CN107021504A - A kind of preparation method of mesoporous IM-5 molecular sieves - Google Patents
A kind of preparation method of mesoporous IM-5 molecular sieves Download PDFInfo
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Abstract
A kind of preparation method of the molecular sieves of mesoporous IM 5, including：(1) by inorganic base or organic base, template obtained mixed solution soluble in water, the molecular sieves of micropore IM 5 is added, solidliquid mixture is obtained, wherein a mole composition for each reactant is Z：B：R：H2O=1：(0.01~0.3)：(0.01~0.20)：In (5~40), above-mentioned material composition, Z is with SiO2The molecular sieves of micropore IM 5 of meter, the mol ratio of the silica/alumina of the molecular sieves of micropore IM 5 is that 40~200, B is inorganic base or organic base, and R is template, and described organic base is that formula is NR1 4OH quaternary ammonium base, described R1For C1~C2Alkyl；Or 1, solidliquid mixture obtained by (1) step is carried out hydrothermal crystallizing processing by 5 pairs of quaternary ammonium bases of (N crassitudes) pentane two, (2) at 120~200 DEG C, and gained solid after processing is dried, is calcined.The method prepare the molecular sieves of mesoporous IM 5 have it is transgranular mesoporous, for alkylation of toluene methanol reaction, with higher activity stability.
Description
Technical field
The present invention is a kind of preparation method of Si-Al molecular sieve, is a kind of mesoporous IM-5 molecules specifically
The preparation method of sieve.
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 preparation method of mesoporous IM-5 molecular sieves, prepared by the method mesoporous
IM-5 molecular sieves have it is transgranular mesoporous, for alkylation of toluene methanol reaction, with higher activity stability.
The preparation method for the mesoporous IM-5 molecular sieves that the present invention is provided, comprises the following steps：
(1) by inorganic base or organic base, template obtained mixed solution soluble in water, micropore IM-5 is added
Molecular sieve, obtains solidliquid mixture, wherein a mole composition for each reactant is Z：B：R：H2O=1：
(0.01~0.3)：(0.01~0.20)：(5~40),
In above-mentioned material composition, Z is with SiO2The micropore IM-5 molecular sieves of meter, the micropore IM-5 molecules
The mol ratio of the silica/alumina of sieve is that 40~200, B is inorganic base or organic base, and R is template, institute
State bromide or villaumite of the template for double (N- crassitudes) the pentamethylene bases of 1,5-；Described organic base is
Formula is NR1 4OH quaternary ammonium base, described R1For C1~C2Alkyl；Or double (the N- methyl pyrroles of 1,5-
Cough up alkane) two quaternary ammonium base of pentane,
(2) by solidliquid mixture obtained by (1) step, water-filling is entered under the conditions of 120~200 DEG C of self-generated pressure
Thermal crystallisation processing, gained solid after processing is dried, is calcined.
The inventive method will it is fired after or the micropore IM-5 molecular sieves of Hydrogen carry out alkaline etching and Crystallizing treatment,
Mesoporous IM-5 molecular sieves are made, described mesopore molecular sieve is used for the catalytic reaction of macromolecular hydrocarbon, can improved
The anti-carbon deposition ability of catalyst.
Brief description of the drawings
Fig. 1 is X-ray diffraction (XRD) figure of sodium form IM-5 molecular sieves prepared by comparative example 1,
The XRD for the Hydrogen IM-5 molecular sieves that Fig. 2 is prepared for contrast 1,
The adsorption-desorption isothermal for the Hydrogen IM-5 molecular sieves that Fig. 3 is prepared for contrast 1,
Transmission electron microscope (TEM) figure for the Hydrogen IM-5 molecular sieves that Fig. 4 is prepared for contrast 1,
Fig. 5 is the adsorption-desorption isothermal of Hydrogen IM-5 molecular sieves prepared by example 3,
Fig. 6 is the transmission electron microscope picture of Hydrogen IM-5 molecular sieves prepared by example 3,
Fig. 7 is the adsorption-desorption isothermal of Hydrogen IM-5 molecular sieves prepared by example 4,
Fig. 8 is the transmission electron microscope picture of Hydrogen IM-5 molecular sieves prepared by example 4,
Fig. 9 is the adsorption-desorption isothermal of Hydrogen IM-5 molecular sieves prepared by example 5,
Figure 10 is the transmission electron microscope picture of Hydrogen IM-5 molecular sieves prepared by example 5,
Figure 11 is the adsorption-desorption isothermal of Hydrogen IM-5 molecular sieves prepared by example 6,
Figure 12 is the transmission electron microscope picture of Hydrogen IM-5 molecular sieves prepared by example 6,
Figure 13 is the adsorption-desorption isothermal of Hydrogen IM-5 molecular sieves prepared by comparative example 4,
Figure 14 is the transmission electron microscope picture of Hydrogen IM-5 molecular sieves prepared by comparative example 4,
Figure 15 is the adsorption-desorption isothermal of Hydrogen IM-5 molecular sieves prepared by comparative example 5,
Figure 16 is the transmission electron microscope picture of Hydrogen IM-5 molecular sieves prepared by comparative example 5.
