CN106830007A - With the molecular sieve catalysts of multi-stage porous SSZ 13 and its synthetic method and application - Google Patents
With the molecular sieve catalysts of multi-stage porous SSZ 13 and its synthetic method and application Download PDFInfo
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Abstract
The invention discloses a kind of molecular sieve catalysts of multi-stage porous SSZ 13 and its synthetic method and application.Preparation method is the auxiliary agent as crystallization synthetic reaction from long chain silane, allotment alkali source, silicon source, silicon source, template, the mol ratio of long chain silane and water, and using being segmented into by the way of Mobile state/static crystallization.Its building-up process including plastic and ageing, crystallization, washing, Template removal and activate, step etc. ion exchange and activation, the molecular sieves of high-crystallinity multi-stage porous SSZ 13 of microporous mesoporous orderly distribution can be obtained.The molecular sieve for obtaining has pore-size distribution of two kinds of sizes including 2~5nm and 5~15nm scopes, micro pore volume>0.20cm3/ g, mesopore volume>0.35cm3/ g, specific surface area>400m2/ g, the yield of crystallization product can reach more than 85%.In addition to micro-pore zeolite advantage, the field such as the advantages of being also equipped with mesoporous material aperture and be conducive to solid tumor greatly, the material is reacted in petrochemical industry, MTO, tail gas clean-up and fine chemistry industry is with a wide range of applications the molecular sieves of this SSZ 13.
Description
Technical field
The present invention relates to a kind of multistage pore canal SSZ-13 molecular sieve catalysts with micropore-mesopore and its synthetic method and
Using, and in particular to long chain organic silanes are added in initial Alusil mixture as crystallization promoting agent, gradually shape in crystallization process
Into the SSZ-13 molecular sieves of the multi-stage artery structure of micropore-mesopore.
Background technology
The molecular sieve particle diameter that traditional preparation method is obtained has serious limit than larger for the molecular sieve catalytic life-span
System.The introducing of multi-stage pore canal molecular sieve concept shortens molecule diffusion length so that product is easier to expand from active sites
It is scattered to outer surface, it is suppressed that the formation of coking, increased the life-span of catalyst.Multi-stage pore canal molecular sieve synthesis has been obtained for industry
The extensive concern on boundary.
Provided in patent CN201610550715 and use a small amount of organic amine template in synthesis seed crystal process, and added
Organosilicon obtains multi-stage porous ZSM-5 molecular sieve as the crystallization method of mesoporous pore creating material.Employed in the patent is short chain
Silane, the pore-size distribution controlled range for obtaining is not big enough.Patent CN201310019315 utilizes cation form there is provided one kind
Face activating agent is template, and silanization zeolite seed crystal is assembled under hydrothermal conditions, synthesizes the side of ZSM-5 zeolite with multilevel pore canals molecular sieve
Method.Its feature is that organosilan is grafted onto on zeolite seed crystal.Can using cationic surfactant in this synthetic method
The mix products of mesoporous impalpable structure and micro-pore zeolite two-phase laminated flow can be obtained.Also other patents, for example
CN201010297898 is disclosed and organosilan is added directly into molecular sieve original solution, is obtained by condensing reflux stirring
Uniform gel, afterwards after static crystallization, roasting removes organic formwork agent and organosilan, obtains hierarchical porous structure ZSM-5 points
Son sieve.However, its synthetic method is cumbersome, it is relatively costly.The ZSM-5 molecular sieve that above-mentioned these patents describe hierarchical porous structure is closed
Into method, building-up process control condition is harsher, can not be applied to the porous level structure of SSZ-13 molecular sieves of 8 yuan of rings apertures
Synthesis.
SSZ-13 molecular sieves are that Americanized scholar Zones is synthesized the eighties in 20th century by hydro-thermal method, belong to micropore
In pore zeolite.It has good heat endurance, simultaneously because the tetrahedral presence of AlO4 and SiO4 in skeleton, makes its bone
Frame has cation exchange and acid adjustability, so that SSZ-13 is provided with good catalytic performance, including hydrocarbon
The catalytic cracking of thing, is hydrocracked, and alkene and aromatic hydrocarbons construction reaction.The SSZ-13 molecular sieves that traditional preparation method is obtained
Particle diameter has serious limitation than larger for the molecular sieve catalytic life-span.The introducing contracting of multistage pore canal SSZ-13 molecular sieve concepts
Short molecule diffusion length so that product is easier to be diffused into outer surface from active sites, it is suppressed that the formation of coking, increases
The life-span of catalyst is added.
