CN105983440A - Composite nanometer thin layer molecular sieve and preparation method and application - Google Patents
Composite nanometer thin layer molecular sieve and preparation method and application Download PDFInfo
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Abstract
The invention provides a preparation method of a beta/nanometer thin layer ZSM-5 composite molecular sieve. The molecular sieve is prepared by adding beta molecular sieve crystalline grains into a synthetic raw material of a nanometer thin layer ZSM-5 molecular sieve through hydrothermal crystallization. The method specifically includes the following steps that firstly, anhydrous ethanol and a template, namely asymmetric gemini quaternary ammonium salt, are added into deionized water to be prepared into a solution A; an aluminum source is added into a sulfuric acid solution to be prepared into a solution B; secondly, B is slowly added into A dropwise and evenly stirred, then beta molecular sieve raw powder is added, and ultrasonic oscillation is conducted for 30 min; thirdly, a silicon source is added and continuously stirred to form initial gel; fourthly, the gel is transferred into a crystallization kettle, and crystallization is conducted for 1-10 days at 100-200 DEG C. The beta/nanometer thin layer ZSM-5 composite molecular sieve prepared through the method is of a nanosheet layered structure, the thickness of the layered structure is 10-80 nm, and the molecular sieve has various adjustable active centers and dual channel structures and high specific surface areas and pore volumes. In a reaction that propylene is selectively prepared through methyl alcohol, compared with a traditional beta and ZSM-5 molecular sieve, the composite molecular sieve has higher propylene selectivity, and compared with P/E, the molecular sieve has longer catalyst service life.
Description
Technical field
The invention belongs to composite molecular screen materials synthesis and catalytic applications, be specifically related to a kind of β/receive for preparing propylene from methanol reaction
The preparation method of rice thin layer ZSM-5 complex type molecular sieve and reactivity worth.
Background technology
The key core of preparing propylene from methanol technology (MTP) is the exploitation of catalyst, how to improve the Propylene Selectivity of catalyst, propylene/second
Alkene (P/E) mass ratio and catalyst life are always the difficult point of this technique.
ZSM-5 and beta-molecular sieve are to be applied to two kinds of common solid acid catalysts in preparing propylene from methanol field.Wherein, ZSM-5 molecular sieve (MFI
Configuration) there is unique three-dimensional 10 ring intersection pore passage structure, a kind of ten-ring straight hole road being parallel to c-axis, another kind is parallel to a axle
Ten-ring S-shaped duct, the pore passage structure of this uniqueness makes ZSM-5 molecular sieve have good shape selective catalysis ability.Methanol is on ZSM-5 molecular sieve
Reaction, both can generate ethylene and aromatic hydrocarbons by " hydrocarbon pond " mechanism, again can with the propylene in product by methylating/cracking Route Generation is more
Propylene and higher olefins, higher olefins generates " hydrocarbon pond " species and the alkane such as toluene by the reaction such as aromatisation and hydrogen migration simultaneously.By less
The restriction of 10 membered ring channels, the composition of " hydrocarbon pond " species is mainly low methylbenzene, and substituent group aromatic hydrocarbons more than tetramethyl is difficult to diffuse out molecular sieve pores
Road, this is conducive to ethylene and the raising of two kinds of selectivity of light olefin of propylene.So, ZSM-5 molecular sieve catalysis MTP reaction, second in products distribution
The selectivity of alkene and propylene is higher, C5+Selectivity relatively low, carbon deposition rate is slow, and catalytic life is longer.
(molecular formula is to report the Shuangzi based quaternary ammonium salt surfactant by asymmetric organic hydrocarbon chain on NATURE recently
C18H37-N+(CH3)2-C6H12-N+(CH3)2-C6H13, it is abbreviated as C18-6-6), successfully synthesize single cell thickness and only have lamellar structure ZSM-5 of 2 nanometers and divide
Son sieve (Minkee Choi, et al.Stable single-unit-cell nanosheets of zeolite MFI as active and
Long-lived catalysts.Nature, 2009,461 (10): 246-250.), and this kind of material is at methanol conversion gasoline processed (MTG)
Reaction has the highest appearance carbon ability, thus improves the life-span of MTG catalyst, but author does not deliver the product that MTG reacts by this catalyst and divides
The impact of cloth.Research shows that MFI nano thin-layer molecular sieve is applied to methanol and converts the reaction of hydrocarbon processed, has the feature of long catalytic life.Patent
CN103626202A reports the preparation method of a kind of nano thin-layer ZSM-5 molecular sieve, compared with traditional spherical or cube ZSM-5 molecular sieve,
This material is a kind of mesoporous-microporomolecular molecular sieve, has the biggest specific surface area and pore volume, and nano-lamellar structure makes orifice throat length short, diffusion
The most excellent, and this material is in MTP reacts, and reduces the probability that secondary response occurs, and the selectivity of propylene improves further, C5+Selection
Property reduce further, have the highest P/E than and the longest catalytic life.We have studied high silica alumina ratio nano thin-layer MFI molecular sieve anti-at MTP
The catalytic effect (Hu et al.Appl.Catal., A 2012,445-446:215-220.) that should go up, Propylene Selectivity is up to 51%, propylene/
Nearly 12.1 (reaction condition T=450 DEG C, P=0.1MPa, the WHSV=1.5h of ethylene mass ratio-1, water/methanol molar ratio is 4: 1, nitrogen carrier gas).