Embodiment
The micropore IM-5 molecular sieves of high silica alumina ratio are carried out alkaline etching and Crystallizing treatment by the present invention simultaneously, i.e., at this
Hydrothermal crystallizing reaction, micropore IM-5 are carried out in the presence of the template of the described alkali of invention and synthesis IM-5 molecular sieves
Desiliconization occurs in the presence of alkali, forms transgranular mesoporous in desiliconization process, simultaneously because the presence of template,
The silicon come off can be recrystallized, and the crystallinity and crystalline form of the molecular sieve of synthesis can be made to keep good, obtained point
The transgranular mesopore diameter of son sieve is 3~20nm, is more evenly distributed on IM-5 crystal grain.The mesoporous IM-5
Molecular sieve improves the duct utilization rate of micropore IM-5 molecular sieves, can for alkylation of toluene methanol reaction
The coking resistivity of catalyst is improved, is increased the service life.
Mesoporous IM-5 molecular sieves prepared by the inventive method, it is transgranular with micropore and abundant transgranular mesoporous
Mesopore diameter preferably 5~20nm.
The inventive method (1) step is to mix micropore IM-5 molecular sieves, template, inorganic base or organic base,
A mole composition for obtained reactant is preferably Z：B：R：H2O=1：(0.02~0.15)：(0.02~0.2)：
(5~25), Z therein is represented with SiO2The micropore IM-5 molecular sieve amounts of meter.
(1) the micropore IM-5 molecular sieves that step is added are fired or Hydrogen molecular sieve, its silica/oxidation
The mol ratio of aluminium is 45~120, preferably 45~110.Preferably 500~600 DEG C of described sintering temperature, during roasting
Between preferably 3~8 hours, it is therefore an objective to remove template remaining in molecular sieve.
Described template is the bromide or villaumite of double (N- crassitudes) the pentamethylene bases of 1,5-, therein
Shown in cation such as formula (I)：
Anion is bromide ion or chlorion.
One or both of described inorganic base preferred NaOH and KOH.Described organic base is formula
For NR1 4OH quaternary ammonium base, described R1For C1~C2Alkyl, such as TMAH (TMAOH),
Tetraethyl ammonium hydroxide (TEAOH).
Organic base described in the inventive method can be also the double quaternary ammonium bases of (N- crassitudes) pentane two of 1,5-,
The alkali that i.e. cation of formula (I) is constituted with hydroxyl, is abbreviated as MPP (OH)2。
The inventive method (2) step is to carry out alkaline etching and Crystallizing treatment to micropore IM-5 molecular sieves, carries out hydro-thermal
Preferably 140~180 DEG C of the temperature of Crystallizing treatment, preferably 2~72 hours time.Product is through dry after Crystallizing treatment
It is dry to produce mesopore molecular sieve.Preferably 90~130 DEG C of described drying temperature, preferably 2~20 hours time.
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
It is that 0.10~1.0MPa, temperature are 400~500 DEG C in pressure using toluene and methanol as raw material under part, charging
Liquid 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.
