attached to, is stood after silicon source is added
For a period of time, the product obtained removes template through post-processings such as high-temperature activations, obtains load type metal catalyst.Chemical grafting
Method is to act on the hydroxyl of metal complex and carrier surface, metal complex is grafted on carrier, then through high-temperature activation etc.
Post-processing is to be made required sample.Dapeng Liu et al. (Catalysis Today, 2009,148 (3-4), 243-250) is logical
Later synthesis grafting and traditional infusion process have prepared the catalyst n i/MCM- that W metal particle is highly dispersed in carrier surface
41 and Ni/SBA-15, and test by carbon dioxide methanation the catalytic performance of the catalyst.The result shows that chemical grafting
Its W metal particle of catalyst obtained by method is highly dispersed in carrier surface, and it is resulting that size is significantly less than traditional infusion process
W metal size, and good catalytic activity is shown to carbon dioxide methanation.If metallic particles can be made in carrier
Tend to be orderly while internal high dispersive or be regularly distributed, then catalyst can play bigger catalytic activity.
There is one-dimensional ten-ring 0.54nm × 0.41nm in [100] direction in EUO type topological structure crystal structure of molecular sieve
Duct also has deep 0.81nm twelve-ring 0.68nm × 0.58nm side pocket in the two sides in ten-ring duct.EU-1, ZSM-50 and
TPZ-3 molecular sieve all has EUO type topological structure, and wherein EU-1 molecular sieve is the more extensive molecular sieve of Recent study, by
In its special cellular structure and acidic character, as the difunctional of isomerization of C-8 aromatics acidity of catalyst constituent element preparation
Catalyst shows good activity and selectivity, quilt in the isopropylation catalysis reaction of C8 aronmatic hysomer, benzene
It is described as the first choice of the xylene isomerization catalysis material of a new generation.EP0923987A1 discloses one kind with EUO structure type zeolites
For the catalyst of basic component.EUO structure type zeolites have one-dimensional reticulated macroporous structure, and skeleton is by silicon oxygen and alumina four
The ten-ring duct of face body composition, oval aperture, in zeolite main aperture road side, there are cage structures.Due to EUO type zeolite
With special structure, and to the good dispersion of metal, high mechanical strength, using EUO type zeolite as acidity of catalyst constituent element
Catalyst shows good aromatics isomerization performance.
Foreign countries have developed a variety of C8 aromatics isomerizations and ethylbenzene conversion process, such as Engelhard Corp, the U.S.
Octafining method, ten thousand method of Isomar and toray company Isolene-II method of Praxair Technology, Inc.Ethylbenzene is different
There are many patent that structure is converted into dimethylbenzene catalyst, the catalyst mainly use ZSM series and SAPO series zeolite etc. for
Acidic components use group VIII metal for hydrogenation active metal component, such as US5028573, EP0151351A, US5276236.This
A little catalyst cannot be taken into account in terms of the selectivity two that conversion of ethylbenzene and ethylbenzene isomerization are converted into dimethylbenzene, conversion of ethylbenzene
When higher, selectivity is poor, and vice versa.
The method grafted using metal complex introduces metal species unit and cluster in EUO molecular sieve, thus
To the sub-nano golden species of high thermal stability, be conducive to EUO molecular sieve catalyst catalytic activity, the stabilization of final Metal Supported
Property and resistance to carbon distribution deactivation raising, be that a kind of high-dispersion loading type molecular sieve catalyst is simple, effective preparation method, tool
There are good application prospect and value.
Summary of the invention
Different from the methods of the dipping of this field routine, co-precipitation, complex-precipitation, coated, the present invention provides a kind of H-types
Molecular sieve carried high-dispersion metal catalyst of EUO and preparation method thereof.The preparation method is come steady by organic thiol ligand
The predecessor of deposit category active matter, the method grafted using metal complex are equal by high dispersion metal active component nanoparticle
Even dispersion loads on EUO molecular sieve, has obtained the finely dispersed metal nanoparticle inside EUO molecular sieve, has realized one
The molecular sieve catalyst of metal species has been wrapped up in pot method synthesis.The monatomic and cluster of metal is introduced in EUO molecular sieve, thus
The sub-nanometer active metal species of high thermal stability are obtained, hydrothermal stability and anti-carbon deactivation are strong, can be in carbon eight
Good activity and selectivity and excellent anticoking capability are shown in aromatic hydrocarbons hydroisomerization reaction.
A kind of molecular sieve carried high-dispersion metal catalyst of H-type EUO of the present invention, it is characterised in that: catalyst is living
Property component group VIII metal nanoparticle high-dispersion load is in H-type EUO molecular sieve pore passage, and tenor is in the catalyst
0.01~2.0wt%；H-type EUO molecular sieve silica alumina ratio is 10~200, assembles elliptical shape ball pattern in nanocrystal, the EUO divides
Son sieve specifically includes several molecular sieve classifications of EU-1, ZSM-50 and TPZ-3, preferably EU-1 molecular sieve.
The preparation method of catalyst of the present invention, it is characterised in that: the molecular sieve carried high dispersion metal of H-type EUO
Catalyst is prepared using one kettle way crystallization synthetic reaction.
