CN107020145A - A kind of mesoporous IM-5 molecular sieves and preparation method - Google Patents
A kind of mesoporous IM-5 molecular sieves and preparation method Download PDFInfo
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
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- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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Abstract
A kind of molecular sieves of mesoporous IM 5, with 300~450m2/ g specific surface area, 0.3~0.50cm3/ g pore volume, most probable mesopore diameter is 3~20nm.The molecular sieves of mesoporous IM 5 of the present invention are made by adding appropriate pore creating material in synthesis material, and described is mesoporous on the molecular sieve crystals of IM 5, alkylation of toluene methanol reaction is used it for, with preferable coking resistivity.
Description
Technical field
The present invention is a kind of Si-Al molecular sieve and preparation method, is a kind of mesoporous IM-5 molecules specifically
Sieve and preparation method.
Background technology
Petro chemical industry and the development of Fine Chemical Industry, and increasingly strict sustainable development and ring
Protect the requirement of production so that the demand to new catalytic material is being continuously increased.
1997, Compagnie Francise des Petroles (IFP) was in WO98/17581A1, and CN1234012A is first public
IM-5 molecular sieves.The molecular sieve has two-dimentional ten-ring pore canal system, in the short-bore that the third dimension is limited
Road, pore canal system is quite similar with ZSM-5 molecular sieve, with good shape selectivity.Meanwhile, IM-5 points
Sub- sifter device has good heat endurance and hydrothermal stability, and catalytic performance is excellent, in petrochemical industry catalytic reaction
In have a wide range of applications, such as hydrogenation/dehydrogenation metallic element load IM-5 molecular sieves can have as catalyst
Effect improves paraffin pour point (US5989410A)；IM-5 molecular sieves and USY are mixed as FCC catalyst,
Improve reaction mass conversion ratio, high yield propylene, butylene (US6007698A).
In addition, IM-5 molecular sieves show excellent catalytic performance in alkylation of toluene methanol reaction, such as
Chinese patent 200910180771.2 is pointed out, in alkylation of toluene methanol reaction, IM-5 molecular sieve catalytics
The toluene conversion and dimethylbenzene selective of agent are respectively 45%~53% and 65%~75%, than ZSM-5 points
Son sieve is significantly improved for the toluene conversion (~35%) and dimethylbenzene selective (60~70%) of catalyst.
For most of reactions by this kind of mesoporous molecular sieve catalysis of ZSM-5 and IM-5, mainly transgranular
Reaction, i.e., be the home court institute of reaction in the duct of molecular sieve.But, due to the less duct of mesoporous molecular sieve
Size (0.5~0.6nm) limits diffusion of some macromoleculars into hole；On the other hand, due to molecular sieve
Crystal grain is general all larger, is unfavorable for reactant molecule and expands to intra-die diffusion and product molecule sieve exterior surface
Dissipate, so as to easily bring the decline of reactivity and stability.
In recent years, the research on mesopore molecular sieve causes people's extensive concern, especially mesoporous ZSM-5
Have made some progress.
Document (D.P.Serrano, J.Aguado.Chem.Mater., 2009,21,641-654), which is reported, to be adopted
Have with a kind of silylating reagent containing phenyl ring come synthesising mesoporous ZSM-5, synthesized mesoporous ZSM-5
3~8nm's is transgranular mesoporous.
Document (J.Kim, C.Jo, R.Ryoo, J.Mater.Chem.A, 2014,2,11905-11912) is introduced
Using parents organosilan surfactant [(CH3O)3SiC3H6N(CH3)2CnH(2n+1)]+Cl-(n=12,16,
18) mesoporous MOR/CHA/FAU molecular sieves can effectively be synthesized, with the MOR molecules being conventionally synthesized
Sieve is compared, and is had more in the alkylated reaction of benzene and phenmethylol using the mesoporous MOR synthesized by this method
High reactivity.
Liu Li it is good et al. (Lijia Liu, Hongbin Wang, Runwei Wang, RSC Adv., 2014,4,
21301-21305./Appl.201410520157.7) small molecule is added in the synthesis of ZSM-5 molecular sieve
METHYLPYRROLIDONE (NMP) has synthesized a kind of " plug-in card " type multi-stage porous ZSM-5, and it is different
More conventional ZSM-5 shows higher cracking activity in the cracking reaction of propyl benzene.