Comparative example 1
(1) IM-5 molecular sieves are prepared
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 3.35g (0.0084mol) 1,5- and 35.99g
Water is mixed, and is then added to 3.00g white carbons (Aerosil 200, Degussa) under conditions of stirring
Solution is stated, then is separately added into 0.228g sodium aluminates (Carlo Erba, 56%Al2O3)、1.053gNaOH
(Prolabo, 98%) and 0.515gNaBr (Scharlau, 99%), a mole composition for reactant mixture is
SiO2：Al2O3：Na2O：NaBr：SDA：H2O=1：0.025：0.283：0.1：0.167：40, its
Middle SDA is double (N- crassitudes) the pentamethylene base dibromo salts of 1,5-.
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 obtains IM-5 molecular sieve-4 As within 6 hours in 550 DEG C of roastings, its XRD
Figure is shown in Fig. 1, and crystallinity is set to 100%, and silica/alumina molar ratio is 35 (using XRF light
Analysis of spectrum, similarly hereinafter).
(2) hydrogen type molecular sieve is prepared
The IM-5 molecular sieves after above-mentioned roasting are taken, the ammonium nitrate solution for being 0.5mol/L with concentration enters in 80 DEG C
Row ion exchange 2 times, every time 2 hours.The molecular sieve of gained after exchange is washed with deionized, then at
90 DEG C of dryings are calcined 3 hours for 2 hours, 550 DEG C, obtain Hydrogen IM-5 molecular sieve D, and its crystallinity is 85.3%,
XRD spectra is shown in Fig. 2, and silica/alumina molar ratio is 35, and adsorption-desorption isothermal is shown in Fig. 3, transmission
Electronic Speculum (TEM) figure is shown in Fig. 4.
Example 1
(1) IM-5 molecular sieves are prepared
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 3.00g (0.0075mol) 1,5- and 2.92g
The NaOH aqueous solution, 0.427g Al (NO that concentration is 50%3)3·9H2O (98%, Junsei), 3.00g are white
Carbon black (Aerosil 200, Degussa) and 45.4g deionized waters be mixed and made into colloid, and reactant mixture rubs
Your composition is SiO2：Al2O3：Na2O：SDA：H2O=1：0.0167：0.365：0.15：40, wherein
SDA is double (N- crassitudes) the pentamethylene base dibromo salts of 1,5-.
Said mixture is stirred 30 minutes in 25 DEG C, the closed crystallizing kettle with polytetrafluoroethyllining lining is moved to
In, it is 100rpm, crystallization rotated under the conditions of 160 DEG C 14 days in rotating speed.Crystallization product is through washing, mistake
Filter, 80 DEG C of dryings 12 hours, obtains IM-5 molecular sieve B, its XRD spectra is shown as IM-5 molecular sieves,
Crystallinity is 90.0%, and silica/alumina molar ratio is 48.
(2) hydrogen type molecular sieve is prepared
Molecular sieve made from (1) step is calcined 5 hours in 550 DEG C, the IM-5 molecular sieves being calcined.
The ammonium nitrate solution for being 0.5mol/L with concentration by the IM-5 molecular sieves after roasting in 80 DEG C carries out ion exchange
2 times, every time 2 hours.Molecular sieve after exchange is washed with deionized, then at 90 DEG C dry 2 hours,
550 DEG C are calcined 3 hours, and Hydrogen IM-5 molecular sieve E are made, and its crystallinity is 80.9%, silica/oxidation
Al mole ratio is 48.
Example 2
(1) by CN102452666A method synthesis IM-5 molecular sieves.
2.88gNaOH and 2.06g NaBr are dissolved in 42.42g deionized waters, 0.17gNaAlO is added2
It is well mixed with 16.02g double (N- crassitudes) the pentamethylene base dibromo salts of 1,5-, under stirring, slow drop
Plus 40g alkaline silica sols (SiO2Content is 30wt%, the production of Beijing flying dragon horse scientific ＆ trading Co., Ltd., pH
It is worth colloid 11.0), is made, continues to stir 2 hours.A mole composition for reactant mixture is SiO2：Al2O3：
Na2O：NaBr：R：H2O=60：0.5：12：6：12:1200.
Obtained colloid is transferred in the crystallizing kettle with polytetrafluoroethyllining lining, crystallization 6 is rotated in 160 DEG C
My god, crystallization product is scrubbed, filtering, and 80 DEG C of dry 12h obtain IM-5 molecular sieve C, its XRD
Spectrogram is shown as IM-5 molecular sieves, and crystallinity is 88.5%.
