CN109748293A - A kind of twin-stage pore size distribution ZSM-35 molecular sieve and the preparation method and application thereof - Google Patents
A kind of twin-stage pore size distribution ZSM-35 molecular sieve and the preparation method and application thereof Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of twin-stage pore size distribution ZSM-35 molecular sieve, this method passes through simple hydrothermal synthesis and pressure discharge operations, prepare the ZSM-35 molecular sieve with 0.5-0.8nm and 1.2-2.0nm twin-stage pore size distribution, and pass through the temperature of adjusting pressure release and control venting duration, the distribution regulation in two kinds of apertures may be implemented,, repeatability height simple with synthetic method, the advantages that controllability is strong, the ZSM-35 molecular sieve of preparation has stronger acid and stability, has important application value for some important catalysis reactions.
Description
Technical field
The invention belongs to technical field of molecular sieve preparation, it is related to a kind of twin-stage pore size distribution ZSM-35 molecular sieve and its preparation side
Method and application.
Background technique
ZSM-35 zeolite is that Mobil company, the U.S. is successfully a kind of with FER (magnesium in last century the seventies later development
Alkali zeolite) topological structure molecular sieve (US4,016,245), it possesses the two-dimensional channel system of square crossing, wherein in parallel with
[001] the ten-ring duct size in face is 0.42 × 0.54nm；Be parallel to [010] face octatomic ring duct size be 0.35 ×
0.48nm.ZSM-35 molecular sieve is widely used in the catalysis of the hydrocarbon conversion because of the two-dimensional channel structure of its distinctive square crossing
In reaction, such as in the isomerization of linear alkene, polymerization, aromatisation and cracking catalysis reaction.
ZSM-35 molecular sieve belongs to micro porous molecular sieve, and micropore can bring biggish specific surface area, but in above-mentioned reaction process
In usually have the generation of carbon distribution, the carbon distribution generated in these reactions can reduce the service life of catalyst.In recent years, more for possessing
The catalysis material research of weight cellular structure receives extensively, has the catalyst of the pore size distribution of different pore size, a side by providing
Face improves the diffusion of reactants and products, reduces the generation of side reaction product and carbon distribution；It on the other hand is to be produced in reaction process
Raw carbon distribution provides more accommodation space, improves catalyst and holds carbon ability, to extend catalyst regeneration cycle.
It is existing multistage pore size distribution molecular screen material be usually realized using various template agent, complex process, cost compared with
It is high.Therefore, need to research and develop that a kind of preparation process is simple at present, the system of the molecular screen material of lower-cost multistage pore size distribution
Preparation Method.
Summary of the invention
An object of the present invention is to provide a kind of twin-stage pore size distribution ZSM-35 molecular sieve, which has two-stage hole diameter
Pore size distribution.
The second object of the present invention is to provide a kind of preparation method of twin-stage pore size distribution ZSM-35 molecular sieve, using this method
A kind of twin-stage pore size distribution ZSM-35 molecular sieve can be made with simple technique.
The three of the object of the invention are to provide a kind of application of twin-stage pore size distribution ZSM-35 molecular sieve.
For this purpose, first aspect present invention provides a kind of twin-stage pore size distribution ZSM-35 molecular sieve, being dispersed with aperture is
The hole and aperture of 0.5-0.8nm is the hole of 1.2-2.0nm.
In some embodiments of the invention, in the twin-stage pore size distribution ZSM-35 molecular sieve, aperture 0.5-0.8nm
Hole and aperture be 1.2-2.0nm the volume ratio in hole be 1:(0.1-1.2).
Second aspect of the present invention provides a kind of preparation method of twin-stage pore size distribution ZSM-35 molecular sieve, comprising:
Step A will be uniformly mixed in reaction kettle by silicon source, silicon source, alkali source, template and water, colloid mixing obtained
Object solution carries out crystallization, obtains ZSM-35 molecular sieve crystallization mother liquor；
Step B, after the completion of crystallization, from the greenhouse cooling of crystallization to the temperature of pressure release, the drain for opening reaction kettle is carried out
Pressure release, the ZSM-35 molecular sieve crystallization mother liquor after obtaining pressure release；
Step C filters the ZSM-35 molecular sieve crystallization mother liquor after pressure release, is washed, is dried, and twin-stage pore size distribution is made
ZSM-35 molecular sieve original powder.