CN101723403A discloses a kind of preparation of the mesoporous ZSM-5 molecular sieve being combined with micropore multi-stage porous
Method, its specific synthetic method be in the synthetic system of ZSM-5 molecular sieve add polysaccharide compound or
Its derivative is filled in the pore creating material inside molecular sieve after being removed by high-temperature roasting as mesoporous pore creating material
It is internally formed in molecular sieve mesoporous, the mesoporous ZSM-5 synthesized by this method is in toluene disproportionation process than normal
The life longer more than 20% of ZSM-5 molecules is advised, more preferable stability is shown.
The content of the invention
It is an object of the invention to provide a kind of mesoporous IM-5 molecular sieves and preparation method, the mesoporous IM-5 molecules
It is mesoporous with what is enriched on the crystal grain of sieve, it can improve its anti-carbon deposition ability for chemical reaction catalyst.
The mesoporous IM-5 molecular sieves that the present invention is provided, with 300~450m2/ g specific surface area,
0.30~0.50cm3/ g pore volume, most probable mesopore diameter is 3~20nm.
Mesoporous IM-5 molecular sieves of the present invention are made by adding appropriate pore creating material in synthesis material, institute
That states is mesoporous on IM-5 molecular sieve crystals, alkylation of toluene methanol reaction is used it for, with preferable
Coking resistivity.
Brief description of the drawings
Fig. 1 is the X-ray diffractogram (XRD) of the synthetic sample of comparative example 1；
Fig. 2 is the transmission electron microscope shape appearance figure (TEM) of the synthetic sample of comparative example 1；
Fig. 3 (a) is the adsorption-desorption isothermal of the synthetic sample of comparative example 1；
Fig. 3 (b) is the graph of pore diameter distribution of the synthetic sample of comparative example 1；
Fig. 4 (a) is the 2-in-1 adsorption-desorption isothermal into sample of comparative example；
Fig. 4 (b) is the 2-in-1 graph of pore diameter distribution into sample of comparative example；
Fig. 5 is the X-ray diffractogram (XRD) of the synthetic sample of present example 1；
Fig. 6 is the transmission electron microscope shape appearance figure (TEM) of the synthetic sample of present example 1；
Fig. 7 (a) is the adsorption-desorption isothermal of the synthetic sample of present example 1；
Fig. 7 (b) is the graph of pore diameter distribution of the synthetic sample of present example 1；
Fig. 8 (a) is the 2-in-1 adsorption-desorption isothermal into sample of present example；
Fig. 8 (b) is the 2-in-1 graph of pore diameter distribution into sample of present example；
Fig. 9 (a) is the adsorption-desorption isothermal of the synthetic sample of present example 3；
Fig. 9 (b) is the graph of pore diameter distribution of the synthetic sample of present example 3；
Figure 10 is the transmission electron microscope shape appearance figure (TEM) of the synthetic sample of present example 4；
Figure 11 (a) is the adsorption-desorption isothermal of the synthetic sample of present example 4；
Figure 11 (b) is the graph of pore diameter distribution of the synthetic sample of present example 4；
Figure 12 (a) is the adsorption-desorption isothermal of the synthetic sample of present example 5；
Figure 12 (b) is the graph of pore diameter distribution of the synthetic sample of present example 5；
Figure 13 (a) is the adsorption-desorption isothermal of the synthetic sample of comparative example 3；
Figure 13 (b) is the graph of pore diameter distribution of the synthetic sample of comparative example 3；
Figure 14 (a) is the adsorption-desorption isothermal of the synthetic sample of comparative example 4；
Figure 14 (b) is the graph of pore diameter distribution of the synthetic sample of comparative example 4.
Embodiment
The IM-5 molecular sieves that the present invention is provided contain micropore and transgranular mesoporous simultaneously, are former in synthesis of molecular sieve
Pore creating material is added in material, or after pre- crystallization, adds pore creating material and carries out crystallization and be made, mesoporous life
Improved into the duct utilization rate of IM-5 molecular sieves is made, it is possible to resolve IM-5 molecular sieves are used for chemical reaction catalyst
When, the problem of deactivation rate is fast.
Specific surface area preferably 320~400m of mesoporous IM-5 molecular sieves of the present invention2/ g, pore volume are preferred
0.30~0.40cm3/ g, wherein most probable mesopore diameter preferably 5~15nm.
The mesoporous IM-5 zeolite crystals that the present invention is provided are strip, and regular appearance, grain size is 150
It is distributed with × 300nm or so, crystal grain transgranular mesoporous.