Being reacted by series silica alumina ratio nano thin-layer HZSM-5 molecular sieve catalytic preparing propylene from methanol, research shows, (anti-under industrial condition
Answering temperature 470 DEG C, methanol quality air speed is 3h-1, water/methanol molar ratio is 1: 1), select suitable silica alumina ratio nano thin-layer ZSM-5 molecular sieve
Sample, the selectivity of reaction purpose product is optimal, longest-lived.Comparing nanometer ZSM-5 molecular sieve with small crystal grains, nano thin-layer HZSM-5 is to methanol
Preparing propylene transformed reaction P/E mass ratio can reach 6.5, is nano-HZSM-5 zeolite 2 times, and wherein the yield of propylene can reach 46.7%, three
Alkene (ethylene, propylene and C4Alkene) yield reaches 78.7%, and the selectivity of aromatic hydrocarbons substantially reduces, and the overall selectivity of triolefin significantly improves (Zhang Shaolong
Deng. Acta PhySico-Chimica Sinica, 2014, (03): 535-543).
Beta-molecular sieve (BEA configuration) has three-dimensional 12 rings intersection pore passage structures, and it is two kinds of structures differences but tight polymorph A
Form with B symbiosis hybrid junction network.Methanol reacts on beta-molecular sieve, and its 12 bigger membered ring channels can accommodate the life of the high methylbenzene replacing number
Becoming, these many methyl substituted benzenes serve as active intermediate in methanol conversion process, and the alkene that major cleavage generates propylene, butylene etc. bigger divides
Son, and the growing amount of ethylene is little.Therefore, the P/E ratio that methanol reacts on beta-molecular sieve catalyst is the highest.On the other hand, beta-molecular sieve is relatively
Big duct makes a lot of C4Above hydrocarbons easily generates and diffuses out, and causes products distribution to offset to heavy constituent, thus propylene product choosing
Selecting property is relatively low, C5+Selectivity higher, carbon deposition rate is very fast, and catalytic life is shorter.
Composite molecular screen refers to use certain synthetic technology, will have the molecular screen material of different pore passage structure and active center by extension altogether
Raw or cladding growth Combination of Methods forms new ordered composite material, and this new material not only remains the characteristic of every kind of ingredient sieve, also simultaneously
Have various active center and dual pore passage structure.Additionally, special structure activity relationship enhances reactant and the product molecule mass transfer between molecular sieve
And synergism, shorten the performance difference between different molecular sieve, optimize the catalytic performance of molecular sieve.
Beta-molecular sieve is joined as crystal seed in the synthesis material of nano thin-layer ZSM-5 molecular sieve, prepare with beta-molecular sieve through hydrothermal crystallizing
For β/nano thin-layer ZSM-5 complex type molecular sieve that nuclear phase, nano thin-layer ZSM-5 molecular sieve are shell phase.Methanol reacts on this composite molecular screen,
The nuclear phase reaction first diffusing into BEA configuration generates few ethylene and more propylene, is diffused out rapidly mutually by the shell of layer structure the most again
Come, reduce the probability that secondary response occurs so that the distribution of product has higher P/E ratio.
In sum, β/nano thin-layer ZSM-5 complex type molecular sieve is expected to have much urging of potentiality as in methanol height selectively producing propene technique
Agent.
Summary of the invention
Technical problem solved by the invention is by adjusting and changing synthesis condition, it is provided that a kind of β/compound point of nano thin-layer ZSM-5
The preparation method of son sieve, the β of preparation/nano thin-layer ZSM-5 complex type molecular sieve, this composite molecular screen due to have multiple can be in the activity of modulation
The heart and dual pore passage structure, advantageously account for the problem such as be not suitable for of poor diffusivity that the MTP molecular sieve of prior art report exists and Acidity, excellent
Change the distribution of methanol product, make the catalytic performance of preparing propylene by methanol transformation significantly improve.This preparation method simple and obtain product quality
Stable.