According to certain embodiments of the present invention, in stepb, cool down 10-60 DEG C, preferably cool down 20-50 DEG C.
In some embodiments of the invention, in stepb, the speed of the cooling is 0.1-5 DEG C/min, preferably
0.25-1.5 DEG C/min, further preferred 0.5-1 DEG C/min.
In other embodiments of the invention, in stepb, the initial pressure of pressure release is 0.6-1.37Mpa.
In other embodiment of the invention, in stepb, venting duration 2-8h, preferably 3-5h.
In some preferred embodiments of the invention, in stepb, pressure in pressure release to reaction kettle be normal pressure (i.e.
0) gauge pressure is.
According to certain embodiments of the present invention, in step, the time of the crystallization is 10-48h, preferably 15-
36h。
In certain embodiments of the present invention, the template includes pyridine, ethylenediamine, ring amine, pyrrolidines and piperazine
One or more of buttocks.
In other embodiments of the invention, source of aluminium includes in aluminum sulfate, boehmite and sodium aluminate
It is one or more of.
In other embodiment of the invention, the silicon source includes silica solution, silicic acid, white carbon black, sodium metasilicate and just
One or more of silester.
In some embodiments of the invention, using twin-stage pore size distribution ZSM-35 molecule prepared by the method for the present invention
Sieve is dispersed with the hole that aperture is 0.5-0.8nm and the hole that aperture is 1.2-2.0nm.
In some further embodiments of the invention, using twin-stage pore size distribution prepared by the method for the present invention
In ZSM-35 molecular sieve, the volume ratio in the hole that the hole and aperture that aperture is 0.5-0.8nm are 1.2-2.0nm is 1:(0.1-1.2).
Third aspect present invention provides a kind of twin-stage pore size distribution ZSM-35 molecular sieve as described in the first aspect of the invention
Or the twin-stage pore size distribution ZSM-35 molecular sieve of method preparation as described in respect of the second aspect of the invention is in lower carbon number hydrocarbons isomerization reaction
Application.
As previously mentioned, the molecular screen material of existing multistage pore size distribution is usually to be realized using various template agent, technique is multiple
It is miscellaneous, higher cost.Compared with the existing technology, the present invention have following characteristics and the utility model has the advantages that
First by simple hydrothermal synthesis and pressure discharge operations, prepare with 0.5-0.8nm and 1.2-2.0nm two-stage hole point
The ZSM-35 molecular sieve of cloth may be implemented the distribution regulation in two kinds of apertures, have synthetic method letter by adjusting the temperature of pressure release
The advantages that single, repeatability height, controllability is strong, the ZSM-35 molecular sieve of preparation has stronger acid and stability, for some
Important catalysis reaction has important application value.In addition, also achieving template using method provided by the present invention
Recycling, reduces the discharge of organic pollutant.
Detailed description of the invention
To be readily appreciated that the present invention, illustrate the present invention below in conjunction with attached drawing.
Fig. 1 is the XRD diagram of product obtained in comparative example 1；
Fig. 2 is product graph of pore diameter distribution obtained in comparative example 1；
Fig. 3 is the XRD diagram of product obtained in comparative example 2；
Fig. 4 is the XRD diagram of product obtained in embodiment 1；
Fig. 5 is product graph of pore diameter distribution obtained in embodiment 1；
Fig. 6 is the XRD diagram of product obtained in embodiment 3；
Fig. 7 is product graph of pore diameter distribution obtained in embodiment 3.
Specific embodiment
To be readily appreciated that the present invention, below in conjunction with embodiment, the present invention will be described in detail, these embodiments only rise
Bright property effect, it is not limited to application range of the invention.If raw material used in the present invention or component are equal without specified otherwise
It can be made by commercial sources or conventional method.