Specifically, the preparation method of catalyst of the present invention the following steps are included:
1) metal precursor, organic thiol ligand, NaOH and water are according to molar ratio 1:(4.0~8.0): (12~20):
(100~500) mixed dissolution, ligand exchange are filtered, washed to obtain water-soluble M-S complex；
2) M-S complex obtained in step 1) is added to shape in the material comprising silicon source, silicon source and inorganic base
At mixed sols, wherein M-S complex: SiO2: Al2O3: inorganic base: organic formwork agent: H2The molar ratio of O is (0.0005
~0.008): 1:(0.005~0.05): (0.02~0.2): (0.05~0.5): (10~50) add EUO molecular sieve seed
It is uniformly mixed, crystal seed accounts for the 1%~10% of mixture solid weight percentage；
3) step 2) mixture is transferred in hydrothermal crystallizing kettle, it is 12~48 hours still aging at 100~150 DEG C, so
After be warming up to 170~190 DEG C of revolving speeds be 50~250rpm under dynamic crystallization 24~168 hours, after the completion of crystallization, filtering,
It washs, it is 12~48 hours dry at 100~130 DEG C, obtain the EUO molecular screen primary powder containing metal M；
4) the EUO molecular screen primary powder containing metal M for obtaining step 3) is roasted 2~10 hours at 500~650 DEG C and is removed
Template obtains EUO molecular sieve powder wherein the heating rate from room temperature to maturing temperature is 1~10 DEG C/min；
5) the EUO molecular sieve powder for obtaining step 4) carries out Na+ ion in ammonium salt exchange removing molecular sieve, carries out again
Calcination process obtains the EUO molecular sieve of H-type；
6) by the product H after step 5) roasting2The reduction of/He gaseous mixture obtains the molecular sieve carried high dispersive gold of H-type EUO
Belong to the catalyst of nanoparticle.
Preferably, metal described in above-mentioned technical proposal be selected from group VIII metal, including Pt, Pd, Rh, Ir, Ru, Re, Au,
It is any in Ag, Cd, it is furthermore preferred that any in Pt, Pd, Rh, Ir, Ru.
Preferably, in above-mentioned technical proposal, in step 1) organic thiol ligand include 3-mercaptopropyi trimethoxy silane,
3- Mercaptopropyltriethoxysilane, methyl-[2- (first sulfydryl) ethyl] amine, is appointed in 2 mercaptopropionic acid ammonium at 2- ammonium mercaptoacetate
It is a kind of.
Preferably, in above-mentioned technical proposal, in step 1) organic thiol ligand include 3-mercaptopropyi trimethoxy silane,
It is any in 3- mercapto propyl-triethoxysilicane；
Preferably, inorganic base includes NaOH, Na in step 2)2O、KOH、K2It is any one or several in O.
Preferably, in above-mentioned technical proposal, metal precursor includes Pt (NH in step 1)3)4]Cl2, acetylacetone,2,4-pentanedione platinum,
[Pt(NH2CH2CH2NH2)2]Cl2、[Pt(NH2CH2CH2NH2)2](NO3)2、Pt(NH3)4](NO3)2、Pd(NH3)4]Cl2, levulinic
Ketone palladium, [Pd (NH2CH2CH2NH2)2]Cl2、[Pd(NH2CH2CH2NH2)2](NO3)2、Pd(NH3)4](NO3)2、Rh(NH3)4]Cl2、
Acetylacetone,2,4-pentanedione rhodium, [Rh (NH2CH2CH2NH2)2]Cl2、[Rh(NH2CH2CH2NH2)2](NO3)2、Rh(NH3)4](NO3)2、Ru
(NH3)4]Cl2, acetylacetone,2,4-pentanedione ruthenium, [Ru (NH2CH2CH2NH2)2]Cl2、[Ru(NH2CH2CH2NH2)2](NO3)2、Ru(NH3)4]
(NO3)2、Ir(NH3)4]Cl2, acetylacetone,2,4-pentanedione iridium, [Ir (NH2CH2CH2NH2)2]Cl2、[Ir(NH2CH2CH2NH2)2](NO3)2、Ir
(NH3)4](NO3)2In any, preferably Pt (NH3)4]Cl2, acetylacetone,2,4-pentanedione platinum, [Pt (NH2CH2CH2NH2)2]Cl2、[Pt
(NH2CH2CH2NH2)2](NO3)2、Pt(NH3)4](NO3)2In it is any.
Preferably, in above-mentioned technical proposal, silicon source includes silica solution, waterglass, sodium metasilicate, Silica hydrogel, silicon in step 2)
It is aerosol, white carbon black, silochrom, methyl silicate, silester, any one or several in silicic acid propyl ester；Silicon source includes sulfuric acid
It is aluminium, sodium aluminate, boehmite, aluminium isopropoxide, aluminum nitrate, aluminium chloride, aluminium oxide, one or more of in aluminium hydroxide；It is inorganic
Alkali is NaOH；In step 5) ammonium salt include ammonium nitrate, it is ammonium sulfate, ammonium chloride, any in ammonium acetate, concentration is 0.2~
2.0mol/L。
Preferably, in above-mentioned technical proposal, in step 2), the organic formwork agent is bi-quaternary ammonium salt template, including
Bis- (N- methylpyrrole) hexanes of 1,6-, bis- (3- methylpyrrole) hexanes of 1,6-, 1,6- bis- (N- methylimidazole) hexanes, 1,
Bis- (the N- methylimidazole quinoline) hexanes of bis- (2,3- methylimidazole) hexanes of 6-, 1,6-, bis- (the N- methyl nafoxidines of 1,6-
) hexane, bis- (N- methylpyrrole) butane of 1,4-, bis- (N- methylpyrrole) pentanes of 1,5-, bis- (the N- methylpyrroles of 1,7-
) heptane, bis- (N- methylpyrrole) octanes of 1,8-, bis- (N- methylpyrrole) butane of 1,4-, bis- (the N- methylpyrroles of 1,5-
) pentane, bis- (N- methylpyrrole) heptane of 1,7-, bis- (N- methylpyrrole) octanes of 1,8-, bis- (the N- methylimidazoles of 1,4-
) butane, bis- (N- methylimidazole) pentanes of 1,5-, bis- (N- methylimidazole) heptane of 1,7-, bis- (the N- methylimidazoles of 1,8-
) octane, bis- (the N- methylimidazole quinoline) butane of 1,4-, bis- (the N- methylimidazole quinoline) pentanes of 1,5-, bis- (the N- methyl miaows of 1,7-
Oxazoline) heptane, in bis- (the N- methylimidazole quinoline) octanes of 1,8- any one, two kinds or more with arbitrary proportion mixing and
At mixture.
Preferably, in above-mentioned technical proposal, step 5) be by the EUO molecular sieve powder after removed template method with 0.5~
5.0mol/L ammonium salt solution is according to mass ratio 1:(5~25) ratio carried out at 60~100 DEG C ion exchange 1~4 time, remove
Na+ ion roasts 2~10 hours for 500~650 DEG C again.