Present invention also offers the preparation method of above-mentioned β/nano thin-layer ZSM-5 complex type molecular sieve, the method comprises the following steps:
(1) in deionized water, add dehydrated alcohol and the gemini surfactant (SDA) of asymmetric group, stir 1～10 hour,
Being preferably 2～5 hours, be configured to A liquid, join in sulfuric acid solution by a certain amount of aluminum source, stirring to mix homogeneously is configured to B liquid.
(2) by A liquid at 30～90 DEG C, preferably 40～60 DEG C water-baths are slowly added dropwise B liquid while stirring, continue at water after addition
Stirring 1～10 hour in bath, preferably 2～5 hours, (quality was the 1～75% of composite molecular screen gross mass, excellent to add the former powder of beta-molecular sieve
Select 2～40%), ultrasonic vibration 30 minutes, hereafter it is slowly added to silicon source, continues stirring 30min, fill into certain deionized water according to residual quantity, continue
It is aged 2～24 hours, preferably 4～10 hours, forms Primogel.
(3) Primogel is transferred to in teflon-lined stainless steel cauldron, crystallization 1～10 at 100～200 DEG C
Obtaining crystallization product after it, product is through filtering, washing and be dried, and the β/nano thin-layer ZSM-5 complex type molecular sieve that can be prepared by high-crystallinity is former
Powder.
During synthesizing this molecular sieve, mixing feed molar consists of: SiO2∶Al2O3∶SDA∶Na2O∶SO4 2-∶H2O∶C2H5OH=1:
(0.01-0.001)∶(0.02-0.24)∶(0.1-0.5)∶(0.06-0.4)∶(10-60)∶(1-20)。
In above-mentioned preparation method, the template of employing is asymmetric Gemini quaternary ammonium salt style surfactant, such as,
CnH2n+1-N+(CH3)2-C6H12-N+(CH3)2-C6H13(it is designated as Cn-6-6, wherein n=12-22), it is 1,6-the hexane double hydroxide of ammonium, halogenide etc..
In above-mentioned preparation method, the silicon source of employing can be waterglass, Ludox, silicic acid, silochrom or white carbon, or above-mentioned
Double silicon sources system that solid forms with liquid silicon source；The aluminum source used can be the one in sodium aluminate, aluminum sulfate, aluminium hydroxide or boehmite
Or multiple mixture.
In step (3), crystallization condition is crystallization 1～10 days at 100～200 DEG C, and wherein optimum condition is under the conditions of 140～150 DEG C
Crystallization 2～6 days.
A kind of method that present invention also offers methanol height selectively producing propene, the method includes using above-mentioned β/nano thin-layer ZSM-5 to be combined
Type molecular sieve is used as the catalyst of reaction.
The preferred reaction condition of said method is temperature 450～500 DEG C, pressure 1atm, and water is 1: 2～3: 1 with the mol ratio of methanol.
In the method for this methanol height selectively producing propene, relative to traditional Z SM-5 molecular sieve, the matter of the propylene/ethylene of this composite molecular screen
Amount ratio reaches 12.1, increases by 3 times than traditional Z SM-5 molecular sieve, and butylene selectivity is high 5 percentage points, extends more than 1 times service life；Relatively
Beta-molecular sieve in comparative example 1, the Propylene Selectivity of this composite molecular screen is high 5 percentage points, extends more than 6 times service life；Relative to
Nano thin-layer ZSM-5 molecular sieve in comparative example 2, the P/E ratio of this composite molecular screen is high 1 times.
The feature of β/nano thin-layer ZSM-5 complex type molecular sieve catalysis that the present invention provides can characterize with the following method:
(1) powder X-ray diffraction (XRD).Use XRD that catalyst crystal formation is characterized, determine that this catalyst is ZSM-5 and beta molecule
The complex type molecular sieve of two kinds of crystalline phases of sieve.
(2) scanning electron microscope (SEM).Use SEM that catalyst pattern is characterized, observation grain morphology directly perceived and size.
(3) preparing propylene from methanol catalytic performance.Use MTP reaction that activity, stability and the selectivity of catalyst are evaluated.
Specifically, the present invention by using beta-molecular sieve to join in the synthesis material of nano thin-layer ZSM-5 molecular sieve as crystal seed, warp
A kind of β/nano thin-layer ZSM-5 complex type molecular sieve that hydrothermal crystallizing prepares, compared with traditional MTP molecular sieve, it has beta-molecular sieve and receives
The feature of rice thin layer ZSM-5 molecular sieve bi-material, have multiple can the active center of modulation, increase specific surface area and pore volume, improve molecular sieve
The diffusion in duct.This make its preparing propylene from methanol react in, when reaction temperature is 450～500 DEG C, and reaction pressure is latm, water and methanol
Mol ratio when being 1: 2～3: 1, the highest once-through propylene selectivity reaches 42.5%, and P/E ratio reaches 12.1, and catalyst life can reach simultaneously
More than 200 hours.