The preparation method of mesoporous IM-5 molecular sieves of the present invention has two kinds, and one kind is in synthesis material
Add after pore creating material, then hydrothermal crystallizing and be made, another is that synthesis material first is carried out into pre- crystallization, is added
Pore creating material is synthesized after hydrothermal crystallizing.
The preparation method for the first mesoporous IM-5 molecular sieve that the present invention is provided, comprises the following steps：
(1) by inorganic base, silicon source, double (N- crassitudes) the pentamethylene base cations of template -1,5-
Salt it is soluble in water, be well mixed, pore creating material and silicon source added thereto, colloid or solidliquid mixture is made,
The mol ratio of wherein each reactant is SiO2：Al2O3：M2O：SDA：PEA：H2O=1：(0.005~0.1)：
(0.1~0.4)：(0.05~0.3)：(0.03~0.4)：(5~50), the M2O is alkali metal oxygen
Compound, SDA is template, and PEA is pore creating material, and described pore creating material is N- alkyl pyrrolidones, institute
State the preferred methyl of substitution alkyl R, ethyl or the poly- ethylene group on N atoms.
(2) colloid obtained by (1) step or solidliquid mixture are moved in crystallizing kettle, 120~200 DEG C, from
Hydrothermal crystallizing 1~15 day, collects solid product, drying under raw pressure.
The preparation method for second of mesoporous IM-5 molecular sieve that the present invention is provided, comprises the following steps：
(1) by inorganic base, silicon source, double (N- crassitudes) the pentamethylene base cations of template -1,5-
Salt it is soluble in water, add silicon source and be well mixed, in 120~150 DEG C of pre- crystallization 1~3 day, then thereto plus
Enter pore creating material, colloid or solidliquid mixture is made, wherein the mol ratio of each reactant is SiO2：Al2O3：
M2O：SDA：PEA：H2O=1：(0.005~0.1)：(0.1~0.4)：(0.05~0.3)：(0.03~0.4)：
(5~50), the M2O is alkali metal oxide, and SDA is template, and PEA is pore creating material, described
Pore creating material be N- alkyl pyrrolidones, the preferred methyl of substitution alkyl, ethyl or poly- on the N atoms
Ethylene group,
(2) colloid obtained by (1) step or solidliquid mixture are moved in crystallizing kettle, 155~200 DEG C, from
Hydrothermal crystallizing 1~15 day, collects solid product, drying under raw pressure.
In the above method, (1) step is the synthesis material for preparing synthesising mesoporous IM-5 molecular sieves, the nothing of addition
Machine alkali source presses M contained therein2O gauge, described M is alkali metal, preferably sodium or potassium, and silicon source presses institute
The Al contained2O3Meter, silicon source presses contained SiO2Meter, first method is by pore creating material and silicon source, silicon source and mould
Plate agent is mixed and made into synthesis material；After second method first mixes silicon source, silicon source, template, carry out pre-
Crystallization, adds pore creating material and synthesis material is made.
In above two method, in final synthesis material made from (1) step, mole composition of each reactant
Preferably SiO2：Al2O3：M2O：SDA：PEA：H2O=1：(0.0083~0.05)：(0.15~0.4)：
(0.08~0.2)：(0.05~0.3)：(7~40).
In the above method, the preferred amorphous silica of silicon source, waterglass, Ludox, solid oxidation
One or more in silicon, solid silicone, diatomite, white carbon and tetraethyl orthosilicate, more preferably Ludox
And/or solid silicone.
The preferred sodium aluminate of described silicon source, sodium metaaluminate, aluminum sulfate, aluminium chloride, aluminum nitrate, aluminium hydroxide,
In one or more in aluminum oxide and boehmite, more preferably sodium metaaluminate, aluminum nitrate and aluminum sulfate
It is one or more.
The preferred sodium hydroxide of described inorganic base or potassium hydroxide.
Described pore creating material is N- alkyl pyrrolidones, shown in its general structure such as formula (I)：
In formula (I), the preferred methyl of substitution alkyl, ethyl or poly- ethylene group on the N atoms are described
The degree of polymerization of ethene preferably 40~300 in poly- ethylene group, preferred compound for METHYLPYRROLIDONE or
At least one of N- ethyl-2-pyrrolidones and polyethylene -2-Pyrrolidone (PVP).