The content of the invention
It is an object of the invention to provide a kind of hierarchical porous structure SSZ-13 molecular sieves of micropore-mesopore, it is catalyzed as one kind
Agent improves catalytic reaction activity, reduces the probability of reaction inactivation, increases catalyst life.
It is an object of the invention to provide a kind of synthesis multistage pore canal by the use of long chain silane compound as crystallization promoting agent
The method of SSZ-13 molecular sieves, the molecular sieve of this pore size distribution structure is conducive to MTO to react.
The technical solution adopted for the present invention to solve the technical problems is organic with alkali source, silicon source, organic formwork agent, long-chain
Silane and water are raw material heating stirring into colloidal sol, then gradually add silicon source according to proportioning, are mixed to form Alusil, room temperature ageing
Afterwards, being placed in carries out crystallization in crystallizing kettle, product filtering, Template removal, ion exchange and activation are obtained into multi-stage porous SSZ-
13 molecular sieve catalysts.
The synthetic method of multistage pore canal SSZ-13 molecular sieves of the present invention, it is characterised in that comprise the following steps that：
1) weigh a certain amount of long chain organic silanes dissolving according to reaction raw materials proportioning and form solution ＆ stir in methyl alcohol
Dispersion, is subsequently adding silicon source, alkali source and organic formwork agent, is stirred 5~10 hours under the conditions of 30~50 DEG C, obtains silicon source mixing
Solution；
2) at 30~80 DEG C, in the silicon source solution formed during 1) silicon source solution is added drop-wise to according to reaction raw materials proportioning,
After being stirred vigorously 30~120min, it is stored at room temperature ageing and obtains silica-alumina gel in 2~12 hours.
3) silicon-aluminum sol obtained in 2) is placed in 120~190 DEG C of points of 2 sections of crystallization in Hydrothermal Synthesiss kettle, second segment temperature
Higher than first paragraph 20 DEG C, after 48~168 hours crystallization are complete, centrifugation goes out solid product, then by solid product spend from
Then sub- water cyclic washing dries 12~48 hours to neutrality under the conditions of 100~130 DEG C, and it is calcined 2 at 400~600 DEG C~
10 hours removing organic formwork agents, obtain multi-stage porous SSZ-13 molecular screen primary powders；
4) by SSZ-13 molecular screen primary powders and NH4 +Solion carries out 400~600 DEG C of roastings after ion exchange, washing, drying
Burning obtains the multi-stage porous SSZ-13 molecular sieve catalysts of H types for 2~10 hours.
Silicon source is with SiO in gel mixture described in synthetic method of the present invention2Meter, silicon source is with Al2O3Meter, organic formwork
In terms of SDA, in terms of LOS, crystallization feed molar proportioning is long chain organic silanes for agent：Na2O：SiO2：Al2O3：SDA：LOS：
H2O=0.35~0.65：1：0.0025~0.02：0.05~0.5：0.01~0.05：10~50.
Involved long chain organic silanes include hexadecyl trimethoxy silane, hexadecane in synthetic method of the present invention
Ethyl triethoxy silicane alkane, octadecyl trimethoxysilane, octadecyltriethoxy silane, octadecyl methyl dimethoxy
Silane, octadecyldimethyl methoxy silane, polyethylene glycol triethoxysilylpropyl ether, 3- (oxygen of 2,3- epoxies third) propyl group three
Methoxy silane, 3- (methacryloxypropyl) propyl trimethoxy silicane, 2- methoxyl group carbonyldioxy ethyl amido ethylamines base third
At least one in base trimethoxy silane, two (3- (methylamino) propyl group) trimethoxy silanes.
In synthetic method of the present invention involved silicon source be white carbon, active silica, sodium metasilicate, silester or
One kind of methyl silicate；Silicon source is aluminium isopropoxide, sodium metaaluminate, aluminum nitrate, aluminum sulfate, aluminium chloride, aluminium hydroxide or intends thin water
One kind of aluminium stone.
Involved organic formwork agent is N, N, N- trimethyl -1- adamantane ammonium hydroxide in synthetic method of the present invention
(TMADa+), any one or two kinds in benzyltrimethylammonium hydroxide (BTMA+).
Crystal pattern described in synthetic method of the present invention is dynamic crystallization or static crystallization, preferably dynamic crystallization mode.
