CN105366687B - A kind of molecular sieves of SAPO 34 and its synthetic method using n-butylamine as template - Google Patents
A kind of molecular sieves of SAPO 34 and its synthetic method using n-butylamine as template Download PDFInfo
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Abstract
This application provides a kind of molecular sieves of SAPO 34, it is characterised in that anhydrous chemical, which forms, is：mNBA·(SixAlyPz)O2, wherein, NBA is n-butylamine, is distributed in molecular sieve cage and duct；M is every mole of (SixAlyPz)O2The molal quantity of middle n-butylamine, m=0.05~0.30；X, y, z represents Si, Al, P molar fraction respectively, and its scope is x=0.05~0.35, y=0.35~0.55, z=0.25~0.45, and x+y+z=1 respectively.The aluminium silicophosphate molecular sieve SAPO 34 of the application synthesis can be used as the catalyst of acid catalyzed reaction, such as methanol to olefins reaction.The application further relates to the molecular sieves of SAPO 34 in CH4、CO2Application in terms of adsorbing separation.
Description
Technical field
The application belongs to SAPO molecular sieve field, and in particular to a kind of SAPO-34 molecular sieves and its synthetic method.
Background technology
Low-carbon alkene, particularly ethene and propylene, are the basic organics of chemical industry, and its demand is increasing.
The production method of low-carbon alkene can be divided into two classes：One kind is petroleum path, and one kind is Non oil-based route.For petroleum path
There are the problem of rise in price, supply is unstable speech, short time, have the problem of petroleum resources reserves are limited for a long time, therefore only lean on
It is inadequate that traditional petroleum path, which carrys out increased low carbon olefine output,.By preparing light olefins from methanol (Methanol to Olefine, letter
MTO) be using coal or natural gas be referred to as technical process of the raw material by low-carbon alkenes such as methanol ethene, propylene, be most promising
Non oil-based route technique.It is methanol abundance, cheap, solid raw material basis can be provided for MTO techniques.MTO techniques
Core technology be catalyst, have high activity, high selectivity and good regenerability catalyst be key point.
Aluminium silicophosphate molecular sieve SAPO-34 with CHA topological structures, due to its suitable pore passage structure and Acidity,
Excellent catalytic performance is showed in methanol-to-olefins (MTO) reaction.
SAPO-34 molecular sieves typically use hydrothermal synthesis method, using water as solvent, carried out in enclosed high pressure kettle.Synthesis group
Dividing includes silicon source, silicon source, phosphorus source, structure directing agent and deionized water.The selection of structure directing agent is for the micro- of synthesis of molecular sieve
Structure, element composition and pattern can produce certain influence, and and then influence its catalytic performance.
The application has synthesized pure phase SAPO-34 molecular sieves using n-butylamine as structure directing agent, under hydrothermal conditions first.
The SAPO-34 molecular sieves of preparation show excellent catalytic performance and gas adsorption separation performance in catalytic reaction.
The content of the invention
According to the one side of the application, there is provided a kind of SAPO-34 molecular sieves containing n-butylamine, the molecular sieve conduct
Catalyst shows excellent catalytic performance in methanol or dimethyl ether conversion are low-carbon alkene reaction, exists as adsorption separating agent
Good selectivity is showed in CH4/CO2 adsorbing separations.
