CN104043477B - ZSM-5/MCM-48 composite molecular sieve, preparation method and application thereof - Google Patents
ZSM-5/MCM-48 composite molecular sieve, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to methanol-to-gasoline catalysts, in particular to a ZSM-5/MCM-48 composite molecular sieve, a preparation method and application thereof. The composite molecular sieve adopts a ZSM-5 microporous molecular sieve as the seed crystal, on the surface of which a MCM-48 mesoporous structure composite molecular sieve that is chemically interlinked at a mesoporous and micropore interface is obtained by overgrowth. The composite molecular sieve undergoes acidification, and then is mixed with a binder to undergo molding and roasting, and the product is used as a catalyst for methanol-to-gasoline (MTG) reaction. The catalyst provided by the invention is used for overgrowth of the mesoporous molecular sieve on the microporous molecular sieve surface, integrates the advantages of the microporous material and the mesoporous material so as to develop the strong points and avoid the weak points and reach a synergistic effect. The catalyst shows good catalytic properties to the methanol-to-gasoline (MTG) reaction, has high selectivity to gasoline products and a low aromatic hydrocarbon content, and extends the carbon chain length. More importantly, the problems of high reaction temperature, high aromatic hydrocarbon content in oil products, and limitation of hydrocarbon compounds only to less than C11 in traditional MTG technologies are solved.
Description
Technical field
The present invention relates to the catalyst of preparing gasoline by methanol, specifically a kind of zsm-5/mcm-48 composite molecular screen and its
Preparation method and application.
Background technology
It is known that micro-pore zeolite molecular sieve becomes modern petroleum because having good molecule shape selectivity and acid catalytic property
Important shape-selective catalyst in chemical industry.But the quick diffusion that its narrow and small pore passage structure have impact on macromole product is overflowed, thus
Limit the distribution of product.With the gradually heaviness of oil, extraordinarily prominent, the institute of sex expression is limited in the aperture of micro porous molecular sieve
To resolve the reaction of macromole and diffusion problem become one of most important technical problem of world oil manufacture field.
In recent years, the mesopore molecular sieve containing al due to its can modulation homogeneous mesopore orbit (2-30nm) and can conduct
A kind of potential acid catalyst attract attention, the disadvantage that hydrothermal stability is poor however, this kind of material exists, acidity is low
End, hinders its application in PETROLEUM PROCESSING.Trace it to its cause, be due to the amorphous feature of its hole wall and big with its association
The presence of amount surface silanol group, it is easy to act on water and other media, causes structure collapse.Therefore, by the hole of mesoporous material
Micro- mesoporous composite material that road advantage is combined with the highly acid of micro porous molecular sieve and the Dominant Facies of stability will certainly become a class
The new catalytic material of great potential.
Up to now, the catalyst for preparing gasoline by methanol is always zsm-5 molecular sieve.High silicon zsm-5 molecular sieve strong
Acid and hydrophobicity, methanol is converted into hydro carbons activity and heat stability are all very high, and methanol conversion almost reaches 100%, but
Lead to the arene content in oil-phase product high, and be easier to coking and need frequent regeneration.Many scholars are in zsm-5 molecular sieve carrier
On loaded some metals or metal-oxide or be directly synthesized acid different zsm-5 molecular sieve catalyst and improved with more preferable
The catalytic performance of catalyst, although these researchs have also discovered the result of certain law, does not all fundamentally find tune
Become the method for products distribution and the coking deactivation prob solving catalyst.Disclose one kind before us and pass through two step crystallization legal systems
Standby zsm-5/mcm-48 molecular sieve based catalyst and its using method (the Chinese invention patent Shen in preparing gasoline by methanol reaction
Please number: 201110195525.1), but also have that catalyst preparation process is loaded down with trivial details, relatively costly and product awaits into one
The problems such as step becomes.
Content of the invention
It is an object of the invention to provide a kind of zsm-5/mcm-48 composite molecular screen and its preparation method and application.