The present inventor has found in the research for preparing ZSM-35 molecular sieve, and after the completion of crystallization, pressure release can be had
The ZSM-35 molecular sieve of different pore size distribution, but the crystallinity of ZSM-35 molecular sieve has and reduces to a certain degree.The present inventor
It finds after further research, after the completion of crystallization, cooling and the pressure release after cooling, can not only obtaining tool, there are two types of apertures point
The ZSM-35 molecular sieve of cloth, and the crystallinity level of the molecular sieve can be maintained to a certain extent.The present inventor pass through into
The distribution regulation in two kinds of apertures may be implemented by the temperature of adjusting pressure release in one step research discovery.The present invention is based on above-mentioned
It was found that make.
Therefore, twin-stage pore size distribution ZSM-35 molecular sieve involved in first aspect present invention has more intact crystal form, phase
90-95% is maintained to the sample crystallinity of not pressure release, and is dispersed with hole and aperture that aperture is 0.5-0.8nm in molecular sieve
For the hole of 1.2-2.0nm.In some embodiments, for example, aperture is 0.5-0.8nm's in twin-stage pore size distribution ZSM-35 molecular sieve
The volume ratio in the hole that hole and aperture are 1.2-2.0nm is 1:(0.1-1.2).
The preparation method of twin-stage pore size distribution ZSM-35 molecular sieve involved in second aspect of the present invention, comprising:
Step A will be uniformly mixed in reaction kettle by silicon source, silicon source, alkali source, template and water, colloid mixing obtained
Object solution carries out crystallization, obtains ZSM-35 molecular sieve crystallization mother liquor；Meanwhile generating the mixed gas containing template；
Step B, after the completion of crystallization, from the greenhouse cooling of crystallization to the temperature of pressure release, the drain for opening reaction kettle is carried out
Pressure release, the ZSM-35 molecular sieve crystallization mother liquor after obtaining pressure release；Meanwhile the template and water vapour of gas phase are liquefied and being returned
It receives；
Step C filters the ZSM-35 molecular sieve crystallization mother liquor after pressure release, is washed, is dried, and twin-stage pore size distribution is made
ZSM-35 molecular sieve original powder.
The present inventor is the study found that in stepb, and control cooling range is at 10-60 DEG C, can be with preferably in 20-50 DEG C
Obtain the ZSM-35 molecular sieve of comparatively ideal twin-stage pore size distribution, for example, be dispersed in molecular sieve aperture be 0.5-0.8nm hole and
Aperture is the hole of 1.2-2.0nm, and aperture be 0.5-0.8nm hole and aperture be 1.2-2.0nm the volume ratio in hole be 1:
(0.1-1.2)。
The present inventor's research also found that in stepb, pressure release temperature and venting duration are to the crystallization of ZSM-35 molecular sieve
Degree has an impact, and pressure release temperature is higher, and venting duration is shorter, and crystallinity reduces more；And under the premise of lower pressure release temperature, control
Cooling rate processed and venting duration can maintain the crystallinity of the obtained ZSM-35 molecular sieve with twin-stage pore size distribution
Higher level.
In some embodiments of the invention, such as control cooling rate is 0.1-5 DEG C/min, preferably 0.25-1.5
DEG C/min, further preferably 0.5-1 DEG C/min；Meanwhile the time for controlling pressure release is 2-8h, preferably 3-5h.Obtained
The sample crystallinity of not pressure release relatively of ZSM-35 molecular sieve with twin-stage pore size distribution maintains 90-95%.
In certain specific embodiments of the invention, the temperature of the crystallization, for example, can be 160-210 DEG C, preferably
It is 165-200 DEG C.The time of the crystallization, for example, can be 10-48h, preferably 15-36h.
In certain specific embodiments of the invention, after crystallization, start to cool down, control cooling rate is 0.1-5
DEG C/min, preferably 0.25-1.5 DEG C/min, further preferred 0.5-1 DEG C/min；10-50 DEG C of cooling preferably cools down 20-30 DEG C
Afterwards, start pressure release；The temperature of the pressure release is 130-200 DEG C, preferably 150-190 DEG C；The initial pressure of pressure release is 0.6-
1.37Mpa；Pressure in pressure release to reaction kettle is normal pressure (i.e. gauge pressure is 0)；The time of pressure release is 2-8h, preferably 3-5h.