(2) Hydrogen IM-5 molecular sieves are prepared.
IM-5 molecular sieves prepared by (1) step are calcined 5 hours through 550 DEG C, the IM-5 molecules being calcined
Sieve.The ammonium chloride solution for being 0.5mol/L with concentration by the IM-5 molecular sieves after roasting in 80 DEG C carries out ion
Exchange 2 times, every time 2 hours.The molecular sieve of gained after exchange is washed with deionized, it is dry then at 90 DEG C
It is calcined 3 hours within dry 2 hours, 550 DEG C, Hydrogen IM-5 molecular sieve F is made, its crystallinity is 78.9%,
Silica/alumina molar ratio is 102.
Example 3
Following instance prepares mesoporous IM-5 molecular sieves of the present invention.
By 0.20gNaOH, 4.80g template 1, double (N- crassitudes) the pentamethylene base dibromo salts of 5- are dissolved in
In 16.20g deionized waters, stir, add that 6g is prepared by the method for example 1 and the IM-5 after being calcined divides
Son sieve, is well mixed, and a mole composition for reactant mixture is Z：B：R：H2O=1：0.05：0.12：9,
Wherein Z is the IM-5 molecular sieves after roasting, and B is template for the alkali NaOH, R added.
Above-mentioned reactant is transferred in autoclaves of the 50ml with polytetrafluoroethyllining lining, 175 DEG C of dynamics
Crystallizing treatment 3 hours, by product washing, filtering, 80 DEG C of dry 12h after processing, obtains mesoporous IM-5 points
Son sieve, its crystallinity is 92.0%.
Mesoporous IM-5 molecular sieves are changed into Hydrogen by the method for example 1 (2) step, the mesoporous IM-5 of Hydrogen is obtained
Molecular sieve G, its silica/alumina molar ratio is 47, and adsorption-desorption isothermal is shown in Fig. 5, and TEM figures are shown in
Have equally distributed mesoporous on Fig. 6, display crystal grain.
Example 4
By 1,5- double (N- crassitude) pentamethylene base two quaternary ammonium bases of the 3.70g concentration for 37 mass %
[MPP(OH)2] the aqueous solution, 0.80g templates 1, double (N- crassitudes) the pentamethylene base dibromo salts of 5-
(MPPBr2) and 22.87g deionized waters it is well mixed, add 6g and press Hydrogen IM-5 prepared by the method for example 1
Molecular sieve E, is well mixed, and a mole composition for reactant mixture is Z：B：R：H2O=1：0.05：0.02：
14。
Above-mentioned reactant is transferred in autoclaves of the 50ml with polytetrafluoroethyllining lining, 175 DEG C of dynamics
Crystallizing treatment 24 hours, product is through washing, filtering after Crystallizing treatment, and 120 DEG C of dry 10h obtain mesoporous
IM-5 molecular screen primary powders, its crystallinity is 101.5%.
Mesoporous IM-5 molecular sieves are changed into Hydrogen by the method for example 1 (2) step, the mesoporous IM-5 of Hydrogen is obtained
Molecular sieve H, its silica/alumina molar ratio is 45, and adsorption-desorption isothermal is shown in Fig. 7, and TEM figures are shown in
Have equally distributed mesoporous on Fig. 8, display crystal grain.
Example 5
By TMAH (TMAOH) aqueous solution, the 4.00g moulds that 2.60g concentration is 35 mass %
Plate agent 1, double (N- crassitudes) the pentamethylene base dibromo salts of 5- and 34.31g deionized waters are well mixed, plus
Enter the Hydrogen IM-5 molecular sieves that 6g is prepared by the method for example 1, be well mixed, mole group of reactant mixture
As Z：B：R：H2O=1：0.10：0.10：20.
Above-mentioned reactant mixture is transferred in autoclaves of the 50ml with polytetrafluoroethyllining lining, 175 DEG C
Dynamic crystallization is handled 48 hours, and by product washing, filtering after Crystallizing treatment, 120 DEG C of dry 10h are obtained
Mesoporous IM-5 molecular sieves, its crystallinity is 92.5%.