The present invention also provides a kind of catalyst by the synthesis of above-mentioned synthetic method as the difunctional of C8 aromatics isomerization
Catalyst, the application in the isomerization reaction of the aromatic compound containing 8 carbon atoms.
In above-mentioned technical proposal, the bifunctional catalyst of C8 aromatics isomerization is being applied to the aromatization containing 8 carbon atoms
When closing in the isomerization reaction of object, the raw material of isomerization reaction is the aromatic compound containing 8 carbon atoms, the item of isomerization reaction
Part are as follows: 300 DEG C~500 DEG C of temperature, 0.3~1.5MPa of hydrogen partial pressure, 0.45~1.9MPa of stagnation pressure, weight space velocity degree (WHSV) are
0.5~10h-1。
This method of the present invention is easy to operate, realizes one pot process and has wrapped up the molecular sieves of metal species and urges
Agent not only has versatility, but also is uniformly embedded into metal active constituent by the method and is distributed in molecular sieve, obtains height
The sub-nanometer Pt species of thermal stability, particle size are small；Metal active centres and acid site can be effectively matched, and molecular sieve will not be because
The difference of coefficient of thermal expansion and rupture, high mechanical strength.Show that preferably catalysis is lived in long chain alkane hygrogenating isomerization reaction
Property, and show excellent anticoking capability.
Detailed description of the invention
The invention will be further described with reference to the accompanying drawings and embodiments:
Attached drawing 1: the molecular sieve carried high dispersive Pt catalyst XRD diagram of EU-1 that embodiment 1 synthesizes
Attached drawing 2: the molecular sieve carried high dispersive Pt catalyst SEM figure of the EU-1 that embodiment 1 synthesizes
Specific embodiment
Embodiment of the present invention and generated effect, but guarantor of the invention are further illustrated by embodiment and comparative example
Shield range is not limited to content listed by embodiment.
Using EU-1 molecular sieve as the Typical Representative of EUO molecular sieve in following embodiment, the H-type EU-1 molecular sieve of preparation is negative
" Pt-HEU-1 " can be expressed as by carrying high dispersive Pt catalyst.
Embodiment 1
This example demonstrates that the method for preparing loaded Pt catalyst on H-type EU-1 molecular sieve:
1) by 0.75g [Pt (NH2CH2CH2NH2) 2] Cl2,2.3152g 3- Mercaptopropyltriethoxysilane, 8.08g
The NaOH solution that concentration is 13.5% carries out mixed dissolution, ligand exchange, is filtered, washed to obtain water-soluble Pt-S coordination
Compound；
2) by 100.0g silester, 1.2255g aluminium isopropoxide, 3.3409g NaOH, bis- (the N- methyl of 10.7614g1,6-
Pyrroles) hexane (being denoted as OSDA1) and 255.4922g deionized water and 1) obtained in the mixing that is formed of Pt-S complex
Gel, n (Pt-S): Na in the gel2O:nSiO2: nAl2O3: nOSDA1:nH2Molar ratio=0.003:0.087:1 of O:
0.0125:0.08:30；The EU-1 molecular sieve seed for adding 5.0291g is uniformly mixed, and gel mixture is transferred to water thereafter
In thermal crystallisation kettle, first 120 DEG C 24 hours still aging, then again at 180 DEG C with 100rpm speed of agitator crystallization 72 hours.Crystallization
Taken out after reaction it is sudden cold, it is 12 hours dry at 105 DEG C by sample filtering, washing, obtain the EU-1 molecular sieve catalyst containing Pt
Original powder.
3) 2) catalyst raw powder obtained by from room temperature to 550 DEG C and is roasted into 6 hours removing moulds with 2 DEG C/min heating rate
Plate agent；Then ion exchange is carried out according to the ratio of mass ratio 1:10 with molecular sieve powder and 1.0mol/L ammonium nitrate solution, taken off
Except Na+Ion, 550 DEG C of roastings obtain the catalyst of the molecular sieve carried Pt oxide of H-type EU-1 in 2 hours again, then use
The H of 100ml/min flow2The Pt-HEU-1 that high-dispersion nano particle is obtained after/He gaseous mixture (H2 content is 10%) reduction is urged
Agent, the mass content of Pt in the catalyst are 0.28wt%, and XRD diffraction pattern and SEM electromicroscopic photograph are respectively such as attached drawing 1 and attached drawing
Shown in 2, catalyst preparation compound used therefor type, H-type EU-1 molecular sieve silica alumina ratio, Pt metal component percentage composition such as 1 institute of table
Show, which is denoted as PtEUO-1.
Embodiment 2
This example demonstrates that the method for preparing loaded Pt catalyst on H-type EU-1 molecular sieve:
1) by 0.5g Pt (NH3)4](NO3)2, 1.0141g 3-mercaptopropyi trimethoxy silane, 9.92g concentration be
6.3% NaOH solution carries out mixed dissolution, ligand exchange, is filtered, washed to obtain water-soluble Pt-S complex；
2) by 100.0g silica solution (SiO2Content: 30wt%), 1.9580g boehmite (Al2O3Content: 65wt%),
Bis- (3- methylpyrrole) hexanes (being denoted as OSDA2) of 2.0174g NaOH, 35.3342g 1,6- and 153.6457g deionized water
The mixed gel formed with Pt-S complex obtained in step 1), n (Pt-S): nNa2O:nSiO in the gel2:
nAl2O3: nOSDA2:nH2Molar ratio=0.0026:0.05:1:0.025:0.25:25 of O；Add EU-1 points of 0.4807g
Son sieve crystal seed is uniformly mixed, and gel mixture is transferred in hydrothermal crystallizing kettle thereafter, and first 140 DEG C 12 hours still aging, so
Afterwards again at 180 DEG C with 150rpm speed of agitator crystallization 96 hours.Taken out after crystallization it is sudden cold, by sample filtering, washing, 120
It is 12 hours dry at DEG C, obtain the EU-1 molecular sieve catalyst original powder containing Pt.