The SAPO-34 molecular sieves anhydrous chemical composition can represent that chemical composition is：
mNBA·(SixAlyPz)O2；
Wherein, NBA is n-butylamine, is distributed in molecular sieve cage and duct；M is every mole of (SixAlyPz)O2Middle n-butylamine
The molal quantity of template, m=0.05~0.30；X, y, z represents Si, Al, P molar fraction respectively, and its scope is x=respectively
0.05~0.35, y=0.35~0.55, z=0.25~0.45, and x+y+z=1.Preferably, the SAPO-34 molecular sieves without
In water chemistry composition, the m span upper limit is optionally from 0.3,0.25,0.24,0.23,0.22 or 0.20, and lower limit is optionally certainly
0.10th, 0.12,0.13,0.16,0.17,0.18 or 0.19；The upper limit of x spans is optionally from 0.23,0.22,0.21,0.20,
0.19, lower limit is optionally from 0.10,0.11,0.14,0.15；The upper limit of y spans is optionally from 0.5,0.49,0.48,0.47,
0.46, lower limit is optionally from 0.40,0.41,0.42,0.43,0.44,0.45；The upper limit of z spans is optionally from 0.40,0.39,
0.37th, 0.35, lower limit is optionally from 0.30,0.31,032,0.33,0.34；And x+y+z=1.It is further preferred that the SAPO-
In 34 molecular sieve anhydrous chemicals composition, x=0.10~0.30, y=0.35~0.50, z=0.25~0.40, and x+y+z=1.
Preferably, the SAPO-34 molecular sieves X ray diffracting spectrum at least contains diffraction maximum as shown in table 1：
Table 1
According to the another aspect of the application, there is provided the synthetic method of the SAPO-34 molecular sieves, it is characterised in that extremely
Comprise the steps of less：
A) deionized water, silicon source, silicon source, phosphorus source and n-butylamine are mixed according to a certain percentage, obtains that there is following mole
The initial gel mixture of proportioning：
SiO2/Al2O3=0.1~1.5；
P2O5/Al2O3=0.5~1.5；
H2O/Al2O3=10~200；
NBA/Al2O3=0.5~8；Wherein, NBA is n-butylamine；
B) initial gel mixture obtained by step a) is loaded into Autoclaves for synthesis, it is closed, 160~240 DEG C are warming up to, certainly
Crystallization 5~72 hours under raw pressure；
C) after crystallization is complete, after solid product separating, washing, drying, the SAPO-34 molecular sieves are produced.
In the Primogel of the step a), the molal quantity of silicon source is with SiO2Molal quantity meter；The molal quantity of silicon source with
Al2O3Meter；The molal quantity of phosphorus source is with P2O5Molal quantity meter.
Preferably, the silicon source in the step a) is in Ludox, active silica, positive esters of silicon acis, metakaolin
One kind at least.
Preferably, the silicon source in the step a) in aluminium salt, activated alumina, aluminum alkoxide, metakaolin extremely
Few one kind.
Preferably, the phosphorus source in the step a) be selected from orthophosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, organic phosphorus compound or
At least one of phosphorous oxides.
Preferably, in the step a) initial gel mixtures, SiO2/Al2O3The molar ratio upper limit optionally from
1.5th, 1.2,0.8, lower limit is optionally from 0.3,0.4,0.5,0.6.
Preferably, in the step a) initial gel mixtures, P2O5/Al2O3The molar ratio upper limit optionally from
1.5th, 1.3,1.2, lower limit is optionally from 0.5,0.9,1.
Preferably, in the step a) initial gel mixtures, H2O/Al2O3The molar ratio upper limit optionally from
200th, 180,160,120, lower limit is optionally from 20,33,67,80；It is further preferred that H2O/Al2O3Molar ratio is 65~200；
It is further preferred that H2O/Al2O3Molar ratio is 101~200.
Preferably, in the step a) initial gel mixtures, NBA/Al2O3The molar ratio upper limit is optionally from 6,5,
4.5th, 4,3,2.5,2, lower limit is optionally from 0.8,1,1.2,1.5；It is further preferred that NBA/Al2O3Molar ratio be 1.5~
5.0, it is further preferred that NBA/Al2O3Molar ratio is 2.0~4.0.
Preferably, the crystallization process in the step b) can be carried out in static state, can also be carried out in dynamic.
In the application, the crystallization process is carried out in the quiescent state, is referred in crystallization process, equipped with initial gel mixture
Synthesis reactor is statically placed in baking oven, and the mixture in synthesis reactor is not stirred.