Accompanying drawing explanation
The XRD spectra of Fig. 1 comparative example 1.It can be seen that it is 7.8 ° and 22.5 ° that the principal character peak preparing sieve sample is positioned at 2 θ values
Near, this is consistent with the diffraction peak of standard beta-molecular sieve sample, illustrates that the sample that the method synthesizes is the pure phase of beta-molecular sieve.
The XRD spectra of Fig. 2 comparative example 2.It can be seen that it is 23.1 °, 23.9 ° that the principal character peak of the sieve sample of preparation is positioned at 2 θ values
And near 24.1 °, for typical MFI structure, there is nano thin-layer structure distinctive feature peak broadening phenomenon simultaneously, the sample that the method synthesizes is described
Product are the pure phase of nano thin-layer ZSM-5 molecular sieve.
The XRD spectra of Fig. 3 embodiment 2.It can be seen that the principal character peak of sieve sample of preparation be positioned at 2 θ values be 7.8 °, 22.5 °,
Near 23.1 °, 23.9 ° and 24.3 °, the diffraction spectrogram coexisted for BEA and two kinds of structures of MFI, it was demonstrated that the sample of the method synthesis is β/nanometer thin
Layer ZSM-5 complex type molecular sieve.
The SEM figure of Fig. 4 comparative example 1.It can be seen that this beta-molecular sieve presents uniform cylindrical pattern, crystallite dimension about 100～
About 200nm.
The SEM figure of Fig. 5 embodiment 2.It can be seen that this β/nano thin-layer ZSM-5 complex type molecular sieve presents the spherical of lamellar intersection
Or ellipse spherical morphology, from the point of view of the elliposoidal crystal grain that single nano lamellar is piled up, crystallite dimension is about at 4 microns, and the thickness of nanometer layer exists
About 40nm～50nm.Being dispersed with minimal amount of roundlet cylindricality crystal grain between the ellipsoid crystal grain that adjacent nano lamellar is piled up, this is the β not being wrapped by
The crystal grain of molecular sieve.
Detailed description of the invention
The realization of the object of the invention is expanded on further below in conjunction with specific embodiments, with help reader understand embodiment of the present invention and
The present invention is produced beneficial effect in implementing, but it is not intended that any restriction to the scope of the present invention.Following comparative example and embodiment are adopted
Surfactant be asymmetric gemini quaternary ammonium salt 1, the halogenide of the double ammonium of 6-hexane, general molecular formula is
CnH2n+1-N+(CH3)2-C6H12-N+(CH3)2-C6H11Br2, referred to as SDA or Cn-6-6。
Comparative example 1
First 0.61g tetraethylammonium bromide (TEABr) template, 0.057g dodecylbenzene sodium sulfonate organic accelerator and the NaOH of 1.85g are taken
Powder, joins in 4.74g deionized water when stirring, after stirring and dissolving, adds 0.03g boehmite (Al2O3＞ 67.0%), continue
Continuous stirring is uniform to system, adds 5g silochrom (SiO2＞ 98.0wt%), strong agitation 2h forms Primogel, wherein mole group of gel
Become 0.0025Al2O3∶SiO2∶0.0175(TEA)2O∶0.28Na2O∶3.2H2O, is transferred to band teflon-lined airtight by Primogel
In stainless steel cauldron, being first placed in 140 DEG C of baking oven crystallization 26h, then be placed in 165 DEG C of baking oven crystallization 20h, product is through filtering, washing and be dried to obtain
The former powder of beta-molecular sieve.The synthetic schemes of embodiment 3 in referenced patent CN102211779B, only changes the inventory in aluminum source.
Comparative example 2
17.2g dehydrated alcohol, 7.62gSDA (C is added in 40g deionized water18-6-6) and 1.5gNaOH, stir under 60 DEG C of heating in water bath
4h is configured to A liquid；By dense for 0.98g H2SO4Add in 44.24g deionized water, after mix homogeneously, add 0.312gAl2(SO4)3·18H2O (＞ 99%)
Stirring to mix homogeneously is configured to B liquid.In A liquid, it is slowly added dropwise B liquid, continues 60 DEG C of stirred in water bath 4h after addition, the most slowly
Add 20g waterglass (SiO2＞ 28.08wt%), continue stirring 30min, fill into certain deionized water according to residual quantity, continue stirring 5h and formed initially
Gel, wherein gel mole consist of 0.005Al2O3∶SiO2∶0.10SDA∶0.30Na2O∶0.12SO4 2-∶50H2O∶4C2H5OH, will be initial
Gel is transferred to in teflon-lined stainless steel cauldron, in 150 DEG C of lower seal crystallization 4d of temperature, product through filtering, washing, dry
Dry, obtain the β/former powder of nano thin-layer ZSM-5 complex type molecular sieve of high-crystallinity.The synthesis side of embodiment 2 in referenced patent CN103626202A
Case, changes the inventory of sodium source, dehydrated alcohol and deionized water.