For achieving the above object, the technical solution used in the present invention is:
A kind of zsm-5/mcm-48 composite molecular screen, composite molecular screen is with zsm-5 micro porous molecular sieve as crystal seed, in its table
Face outgrowth mcm-48 meso-hole structure at mesoporous and microvia interface chemistry interconnection composite molecular screen.
Described composite molecular screen is mcm-48 outgrowth on zsm-5 surface；Wherein zsm-5 crystal seed is grain of uniform size
The isometric particle of footpath 1-2um, average pore size 2.5nm；Mcm-48 crystalline phase is the granule of 0.1-0.2um, average pore size 4.0nm.Than
Surface area 567.9m2/ g, pore volume 0.408cm3/g.
Described zsm-5/mcm-48 composite molecular screen obtains as follows,
A) template, silicon source and alkali source are dissolved in deionized water, stir to clarify rear Deca silicon source, stirring, prepared mcm-
48 precursor solutions；Wherein according to the molar ratio, silicon source: template: alkali source: silicon source: deionized water is: 0.3-2.0:0.1-1.0:
0.1-1.0:0.01-0.05:50-200；
B), after zsm-5 micro porous molecular sieve being processed with aqueous slkali, it is added in above-mentioned mcm-48 precursor solution, stirs
Move into after mixing in hydrothermal reaction kettle, crystallization under the hydrothermal condition of self-generated pressure and crystallization temperature, gained crystallization liquid is through filtering, washing
Wash, dry, after roasting zsm-5/mcm-48 composite molecular screen.
In described step a), template is cetyl trimethylammonium bromide or octadecyl trimethyl ammonium chloride replaces；Aluminum
Source is aluminum isopropylate., aluminum sulfate or aluminum nitrate；Silicon source is tetraethyl orthosilicate, Ludox, sodium silicate or silica gel；Alkali source is hydroxide
Sodium；
In described step b), aqueous slkali is sodium hydroxide or sodium fluoride aqueous solution.
The preparation method of zsm-5/mcm-48 composite molecular screen,
A) template, silicon source and alkali source are dissolved in deionized water, stir to clarify rear Deca silicon source, stirring, prepared mcm-
48 precursor solutions；Wherein according to the molar ratio, silicon source: template: alkali source: silicon source: deionized water is: 0.3-2.0:0.1-1.0:
0.1-1.0:0.01-0.05:50-200；
B), after zsm-5 micro porous molecular sieve being processed with aqueous slkali, it is added in above-mentioned mcm-48 precursor solution, stirs
Move into after mixing in hydrothermal reaction kettle, crystallization under the hydrothermal condition of self-generated pressure and crystallization temperature, gained crystallization liquid is through filtering, washing
Wash, dry, after roasting zsm-5/mcm-48 composite molecular screen.
In described step a), template is cetyl trimethylammonium bromide or octadecyl trimethyl ammonium chloride replaces；Aluminum
Source is aluminum isopropylate., aluminum sulfate or aluminum nitrate；Silicon source is tetraethyl orthosilicate, Ludox, sodium silicate or silica gel；Alkali source is hydroxide
Sodium；
Described step b) by zsm-5 micro porous molecular sieve concentration be 0.1-1.0mol/l sodium hydroxide or sodium fluoride water-soluble
Liquid, treatment temperature 60-90 DEG C, process time 2-6h.
The crystallization temperature of described step b) is 100-180 DEG C, and crystallization time is 40-100 hour；Baking temperature is 90-120
DEG C, drying time 6-24 hour；Sintering temperature is 450-650 DEG C, and roasting time is 4-10 hour.
The application of zsm-5/mcm-48 composite molecular screen, described composite molecular screen acidified after and binding agent mixed-forming,
Roasting, then as the catalyst in preparing gasoline by methanol (mtg) reaction.