The salting liquid for being related to the ammonium ion that SSZ-13 molecular sieves carry out ion exchange in the present invention is ammonium nitrate, sulfuric acid
The aqueous solution of ammonium, ammonium chloride or ammonium hydrogen carbonate, the concentration of ammonium ion is 0.5~1.5mol/L.
The present invention provides the SSZ-13 molecular sieves of the multistage pore canal that above-mentioned synthetic method is obtained, and is characterised by that its duct exists<
2nm, 2~5nm and 5~15nm scopes have pore-size distribution, micro pore volume>0.20cm3/ g, mesopore volume>0.35cm3/ g, compares table
Area>400m2/g。
The present invention provides above-mentioned molecular sieve to be had in the field such as methanol-to-olefins (MTO) or tail gas catalyzed reduction reaction (SCR)
In application.
The multi-stage porous SSZ-13 molecular sieves that the present invention is obtained are also equipped with mesoporous material aperture in addition to micro-pore zeolite advantage
The advantages of being conducive to solid tumor greatly.Multistage pore canal SSZ-13 molecular sieves are obtained as the auxiliary agent of synthesis by the use of long chain silane,
Relative to other soft templates synthesis hierarchical zeolite have it is cheap, be easy to get the characteristics of, the material petrochemical industry, Coal Chemical Industry and
The fields such as fine chemistry industry are with a wide range of applications, particularly in methanol-to-olefins (MTO) and tail gas catalyzed reduction reaction
Etc. (SCR) there is good application in field, not only improves the service life of catalytic reaction activity but also the catalyst of extension.
Brief description of the drawings
Below in conjunction with the accompanying drawings and embodiment the invention will be further described：
Fig. 1 is the multi-stage porous SSZ-13 molecular sieve XRDs of sample 1 in embodiments of the invention 1；
Fig. 2 is the multi-stage porous SSZ-13 molecular sieves SEM figures of sample 1 in embodiments of the invention 1.
Specific embodiment
Embodiment of the present invention and produced effect are further illustrated by embodiment and comparison example,
But protection scope of the present invention is not limited to the content listed by embodiment.
Embodiment 1
According to listed in table 1, reaction raw materials proportioning weighs quantitative long chain organic silanes dissolving and forms solution in methyl alcohol
And dispersed with stirring, silicon source, alkali source are subsequently adding, stirred 6 hours under the conditions of 40 DEG C,
Obtain silicon source mixed solution；At 60 DEG C, silicon source solution is added drop-wise to silicon source according to reaction raw materials proportioning and mixes molten
In liquid, after being stirred vigorously 90min, mixture gel is obtained within still aging 12 hours.Mixture gel is placed in Hydrothermal Synthesiss kettle
In 120~190 DEG C of points of 2 sections of crystallization, second segment temperature is higher than first paragraph 20 DEG C, and after crystallization is complete, centrifugation goes out solid product
Thing, then by solid matter with deionized water cyclic washing to neutrality, then dried 24 hours under the conditions of 120 DEG C, and at 550 DEG C
4 hours removing organic formwork agents of roasting, obtain multi-stage porous SSZ-13 molecular screen primary powders；By SSZ-13 molecular screen primary powders with
The NH of 1.0mol/L4 +Solion is according to solid-to-liquid ratio=1:10 ratio carried out at 90 DEG C ion exchange 2 hours, washing, 120 DEG C
550 DEG C are calcined the multi-stage porous SSZ-13 molecular sieve catalysts for obtaining H types for 2 hours after drying 24 hours.Synthesized SSZ-13 molecules
The former powder sample 1~20 of sieve#Primogel in type of feed and proportioning, crystallization temperature, crystallization time, ammonium ion salt species with
And yield and the silica alumina ratio difference of products therefrom are as shown in Table 1 and Table 2.The SSZ-13 zeolite products have micropore-mesopore
Hierarchical porous structure pattern, 2~15nm of mesopore orbit size range.
Table 1
Table 2
Embodiment 2
To SSZ-13 sieve samples 1~20 synthesized in embodiment 1 using the types of Micromeritics ASAP 2020
Nitrogen physisorption instrument carries out phenetic analysis.The preprocess method of sample is as follows before analysis：At normal temperatures by sieve sample
Vacuumize process, after vacuum condition is reached, 2h is processed at 130 DEG C；Afterwards 2h is processed at 350 DEG C.Nitrogen physisorption result
Show, the micropore size of sample 1~20 be 0.3~0.5nm, containing mesoporous pore size distribution, mesoporous average pore size, mesopore volume and
Specific surface area is as shown in table 3.