Embodiment 1
34.4g dehydrated alcohol, 6.1gSDA (C is added in 40g deionized water20-6-6) and 1.0gNaOH, stir under 60 DEG C of heating in water bath
4h is configured to A liquid；By dense for 0.49g H2SO4Add in 27.32g deionized water, after mix homogeneously, add 0.104gAl2(SO4)3·18H2O (＞ 99%)
Stirring to mix homogeneously is configured to B liquid.In A liquid, it is slowly added dropwise B liquid, continues after addition, 60 DEG C of stirred in water bath 2h, to add
The former powder of beta-molecular sieve that 0.11g synthesizes according to comparative example 1 scheme, ultrasonic vibration 30 minutes, hereafter it is slowly added to 20g waterglass
(SiO2＞ 28.08wt%), continue stirring 30min, fill into certain deionized water according to residual quantity, continue stirring 5h and form Primogel, wherein gel
Mole consist of 0.00167Al2O3∶SiO2∶0.08SDA∶0.20Na2O∶0.06SO4 2-∶40H2O∶8C2H5OH, transfers to band by Primogel
Have in teflon-lined stainless steel cauldron, in 140 DEG C of lower seal crystallization 5d of temperature, product through filtering, washing, be dried, obtain high knot
The β of crystalline substance degree/former powder of nano thin-layer ZSM-5 complex type molecular sieve.
Embodiment 2
17.2g dehydrated alcohol, 7.62gSDA (C is added in 40g deionized water18-6-6) and 1.5gNaOH, stir under 60 DEG C of heating in water bath
4h is configured to A liquid；By dense for 0.98g H2SO4Add in 44.24g deionized water, after mix homogeneously, add 0.156gAl2(SO4)3·18H2O (＞ 99%)
Stirring to mix homogeneously is configured to B liquid.In A liquid, it is slowly added dropwise B liquid, continues after addition, 60 DEG C of stirred in water bath 4h, to add
The former powder of beta-molecular sieve that 0.28g synthesizes according to comparative example 1 scheme, ultrasonic vibration 30 minutes, hereafter it is slowly added to 20g waterglass
(SiO2＞ 28.08wt%), continue stirring 30min, fill into certain deionized water according to residual quantity, continue stirring 5h and form Primogel, wherein gel
Mole consist of 0.0025Al2O3∶SiO2∶0.10SDA∶0.30Na2O∶0.12SO4 2-∶50H2O∶4C2H5OH, Primogel is transferred to
In teflon-lined stainless steel cauldron, in 150 DEG C of lower seal crystallization 4d of temperature, product through filtering, washing, be dried, obtain highly crystalline
β/former the powder of nano thin-layer ZSM-5 complex type molecular sieve of degree.
Embodiment 3
25.8g dehydrated alcohol, 9.14gSDA (C is added in 40g deionized water22-6-6) and 0.5gNaOH, stir under 60 DEG C of heating in water bath
3h is configured to A liquid；By dense for 1.47g H2SO4Add in 35.76g deionized water, after mix homogeneously, add 0.156gAl2(SO4)3·18H2O (＞ 99%)
Stirring to mix homogeneously is configured to B liquid.In A liquid, it is slowly added dropwise B liquid, continues after addition, 60 DEG C of stirred in water bath 4h, to add
The former powder of beta-molecular sieve that 0.56g synthesizes according to comparative example 1 scheme, ultrasonic vibration 30 minutes, hereafter it is slowly added to 20g waterglass
(SiO2＞ 28.08wt%), continue stirring 30min, fill into certain deionized water according to residual quantity, continue stirring 6h and form Primogel, wherein gel
Mole consist of 0.0025Al2O3∶SiO2∶0.12SDA∶0.10Na2O∶0.18SO4 2-∶45H2O∶6C2H5OH, Primogel is transferred to
In teflon-lined stainless steel cauldron, in 160 DEG C of lower seal crystallization 3d of temperature, product through filtering, washing, be dried, obtain highly crystalline
β/former the powder of nano thin-layer ZSM-5 complex type molecular sieve of degree.