Described composite molecular screen nh for 0.05mol/l through concentration4no3Aqueous solution is acidified, and acidifying solution is carried out in 60-90 DEG C
Ion exchange, swap time is 1-4 hour, exchange times 2-5 time；And 6-24 hour is dried after 90-120 DEG C, finally with
400-600 DEG C of roasting 2-6 hour；By the composite molecular screen of acidifying and the binding agent ratio of 100-80:0-20 by weight percentage
Mix homogeneously, kneading and compacting, is reacted after drying, roasting, as preparing gasoline by methanol (mtg) reaction in fixed bed reactors
In catalyst, fixed bed reaction condition is: temperature 340-420 DEG C, pressure 0.1-2mpa, mass space velocity 1-2.5h-1.
Described binding agent is aluminium oxide, kieselguhr, boehmite or silicon dioxide.
Advantage for present invention:
Catalyst of the present invention shows good catalytic performance to gas production by methanol oil (mtg) reaction, not only effectively reduces
Reaction temperature, has higher selectivity and less arene content to gasoline product, and the present invention solves in traditional mtg technology simultaneously
In the reaction temperature height of presence, oil product, arene content is high, and carbon chain lengths only limit c11 problem below.There is provided a kind of inexpensive, high
Having compared with low reaction temperatures, higher methanol conversion and gasoline product selectivity, less arene content of effect, extends carbon
Chain length is prepared the zsm-5/mcm-48 composite molecular screen of gasoline to c15 alkanes by methanol.
Zsm-5/mcm-48 micro- mesoporous composite molecular sieve material of present invention synthesis, is prepared based on this material further
Catalyst is simultaneously applied to preparing gasoline by methanol reaction.Synthesized zsm-5/mcm-48 composite has the advantage that
1. there is stronger mass transport performance (compared with zeolite zsm-5)；
2. less diffusion-restricted (compared with zeolite zsm-5)；
3. there is weaker acidity (compared with zeolite zsm-5), but have more more acidic site than mcm-48；
4. its crystallization or partially-crystallized hole wall, there is the hydrothermal stability more higher than mcm-48 and mechanical strength；
5. its bimodal duct provides preferable nano-reactor for macromolecular reaction；
6. preparation method is simple, is suitable for amplifying, inexpensive efficient.
Comprehensive above feature, mesoporous molecular sieve overgrowth on microporous molecular sieve surface of the present invention, on the one hand passes through micropore material
Material and the advantage integration of mesoporous material, make the two maximize favourable factors and minimize unfavourable ones, synergism；On the other hand, mesoporous material pass through transition zone with
Poromerics surface forms chemistry interconnection, improves the hydrothermal stability of composite.In addition synthetic method modulation catalysis of the present invention
The Nomenclature Composition and Structure of Complexes of agent can improve the low temperature active of mtg reaction, improves the distribution of oil product hydrocarbon product, extends carbon chain lengths.
Brief description
Fig. 1 is the scanning electron microscope (SEM) photograph of hzsm-5/mcm-48 composite molecular screen provided in an embodiment of the present invention.
The scanning electron microscope (SEM) photograph of the composite molecular screen that Fig. 2 provides for comparative example of the present invention.
Specific embodiment
The technical solution used in the present invention is as follows:
A) template cetyl trimethylammonium bromide ctab, silicon source aluminum isopropylate. and alkali source naoh are dissolved in deionized water
In, stir to clarify rear Deca silicon source teos, stirring, prepared mcm-48 precursor solution.Silicon source: template: alkali: al:h2O presses
Mol ratio is: 0.3-2.0:0.1-1.0:0.1-1.0:0.01-0.05:50-200；
B) will after zsm-5 micro porous molecular sieve alkaline solution treatment, be added in above-mentioned mcm-48 precursor solution, after stirring
Move in hydrothermal reaction kettle, crystallization 40-100h under the hydrothermal condition of self-generated pressure and 100-200 DEG C of crystallization temperature, filters, washes
Wash, be dried, after roasting zsm-5/mcm-48 composite molecular screen；
C) by zsm-5/mcm-48 with acid solution carries out ion exchange, roasting obtains acid hzsm-5/mcm-48 compound molecule
Sieve；
D) press hzsm-5/mcm-48 to mix homogeneously with weight of binder percentage ratio 100-80:0-20, with volumetric concentration < 10%
Dilute nitric acid solution kneading and compacting, dry, after roasting catalyst.