In the application, the crystallization process is carried out in a dynamic state, refers to the synthesis reactor equipped with initial gel mixture in crystalline substance
During change, in nonstatic state, such as overturn, rotate；Or in crystallization process, the mixture inside synthesis reactor is carried out
Stirring.
Preferably, the crystallization temperature range limit in the step b) is optionally from 240 DEG C, 225 DEG C, and lower limit is optionally from 180
℃、190℃、200℃、205℃、215℃；It is further preferred that the crystallization temperature scope in the step b) is 190~240
℃；It is further preferred that the crystallization temperature scope in the step b) is 211~240 DEG C.In crystallization process, temperature can be with
Change in 160~240 DEG C or any of the above-described preferred range, can also stablize at 160~240 DEG C or any of the above-described
A certain temperature in preferred range.Preferably, in crystallization process, crystallization temperature is at 160~240 DEG C or any of the above-described excellent
Amplitude of variation in temperature range is selected to be no more than 10 DEG C；It is further preferred that crystallization temperature is stable at 160~240 DEG C or above-mentioned
A certain value in any preferred range.
Preferably, the crystallization time range limit in the step b) is optionally from 72 hours, 60 hours, 48 hours, lower limit
Optionally from 15 hours, 24 hours, 36 hours.
According to the another aspect of the application, there is provided a kind of catalyst of acid catalyzed reaction, it is by above-mentioned SAPO-34
Molecular sieve and/or the SAPO-34 molecular sieves synthesized according to the above method obtain through being calcined in 400~700 DEG C of air.
According to the another aspect of the application, there is provided a kind of oxygenatedchemicals converts the catalyst of olefine reaction processed, and it is logical
Above-mentioned SAPO-34 molecular sieves and/or the SAPO-34 molecular sieves synthesized according to the above method are crossed through being roasted in 400~700 DEG C of air
Burning obtains.
According to the another aspect of the application, there is provided a kind of CH4/CO2Adsorption and separation material, it is by above-mentioned SAPO-34
Molecular sieve and/or the SAPO-34 molecular sieves synthesized according to the above method obtain through being calcined in 400~700 DEG C of air.
Beneficial effect caused by herein described technical scheme energy includes：
(1) a kind of SAPO-34 molecular sieves containing n-butylamine are obtained.
(2) the SAPO-34 molecular sieves prepared are shown excellent in methanol or dimethyl ether conversion are low-carbon alkene reaction
Catalytic performance.
(3) the SAPO-34 molecular sieves prepared show good ethanol conversion in the reaction of ethanol dehydration ether
With ether selectivity.
(4) the SAPO-34 molecular sieves prepared are in CH4/CO2Good selectivity is showed in adsorbing separation.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph (SEM) of synthetic product in embodiment 1.
Embodiment
Element composition is determined using the Magix 2424X type ray fluorescence analysis instrument (XRF) of Philips companies.
X-ray powder diffraction material phase analysis (XRD) uses X ' the Pert PRO of Dutch PANalytical (PANalytical) company
X-ray diffractometer, Cu targets, K α radiation source (λ=0.15418nm), voltage 40KV, electric current 40mA.
SEM morphology analysis uses Scientific Instrument Factory of C.A.S KYKY-AMRAY-1000B type SEM.
Nuclear magnetic resonance of carbon (13C MAS NMR) analyze the Infinity plus400WB solids for using Varian companies of the U.S.
Magnetic resonance spectroscopy analyzer, with BBO MAS probes, magnetic manipulation field intensity is 9.4T.
The Vario EL Cube elemental analysers that CHN elementary analyses are manufactured using Germany.
The application is described in detail below by embodiment, but the application is not limited to these embodiments.