Embodiment 4
43g dehydrated alcohol, 4.57gSDA (C is added in 40g deionized water16-6-6) and 2.0gNaOH, stir under 60 DEG C of heating in water bath
4h is configured to A liquid；By dense for 1.96g H2SO4Add in 18.85g deionized water, after mix homogeneously, add 0.624gAl2(SO4)3·18H2O (＞ 99%)
Stirring to mix homogeneously is configured to B liquid.In A liquid, it is slowly added dropwise B liquid, continues after addition, 60 DEG C of stirred in water bath 5h, to add
The former powder of beta-molecular sieve that 1.12g synthesizes according to comparative example 1 scheme, ultrasonic vibration 30 minutes, hereafter it is slowly added to 20g waterglass
(SiO2＞ 28.08wt%), continue stirring 30min, fill into certain deionized water according to residual quantity, continue stirring 1h and form Primogel, wherein gel
Mole consist of 0.01Al2O3∶SiO2∶0.06SDA∶0.40Na2O∶0.24SO4 2-∶35H2O∶10C2H5OH, Primogel is transferred to
In teflon-lined stainless steel cauldron, in 170 DEG C of lower seal crystallization 3d of temperature, product through filtering, washing, be dried, obtain highly crystalline
β/former the powder of nano thin-layer ZSM-5 complex type molecular sieve of degree.
Embodiment 5
51.6g dehydrated alcohol, 10.67gSDA (C is added in 30g deionized water14-6-6) and 2.5gNaOH, stir under 60 DEG C of heating in water bath
Mix 5h and be configured to A liquid；By dense for 2.45g H2SO4Add in 20.39g deionized water, after mix homogeneously, add 0.0624gAl2(SO4)3·18H2O (＞ 99%)
Stirring to mix homogeneously is configured to B liquid.In A liquid, it is slowly added dropwise B liquid, continues after addition, 60 DEG C of stirred in water bath 5h, to add
The former powder of beta-molecular sieve that 2.24g synthesizes according to comparative example 1 scheme, ultrasonic vibration 30 minutes, hereafter it is slowly added to 20g waterglass
(SiO2＞ 28.08wt%), continue stirring 30min, fill into certain deionized water according to residual quantity, continue stirring 10h and form Primogel, Qi Zhongning
Glue mole consist of 0.001Al2O3∶SiO2∶0.14SDA∶0.50Na2O∶0.30SO4 2-∶30H2O∶12C2H5OH, transfers to band by Primogel
Have in teflon-lined stainless steel cauldron, in 100 DEG C of lower seal crystallization 10d of temperature, product through filtering, washing, be dried, obtain high
The β of degree of crystallinity/former powder of nano thin-layer ZSM-5 complex type molecular sieve.
Embodiment 6
60.2g dehydrated alcohol, 3.05gSDA (C is added in 20g deionized water12-6-6) and 1.5gNaOH, stir under 60 DEG C of heating in water bath
2h is configured to A liquid；By dense for 2.94g H2SO4Add in 21.93g deionized water, after mix homogeneously, add 0.312gAl2(SO4)3·18H2O (＞ 99%)
Stirring to mix homogeneously is configured to B liquid.In A liquid, it is slowly added dropwise B liquid, continues after addition, 60 DEG C of stirred in water bath 1h, to add
The former powder of beta-molecular sieve that 1.68g synthesizes according to comparative example 1 scheme, ultrasonic vibration 30 minutes, hereafter it is slowly added to 20g waterglass
(SiO2＞ 28.08wt%), continue stirring 30min, fill into certain deionized water according to residual quantity, continue stirring 7h and form Primogel, wherein gel
Mole consist of 0.005Al2O3∶SiO2∶0.04SDA∶0.30Na2O∶0.36SO4 2-∶25H2O∶14C2H5OH, Primogel is transferred to
In teflon-lined stainless steel cauldron, in 120 DEG C of lower seal crystallization 8d of temperature, product through filtering, washing, be dried, obtain highly crystalline
β/former the powder of nano thin-layer ZSM-5 complex type molecular sieve of degree.
Embodiment 7
8.6g dehydrated alcohol, 1.52gSDA (C is added in 20g deionized water18-6-6) and 1.5gNaOH, stir under 60 DEG C of heating in water bath
3h is configured to A liquid；By dense for 3.27g H2SO4Add in 13.47g deionized water, after mix homogeneously, add 0.208gAl2(SO4)3·18H2O (＞ 99%)
Stirring to mix homogeneously is configured to B liquid.In A liquid, it is slowly added dropwise B liquid, continues after addition, 60 DEG C of stirred in water bath 4h, to add
The former powder of beta-molecular sieve that 0.28g synthesizes according to comparative example 1 scheme, ultrasonic vibration 30 minutes, hereafter it is slowly added to 20g waterglass
(SiO2＞ 28.08wt%), continue stirring 30min, fill into certain deionized water according to residual quantity, continue stirring 5h and form Primogel, wherein gel
Mole consist of 0.0033Al2O3∶SiO2∶0.02SDA∶0.30Na2O∶0.40SO4 2-∶20H2O∶2C2H5OH, Primogel is transferred to
In teflon-lined stainless steel cauldron, in 180 DEG C of lower seal crystallization 4d of temperature, product through filtering, washing, be dried, obtain highly crystalline
β/former the powder of nano thin-layer ZSM-5 complex type molecular sieve of degree.