The catalyst of the present invention is used in the reaction of preparing gasoline by methanol, is reacted in fixed bed reactors, reacts bar
Part is: temperature 340-420 DEG C, pressure 0.1-2mpa, mass space velocity 1-2.5h-1.
With reference to embodiment, the present invention is further illustrated.
Embodiment 1
Prepared by zsm-5/mcm-48 composite molecular screen:
In the preparation of zsm-5/mcm-48 composite molecular screen, the mol ratio of each raw material is: teos:ctab:naoh:al:h2o=
1.0:0.12:0.4:0.0125:56.
4.459g cetyl trimethylammonium bromide (ctab), 1.432g sodium hydroxide is mixed with 100.89g deionized water,
0.26g aluminum isopropylate. is added in above-mentioned solution, 35 DEG C of constant temperature stir to clarify, and are added dropwise over 21.24g tetraethyl orthosilicate
(teos), adjust ph=10-11 with 50wt% aqueous acetic acid, stir 4h, prepared mcm-48 precursor solution.
By zsm-5(si/al=38, Nankai's catalyst plant) in the naoh aqueous solution of 0.5mol/l, 75 DEG C of constant temperature stirrings
4h, filters, and washs neutral to filtrate, 110 DEG C are dried 12h, 550 DEG C of roasting 6h.It is then ground to the granule of 280-300 mesh, delay
Delay in the precursor solution being added to mcm-48,2h is stirred at room temperature, 120 DEG C of crystallization 72h, filter, washing to filtrate is in neutrality,
110 DEG C are dried 12h, 550 DEG C of roasting 6h, obtain zsm-5/mcm-48 composite molecular screen.
Scanning electron microscope (sem) result of gained sample is as shown in Figure 1.It is characterized as main body, big with zsm-5 crystalline phase
Substantially connection grows a lot of little particles being characterized as main body with mcm-48 crystalline phase on little uniform isometric particle surface.
The preparation of catalyst:
With 0.05mol/l nh under the conditions of 75 DEG C4no3Solion exchanges 2h, filters, 110 DEG C are dried 12h, 500 DEG C of roastings
4h.This ion exchange process is in triplicate.The good hzsm-5/mcm-48 of ion exchange and boehmite compare 95:5 according to weight
Mixing, and the dilute hno with volumetric concentration 3%3Acid stirring, is dried 12h, 550 DEG C of roasting 6h.Obtain final product the zsm-5/ for mtg reaction
Mcm-48 modified molecular screen base catalyst.
Using described catalyst as the catalyst in preparing gasoline by methanol reaction:
Catalyst breakage is sized to 40-60 mesh, weighs the pressurization static bed reaction of rustless steel that 1.4g is seated in internal diameter 10mm
In device, temperature programming under the pressure setting, when waiting reaction tube actual temperature to reach desired reaction temperature, methanol passes through constant-flux pump
Entering preheater with flow is the n of 20ml/min2Carrier gas mixes, and the temperature of preheater is 180 DEG C, enters subsequently in reactor
Row reaction, reaction condition is: 360 DEG C of temperature, pressure 0.5mpa, air speed 2h-1, sample analysis after stable reaction 2h.Reaction result
It is shown in Table 1.
Embodiment 2
Prepared by zsm-5/mcm-48 composite molecular screen:
The mol ratio that zsm-5/mcm-48 composite molecular screen prepares each raw material is: na2sio3:otac:naoh:al:h2o=
0.8:0.4:0.55:0.025:120.