Mesoporous IM-5 molecular sieves are changed into Hydrogen by the method for example 1 (2) step, the mesoporous IM-5 of Hydrogen is obtained
Molecular sieve I, its silica/alumina molar ratio is 46, and adsorption-desorption isothermal is shown in Fig. 9, and TEM figures are shown in
Have equally distributed mesoporous on Figure 10, display crystal grain.
Example 6
By 1.85g concentration for 37 mass % the double quaternary ammonium bases of (N- crassitudes) pentamethylene base two of 1,5-,
Mixed in 2.40g templates 1, double (N- crassitudes) the pentamethylene base dibromo salts of 5- and 24.04g deionized waters
Uniformly, add 6g to be well mixed by the Hydrogen IM-5 molecular sieves F of the method for example 2 preparation, reactant mixture
Mole composition be Z：B：R：H2O=1：0.025：0.06：14.
Above-mentioned reactant is transferred in autoclaves of the 50ml with polytetrafluoroethyllining lining, 175 DEG C of dynamics
Crystallizing treatment 24 hours.By product washing, filtering after Crystallizing treatment, 120 DEG C of dry 10h obtain mesoporous
IM-5 molecular sieves, its sample crystallinity is 98.1%.
Mesoporous IM-5 molecular sieves are changed into Hydrogen by the method for example 1 (2) step, the mesoporous IM-5 of Hydrogen is obtained
Molecular sieve J, its silica/alumina molar ratio is 95, and adsorption-desorption isothermal is shown in Figure 11, and TEM figures are shown in
Have equally distributed mesoporous on Figure 12, display crystal grain.
Comparative example 4
This comparative example explanation can not synthesising mesoporous IM-5 molecular sieves using quaternary ammonium base TPAOH.
By TPAOH (TPAOH) aqueous solution, the 4.80g moulds that 4.07g concentration is 25 mass %
Plate agent 1, double (N- crassitudes) the pentamethylene base dibromo salts of 5- and 22.15g deionized waters are well mixed, plus
Enter the Hydrogen IM-5 molecular sieves F that 6g prepared by the method for example 2 to be well mixed, mole group of reactant mixture
As Z：B：R：H2O=1：0.05：0.12：14.
Above-mentioned reactant mixture is transferred in autoclaves of the 50ml with polytetrafluoroethyllining lining, 175 DEG C
Dynamic crystallization is handled 24 hours.By product washing, the filtering after Crystallizing treatment, 80 DEG C of dry 12h are obtained
Molecular sieve, XRD spectra is shown as IM-5 molecular sieves, and its crystallinity is 95.2%.
IM-5 molecular sieves are changed into Hydrogen by the method for example 1 (2) step, Hydrogen IM-5 molecular sieve K are obtained,
Its silica/alumina molar ratio is 93, and adsorption-desorption isothermal is shown in Figure 13, and hysteresis loop is not obvious, explanation
There is no mesoporous, TEM figures are shown on Figure 14, display crystal grain without mesoporous distribution.
Comparative example 5
This comparative example explanation is used to low silica-alumina ratio IM-5 molecular sieves (silica/alumina molar ratio is 35)
The result of alkaline etching Crystallizing treatment.
By the MPP (OH) that 1.85g concentration is 37 mass %2The aqueous solution, 2.40g templates 1, the double (N- of 5-
Crassitude) pentamethylene base dibromo salt and 24.04g deionized waters be well mixed, adds 6g by comparative example 1
Hydrogen IM-5 molecular sieves D (silica/alumina molar ratio is 35) prepared by method, is well mixed, instead
Mole composition for answering mixture is Z：B：R：H2O=1：0.025：0.06：14.
Above-mentioned reactant mixture is transferred in autoclaves of the 50ml with polytetrafluoroethyllining lining, 175 DEG C
Dynamic crystallization is handled 24 hours, and by product washing, the filtering after Crystallizing treatment, 80 DEG C of dry 12h are obtained
Molecular sieve, XRD spectra is shown as IM-5 molecular sieves, and its crystallinity is 93.2%.
IM-5 molecular sieves are changed into Hydrogen by the method for example 1 (2) step, Hydrogen IM-5 molecular sieve L are obtained,
Its silica/alumina molar ratio is 33, and adsorption-desorption isothermal is shown in Figure 15, and hysteresis loop is not obvious, explanation
There is no mesoporous, TEM figures are shown on Figure 16, display crystal grain without mesoporous distribution.