Described template is double (N- crassitudes) the pentamethylene base cations of 1,5-, its structural formula such as formula
(II) shown in,
Anion with the cation coordination into salt can be chlorine or bromine, preferably bromine, and template preferably is 1,
Double (N- crassitudes) the pentamethylene base dibromo salts of 5-.
Pre- crystallization in second method is by synthesis material pre- crystallization, described pre- crystallization at a lower temperature
Preferably 130~140 DEG C of temperature, preferably 24~50 hours time.
(2) step is the hydrothermal crystallizing of synthesis material in methods described, and crystallization is carried out at autogenous pressures, the
A kind of preferably 140~180 DEG C of method hydrothermal crystallizing temperature, preferably 4~10 days hydrothermal crystallizing time.Second of side
Preferably 160~190 DEG C of hydrothermal crystallizing temperature described in method, preferably 3~10 days hydrothermal crystallizing time.
Described crystallization product produces mesoporous IM-5 molecular sieves, the drying temperature after washing and drying
It is preferred that 80~120 DEG C.Template therein can be removed after molecular sieve is fired after drying, sintering temperature is preferred
550~650 DEG C.
The mesoporous IM-5 molecular sieves that the present invention is provided, cracking reaction or the alkane of aromatic hydrocarbons available for macromolecular hydrocarbon
Group-transfer or the catalyst of alkylated reaction, are such as used for alkylation of toluene methanol reaction, in gas phase non-hydrogen bar
Under part, using toluene and methanol as raw material, it is that 0.10~1.0MPa, temperature are 400~500 DEG C in pressure, enters
Feed liquid body air speed is 1.0~4.0h-1Under conditions of reacted.
The present invention is further described below by example, but the present invention is not limited thereto.
In present example and comparative example, the AS-3, AS-6 produced using Quantachrome instrument companies
The method that static n2 absorption apparatus determines molecular sieve physical parameter is as follows：
(1) sample is placed in sample processing system, 1.33 × 10 is evacuated at 300 DEG C-2Pa, insulation is protected
4h is pressed, sample is purified,
(2) under liquid nitrogen temperature 77K (- 196 DEG C), measurement purification sample is not pressing P/P on year-on-year basis0(P is
N2Partial pressure, P0For N2Saturated vapor pressure) under the conditions of to the adsorbance and desorption rate of nitrogen, obtain N2
Adsorption-desorption isothermal curve, then calculates specific surface area using two parameter BET formula, takes than pressure P/P0=0.98
Following adsorbance is the pore volume of sample, and the pore size distribution curve of hollow sections is calculated using BJH formula.
Comparative example 1
With document Determination of the Pore Topology of Zeolite IM-5by Means of
CatalyticTest Reactions and Hydrocarbon Adsorption Measurements.(Journal of
Catalysis 2000:189,382~394) disclosed in method synthesis IM-5 molecular sieves.
By double (N- crassitudes) the pentamethylene base dibromo salts of 1,5-s of the 3.35g containing 0.0084molBe dissolved in 36.00g deionized waters, then by 3.00g white carbons (Aerosil 200,
Degussa above-mentioned solution) is added under conditions of stirring, then is separately added into 0.228g sodium aluminates (Carlo
Erba, 56%Al2O3), 1.053gNaOH (Prolabo, 98%) and 0.515gNaBr (Scharlau, 99%)
Well mixed, a mole composition for reactant mixture is SiO2：Al2O3：Na2O：NaBr：SDA：H2O=1：
0.025：0.283：0.1：0.167：40, wherein SDA are double (N- crassitudes) the pentamethylene bases of 1,5-
Dibromo salt.
Said mixture is stirred into 30 minutes obtained colloids in 25 DEG C, the colloid is transferred to band polytetrafluoro
In the closed crystallizing kettle of ethene liner, in 175 DEG C of crystallization 10 days.Crystallization product is through washing, filtering, gained
Solid is dried 12 hours in 80 DEG C, and 550 DEG C of roastings obtain IM-5 molecular sieve N for 5 hours, and its XRD is shown in
Fig. 1, crystallinity is set to 100%, and transmission electron microscope photo is shown in Fig. 2, and adsorption-desorption and pore size distribution curve are as schemed
Shown in 3 (a) and Fig. 3 (b), specific surface area and pore volume are shown in Table 2.
Comparative example 2
With document Synthesis, characterization, and catalytic properties of zeolites IM-5
and NU-88(Journal of Catalysis 2003:215151~170) disclosed in method synthesis IM-5 point
Son sieve.