3) by catalyst raw powder obtained by step 2) with 5 DEG C/min heating rate from room temperature to 550 DEG C and roast 4 hours it is de-
Template agent removing；Then ion friendship is carried out according to the ratio of mass ratio 1:20 with molecular sieve powder and 0.5mol/L ammonium chloride solution
It changes, removes Na+Ion, 550 DEG C of roastings obtain the catalyst of the molecular sieve carried Pt oxide of H-type EU-1 in 2 hours again, then use
The H of 100ml/min flow2The Pt-HEU-1 that high-dispersion nano particle is obtained after/He gaseous mixture (H2 content is 10%) reduction is urged
Agent, the mass content of Pt in the catalyst are 0.80wt%, catalyst preparation compound used therefor type, H-type EU-1 molecular sieve
Silica alumina ratio, Pt metal component percentage composition are as shown in table 1, which is denoted as PtEUO-1.
Embodiment 3
This example demonstrates that the method for preparing loaded Pt catalyst on H-type EU-1 molecular sieve:
1) by 0.85g [Pt (NH2CH2CH2NH2)2](NO3)2, 1.2671g 2- ammonium mercaptoacetate, 11.61g concentration be
10.0% NaOH solution carries out mixed dissolution, ligand exchange, is filtered, washed to obtain water-soluble Pt-S ligand compound
Object；
2) by 100.0g waterglass (SiO2Content: 25.0wt%, Na2O content: 7.5wt%), 5.0505g sodium aluminate
(Al2O3Content: 37.38wt%, Na2O content: 29.22wt%), 3.2623g NaOH, bis- (the N- methyl miaows of 17.7919g 1,6-
Azoles) Pt-S complex obtained in hexane (being denoted as OSDA3) and 34.2349g deionized water and step 1) formed it is mixed
Gel is closed, n (Pt-S): nSiO in the gel2: nAl2O3: nNaOH:n (OSDA3): nH2Molar ratio=0.0047:0.10 of O:
1:0.05:0.15:15.0；The EU-1 molecular sieve seed for adding 2.8411g is uniformly mixed, and is thereafter transferred to gel mixture
In hydrothermal crystallizing kettle, first 150 DEG C 24 hours still aging, then again at 190 DEG C with 80rpm speed of agitator crystallization 60 hours.It is brilliant
Change take out after reaction it is sudden cold, it is 24 hours dry at 100 DEG C by sample filtering, washing, obtain the EU-1 molecular sieve catalytic containing Pt
Agent original powder.
3) by catalyst raw powder obtained by step 2) with 5 DEG C/min heating rate from room temperature to 550 DEG C and roast 4 hours it is de-
Template agent removing；Then ion friendship is carried out according to the ratio of mass ratio 1:15 with molecular sieve powder and 1.5mol/L ammonium sulfate
It changes, removes Na+Ion, 550 DEG C of roastings obtain the catalyst of the molecular sieve carried Pt oxide of H-type EU-1 in 2 hours again, then use
The H of 100ml/min flow2The Pt-HEU-1 that high-dispersion nano particle is obtained after/He gaseous mixture (H2 content is 10%) reduction is urged
Agent, the mass content of Pt in the catalyst are 1.37wt%, catalyst preparation compound used therefor type, H-type EU-1 molecular sieve
Silica alumina ratio, Pt metal component percentage composition are as shown in table 1, which is denoted as PtEUO-3.
Embodiment 4
This example demonstrates that the method for preparing loaded Pt catalyst on H-type EU-1 molecular sieve:
1) by 0.35g acetylacetone,2,4-pentanedione platinum, 0.3885g 2 mercaptopropionic acid ammonium, 6.98g concentration be 8.2% NaOH solution into
Row mixed dissolution, ligand exchange are filtered, washed to obtain water-soluble Pt-S complex；
2) by 100.0g silicon aerosol, 9.2430g aluminum sulfate octadecahydrate (purity 99%), 15.9776gNaOH,
In bis- (2,3- methylimidazole) hexanes (OSDA4) of 232.3685g 1,6- and 589.7505g deionized water and step 1)
The mixed gel that the Pt-S complex that arrives is formed, n (Pt-S): nNa2O:nSiO in the gel2: nAl2O3: n (OSDA4):
nH2Molar ratio=0.00054:0.12:1:0.00833:0.45:20.0 of O；Add the EU-1 molecular sieve seed of 2.7250g
It is uniformly mixed, gel mixture is transferred in hydrothermal crystallizing kettle thereafter, first 100 DEG C 48 hours still aging, then again 180
DEG C with 200rpm speed of agitator crystallization 120 hours.Taken out after crystallization it is sudden cold, it is dry at 120 DEG C by sample filtering, washing
12 hours, obtain the EU-1 molecular sieve catalyst original powder containing Pt.
3) by catalyst raw powder obtained by step 2) with 5 DEG C/min heating rate from room temperature to 550 DEG C and roast 4 hours it is de-
Template agent removing；Then ion friendship is carried out according to the ratio of mass ratio 1:10 with molecular sieve powder and 2.5mol/L ammonium nitrate solution
It changes, removes Na+Ion, 550 DEG C of roastings obtain the catalyst of the molecular sieve carried Pt oxide of H-type EU-1 in 2 hours again, then use
The H of 100ml/min flow2The Pt-HEU-1 that high-dispersion nano particle is obtained after/He gaseous mixture (H2 content is 10%) reduction is urged
Agent, the mass content of Pt in the catalyst are 0.16wt%, catalyst preparation compound used therefor type, H-type EU-1 molecular sieve
Silica alumina ratio, Pt metal component percentage composition are as shown in table 1, which is denoted as PtEUO-4.