Embodiment 1
Each feed molar proportion scale, crystallization condition are shown in Table 2.Specific blending process is as follows, by 15.10g boehmites
(Al2O3Weight/mass percentage composition 67.5%) and 120g deionized waters it is well mixed after 23.06g phosphoric acid (H is added dropwise3PO4Quality percentage
Content 85%), 6g active silicas are stirring evenly and then adding into, 14.6g n-butylamines is eventually adding, stirs and gel is made,
Gel is transferred in stainless steel cauldron.The mol ratio of synthetic system each component is：
2.0NBA:1.0SiO2:1.0Al2O3:1.0P2O5:66.7H2O。
After reactor is put into baking oven, crystallization 24h under temperature programming to 200 DEG C of dynamics.After crystallization terminates, by solid product
Centrifugation, washing, after being dried in 100 DEG C of air, produce the SAPO-34 sieve samples.
The Zeolite synthesis dispensing of table 2, crystallization condition and gained sample component table *
Embodiment 2~19
Specific proportion scale and crystallization condition are shown in Table 2, and specific blending process is the same as embodiment 1.
The sample structure of embodiment 20 and composition analysis
Embodiment 1-19 sample is characterized using X-ray powder diffraction, as a result shown, the gained of embodiment 1~19
Sample is respectively provided with the architectural feature of SAPO-34 molecular sieves.Using the gained sample of embodiment 1 as Typical Representative, its XRD diffraction data knot
Fruit is as shown in table 3.The X-ray powder diffraction data result of the gained sample of embodiment 2~19 is close with table 3, i.e. peak position and shape
Shape is identical, is fluctuated according to the change peak relative peak intensities of synthesis condition in the range of ± 10%.
Using the inorganic and organic composition of the gained sample of XRF and CHN elementary analyses embodiment 1~19, the results are shown in Table in 2
The data of " product Elemental Composition analyses result " one row.
The gained sample of embodiment 1~19 is carried out13C MAS NMR analyze, by with n-butylamine13C MAS NMR standards
Spectrogram compares, and finds there was only the formant of n-butylamine in sample.
The XRD results of the sample of 3 embodiment of table 1
Embodiment 21
The gained sample of embodiment 1 is passed through air roasting 4 hours at 550 DEG C, then tabletting, crushing and screening to 20~40
Mesh.Weigh 5.0g samples and add the tank reactor equipped with 30ml ethanol, carry out ethanol dehydration reaction.Reaction temperature is set in
150 kettles, react and carried out under stirring.Reaction result shows, ethanol conversion is up to 95%, and ether is selectively in product
90%.
Embodiment 22
The gained sample of embodiment 1 is passed through air roasting 4 hours at 550 DEG C, then tabletting, crushing and screening to 20~40
Mesh.Weigh 1.0g samples and load fixed bed reactors, carry out MTO reaction evaluatings.Lead to nitrogen activation at 550 DEG C 1 hour, then
450 DEG C are cooled to be reacted.Methanol is carried by nitrogen, nitrogen flow rate 60ml/min, methanol weight air speed 2.0h-1.Reaction
Product is analyzed (Varian3800, fid detector, capillary column PoraPLOT Q-HT) by online gas-chromatography.As a result show
In table 4.
The preparing olefin by conversion of methanol reaction result of the sample of table 4
Embodiment 23
The sample that embodiment 1 obtains is passed through air roasting 4 hours at 550 DEG C.CO2、CH4Adsorption isotherm by
The devices of Micrometrics ASAP 2020 measure.The degassing of 350 shapes pre-processes 4 hours sample under vacuum conditions before measurement.Inhale
Attached test constant temperature is attached 25, and pressure is 101kPa.
The CO of the sample of table 52/CH4Adsorbing separation result
It is not for limiting claim, any this area skill although the application is disclosed as above with preferred embodiment
Art personnel can make some possible variations and modification on the premise of the application design is not departed from, therefore the application
Protection domain should be defined by the scope that the application claim is defined.