By double (N- crassitudes) the pentamethylene base dibromo salts of 1,5-s of the 3.00g containing 0.0075mol with
2.92gNaOH concentration is the 50 mass % aqueous solution, 0.427gAl (NO3)3·9H2O (98%, Junsei),
3.00g white carbons (Aerosil 200, Degussa) and 34.26g deionized waters are mixed and made into colloid, and reaction is mixed
A mole composition for compound is SiO2：Al2O3：Na2O：SDA：H2O=1：0.0167：0.365：0.15：
40, wherein SDA are double (N- crassitudes) the pentamethylene base dibromo salts of 1,5-.
Said mixture is stirred 30 minutes in 25 DEG C, the closed crystalline substance with polytetrafluoroethyllining lining is then moved to
Change in kettle, be 100rpm, crystallization rotated under the conditions of 160 DEG C 14 days in rotating speed.Crystallization product through washing,
Filtering, solid obtain molecular sieve M in 5 hours in 80 DEG C of dry hours, and in 550 DEG C of roastings, its XRD
Figure is shown as IM-5 molecular sieves, and crystallinity is 90.0%, and its transmission electron microscope photo is similar with Fig. 2, and absorption-
Desorption and pore size distribution curve are shown in Fig. 4 (a) and Fig. 4 (b) respectively, and specific surface area and pore volume are shown in Table 2.
Example 1
Mesoporous IM-5 molecular sieves are prepared with the inventive method.
By 0.14g NaAlO2, 1.39gNaOH, 3.00g template 1, double (the N- crassitudes) penta of 5-
Support group dibromo salt is dissolved in 30.00g deionized waters, is stirred, and adds 0.25g pore creating material N- methyl -2-
Pyrrolidones (NMP), under stirring, adds 10.00g Ludox (SiO2The mass % of content 30) mixing
Uniformly, a mole composition for gained reactant mixture is SiO2：Al2O3：Na2O：SDA：PEA：H2O=1：
0.0167：0.365：0.15：0.05：40, wherein PEA are pore creating material, and SDA is template, similarly hereinafter.
Obtained reactant mixture colloid is transferred to closed crystallizing kettles of the 100mL with polytetrafluoroethyllining lining
In, the lower dynamic crystallization of 160 DEG C of stirrings 14 days, crystallization product is through washing, filtering, and solid is dry in 80 DEG C
Dry 12 hours, 550 DEG C were calcined 5 hours, obtain molecular sieve-4 A, and its crystallinity is 87.0%, and XRD is shown in
Fig. 5, is shown as IM-5 molecular sieves, transmission electron microscope photo see on Fig. 6, display crystal grain have it is mesoporous be uniformly distributed,
Adsorption-desorption and pore size distribution curve are shown in Fig. 7 (a) and Fig. 7 (b) respectively, and specific surface area and pore volume are shown in
Table 2.
Example 2
By 0.23g AlCl3, 1.46gNaOH, 3.00g template 1, double (N- crassitudes) the pentamethylene bases of 5-
Dibromo salt is dissolved in 35.75g deionized waters, is stirred, and adds 0.28g pore creating material N- ethyl -2- pyrroles
Alkanone (NEP), under stirring, adds solid silicone 3.25g (SiO2Content is 92.17 mass %), mix
Close uniform, a mole composition for gained reactant mixture is SiO2：Al2O3：Na2O：SDA：PEA：H2O=1：
0.0167：0.365：0.15：0.05：40.
Obtained reactant mixture colloid is transferred to closed crystallizing kettles of the 100mL with polytetrafluoroethyllining lining
In, the lower dynamic crystallization of 160 DEG C of stirrings 14 days, crystallization product is through washing, filtering, and solid is in 120 DEG C
Dry 8 hours, 550 DEG C are calcined 3 hours, obtain molecular sieve B, its XRD is shown as IM-5 molecules
Sieve, crystallinity is 93.3%, and adsorption-desorption and pore size distribution curve are shown in Fig. 8 (a) and Fig. 8 (b) respectively,
Specific surface area and pore volume are shown in Table 2.
Example 3
By 0.14g NaAlO2, 1.39gNaOH, 3.00g template 1, double (the N- crassitudes) penta of 5-
Alkane dibromo salt is dissolved in 36.00g deionized waters, is stirred, and adds 12.50g pore creating material polyethylene -2-
Pyrrolidones (PVP), the degree of polymerization of PVP medium vinyls is 45, under stirring, adds white carbon 3.00g,
Well mixed, a mole composition for gained reactant mixture is SiO2：Al2O3：Na2O：SDA：PEA：
H2O=1：0.0167：0.365：0.15：0.05：40.