Embodiment 5
This example demonstrates that the method for preparing loaded Pt catalyst on H-type EU-1 molecular sieve:
1) by 1.5g [Pt (NH2CH2CH2NH2)2]Cl2, 3.8131g 3-mercaptopropyi trimethoxy silane, 36.98g it is dense
Degree carries out mixed dissolution, ligand exchange for 5.5% NaOH solution, is filtered, washed to obtain water-soluble Pt-S coordinationization
Close object；
2) by 100.0g silica solution (SiO2Content: 30wt%), nine water aluminum nitrate (purity 98%) of 1.1945g,
Bis- (the N- methylimidazole quinoline) hexanes (OSDA5) of 10.8938g NaOH, 51.9779g 1,6- and 378.8250g deionized water with
The mixed gel that Pt-S complex obtained in step 1) is formed, n (Pt-S): nNa2O:nSiO in the gel2: nAl2O3:
N (OSDA5): nH2Molar ratio=0.0052:0.27:1:0.00625:0.36:50.0 of O；Add EU-1 points of 2.3523g
Son sieve crystal seed is uniformly mixed, and gel mixture is transferred in hydrothermal crystallizing kettle thereafter, and first 130 DEG C 36 hours still aging, so
Afterwards again at 180 DEG C with 120rpm speed of agitator crystallization 48 hours.Taken out after crystallization it is sudden cold, by sample filtering, washing, 105
It is 24 hours dry at DEG C, obtain the EU-1 molecular sieve catalyst original powder containing Pt.
3) by catalyst raw powder obtained by step 2) with 2 DEG C/min heating rate from room temperature to 500 DEG C and roast 8 hours it is de-
Template agent removing；Then ion friendship is carried out according to the ratio of mass ratio 1:10 with molecular sieve powder and 1.5mol/L ammonium chloride solution
It changes, removes Na+Ion, 550 DEG C of roastings obtain the catalyst of the molecular sieve carried Pt oxide of H-type EU-1 in 2 hours again, then use
The H of 100ml/min flow2The Pt-HEU-1 that high-dispersion nano particle is obtained after/He gaseous mixture (H2 content is 10%) reduction is urged
Agent, the mass content of Pt in the catalyst are 1.59wt%, catalyst preparation compound used therefor type, H-type EU-1 molecular sieve
Silica alumina ratio, Pt metal component percentage composition are as shown in table 1, which is denoted as PtEUO-5.
Embodiment 6
This example demonstrates that the method for preparing loaded Pt catalyst on H-type EU-1 molecular sieve:
1) by 1.5g Pt (NH3)4](NO3)2, 7.3889g 3- Mercaptopropyltriethoxysilane, 12.63g concentration be
17.2% NaOH solution carries out mixed dissolution, ligand exchange, is filtered, washed to obtain water-soluble Pt-S ligand compound
Object；
2) by 80.0g silochrom (SiO2Content: 95wt%), 0.5034g aluminium hydroxide (purity 98%), 6.1328g
Bis- (the N- methyl nafoxidine) hexanes (OSDA3) of NaOH, 109.4003g 1,6- and 705.3501g deionized water and step 1)
Obtained in the mixed gel that is formed of Pt-S complex, n (Pt-S): nSiO in the gel2: nAl2O3: nNaOH:n
(OSDA3): nH2Molar ratio=0.00306:0.36:1:0.005:0.06:35.0 of O；Add the EU-1 molecule of 3.8443g
It sieves crystal seed to be uniformly mixed, gel mixture is transferred in hydrothermal crystallizing kettle thereafter, first 110 DEG C 48 hours still aging, then
Again at 175 DEG C with 180rpm speed of agitator crystallization 144 hours.Taken out after crystallization it is sudden cold, by sample filtering, washing, 110 DEG C
Lower drying 24 hours obtains the EU-1 molecular sieve catalyst original powder containing Pt.
3) by catalyst raw powder obtained by step 2) with 4 DEG C/min heating rate from room temperature to 500 DEG C and roast 6 hours it is de-
Template agent removing；Then ion friendship is carried out according to the ratio of mass ratio 1:20 with molecular sieve powder and 1.0mol/L ammonium acetate solution
It changes, removes Na+Ion, 550 DEG C of roastings obtain the catalyst of the molecular sieve carried Pt oxide of H-type EU-1 in 2 hours again, then use
The H of 100ml/min flow2The Pt-HEU-1 that high-dispersion nano particle is obtained after/He gaseous mixture (H2 content is 10%) reduction is urged
Agent, the mass content of Pt in the catalyst are 0.98wt%, catalyst preparation compound used therefor type, H-type EU-1 molecular sieve
Silica alumina ratio, Pt metal component percentage composition are as shown in table 1, which is denoted as PtEUO-6.
Comparative example 1:
EU-1 molecular sieve is synthesized according to patent CN01121442 embodiment and prepares Pt-HEU-1 molecular sieve catalyst:
1) 3530g benzyl dimethyl amine (98%) and 3260g benzyl chlorine (99%) are diluted in 42.92g water, so
38.45g SiO2 colloidal sol (Ludox HS40,40%SiO2) is added afterwards, prepares the solution I being made of silicon and structural agent precursor.
Then 0.610g solid sodium hydroxide (99%) and 0.496g solid sodium aluminate (46%A12O3,33%Na2O) are dissolved in
In 5.36g water, solution II is prepared.Solution I is added in solution II under stiring, 5.36g water is then added.It is mixed
Until uniform.The mixture allowed is stirred to react 3 days in 180 DEG C at autogenous pressures in 125ml autoclave pressure.In cooling
Afterwards, filtration product is washed with deionized, then 120 DEG C of dry 12h, is warming up to 550 DEG C of roasting 4h to get EU-1 molecular sieve is arrived
Original powder.
2) EU-1 molecular screen primary powder and 1.0mol/L ammonium nitrate solution are carried out according to the ratio of mass ratio 1:10 at 90 DEG C
Ion exchange 2 times, remove Na+Ion, 550 DEG C of roastings obtain H-type EU-1 molecular sieve in 2 hours again.