In some embodiments of the invention, in step, silicon source and silicon source molar ratio are with SiO2/Al2O3It is calculated as
(5-100):1；The molar ratio of the template and silicon source is with R/SiO2It is calculated as (0.1-2.0): 1, wherein R represents template；Institute
The molar ratio of alkali source and silicon source is stated with OH-/SiO2It is calculated as (0.1-1.0): 1, the molar ratio of the water and silicon source is with H2O/SiO2Meter
For (10-100): 1.
In the present invention, source of aluminium includes one or more of aluminum sulfate, boehmite and sodium aluminate；The silicon source
Including one or more of silica solution, silicic acid, white carbon black, sodium metasilicate and ethyl orthosilicate.
In the present invention, the template includes one or more of pyridine, ethylenediamine, ring amine, pyrrolidines and piperazine buttocks.
According to the method for the present invention, in stepb, the amount of the template of recycling is by the total of the template that is added in step A
The 50wt%-85wt% of weight, preferably 60wt%-85wt%, further preferably 70wt%-85wt%.
The mode that the template of gas phase and water vapour are liquefied and recycled in the present invention is not particularly limited, can
The template and water vapour of gas phase are liquefied and be recycled using method and apparatus conventional in the art, for example, can be with
The template and water vapour of gas phase are liquefied and recycled using heat exchanger and/or condenser.
In the actual operation process, during the hydrothermal synthesis of step A, as the temperature rises, in reaction kettle body just
The saturated vapor pressure of water can be generated, this is equivalent to the pressure (i.e. self-generated pressure) that reaction system itself generates, and is not outer to pressure.
Therefore, crystallization process is the temperature in crystallization, is carried out under self-generated pressure, and during this, the pressure of crystallization is self-generated pressure,
For 0.5-1.7MPa.
Heretofore described one word of water, be not particularly illustrated or it is specified in the case where refer to deionized water or distilled water or
Ultrapure water.
Heretofore described term " twin-stage pore size distribution ZSM-35 molecular sieve ", which refers to, is dispersed with two kinds in ZSM-35 molecular sieve
The hole in size or aperture.
X-ray powder diffraction material phase analysis (XRD) uses the X ' PertPRO of Dutch Panaco (PANalytical) company
X-ray diffractometer, Cu target, K α radiation source (λ=0.15418nm), voltage 40KV, electric current 40mA.
N2Physical absorption analysis uses the Micromeritics ASAP 2020HD88 type physical absorption of Merck & Co., Inc, the U.S.
Analysis-e/or determining.
Embodiment
Comparative example 1:
(1) be stirred at room temperature first under state by 50 grams of aluminum sulfate (analysis it is pure, content be greater than 99.5%) is added to
In the deionized water of 785.7ml, stir 40 minutes.After being completely dissolved to aluminum sulfate, it is slowly added to 720 grams of silica solution (SiO2
The silica solution that content is 25%), it stirs 1 hour, is then slowly added into 72 grams of sodium hydroxide, stir 1h, 148ml hexamethylene is added
Amine stirs evenly obtained colloid admixture solution as template.The colloid admixture solution has following mole of composition: OH-:
Al2O3:SiO2:R:H2O=0.6:0.025:1:0.5:25.Colloid admixture solution is transferred in autoclave in 200 DEG C and spontaneous
Under pressure after crystallization 15 hours, stop crystallization, obtains ZSM-35 molecular sieve crystallization mother liquor, meanwhile, it is also produced in reaction system
The raw mixed gas containing template.
(2) ZSM-35 molecular sieve crystallization mother liquor obtains white powder (i.e. by cooling down, being filtered, washed, drying, roasting
ZSM-35 molecular sieve original powder).
X-ray powder diffraction material phase analysis (XRD) is carried out to ZSM-35 molecular sieve original powder obtained, the result is shown in Figure 1；It is right
ZSM-35 molecular sieve original powder obtained carries out N2Physical absorption analysis, is as a result shown in Fig. 2.