13.922g octadecyl trimethyl ammonium chloride (otac), 2.212g sodium hydroxide is mixed with 216.45g deionized water
Close, 0.511g aluminum isopropylate. is added in above-mentioned solution, 35 DEG C of constant temperature stir to clarify, and are added dropwise over 9.765 sodium silicate
(na2sio3), adjust ph=10-11 with 50wt% aqueous acetic acid, stir 4h, prepared mcm-48 precursor solution.
By zsm-5(si/al=38, Nankai's catalyst plant) in the naf aqueous solution of 0.3mol/l, at 60 DEG C of constant temperature stirrings
Reason 6h, filters, and to neutrality, 100 DEG C are dried 16h to wash filtrate, 550 DEG C of roasting 6h.It is then ground to the granule of 280-300 mesh,
It is added slowly in the precursor solution of mcm-48,2h is stirred at room temperature, 150 DEG C of crystallization 60h, filter, washing to filtrate is in neutrality,
80 DEG C are dried 20h, 550 DEG C of roasting 6h, obtain zsm-5/mcm-48 composite molecular screen.
The preparation of catalyst:
With 0.05mol/l nh under the conditions of 60 DEG C4no3Solion exchanges 5h, filters, 60 DEG C are dried 20h, 500 DEG C of roastings
4h.This ion exchange process is in triplicate.The good hzsm-5/mcm-48 of ion exchange and boehmite compare 90 according to weight:
10 mixing, and the dilute hno with volumetric concentration 5%3Acid stirring, 100 DEG C are dried 12h, 550 DEG C of roasting 6h.Obtain final product for mtg reaction
Zsm-5/mcm-48 modified molecular screen base catalyst.Using gained catalyst according to described in embodiment 1 as preparing gasoline by methanol
Catalyst in reaction, results of property is referring to table 1.
Embodiment 3
Prepared by zsm-5/mcm-48 composite molecular screen:
The mol ratio that zsm-5/mcm-48 composite molecular screen prepares each raw material is: na2sio3:ctab:naoh:al:h2o=
1.4:0.75:0.7:0.0355:165.
27.333g cetyl trimethylammonium bromide (ctab) 2.812g sodium hydroxide is mixed with 297.02g deionized water,
By 1.215g aluminum sulfate (al2(so4)3) be added in above-mentioned solution, 35 DEG C of constant temperature stir to clarify, and are added dropwise over 17.088 silicon
Sour sodium (na2sio3), adjust ph=10-11 with 50wt% aqueous acetic acid, stir 4h, prepared mcm-48 precursor solution.
By zsm-5(si/al=38, Nankai's catalyst plant) in the naoh aqueous solution of 0.7mol/l, at 80 DEG C of constant temperature stirrings
Reason 3h, filters, and to neutrality, 120 DEG C are dried 10h to wash filtrate, 550 DEG C of roasting 6h.It is then ground to the granule of 280-300 mesh,
It is added slowly in the precursor solution of mcm-48,2h is stirred at room temperature, 160 DEG C of crystallization 45h, filter, washing to filtrate is in neutrality,
100 DEG C are dried 15h, 550 DEG C of roasting 6h, obtain zsm-5/mcm-48 composite molecular screen.
The preparation of catalyst:
With 0.1mol/l nh under the conditions of 80 DEG C4no3Solion exchanges 2h, filters, 100 DEG C are dried 15h, 500 DEG C of roastings
4h.This ion exchange process is in triplicate.The good hzsm-5/mcm-48 of ion exchange and boehmite compare 95:5 according to weight
Mixing, and the dilute hno with volumetric concentration 7%3Acid stirring, 100 DEG C are dried 12h, 550 DEG C of roasting 6h.Obtain final product for mtg reaction
Gained catalyst is reacted as preparing gasoline by methanol by zsm-5/mcm-48 modified molecular screen base catalyst according to described in embodiment 1
In catalyst, results of property is referring to table 1.