3) by PVP the and 60m1 alcohol solution-forming of 0.5g [Pt (NH3) 4] (NO3) 2,0.83g, H-type EU-1 molecule is added
12h, 80 DEG C of water bath methods, 80 DEG C of vacuum drying 12h, 350 DEG C of roasting 12h in air atmosphere, in quality is stirred at room temperature in sieve
Score is that 300 DEG C of roasting 2h obtain Pt-HEU-1 molecular sieve catalyst in 10%H2/N2, and mass content is Pt in the catalyst
0.75wt%, H-type EU-1 silica alumina ratio (nSiO2/nAl2O3) it is 112, catalyst preparation compound used therefor type, H-type EU-1 molecule
Sieve silica alumina ratio, Pt metal component percentage composition are as shown in table 1, which is denoted as PtEUVS-1.
Comparative example 2:
EU-1 molecular sieve is synthesized according to patent CN201610102491 embodiment and prepares Pt-HEU-1 molecular sieve catalyst:
1) 6.0g deionized water and 0.22g sodium hydroxide, 0.5g hexamethylene bromide, 1.2g white carbon black (solid content are taken
92wt%), 0.14g sodium metaaluminate (Al2O3: 41wt%) mixing, 2h is stirred, is placed in reaction kettle, carries out first time ageing: old
Change 80 DEG C of temperature, digestion time is for 24 hours.γ-glycidyl ether oxygen propyl trimethoxy of silicon source 3mol% is added after ageing
Silane.Carry out second of ageing again: 100 DEG C of Aging Temperature, digestion time 12h.In 170 DEG C of crystallization 60h after ageing, filter
Simultaneously 120 DEG C of dry 12h are washed, 550 DEG C of roasting 4h is warming up to, obtains EU-1 molecular screen primary powder.
2) by above-mentioned EU-1 molecular screen primary powder by 80 DEG C with the ammonium chloride solution of 1.0mol/L according to solid-liquid mass ratio
1:20 carries out ion exchange 2 times and then calcines 6 hours in 120 DEG C of dryings and 540 DEG C to be converted to H-type EU-1.
3) 17.85g H-type EU-1 molecular sieve is placed in 86.4g concentration as carrier is 0.02mol/L chloroplatinic acid
(H2PtCl6) in aqueous solution, 6h is stirred at 80 DEG C；It then heats to 90 DEG C to be evaporated aqueous solution, and the dry 12h at 105 DEG C,
The solid content of load chloroplatinic acid is obtained, the solid content for loading chloroplatinic acid is roasted into 6h in 450 DEG C of air atmospheres, in mass fraction
For 10%H2/N2In 300 DEG C of roasting 4h obtain Pt-HEU-1 molecular sieve catalyst, content is 0.75wt%, H to Pt in the catalyst
Type EU-1 silica alumina ratio (nSiO2/nAl2O3) it is 32, catalyst preparation compound used therefor type, H-type EU-1 molecular sieve silica alumina ratio, Pt
Metal component percentage composition is as shown in table 1, which is denoted as PtEUVS-2.
Comparative example 3:
EU-1 molecular sieve is synthesized according to patent CN201610255048 embodiment: taking 1.35mol dimethyl stearyl [3-
(trimethoxy silicon substrate) propyl] ammonium chloride, it is dissolved in 16% methanol aqueous solution of 750ml, 300g is added after dissolving completely
The silica of (5mol) specific surface area 200m2/g, partial size 12nm, are poured into 2000ml three-necked flask, 100 DEG C of return stirrings
10h, by obtained solid ethanol washing, 100 DEG C of dryings, grinding obtains the SiO 2 powder of surface silanization.
2.6g sodium hydroxide is added in 10ml distilled water, 2.0g sodium metaaluminate (Al is added after stirring clarification2O3:
41wt%), the double ammonium dissolution clarifications of 17.2g hexamethyl bromination are added after being completely dissolved, add 0.8g sodium fluoride and 0.8g nitric acid
Ammonium is added 0.4g crystal seed and dissolves 20min, is eventually adding the SiO 2 powder of above-mentioned surface silanization after clarification to be dissolved
42.2g stirs 4h at room temperature, obtains silica-alumina gel.
Obtained silica-alumina gel is fitted into the reaction kettle with polytetrafluoroethyllining lining of sealing, 100 DEG C of pre- crystallization 16h,
Then heat to 160 DEG C of crystallization 12 days.Obtained solid product is taken out, is washed to neutrality with distillation, 120 DEG C of dry 12h are warming up to
550 DEG C of logical oxygen roast 4h, obtain mesoporous EU-1 molecular screen primary powder.
3) by above-mentioned EU-1 molecular screen primary powder by 80 DEG C with the ammonium chloride solution of 1.0mol/L according to solid-liquid mass ratio
1:20 carries out ion exchange 2 times and then calcines 6 hours in 120 DEG C of dryings and 540 DEG C to be converted to H-type EU-1.
It is 0.02mol/L chloroplatinic acid (H that 17.85g H-type EU-1 molecular sieve, which is placed in 86.4g concentration as carrier,2PtCl6)
In aqueous solution, 6h is stirred at 80 DEG C；It then heats to 90 DEG C to be evaporated aqueous solution, and the dry 12h at 105 DEG C, be loaded
The solid content for loading chloroplatinic acid is roasted 6h in 450 DEG C of air atmospheres by the solid content of chloroplatinic acid, is 10% in mass fraction
H2/N2In 300 DEG C of roasting 4h obtain Pt-HEU-1 molecular sieve catalyst, content is 0.75wt%, H-type EU-1 to Pt in the catalyst
Silica alumina ratio (nSiO2/nAl2O3) it is 86, catalyst preparation compound used therefor type, H-type EU-1 molecular sieve silica alumina ratio, Pt metal group
Divide percentage composition as shown in table 1, which is denoted as PtEUVS-3.