Refering to fig. 1 it is found that it is the ZSM-35 with FER topological structure that product obtained by comparison 1, which measures its crystal phase through XRD,
Molecular sieve, crystallinity are set to 100%.
Refering to Fig. 2 it is found that measuring through nitrogen adsorption methods, product aperture integrated distribution is in 0.5- obtained by comparative example 1
0.8nm。
Comparative example 2:
(1) be stirred at room temperature first under state by 50 grams of aluminum sulfate (analysis it is pure, content be greater than 99.5%) is added to
In the deionized water of 785.7ml, stir 40 minutes.After being completely dissolved to aluminum sulfate, it is slowly added to 720 grams of silica solution (SiO2
The silica solution that content is 25%), it stirs 1 hour, is then slowly added into 72 grams of sodium hydroxide, stir 1h, 148ml hexamethylene is added
Amine stirs evenly obtained colloid admixture solution as template.The colloid admixture solution has following mole of composition: OH-:
Al2O3:SiO2:R:H2O=0.6:0.025:1:0.5:25.Colloid admixture solution is transferred in autoclave in 200 DEG C and spontaneous
Under pressure after crystallization 15 hours, stop crystallization, obtains ZSM-35 molecular sieve crystallization mother liquor, meanwhile, it is also produced in reaction system
The raw mixed gas containing template.
(2) after crystallization, pressure discharge operations are directly carried out, until pressure (gauge pressure) is zero in kettle, venting duration control exists
2h, the ZSM-35 molecular sieve crystallization mother liquor after obtaining pressure release；Gas phase portion in reaction system is the mixed of cyclohexylamine and vapor
Object is closed, after heat exchanger recycles heat, condenser condensation is introduced by pipeline, is directly recovered to fluid reservoir.
(3) the ZSM-35 molecular sieve crystallization mother liquor after pressure release is filtered, washed, is dried, is roasted, and obtains ZSM-35 molecular sieve
Original powder.
X-ray powder diffraction material phase analysis (XRD) is carried out to ZSM-35 molecular sieve original powder obtained, as a result sees Fig. 3.
Refering to Fig. 3, product obtained by comparative example 2 measures its crystal phase through XRD as the ZSM-35 with FER topological structure points
Son sieve, but molecular sieve crystallinity drops to the 60% of not pressure release sample.
Embodiment 1: ZSM-35 molecular sieve is prepared using cyclohexylamine amine as template
(1) be stirred at room temperature first under state by 50 grams of aluminum sulfate (analysis it is pure, content be greater than 99.5%) is added to
In the deionized water of 785.7ml, stir 40 minutes.After being completely dissolved to aluminum sulfate, it is slowly added to 720 grams of silica solution (SiO2
The silica solution that content is 25%), it stirs 1 hour, is then slowly added into 72 grams of sodium hydroxide, stir 1h, 148g hexamethylene is added
Amine stirs evenly obtained colloid admixture solution as template.The colloid admixture solution has following mole of composition: OH-:
Al2O3:SiO2:R:H2O=0.6:0.025:1:0.5:25.Colloid admixture solution is transferred in autoclave in 200 DEG C and spontaneous
Crystallization 15 hours under pressure, crystallization terminates, and obtains ZSM-35 molecular sieve crystallization mother liquor, meanwhile, it also generates and contains in reaction system
The mixed gas of template.
(2) cooled down by cooling coil, from 200 DEG C (crystallization temperature) coolings, 20 DEG C to 180 DEG C (pressure release temperature), let out
Press operation, until pressure (gauge pressure) is zero in kettle, the ZSM-35 molecular sieve crystallization mother liquor after obtaining pressure release；The initial pressure of pressure release
For 1.0Mpa, control cooling rate is 0.5 DEG C/min, and control venting duration is 2h；Gas phase portion in reaction system is hexamethylene
The mixture of amine and vapor introduces condenser condensation by pipeline, is directly recovered to liquid storage after heat exchanger recycles heat
Tank.