Example 7~10
The catalytic performance of the Hydrogen IM-5 molecular sieves prepared to the inventive method is evaluated.
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, 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, molecular sieve used in each example
Numbering and reaction result are 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%
Comparative example 6~10
Evaluate the catalytic performance of molecular sieve prepared by comparative example.
Hydrogen IM-5 molecular sieves and comparative example 1,4,5 system prepared by the method for example 7 to example 1~2
The standby catalytic performance without mesoporous Hydrogen IM-5 molecular sieves is evaluated, used in each example molecular sieve numbering and
Reaction result is shown in Table 1.
Table 1
As shown in Table 1, the mesoporous H-IM-5 molecular sieves that prepared by the present invention are than micro- used in comparative example 6~8
Hole H-IM-5 molecular sieves, with the extension in reaction time, are received with more preferable toluene conversion and dimethylbenzene
Rate, illustrates that mesoporous H-IM-5 molecular sieves have preferably activity and stability.Equally, with not containing mesopore
H-IM-5 molecular sieves prepared by comparative example 4,5 are compared, mesoporous IM-5 molecular sieves prepared by the inventive method
Also show that higher activity stability.
Claims (5)
1. a kind of preparation method of mesoporous IM-5 molecular sieves, comprises the following steps：
(1) by inorganic base or organic base, template obtained mixed solution soluble in water, micropore IM-5 is added
Molecular sieve, obtains solidliquid mixture, wherein a mole composition for each reactant is Z：B：R：H2O=1：
(0.01~0.3)：(0.01~0.20)：(5~40),
In above-mentioned material composition, Z is with SiO2The micropore IM-5 molecular sieves of meter, the micropore IM-5 molecules
The mol ratio of the silica/alumina of sieve is that 40~200, B is inorganic base or organic base, and R is template, institute
State bromide or villaumite of the template for double (N- crassitudes) the pentamethylene bases of 1,5-；Described organic base is
Formula is NR1 4OH quaternary ammonium base, described R1For C1~C2Alkyl；Or double (the N- methyl pyrroles of 1,5-
Cough up alkane) two quaternary ammonium base of pentane,
(2) by solidliquid mixture obtained by (1) step, water-filling is entered under the conditions of 120~200 DEG C of self-generated pressure
Thermal crystallisation processing, gained solid after processing is dried, is calcined.
2. in accordance with the method for claim 1, it is characterised in that (1) in step, mole group of reactant
As Z：B：R：H2O=1：(0.02~0.15)：(0.02~0.2)：(5~25).
3. according to the method described in claim 1 or 2, it is characterised in that (1) the micropore IM-5 added
Molecular sieve is fired or Hydrogen IM-5 molecular sieves, and the mol ratio of its silica/alumina is 45~120.
4. according to the method described in claim 1 or 2, it is characterised in that inorganic base is NaOH and KOH
One or both of.
5. in accordance with the method for claim 1, it is characterised in that (2) temperature of step hydrothermal crystallizing processing
For 140~180 DEG C, hydrothermal crystallizing processing time is 2~72 hours.
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| CN109592697A (en) * | 2017-09-30 | 2019-04-09 | 中国石油化工股份有限公司 | IM-5 molecular sieve and its synthetic method |
| CN110075910A (en) * | 2018-01-26 | 2019-08-02 | 中国科学院大连化学物理研究所 | A kind of method of modifying for ethyl alcohol and benzene alkylation reaction IM-5 molecular sieve catalyst |
| CN116332202A (en) * | 2023-03-30 | 2023-06-27 | 华东师范大学 | ECNU-30 molecular sieve, preparation method and catalytic application thereof |
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| CN109592697A (en) * | 2017-09-30 | 2019-04-09 | 中国石油化工股份有限公司 | IM-5 molecular sieve and its synthetic method |
| CN110075910A (en) * | 2018-01-26 | 2019-08-02 | 中国科学院大连化学物理研究所 | A kind of method of modifying for ethyl alcohol and benzene alkylation reaction IM-5 molecular sieve catalyst |
| CN116332202A (en) * | 2023-03-30 | 2023-06-27 | 华东师范大学 | ECNU-30 molecular sieve, preparation method and catalytic application thereof |
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