Table 1
Application Example: evaluation catalyst property
C8 aromatics isomerization applicating expedition is carried out to the catalyst that above-described embodiment 1~6 and comparative example 1~3 obtain:
Stainless steel reactor on small fixed reaction unitMiddle filling 10g catalyst,
At 300 DEG C, under the conditions of 0.1MPa, in the H that flow velocity is 100ml/min2Middle processing 3h.By C8Aroamtic hydrocarbon raw material is used tricks by surge tank
Amount, which is pumped into reactor and contacts with the catalyst of heat, is reacted, and product enters high pressure knockout drum, and liquid product is by its bottom point
It measures out and with electronic scale.Raw material and product use 6890 gas chromatograph fid detector of Agilent to analyze respectively.
Reaction condition are as follows: 375 DEG C, 1.0MPa, hydrogen/hydrocarbon molar ratio 5:l, feedstock quality air speed 3.5h-1.In C8 aromatic hydrocarbons material
The content ratio of each component is as shown in table 2, and catalyst title and evaluation effect are as shown in table 3.
Evaluation index: according to activity (meta-xylene conversion ratio CMX/ %, conversion of ethylbenzene CEB/ % and paraxylene PX is flat
Weigh content value PX/ Σ X/%) and selectivity (PX/OX ratio, xylene loss XL/ %) evaluation catalyst performance.
It related calculation formula based on constituent mass content and is defined as follows:
Σ X=PX+OX+MX
PX balanced contents value: PX/ Σ X=PX/ (PX+MX+OX) × 100%
Table 2:C8The content ratio of each component in aromatic hydrocarbons material
| Ingredient names | Non-aromatics | Benzene | Toluene | Ethylbenzene | Paraxylene | Meta-xylene | Ortho-xylene | C9+ aromatic hydrocarbons |
| Content wt% | 9.62 | 0.03 | 0.52 | 16.92 | 0.19 | 54.98 | 17.70 | 0.04 |
Table 3: evaluating catalyst effect
| Number | Catalyst | CMX/ % | CEB, wt% | PX/ Σ X, wt% | PX/OX ratio | XL/ % |
| Embodiment 1 | PtEUO-1 | 27.8 | 54.96 | 23.93 | 1.06 | 3.7 |
| Embodiment 2 | PtEUO-2 | 27.1 | 50.89 | 23.71 | 1.05 | 2.3 |
| Embodiment 3 | PtEUO-3 | 27.3 | 49.35 | 23.73 | 1.08 | 2.9 |
| Embodiment 4 | PtEUO-4 | 27.5 | 52.78 | 23.91 | 1.12 | 3.7 |
| Embodiment 5 | PtEUO-5 | 27.4 | 50.95 | 23.90 | 1.09 | 3.2 |
| Embodiment 6 | PtEUO-6 | 27.6 | 50.47 | 23.91 | 1.15 | 2.9 |
| Comparative example 1 | PtEUVS-1 | 25.3 | 33.46 | 22.34 | 2.1 | 7.7 |
| Comparative example 2 | PtEUVS-2 | 24.9 | 33.04 | 22.39 | 1.4 | 16.2 |
| Comparative example 3 | PtEUVS-3 | 25.2 | 33.43 | 22.41 | 1.1 | 16.6 |
As can be seen from Table 3, high score is loaded on the H-type EU-1 molecular sieve for the method preparation that the embodiment of the present invention 1~6 provides
It dissipates property Pt metal catalyst and is applied to C8Aromatics isomerization reaction, catalyst performance have reached following index: MX conversion ratio
(CMX/ %) > 27%, conversion of ethylbenzene CEB/ % > 49%, PX balanced contents value (PX/ Σ X/%) > 23.7%, basically reach heat
Mechanical balance value, xylene loss (XL/ %) < 4%；And catalyst performance index prepared in comparative example 1~3: CMX/ %
< 26%, CEB/ % < 49%, PX/ Σ X/% < 22.5%, XL/ % > 7.0%, this illustrate embodiment provide catalyst on have
Product yield, conversion of ethylbenzene and the C of higher PX mesh8Aromatics yield, it was demonstrated that the catalyst has C8Aromatics isomerization reaction is good
Good activity.
Examples detailed above is technical conception and technical characteristics to illustrate the invention, can not be limited with this of the invention
Protection scope.The equivalent transformation or modification that all essence according to the present invention is done, should all cover in protection scope of the present invention
Within.
Claims (9)
1. a kind of molecular sieve carried high-dispersion metal catalyst of H-type EUO, it is characterised in that: catalyst activity component VIII group gold
Belong to nanoparticle high-dispersion load in H-type EUO molecular sieve pore passage, tenor is 0.01~2.0wt% in the catalyst；
H-type EUO molecular sieve silica alumina ratio be 10~200, in nanocrystal assemble elliptical shape ball pattern, the EUO molecular sieve be selected from EU-1,
ZSM-50 or TPZ-3 type molecular sieve.
2. catalyst described in claim 1, wherein group VIII metal is appointed in Pt, Pd, Rh, Ir, Ru, Re, Au, Ag, Cd
It is a kind of.
3. the preparation method of catalyst described in claim 1, it is characterised in that: the molecular sieve carried high dispersion metal of H-type EUO
Catalyst is prepared using one kettle way crystallization synthetic reaction.
4. the preparation method of catalyst as claimed in claim 1 or 2, comprising the following steps:
1) metal precursor, organic thiol ligand, NaOH and water are according to molar ratio 1:(4.0~8.0): (12~20): (100~
500) mixed dissolution, ligand exchange are filtered, washed to obtain water-soluble M-S complex；
2) M-S complex obtained in step 1) is added in the material comprising silicon source, silicon source and inorganic base, formation
M-S complex in mixture: inorganic base: SiO2: Al2O3: organic formwork agent: H2The molar ratio of O be (0.0005~
0.008): (0.02~0.2): 1:(0.005~0.05): (0.05~0.5): (10~50) it is brilliant to add H-type EUO molecular sieve
Kind is uniformly mixed, and crystal seed accounts for the 1%~10% of mixture solid weight percentage；
3) step 2) mixture is transferred in hydrothermal crystallizing kettle, it is 12~48 hours still aging at 100~150 DEG C, then rise
Temperature is after the completion of crystallization, to be filtered, washed dynamic crystallization 24~168 hours under 50~250rpm to 170~190 DEG C of revolving speeds,
It is 12~48 hours dry at 100~130 DEG C, obtain the EUO molecular screen primary powder containing metal M；
4) the EUO molecular screen primary powder containing metal M for obtaining step 3) is in 500~650 DEG C of roastings, 2~10 hours removing templates
Agent obtains EUO molecular sieve powder wherein the heating rate from room temperature to maturing temperature is 1~10 DEG C/min；
5) the EUO molecular sieve powder for obtaining step 4) carries out Na in ammonium salt exchange removing molecular sieve+Ion is roasted again
Processing, obtains the EUO molecular sieve of H-type；
6) by the product H after step 5) roasting2The reduction of/He gaseous mixture, obtains the molecular sieve carried high dispersion metal nanometer of H-type EUO
The catalyst of particle.