Obtained reactant mixture colloid is transferred to closed crystallizing kettles of the 100ml with polytetrafluoroethyllining lining
In, 160 DEG C of lower dynamic crystallizations of stirring 14 days stop crystallization, product through washing, filtering, solid in
100 DEG C of dryings 10 hours, 550 DEG C are calcined 4 hours, obtain molecular sieve C, its XRD is shown as IM-5
Molecular sieve, products obtained therefrom crystallinity is 85.7%, adsorption-desorption and pore size distribution curve such as Fig. 9 (a) and figure
Shown in 9 (b), specific surface area and pore volume are shown in Table 2.
Example 4
This example prepares mesoporous IM-5 molecular sieves of the invention using the method for pre- crystallization.
By 0.205g NaAlO2, 0.80gNaOH, 2.40g template 1,5- double (N- crassitudes)
Pentamethylene base dibromo salt is dissolved in 29.67g deionized waters, under stirring, adds 3.33g solid silicones (SiO2Contain
Measure as 90 mass %), it is well mixed.Obtained colloid is transferred to 100ml with polytetrafluoroethyllining lining
In closed reactor, in 140 DEG C of pre- crystallization 2 days, 25 DEG C are cooled to, 0.848g pore creating material N- is added
Ethyl-2-pyrrolidone (NEP), stirs, and gained reactant mixture mole composition is SiO2：Al2O3：
Na2O：SDA：PEA：H2O=1：0.025：0.225：0.12：0.15：15.
The reactant mixture of expanding agent will be added in 175 DEG C of crystallization 4 days at autogenous pressures, crystallization production
Thing is through washing, filtering, and solid is dried 8 hours in 120 DEG C, and 550 DEG C are calcined 3 hours, obtain molecular sieve D,
Its XRD spectra is shown as IM-5 molecular sieves, and crystallinity is 93.2%, and transmission electron microscope photo is shown in Figure 10 (a)
With Figure 10 (b), display crystal grain on have it is mesoporous be uniformly distributed, adsorption-desorption and pore size distribution curve are shown in respectively
Figure 11 (a) and Figure 11 (b), specific surface area and pore volume are shown in Table 2.
Example 5
By 0.205g NaAlO2, 0.80gNaOH, 2.40g template 1,5- double (N- crassitudes)
Pentamethylene base dibromo salt is dissolved in 13.17g deionized waters, under stirring, adds 3.33g solid silicones (SiO2Contain
Measure as 90 mass %), it is well mixed.Obtained colloid is transferred to 100ml with polytetrafluoroethyllining lining
In closed reactor, 140 DEG C of pre- crystallization 2 days are cooled to 25 DEG C, add 1.696g pore creating material N- ethyls -2-
Pyrrolidones (NEP) stirs, and gained reactant mixture mole composition is SiO2：Al2O3：Na2O：
SDA：PEA：H2O=1：0.025：0.225：0.12：0.30：15.
By add expanding agent reactant mixture under 175 DEG C, self-generated pressure crystallization 4 days, crystallization product warp
Washing, filtering, solid are dried 10 hours in 100 DEG C, and 550 DEG C are calcined 3 hours, obtain molecular sieve E,
Its XRD is shown as IM-5 molecular sieves, and crystallinity is 85.5%, adsorption-desorption and pore size distribution curve point
Figure 12 (a) and Figure 12 (b) are not seen, and specific surface area and pore volume are shown in Table 2.
Comparative example 3
By 0.205g NaAlO2, 0.80gNaOH, 2.40g template 1,5- double (N- crassitudes)
Pentamethylene base dibromo salt is dissolved in 13.17g deionized waters, under stirring, adds 3.33g solid silicones (SiO2Contain
Measure as 90 mass %), it is well mixed, obtained colloid is transferred to 100ml with polytetrafluoroethyllining lining
In closed reactor, 140 DEG C of pre- crystallization 2 days are cooled to 25 DEG C, add 0.113g pore creating material N- ethyls -2-
Pyrrolidones (NEP) stirs, and gained reactant mixture mole composition is SiO2：Al2O3：Na2O：
SDA：PEA：H2O=1：0.025：0.225：0.12：0.02：15.