(3) the ZSM-35 molecular sieve crystallization mother liquor after pressure release filtered, washed, dried, roasted, obtain two-stage hole point
Cloth ZSM-35 molecular sieve original powder.
X-ray powder diffraction material phase analysis (XRD) is carried out to ZSM-35 molecular sieve original powder obtained, as a result sees Fig. 4；It is right
ZSM-35 molecular sieve original powder obtained carries out N2Physical absorption analysis, is as a result shown in Fig. 5.
Refering to Fig. 4 it is found that 1 products therefrom of embodiment measures its crystal phase through XRD as the ZSM-35 with FER topological structure points
Son sieve, opposite (compared with comparative example 1) crystallinity are 90%.
Refering to Fig. 5 it is found that measuring through nitrogen adsorption methods, the aperture integrated distribution of 1 products therefrom of embodiment is in 0.5-0.8nm
And 1.2-2.0nm, there is diplopore distribution characteristics.And aperture be 0.5-0.8nm hole and aperture be 1.2-2.0nm hole volume
Than for 1:1.2.
Embodiment 2:
The present embodiment step (1) and (3) are same as Example 1, except that step (2):
Cooled down by cooling coil, from 200 DEG C (crystallization temperature) coolings, 30 DEG C to 170 DEG C (pressure release temperature), carries out pressure release
Operation until kettle in pressure (gauge pressure) be zero, obtain pressure release after ZSM-35 molecular sieve crystallization mother liquor；The initial pressure of pressure release is
0.8Mpa, control cooling rate are 0.7 DEG C/min, control venting duration 5h；Gas phase portion in reaction system be cyclohexylamine and
The mixture of vapor introduces condenser condensation by pipeline, is directly recovered to fluid reservoir after heat exchanger recycles heat.
X-ray powder diffraction material phase analysis (XRD) is carried out to ZSM-35 molecular sieve original powder obtained, as a result (does not give figure
Show) show that product obtained by embodiment 2 measures its crystal phase for the ZSM-35 molecular sieve with FER topological structure, relatively through XRD
(compared with comparative example 1) crystallinity is 95%.
N is carried out to ZSM-35 molecular sieve original powder obtained2As a result physical absorption analysis (is unillustrated) and shows to implement
The aperture integrated distribution of 2 products therefrom of example has diplopore distribution characteristics in 0.5-0.8nm and 1.2-2.0nm.And aperture is 0.5-
The volume ratio in the hole that the hole and aperture of 0.8nm is 1.2-2.0nm is 1:0.8.
Embodiment 3:
The present embodiment step (1) and (3) are same as Example 1, except that step (2):
Cooled down by cooling coil, from 200 DEG C (crystallization temperature) coolings, 50 DEG C to 150 DEG C (pressure release temperature), carries out pressure release
Operation until kettle in pressure (gauge pressure) be zero, obtain pressure release after ZSM-35 molecular sieve crystallization mother liquor；The initial pressure of pressure release is
0.6Mpa, control cooling rate are 1.0 DEG C/min, control venting duration 5h；Gas phase portion in reaction system be cyclohexylamine and
The mixture of vapor introduces condenser condensation by pipeline, is directly recovered to fluid reservoir after heat exchanger recycles heat.
X-ray powder diffraction material phase analysis (XRD) is carried out to ZSM-35 molecular sieve original powder obtained, as a result sees Fig. 6；It is right
ZSM-35 molecular sieve original powder obtained carries out N2Physical absorption analysis, is as a result shown in Fig. 7.
Refering to Fig. 6 it is found that 3 products therefrom of embodiment measures its crystal phase through XRD as the ZSM-35 with FER topological structure points
Son sieve, opposite (compared with comparative example 1) crystallinity are 95%.
Refering to Fig. 7 it is found that measuring through nitrogen adsorption methods, the aperture integrated distribution of 3 products therefrom of embodiment is in 0.5-0.8nm
And 1.2-2.0nm, there is diplopore distribution characteristics.And aperture be 0.5-0.8nm hole and aperture be 1.2-2.0nm hole volume
Than for 1:0.2.