5. preparation method as claimed in claim 4, group VIII metal are any in Pt, Pd, Rh, Ir, Ru, Re, Au, Ag, Cd
Kind, it is preferably any in Pt, Pd, Rh, Ir, Ru.
6. preparation method as claimed in claim 4, it is characterised in that: organic thiol ligand is selected from 3- mercaptopropyi three in step 1)
Methoxy silane, 3- Mercaptopropyltriethoxysilane, 2- ammonium mercaptoacetate, methyl-[2- (first sulfydryl) ethyl] amine, 2- sulfydryl
It is any in propionic acid ammonium；Metal precursor is selected from Pt (NH in step 1)3)4]Cl2, acetylacetone,2,4-pentanedione platinum, [Pt (NH2CH2CH2NH2)2]
Cl2、[Pt(NH2CH2CH2NH2)2](NO3)2、Pt(NH3)4](NO3)2、Pd(NH3)4]Cl2, palladium acetylacetonate, [Pd
(NH2CH2CH2NH2)2]Cl2、[Pd(NH2CH2CH2NH2)2](NO3)2、Pd(NH3)4](NO3)2、Rh(NH3)4]Cl2, acetylacetone,2,4-pentanedione
Rhodium, [Rh (NH2CH2CH2NH2)2]Cl2、[Rh(NH2CH2CH2NH2)2](NO3)2、Rh(NH3)4](NO3)2、Ru(NH3)4]Cl2, second
Acyl acetone ruthenium, [Ru (NH2CH2CH2NH2)2]Cl2、[Ru(NH2CH2CH2NH2)2](NO3)2、Ru(NH3)4](NO3)2、Ir(NH3)4]
Cl2, acetylacetone,2,4-pentanedione iridium, [Ir (NH2CH2CH2NH2)2]Cl2、[Ir(NH2CH2CH2NH2)2](NO3)2、Ir(NH3)4](NO3)2In appoint
It is a kind of；Inorganic base is selected from NaOH, Na in step 2)2O、KOH、K2At least one of O；Silicon source is selected from silica solution, water glass in step 2)
Glass, sodium metasilicate, Silica hydrogel, silicon aerosol, white carbon black, silochrom, methyl silicate, silester, at least one in silicic acid propyl ester
Kind；Silicon source is in aluminum sulfate, sodium aluminate, boehmite, aluminium isopropoxide, aluminum nitrate, aluminium chloride, aluminium oxide, aluminium hydroxide
It is at least one；Organic formwork agent described in step 2) is bi-quaternary ammonium salt template；Ammonium salt is selected from ammonium nitrate, sulfuric acid in step 5)
Ammonium, ammonium chloride, any in ammonium acetate, concentration is 0.2~2.0mol/L.
7. any preparation method of claim 4-6, it is characterised in that: organic thiol ligand is selected from 3- mercapto in step 1)
It is any in base propyl trimethoxy silicane, 3- mercapto propyl-triethoxysilicane；Metal precursor is selected from Pt (NH in step 1)3)4]
Cl2, acetylacetone,2,4-pentanedione platinum, [Pt (NH2CH2CH2NH2)2]Cl2、[Pt(NH2CH2CH2NH2)2](NO3)2、Pt(NH3)4](NO3)2In appoint
It is a kind of；Inorganic base is NaOH in step 2).
8. any preparation method of claim 4-6, which is characterized in that organic formwork agent described in step 2) is selected from 1,
Bis- (N- methylpyrrole) hexanes of 6-, bis- (3- methylpyrrole) hexanes of 1,6-, 1,6- bis- (N- methylimidazole) hexanes, 1,6-
Bis- (the N- methylimidazole quinoline) hexanes of bis- (2,3- methylimidazole) hexanes, 1,6-, 1,6- bis- (N- methyl nafoxidines)
Bis- (N- methylpyrrole) butane of hexane, 1,4-, bis- (N- methylpyrrole) pentanes of 1,5-, 1,7- bis- (N- methylpyrrole) heptan
Bis- (N- methylpyrrole) octanes of alkane, 1,8-, bis- (N- methylpyrrole) butane of 1,4-, bis- (the N- methylpyrroles) penta of 1,5-
Bis- (N- methylpyrrole) heptane of alkane, 1,7-, bis- (N- methylpyrrole) octanes of 1,8-, bis- (N- methylimidazole) fourths of 1,4-
Bis- (N- methylimidazole) pentanes of alkane, 1,5-, bis- (N- methylimidazole) heptane of 1,7-, 1,8- bis- (N- methylimidazoles) are pungent
Bis- (the N- methylimidazole quinoline) butane of alkane, 1,4-, bis- (the N- methylimidazole quinoline) pentanes of 1,5-, bis- (the N- methylimidazole quinolines of 1,7-
) heptane, at least one of bis- (N- methylimidazole quinoline) octanes of 1,8-.
9. preparation method according to any one of claims 8, it is characterised in that: step 5) is by the EUO molecular sieve powder after removed template method
End with 0.5~5.0mol/L ammonium salt solution according to mass ratio 1:(5~25) ratio ion exchange 1 is carried out at 60~100 DEG C
~4 times, Na+ ion is removed, is roasted 2~10 hours for 500~650 DEG C again.
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Application publication date: 20190528 |