Table 3
Embodiment 3
XRD is carried out to sample 1~20 prepared in embodiment 1 to characterize to confirm as SSZ-13 molecular sieves.Used instrument
Device is PANalytical X ' Pert type X-ray diffractometers, and copper target, K α radiation source instrument operating voltage is 40kv, operating current
It is 40mA.The XRD spectra of resulting sample 1~20 is consistent with the feature spectrogram of standard SSZ-13 molecular sieves.Typical XRD
Spectrum (such as Fig. 1) is with sample 1 as representative, and 2 θ are as shown in table 4 in 5 °~50 ° main diffraction peak positions and peak intensity.Other sample numbers
According to result compared with sample 1, diffraction maximum location and shape are identical, according to the change relative peak intensities of synthesis condition in ± 5% scope
Interior fluctuation, shows that synthetic product has the feature of SSZ-13 molecular sieve structures.
Table 4
Embodiment 4
Electronic Speculum sign is scanned to 1~20 sample prepared in embodiment 1.Used instrument is Hitachi
SU8020 field emission scanning electron microscopes, accelerating potential is 25kV.Scanning electron microscope (SEM) photograph shows, the pattern of sample 1~20 is rendered as micro-
Hole-mesoporous and deposit it is multistage poroid.Typical scanning electron microscope (SEM) photograph with sample 1 as representative, as shown in Figure 2.
Embodiment 5
The evaluation of catalyst：1~8 catalyst raw powder resulting in embodiment 1 is carried out into compressing tablet, 20~40 are crushed to
Mesh.Weigh 0.3g samples and load fixed bed reactors, carry out MTO evaluations.Lead to nitrogen activation 1.5 hours at 500 DEG C, then drop
Temperature is to 450 DEG C.Methyl alcohol is carried by nitrogen, and nitrogen flow rate is 15ml/min, methanol weight air speed 4.0h-1.Resulting product by
Online gas-chromatography (Agilent7890) is analyzed, and the results are shown in Table 5.From which it can be seen that 8 samples be respectively provided with it is high
Catalytic life, while the total recovery of ethene and propylene has exceeded 83.0%.
Table 5
t50：Conversion ratio was reduced to for 50% time experienced from 100%；t98：Conversion ratio is reduced to 98% institute from 100%
The time of experience.
As can be seen from Table 5, multi-stage porous SSZ-13 molecular sieve catalysts prepared by the method that the present invention is provided react in MTO
In, with low-carbon alkene (C higher2 =+C3 =) selectivity is up to more than 84%, and conversion ratio drops to the conversion longevity before 50%
Life illustrated that there is the multi-stage porous SSZ-13 molecular sieve catalysts MTO to react the good life-span more than 13 hours.
The embodiment only technology design and feature to illustrate the invention, its object is to allow person skilled in the art
Scholar will appreciate that present disclosure and implement according to this that it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent change or modification that Spirit Essence is made, should all be included within the scope of the present invention.
Claims (11)
1. a kind of synthetic method of the multi-stage artery structure SSZ-13 molecular sieves containing micropore-mesopore, it is characterised in that：Use alkali
Source, silicon source, organic formwork agent, long chain organic silanes and water are raw material heating stirring into colloidal sol, are then gradually added according to proportioning
Silicon source, is mixed to form silica-alumina gel, and after room temperature ageing, being placed in carries out crystallization in crystallizing kettle, by product filtering, stripper plate
Agent, ion exchange and activation obtain multi-stage porous SSZ-13 molecular sieve catalysts.
2. synthetic method according to claim 1, it is characterised in that：Silicon source is with SiO in gel mixture2Meter, silicon source with
Al2O3Meter, in terms of SDA, in terms of LOS, crystallization feed molar proportioning is long chain organic silanes organic formwork agent：Na2O：
SiO2：Al2O3：SDA：LOS：H2O=0.35~0.65：1：0.0025~0.02：0.05~0.5：0.01~0.05：10~50.