By add expanding agent reactant mixture under 175 DEG C, self-generated pressure crystallization 4 days, crystallization product warp
Washing, filtering, solid are dried 12 hours in 80 DEG C, and 550 DEG C are calcined 3 hours, obtain molecular sieve K, its
XRD is shown as IM-5 molecular sieves, and crystallinity is 97.3%, adsorption-desorption and pore size distribution curve difference
See Figure 13 (a) and Figure 13 (b), specific surface area and pore volume are shown in Table 2.
Comparative example 4
By 0.205g NaAlO2, 0.80gNaOH, 2.40g template 1, double (N- crassitudes) pentamethylenes of 5-
Base dibromo salt and 2.48g pore creating material METHYLPYRROLIDONE (NMP) are dissolved in 13.17g deionized waters
In, under stirring, add 3.33g solid silicones (SiO2Content is 90 mass %) it is well mixed, gained is anti-
Mole composition for answering mixture is SiO2：Al2O3：Na2O：SDA：PEA：H2O=1：0.025：0.225：
0.12：0.50：15, obtained colloid is transferred to closed reactors of the 100ml with polytetrafluoroethyllining lining
In, 140 DEG C of crystallization 2 days, then temperature is improved to 175 DEG C of crystallization 4 days, crystallization product through washing, filtering,
Solid is dried 12 hours in 80 DEG C, and 550 DEG C are calcined 3 hours, obtain molecular sieve Z, its XRD is shown
For IM-5 molecular sieves, crystallinity is 80.4%, and adsorption-desorption and pore size distribution curve are shown in Figure 14 (a) respectively
With Figure 14 (b), specific surface area and pore volume are shown in Table 2.
Comparative example 5~8
Evaluate the catalytic performance of IM-5 molecular sieves prepared by comparative example 1~4.
(1) H-IM-5 molecular sieves are prepared
It is with concentration respectively by NaIM-5 molecular sieves N, M, K, Z for being prepared in comparative example 1~4 sequentially
0.5mol/L ammonium nitrate solution carries out ion exchange 2 times, every time 2 hours in 80 DEG C.By point after exchange
Son sieve is washed with deionized, and dries and is calcined 5 hours then at 90 DEG C for 2 hours, 550 DEG C, H-IM-5 is made
Molecular sieve.
(2) catalytic performance of the H-IM-5 molecular sieves in alkylation of toluene methanol reaction is investigated
On fixed-bed reactor, 2.04gH-IM-5 molecular sieves are loaded, N is used2For carrier gas, by Jia Ben ︰
Methanol molar ratio is passed through toluene and methanol for 2 ︰ 1 amount, in 440 DEG C, 0.5MPa, feedstock quality air speed
2.0h-1, carrier gas N2With mixed material mol ratio be 20 under conditions of reacted, molecule used in each comparative example
The reaction result of sieve is shown in Table 1.
In table 1,
Toluene conversion=(toluene total mole number in aromatic hydrocarbons total mole number-product in product)/(aromatic hydrocarbons in product
Total mole number) × 100%
Dimethylbenzene yield=(dimethylbenzene molal quantity in product)/(aromatic hydrocarbons total mole number in product) × 100%
Example 6~10
The mesoporous NaIM-5 molecular sieves prepared in example 1~5 are taken to carry out ammonium exchange system by the method for comparative example 5
Into hydrogen type molecular sieve, alkylation of toluene methanol reaction is used further to, reaction condition is identical with comparative example 5, each reality
The reaction result of example molecular sieve used is shown in Table 1.
As shown in Table 1, what mesoporous H-IM-5 molecular sieve-4 As~E that prepared by the inventive method was prepared with comparative example
H-IM-5 molecular sieves N, M, K, Z is compared, during initial reaction, toluene conversion and dimethylbenzene yield compared with
It is close, with the extension in reaction time, mesoporous H-IM-5 molecular sieves prepared by the present invention have more preferable
Dimethylbenzene yield is still higher after toluene conversion and dimethylbenzene yield, reaction 50h, illustrates that the present invention prepares
Mesoporous H-IM-5 molecular sieves have preferable activity stability.
Table 1
Table 2
The micropore is the hole that diameter is less than 2nm.
Claims (13)
1. a kind of mesoporous IM-5 molecular sieves, with 300~450m2/ g specific surface area, 0.3~0.50cm3/g
Pore volume, most probable mesopore diameter be 3~20nm.