Embodiment 8
86g dehydrated alcohol, 13.72gSDA (C is added in 40g deionized water20-6-6) and 1.5gNaOH, stir under 60 DEG C of heating in water bath
4h is configured to A liquid；By dense for 0.98g H2SO4Add in 52.69g deionized water, after mix homogeneously, add 0.125gAl2(SO4)3·18H2O (＞ 99%)
Stirring to mix homogeneously is configured to B liquid.In A liquid, it is slowly added dropwise B liquid, continues after addition, 60 DEG C of stirred in water bath 3h, to add
The former powder of beta-molecular sieve that 0.56g synthesizes according to comparative example 1 scheme, ultrasonic vibration 30 minutes, hereafter it is slowly added to 20g waterglass
(SiO2＞ 28.08wt%), continue stirring 30min, fill into certain deionized water according to residual quantity, continue stirring 8h and form Primogel, wherein gel
Mole consist of 0.002Al2O3∶SiO2∶0.18SDA∶0.30Na2O∶0.12SO4 2-∶55H2O∶20C2H5OH, Primogel is transferred to
In teflon-lined stainless steel cauldron, in 150 DEG C of lower seal crystallization 6d of temperature, product through filtering, washing, be dried, obtain highly crystalline
β/former the powder of nano thin-layer ZSM-5 complex type molecular sieve of degree.
Embodiment 9
4.3g dehydrated alcohol, 18.29gSDA (C is added in 60g deionized water18-6-6) and 2.56gNaOH, stir under 60 DEG C of heating in water bath
Mix 1h and be configured to A liquid；By dense for 2.50g H2SO4Add in 61.15g deionized water, after mix homogeneously, add 0.067gNaAlO2(Al2O3＞ 41.0%)
Stirring to mix homogeneously is configured to B liquid.In A liquid, it is slowly added dropwise B liquid, continues after addition, 60 DEG C of stirred in water bath 4h, to add
The former powder of beta-molecular sieve that 1.12g synthesizes according to comparative example 1 scheme, ultrasonic vibration 30 minutes, hereafter it is slowly added to 16g Ludox (SiO2＞ 40.0wt%),
Continue stirring 30min, fill into certain deionized water according to residual quantity, continue stirring 4h and form Primogel, wherein mole the consisting of of gel
0.0025Al2O3∶SiO2∶0.24SDA∶0.30Na2O∶0.24SO4 2-∶60H2O∶1C2H5OH, transfers to Primogel with in politef
In the stainless steel cauldron of lining, in 200 DEG C of lower seal crystallization 1d of temperature, product through filtering, washing, dry, obtain the β/nanometer of high-crystallinity
The former powder of thin layer ZSM-5 complex type molecular sieve.
Embodiment 10
This example demonstrates that the β/nano thin-layer ZSM-5 complex type molecular sieve of the method synthesis using the present invention to provide reacts at preparing propylene from methanol
In application effect.
By first for former for the ZSM-5 molecular sieve in embodiment 2 powder 6 hours removed template methods of roasting at 550 DEG C.Then in 90 DEG C of water-baths
Exchanging 2 hours with the ammonium nitrate solution of 1mol/L, solid-liquid mass ratio is 1: 10, then roasting 6 hours at 550 DEG C.This process is repeated twice,
Obtain the sample of protonation, named B-NZ5.As a comparison, take the beta-molecular sieve according to the synthesis of comparative example 1 scheme, process as stated above,
The named B of sample obtained；Take the nano thin-layer ZSM-5 molecular sieve according to the synthesis of comparative example 2 scheme, process as stated above, the sample obtained
Named NZ5；Take the Cubic ZSM-5 molecular sieve that commercially available silica alumina ratio is 200, process as stated above, the named CZ5 of sample obtained.
Serialization fixed bed reactors are used to investigate above-mentioned catalyst activity and selectivity in preparing propylene from methanol reacts.Reaction tube is 10mm
The stainless steel tube of × 530mm, loaded catalyst is 1.0g, and reaction temperature is 450～500 DEG C, and air speed is 1.5h-1, system pressure 1atm.Adopt
With the type gas chromatogram on-line analysis of Agilent 7890A, product C1～C5Component uses HP-PlotQ capillary column (30m × 0.53mm) to analyze.