3. multi-stage porous SSZ-13 Zeolite synthesis method according to claim 1, it is characterised in that comprise the following steps that：
1) weigh a certain amount of long chain organic silanes dissolving according to reaction raw materials proportioning and form solution ＆ stir dispersion in methyl alcohol,
Silicon source, alkali source and organic formwork agent are subsequently adding, are stirred 5~10 hours under the conditions of 30~50 DEG C, obtain silicon source mixed solution；
2) at 30~80 DEG C, in the silicon source solution formed during 1) silicon source solution is added drop-wise to according to reaction raw materials proportioning, acutely
After 30~120min of stirring, it is stored at room temperature ageing and obtains silicon-aluminum sol in 2~12 hours；
3) silicon-aluminum sol obtained in 2) is placed in 120~190 DEG C of points of 2 sections of crystallization in Hydrothermal Synthesiss kettle, second segment temperature compares
One section high 20 DEG C, after 48~168 hours crystallization are complete, centrifugation goes out solid product, then by solid matter with deionized water
Then cyclic washing dries 12~48 hours to neutrality under the conditions of 100~130 DEG C, and small in 400~600 DEG C of roastings 2~10
When remove organic formwork agent, obtain multi-stage porous SSZ-13 molecular screen primary powders；
4) by SSZ-13 molecular screen primary powders and NH4 +Solion carries out 400~600 DEG C of roastings 2 after ion exchange, washing, drying
Obtain within~10 hours the multi-stage porous SSZ-13 molecular sieve catalysts of H types.
4. synthetic method according to claim 1, it is characterised in that：Long chain organic silanes include hexadecyl trimethoxy
Silane, hexadecyl, octadecyl trimethoxysilane, octadecyltriethoxy silane, octadecyl
Methyl dimethoxysilane, octadecyldimethyl methoxy silane, polyethylene glycol triethoxysilylpropyl ether, 3- (2,3- rings
The oxygen of oxygen third) propyl trimethoxy silicane, 3- (methacryloxypropyl) propyl trimethoxy silicane, 2- methoxyl group carbonyldioxy ethylamines
At least one in base ethyl aminocarbonyl propyl trimethoxy silane, two (3- (methylamino) propyl group) trimethoxy silanes.
5. synthetic method according to claim 3, it is characterised in that：Silicon source is white carbon, active silica, silicic acid
One kind of sodium, silester or methyl silicate.
6. synthetic method according to claim 3, it is characterised in that：Silicon source be aluminium isopropoxide, sodium metaaluminate, aluminum nitrate,
One kind of aluminum sulfate, aluminium chloride, aluminium hydroxide or boehmite.
7. synthetic method according to claim 3, it is characterised in that：Organic formwork agent is N, N, N- front three in step (1)
Any one or two kinds in base -1- adamantane ammonium hydroxide, benzyltrimethylammonium hydroxide.
8. the synthetic method according to claim 1 and 3, it is characterised in that：In step (1) crystal pattern be dynamic crystallization or
Static crystallization.
9. the synthetic method according to claim 1 and 3, it is characterised in that：NH in step (4)4 +Solion is ammonium ion
Salting liquid, selected from the aqueous solution of ammonium nitrate, ammonium sulfate, ammonium chloride or ammonium hydrogen carbonate, the concentration of ammonium ion for 0.5~
1.5mol/L。
10. the SSZ-13 molecular sieves of the multistage pore canal that the synthetic method as described in claim 1~7 any one is obtained, described point
Sub- sieve aperture road exists<2nm, 2~5nm and 5~15nm scopes have pore-size distribution, micro pore volume>0.20cm3/ g, mesopore volume>
0.35cm3/ g, specific surface area>400m2/g。
Application of 11. molecular sieves as claimed in claim 10 in methanol-to-olefins or tail gas catalyzed reduction reaction.
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| CN106745036A (en) * | 2017-03-17 | 2017-05-31 | 中触媒新材料股份有限公司 | With the microporous mesoporous molecular sieves of multi-stage porous SSZ 13 and its synthetic method and application |
| CN106745035A (en) * | 2017-03-17 | 2017-05-31 | 中触媒新材料股份有限公司 | A kind of molecular sieves of multi-stage porous SSZ 13 and its synthetic method and application |
| CN108249457A (en) * | 2018-03-19 | 2018-07-06 | 深圳科冠华太新材料技术有限公司 | A kind of method that self-assembly method prepares multilevel hierarchy SAPO-34 molecular sieves |
| CN108584982A (en) * | 2018-07-03 | 2018-09-28 | 正大能源材料(大连)有限公司 | A method of synthesizing flat SSZ-13 molecular sieves with mixed templates |
| CN108862314A (en) * | 2018-08-20 | 2018-11-23 | 中触媒新材料股份有限公司 | One kind is with multi-stage porous and wide silica alumina ratio EUO structure molecular screen and synthetic method |
| CN108946756A (en) * | 2018-08-20 | 2018-12-07 | 中触媒新材料股份有限公司 | A kind of multi-stage porous EUO structure molecular screen and its synthetic method |
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