2. according to the mesoporous IM-5 molecular sieves described in claim 1, it is characterised in that described mesoporous IM-5
The specific surface area of molecular sieve is 320~400m2/ g, pore volume are 0.3~0.4cm3/ g, most probable mesopore diameter is
5~15nm.
3. the preparation method of mesoporous IM-5 molecular sieves, comprises the following steps described in a kind of claim 1：
(1) by inorganic base, silicon source, double (N- crassitudes) the pentamethylene base cations of template -1,5-
Salt it is soluble in water, be well mixed, pore creating material and silicon source added thereto, colloid or solidliquid mixture is made,
The mol ratio of wherein each reactant is SiO2：Al2O3：M2O：SDA：PEA：H2O=1：(0.005~0.1)：
(0.1~0.4)：(0.05~0.3)：(0.03~0.4)：(5~50), the M2O is alkali metal oxygen
Compound, SDA is template, and PEA is pore creating material, and described pore creating material is N- alkyl pyrrolidones, institute
The preferred methyl of substitution alkyl, ethyl or the poly- ethylene group on N atoms are stated,
(2) colloid obtained by (1) step or solidliquid mixture are moved in crystallizing kettle, 120~200 DEG C, from
Hydrothermal crystallizing 1~15 day, collects solid product, drying under raw pressure.
4. in accordance with the method for claim 3, it is characterised in that (1) mole of each reactant described in step
Constitute as SiO2：Al2O3：M2O：SDA：PEA：H2O=1：(0.0083~0.05)：(0.15~0.4)：
(0.08~0.2)：(0.05~0.3)：(7~40).
5. the preparation method of mesoporous IM-5 molecular sieves, comprises the following steps described in a kind of claim 1：
(1) by inorganic base, silicon source, double (N- crassitudes) the pentamethylene base cations of template -1,5-
Salt it is soluble in water, add silicon source and be well mixed, in 120~150 DEG C of pre- crystallization 1~3 day, then thereto plus
Enter pore creating material, colloid or solidliquid mixture is made, wherein the mol ratio of each reactant is SiO2：Al2O3：
M2O：SDA：PEA：H2O=1：(0.005~0.1)：(0.1~0.4)：(0.05~0.3)：(0.03~0.4)：
(5~50), the M2O is alkali metal oxide, and SDA is template, and PEA is pore creating material, described
Pore creating material be N- alkyl pyrrolidones, the preferred methyl of substitution alkyl, ethyl or poly- on the N atoms
Ethylene group,
(2) colloid obtained by (1) step or solidliquid mixture are moved in crystallizing kettle, 155~200 DEG C, from
Hydrothermal crystallizing 1~15 day, collects solid product, drying under raw pressure.
6. in accordance with the method for claim 5, it is characterised in that (1) mole of each reactant described in step
Constitute as SiO2：Al2O3：M2O：SDA：PEA：H2O=1：(0.0083~0.05)：(0.15~0.4)：
(0.08~0.2)：(0.05~0.3)：(7~40).
7. according to the method described in claim 3 or 5, it is characterised in that the silicon source is amorphous dioxy
SiClx, waterglass, Ludox, solid oxidation silicon, solid silicone, diatomite, white carbon and positive silicic acid second
One or more in ester.
8. according to the method described in claim 3 or 5, it is characterised in that source of aluminium is sodium aluminate, partially
One kind in sodium aluminate, aluminum sulfate, aluminium chloride, aluminum nitrate, aluminium hydroxide, aluminum oxide and boehmite
Or it is a variety of.
9. according to the method for claim 3 or 5, it is characterised in that the inorganic base is sodium hydroxide or hydrogen
Potassium oxide.
10. according to the method described in claim 3 or 5, it is characterised in that described pore creating material is N- methyl
At least one in -2-Pyrrolidone or N- ethyl-2-pyrrolidones and poly- ethylene group -2-Pyrrolidone (PVP)
Kind.
11. according to the method described in claim 3 or 5, it is characterised in that double (the N- first of 1 described, 5-
Base pyrrolidines) pentamethylene base cation salt be its bromide.
12. in accordance with the method for claim 3, it is characterised in that (2) the hydrothermal crystallizing temperature described in step
Spend for 140~180 DEG C, the hydrothermal crystallizing time is 4~10 days.
13. in accordance with the method for claim 5, it is characterised in that (2) the hydrothermal crystallizing temperature described in step
Spend for 160~190 DEG C, the hydrothermal crystallizing time is 3~10 days.
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