Embodiment 4
Difference from Example 1 is, gained catalyst is carried out instead as the catalyst in preparing gasoline by methanol reaction
At once, reaction temperature is 380 DEG C.Reaction result is shown in Table 1.
Embodiment 5
Difference from Example 1 is, gained catalyst is carried out instead as the catalyst in preparing gasoline by methanol reaction
At once, reaction temperature is 400 DEG C.Reaction result is shown in Table 1.
Embodiment 6
Difference from Example 1 is, gained catalyst is carried out instead as the catalyst in preparing gasoline by methanol reaction
At once, reaction temperature is 420 DEG C.Reaction result is shown in Table 1.
Embodiment 7
Difference from Example 1 is, gained catalyst is carried out instead as the catalyst in preparing gasoline by methanol reaction
At once, reaction pressure is 1.0mpa.Reaction result is shown in Table 1.
Embodiment 8
It is with difference from Example 1, gained catalyst is carried out as the catalyst in preparing gasoline by methanol reaction
During reaction, reaction pressure is 1.5mpa.Reaction result is shown in Table 1.
Embodiment 9
Difference from Example 1 is, gained catalyst is carried out instead as the catalyst in preparing gasoline by methanol reaction
At once, reaction velocity is 1h-1.Reaction result is shown in Table 1.
Embodiment 10
Difference from Example 1 is, gained catalyst is carried out instead as the catalyst in preparing gasoline by methanol reaction
At once, reaction velocity is 1.5h-1.Reaction result is shown in Table 1.
Table 1: embodiment 1-10 catalyst mtg reactivity worth evaluation result
Note: in oil product yield=product, all carbon numbers are more than quality × 100 of the 5 quality/reactant methanol of hydrocarbon；
It is applied to the catalyst in preparing gasoline by methanol in above-described embodiment 4-10, be embodiment 1 gained catalyst.
Comparative example
The mol ratio that zsm-5/mcm-48 composite molecular screen prepares each raw material is: n-butylamine: teos:ctab:naoh:
al:h2o=0.186:1:0.1:0.5:0.015:105.The aqueous solution of 4.07g mass concentration 25% is mixed with 57.973g deionized water
Close, 0.3064g aluminum isopropylate. is added in above-mentioned solution, 35 DEG C of constant temperature stir to clarify, is added dropwise over the positive silicic acid of 21.24g
Ethyl ester (teos), adds 0.22g sodium hydroxide in above-mentioned solution, continues stirring 2h, moves into 100 DEG C of crystallization 6h in reactor.
After the completion of crystallization, take out reactor, be cooled to room temperature, the precursor solution of prepared zsm-5.3.72g cetyl trimethyl bromine
Change ammonium (ctab) to be dissolved in the aqueous solution of 133.54g sodium hydroxide mass concentration 1.34%, 32 DEG C stir to clarify, and are added dropwise over
The precursor solution of zsm-5, adjusts ph=10-11 with mass concentration 50% aqueous acetic acid, 3h is stirred at room temperature, 150 DEG C of crystallization 8h,
Filter, washing to filtrate is in neutrality, and 50 DEG C are dried 24h, 550 DEG C of roasting 6h, obtain zsm-5/mcm-48 composite molecular screen.
Scanning electron microscope (sem) result of gained sample is as shown in Figure 2.It is characterized as main body, big with zsm-5 crystalline phase
Little uniform isometric particle and the alternate Hybrid connections of unordered granule being characterized as main body with mcm-48 crystalline phase.
With 0.1mol/l nh4no3 solution 200ml ion exchange 2h under the conditions of 90 DEG C, filter, 50 DEG C are dried 24h, 500
DEG C roasting 5h.This ion exchange process is repeated 2 times.The good hzsm-5/mcm-48 of ion exchange and kieselguhr compare 90 according to weight:
10 mixing, and the dilute hno3 acid stirring with volumetric concentration 5%, are dried 12h, 550 DEG C of roasting 6h.Obtain final product the zsm- for mtg reaction
5/mcm-48 modified molecular screen base catalyst.