Table 1 catalyst performance in MTP reacts
| Catalyst | Methanol conversion/% | Ethylene/% | Propylene/% | Butylene/% | C5+/ % | P/E | Catalytic lifea/ hour |
| B | 100 | 2.2 | 37.6 | 29.7 | 23.8 | 17.1 | 30 |
| NZ5 | 100 | 7.2 | 46.7 | 24.8 | 13.4 | 6.5 | 350 |
| B-NZ5 | 100 | 3.5 | 42.5 | 27.5 | 20.5 | 12.1 | 200 |
| CZ5 | 100 | 14.0 | 42.0 | 22.0 | 15.0 | 3.0 | 100 |
aKeep the response time of more than 90% methanol conversion.
Claims (10)
1. β/nano thin-layer ZSM-5 complex type molecular sieve, it is characterised in that this molecular sieve has the Acidity of adjustable change and dual pore passage structure,
Having high specific surface area and pore volume, good duct is configured with reaction and the diffusion beneficially improving reactant molecule simultaneously.
The preparation method of β the most according to claim 1/nano thin-layer ZSM-5 complex type molecular sieve, it is characterised in that the method include with
Lower step:
(1) in deionized water, add dehydrated alcohol and the gemini surfactant (SDA) of asymmetric group, stir 1～10 hour, excellent
Electing as 2～5 hours, be configured to A liquid, join in sulfuric acid solution by a certain amount of aluminum source, stirring to mix homogeneously is configured to B liquid.
(2) by A liquid at 30～90 DEG C, preferably 40～60 DEG C water-baths are slowly added dropwise B liquid while stirring, continue in water-bath after addition
Middle stirring 1～10 hours, preferably 2～5 hours, add the former powder of beta-molecular sieve (quality be composite molecular screen gross mass 1～75%, preferably 2～
40%), ultrasonic vibration 30 minutes, hereafter it is slowly added to silicon source, continues stirring 30min, fill into certain deionized water according to residual quantity, continue ageing 2
～24 hours, preferably 4～10 hours, form Primogel.
(3) Primogel is transferred to in teflon-lined stainless steel cauldron, crystallization 1～after 10 days at 100～200 DEG C
Obtaining crystallization product, product, through filtering, washing and be dried, can be prepared by the β/former powder of nano thin-layer ZSM-5 complex type molecular sieve of high-crystallinity.
The preparation method of nanometer laminated structure ZSM-5 molecular sieve the most according to claim 2, it is characterised in that the mixing in building-up process
Feed molar consists of: Al2O3∶SiO2∶SDA∶NaO2∶SO4 2-H2O∶C2H5OH=(0.01-0.001): 1: (0.02-0.24): (0.1-0.5):
(0.06-0.4)∶(10-60)∶(1-20)。
The preparation method of β the most according to claim 2/nano thin-layer ZSM-5 complex type molecular sieve, it is characterised in that add in synthetic system
The gemini quaternary ammonium salt template of asymmetric group strengthens the structure-directing effect with layer structure molecular sieve.
The preparation method of β the most according to claim 2/nano thin-layer ZSM-5 complex type molecular sieve, it is characterised in that the template of employing is
Asymmetric Gemini quaternary ammonium salt style surfactant, such as, CnH2n+1-N+(CH3)2-C6H12-N+(CH3)2-C6H13(it is designated as Cn-6-6, wherein n=12-22), for
1,6-the hexane double hydroxide of ammonium, halogenide etc..
The preparation method of β the most according to claim 2/nano thin-layer ZSM-5 complex type molecular sieve, it is characterised in that the silicon source of employing can
Think waterglass, Ludox, silicic acid, silochrom or white carbon, or double silicon sources system that above-mentioned solid forms with liquid silicon source；Use
Aluminum source can be one or more mixture in sodium aluminate, aluminum sulfate, aluminium hydroxide or boehmite.
The preparation method of β the most according to claim 2/nano thin-layer ZSM-5 complex type molecular sieve, it is characterised in that crystallization condition be
Crystallization 1～10 days at 100～200 DEG C, wherein optimum condition is crystallization 2-6 days under the conditions of 140～150 DEG C.
8. a method for methanol height selectively producing propene, the method includes the β described in claim 1/compound molecule of nano thin-layer ZSM-5
Sieve is used as the catalyst of reaction.
The method of methanol height selectively producing propene the most according to claim 8, it is characterised in that described reaction condition be temperature 450～
500 DEG C, pressure latm, water is 1: 2～3: 1 with the mol ratio of methanol.
The method of methanol height selectively producing propene the most according to claim 8, it is characterised in that relative to traditional Z SM-5 molecular sieve, should
The mass ratio of the propylene/ethylene of composite molecular screen reaches 12.1, increases by 3 times than traditional Z SM-5 molecular sieve, and butylene selectivity is high 5 percentage points,
Extend more than 1 times service life；Relative to conventional beta molecular sieve, the Propylene Selectivity of this composite molecular screen is high 5 percentage points, and service life extends
More than 6 times.
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