Comparative example 1-3 and comparative example 1 and 2 it is known that the method for the present invention can prepare with 0.5-0.8nm and
The distribution of 1.2-2.0nm diplopore and the higher ZSM-35 molecular sieve of crystallinity；By adjusting the temperature of pressure release, two kinds of holes may be implemented
The distribution of diameter regulates and controls；Also, pressure release temperature and venting duration have an impact to the crystallinity of ZSM-35 molecular sieve, and pressure release temperature is got over
Height, venting duration is shorter, and crystallinity reduces more；And under the premise of lower pressure release temperature, by control cooling rate and let out
The sample crystallinity of not pressure release relatively of the time of pressure, the obtained ZSM-35 molecular sieve with twin-stage pore size distribution can maintain
In 90-95%.The present invention has many advantages, such as that synthetic method is simple, repeatability is high, and controllability is strong.In addition, being mentioned using the present invention
The method of confession can also realize the recycling of template, reduce the discharge of organic pollutant.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (10)
1. a kind of twin-stage pore size distribution ZSM-35 molecular sieve, being dispersed with hole that aperture is 0.5-0.8nm and aperture is 1.2-2.0nm
Hole.
2. twin-stage pore size distribution ZSM-35 molecular sieve according to claim 1, which is characterized in that in the twin-stage pore size distribution
In ZSM-35 molecular sieve, the volume ratio in the hole that the hole and aperture that aperture is 0.5-0.8nm are 1.2-2.0nm is 1:(0.1-1.2).
3. a kind of preparation method of twin-stage pore size distribution ZSM-35 molecular sieve, comprising:
Step A will be uniformly mixed in reaction kettle by silicon source, silicon source, alkali source, template and water, and colloid admixture obtained is molten
Liquid carries out crystallization, obtains ZSM-35 molecular sieve crystallization mother liquor；
Step B, after the completion of crystallization, from the greenhouse cooling of crystallization to the temperature of pressure release, the drain for opening reaction kettle carries out pressure release,
ZSM-35 molecular sieve crystallization mother liquor after obtaining pressure release；
Step C filters the ZSM-35 molecular sieve crystallization mother liquor after pressure release, is washed, is dried, and twin-stage pore size distribution ZSM- is made
35 molecular screen primary powders.
4. according to the method described in claim 3, preferably cool down 20-50 it is characterized in that, in stepb, cooling down 10-60 DEG C
℃。
5. according to the method described in claim 4, it is characterized in that, in stepb, the speed of the cooling is 0.1-5 DEG C/
Min, preferably 0.25-1.5 DEG C/min, further preferred 0.5-1 DEG C/min.
6. the method according to any one of claim 3-5, which is characterized in that in stepb, the initial pressure of pressure release
For 0.6-1.37MPa；And/or the time of pressure release is 2-8h, preferably 3-5h；And/or the pressure in pressure release to reaction kettle is
Normal pressure.
7. the method according to any one of claim 3-6, which is characterized in that the template includes pyridine, second two
One or more of amine, ring amine, pyrrolidines and piperazine buttocks；And/or source of aluminium includes aluminum sulfate, boehmite and aluminium
One or more of sour sodium；And/or the silicon source includes in silica solution, silicic acid, white carbon black, sodium metasilicate and ethyl orthosilicate
One or more.
8. the method according to any one of claim 3-7, which is characterized in that the twin-stage pore size distribution ZSM-35 molecule
The hole that aperture is 0.5-0.8nm and the hole that aperture is 1.2-2.0nm are dispersed in sieve.
9. according to the method described in claim 8, it is characterized in that, aperture is in the twin-stage pore size distribution ZSM-35 molecular sieve
The volume ratio in the hole that the hole and aperture of 0.5-0.8nm is 1.2-2.0nm is 1:(0.1-1.2).
10. twin-stage pore size distribution ZSM-35 molecular sieve as claimed in claim 1 or 2 or such as any one of claim 3-9 institute
Application of the twin-stage pore size distribution ZSM-35 molecular sieve for the method preparation stated in lower carbon number hydrocarbons isomerization reaction.
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