Catalyst breakage is sized to 40-60 mesh, weighs the pressurization static bed reaction of rustless steel that 2.6g is seated in internal diameter 10mm
In device, temperature programming under the pressure setting, when waiting reaction tube actual temperature to reach desired reaction temperature, methanol passes through constant-flux pump
Enter the n2 carrier gas that preheater is 10ml/min with flow to mix, the temperature of preheater is 180 DEG C, enters subsequently in reactor
Row reaction, reaction condition is: 400 DEG C of temperature, pressure 0.5mpa, mass space velocity 2h-1, sample analysis after stable reaction 2h.Reaction
The results are shown in Table 1.
Claims (8)
1. a kind of zsm-5/mcm-48 composite molecular screen it is characterised in that: composite molecular screen is with zsm-5 micro porous molecular sieve as crystalline substance
Kind, in the composite molecular screen of its surface outgrowth mcm-48 meso-hole structure chemistry interconnection at mesoporous and microvia interface；
Described composite molecular screen is mcm-48 outgrowth on zsm-5 surface；Wherein zsm-5 crystal seed is particle diameter 1- of uniform size
2 μm of isometric particle, average pore size 2.5nm；Mcm-48 crystalline phase is 0.1-0.2 μm of granule, average pore size 4.0nm, specific surface
Long-pending 567.9m2/ g, pore volume 0.408cm3/g；
Described zsm-5/mcm-48 composite molecular screen obtains as follows,
A) template, silicon source and alkali source are dissolved in deionized water, stir to clarify rear Deca silicon source, and stirring, before prepared mcm-48
Drive liquid solution；Wherein according to the molar ratio, silicon source: template: alkali source: silicon source: deionized water is: 0.3-2.0:0.1-1.0:0.1-
1.0:0.01-0.05:50-200；
B), after zsm-5 micro porous molecular sieve being processed with aqueous slkali, it is added in above-mentioned mcm-48 precursor solution, after stirring
Move into hydrothermal reaction kettle in, crystallization under the hydrothermal condition of self-generated pressure and crystallization temperature, gained crystallization liquid through filter, washing,
Zsm-5/mcm-48 composite molecular screen is obtained after drying, roasting.
2. the zsm-5/mcm-48 composite molecular screen as described in claim 1 it is characterised in that:
In described step a), template is cetyl trimethylammonium bromide or octadecyl trimethyl ammonium chloride；Silicon source is isopropyl
Aluminium alcoholates, aluminum sulfate or aluminum nitrate；Silicon source is tetraethyl orthosilicate, Ludox, sodium silicate or silica gel；Alkali source is sodium hydroxide；
In described step b), aqueous slkali is sodium hydroxide or sodium fluoride aqueous solution.
3. the zsm-5/mcm-48 composite molecular screen described in a kind of claim 1 preparation method it is characterised in that:
Described zsm-5/mcm-48 composite molecular screen obtains as follows,
A) template, silicon source and alkali source are dissolved in deionized water, stir to clarify rear Deca silicon source, and stirring, before prepared mcm-48
Drive liquid solution；Wherein according to the molar ratio, silicon source: template: alkali source: silicon source: deionized water is: 0.3-2.0:0.1-1.0:0.1-
1.0:0.01-0.05:50-200；
B), after zsm-5 micro porous molecular sieve being processed with aqueous slkali, it is added in above-mentioned mcm-48 precursor solution, after stirring
Move into hydrothermal reaction kettle in, crystallization under the hydrothermal condition of self-generated pressure and crystallization temperature, gained crystallization liquid through filter, washing,
Zsm-5/mcm-48 composite molecular screen is obtained after drying, roasting.
4. the zsm-5/mcm-48 composite molecular screen as described in claim 3 preparation method it is characterised in that:
In described step a), template is cetyl trimethylammonium bromide or octadecyl trimethyl ammonium chloride；Silicon source is isopropyl
Aluminium alcoholates, aluminum sulfate or aluminum nitrate；Silicon source is tetraethyl orthosilicate, Ludox, sodium silicate or silica gel；Alkali source is sodium hydroxide；
Described step b) by zsm-5 micro porous molecular sieve concentration be 0.1-1.0mol/l sodium hydroxide or sodium fluoride aqueous solution at
Reason, treatment temperature 60-90 DEG C, process time 2-6h.
5. the zsm-5/mcm-48 composite molecular screen as described in claim 3 preparation method it is characterised in that: described step b)
Crystallization temperature be 100-180 DEG C, crystallization time be 40-100 hour；Baking temperature is 90-120 DEG C, and drying time, 6-24 was little
When；Sintering temperature is 450-650 DEG C, and roasting time is 4-10 hour.
6. a kind of application of the zsm-5/mcm-48 composite molecular screen as described in claim 1 it is characterised in that: described compound point
Son sieves acidified rear and binding agent mixed-forming, roasting, then as the catalyst in preparing gasoline by methanol (mtg) reaction.
7. the zsm-5/mcm-48 composite molecular screen as described in claim 6 application it is characterised in that: described composite molecular screen
Through the nh for 0.05mol/l for the concentration4no3Aqueous solution is acidified, and acidifying solution carries out ion exchange in 60-90 DEG C, and swap time is 1-4
Hour, exchange times 2-5 time；And 6-24 hour is dried after 90-120 DEG C, finally with 400-600 DEG C of roasting 2-6 hour；By acid
The composite molecular screen changed and the ratio mix homogeneously of binding agent 100-80:0-20 by weight percentage, kneading and compacting, dry, roast
Reacted in fixed bed reactors after burning, as the catalyst in preparing gasoline by methanol (mtg) reaction, fixed bed reaction condition
For: temperature 340-420 DEG C, pressure 0.1-2mpa, mass space velocity 1-2.5h-1.
8. the zsm-5/mcm-48 composite molecular screen as described in claim 7 application it is characterised in that: described binding agent be oxygen
Change aluminum, kieselguhr, boehmite or silicon dioxide.
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| CN108298559B (en) * | 2018-01-03 | 2021-08-06 | 瑞声光电科技(常州)有限公司 | Molecular sieve, sound-absorbing material using molecular sieve and loudspeaker |
| CN108441245B (en) * | 2018-01-31 | 2020-08-28 | 江苏大学 | Modified composite molecular sieve and preparation method and application thereof |
| CN109174174B (en) * | 2018-08-20 | 2021-06-11 | 太原理工大学 | HZSM-5/SAPO-5 core-shell molecular sieve, and preparation method and application thereof |
| CN110721733A (en) * | 2019-09-17 | 2020-01-24 | 中国科学院青岛生物能源与过程研究所 | Catalyst for preparing aviation oil by oligomerization of low-carbon hydrocarbon and preparation method and application thereof |
| CN112691650B (en) * | 2019-10-23 | 2022-09-06 | 中国石油化工股份有限公司 | Adsorbent and preparation method and application thereof |
| CN111592007A (en) * | 2020-05-22 | 2020-08-28 | 萍乡市石化填料有限责任公司 | Method for growing mesoporous molecular sieve by attaching crystals on surface of microporous molecular sieve |
| CN114433037B (en) * | 2020-10-20 | 2024-01-26 | 中国石油化工股份有限公司 | Preparation method of M41S mesoporous material adsorbent, M41S mesoporous material adsorbent and application |
| CN114538462B (en) * | 2022-02-22 | 2023-06-30 | 复旦大学 | MFI/MEL composite molecular sieve and preparation method and application thereof |
| CN115770614A (en) * | 2022-12-15 | 2023-03-10 | 江西省科学院应用化学研究所 | Composite molecular sieve catalyst and application thereof |
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