Claims (13)
1. a kind of SAPO-34 molecular sieves, it is characterised in that the molecular sieve anhydrous chemical composition is expressed as：
mNBA(SixAlyPz)O2,
Wherein, NBA is n-butylamine；M is every mole of (SixAlyPz)O2The molal quantity of middle n-butylamine, m=0.05~0.30；x、y、z
Si, Al, P molar fraction are represented respectively, its scope is x=0.05~0.35 respectively, y=0.35~0.55, z=0.25~
0.45, and x+y+z=1；
The X ray diffracting spectrum of the SAPO-34 molecular sieves at least has diffraction maximum in following position：
。
2. SAPO-34 molecular sieves according to claim 1, it is characterised in that the anhydrous chemical of the SAPO-34 molecular sieves
In composition, x=0.10~0.30, y=0.35~0.50, z=0.25~0.40, and x+y+z=1.
A kind of 3. method for synthesizing SAPO-34 molecular sieves described in claim 1, it is characterised in that including at least following steps：
A) deionized water, silicon source, silicon source, phosphorus source and n-butylamine are mixed according to a certain percentage, obtains that there is following mol ratio
Initial gel mixture：
SiO2/Al2O3=0.10~1.2；
P2O5/Al2O3=0.9~1.3；
H2O/Al2O3=10~200；
NBA/Al2O3=0.5~8；NBA is n-butylamine；
B) initial gel mixture obtained by step a) is loaded into Autoclaves for synthesis, it is closed, 160~240 DEG C are warming up to, in spontaneous pressure
Crystallization 5~72 hours under power；
C) after crystallization is complete, after solid product separating, washing, drying, the SAPO-34 molecular sieves are produced.
4. in accordance with the method for claim 3, it is characterised in that NBA/Al in the step a) initial gel mixtures2O3Rub
Your proportion is 1.5~5.0.
5. in accordance with the method for claim 3, it is characterised in that NBA/Al in the step a) initial gel mixtures2O3Rub
Your proportion is 2.0~4.0.
6. in accordance with the method for claim 3, it is characterised in that H in the step a) initial gel mixtures2O/Al2O3Rub
Your proportion is 65~200.
7. in accordance with the method for claim 3, it is characterised in that H in the step a) initial gel mixtures2O/Al2O3Rub
Your proportion is 101~200.
8. in accordance with the method for claim 3, it is characterised in that the crystallization process in the step b) is under either statically or dynamically
Carry out.
9. in accordance with the method for claim 3, it is characterised in that the crystallization temperature in the step b) is 190~240 DEG C.
10. in accordance with the method for claim 3, it is characterised in that the crystallization temperature in the step b) is 211~240 DEG C.
11. a kind of catalyst of acid catalyzed reaction, it is characterised in that according to the SAPO-34 described in any one of claim 1~2
Molecular sieve and/or the SAPO-34 molecular sieves that are synthesized according to any one of claim 3~10 methods described are through 400~700 DEG C of air
Middle roasting obtains.
12. a kind of oxygenatedchemicals converts the catalyst of olefine reaction processed, it is characterised in that according to any one of claim 1~2
Described SAPO-34 molecular sieves and/or the SAPO-34 molecular sieves synthesized according to any one of claim 3-10 methods described pass through
It is calcined and obtains in 400~700 DEG C of air.
A kind of 13. CH4/CO2Adsorption and separation material, it is characterised in that according to the SAPO-34 described in any one of claim 1~2
Molecular sieve and/or the SAPO-34 molecular sieves that are synthesized according to any one of claim 3~10 methods described are through 400~700 DEG C of air
Middle roasting obtains.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4440871A (en) * | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
| CN101125665A (en) * | 2007-08-08 | 2008-02-20 | 华陆工程科技有限责任公司 | Method for preparing SAPO-34 molecular sieve by liquid phase crystallization method |
| CN103864097A (en) * | 2012-12-10 | 2014-06-18 | 中国科学院大连化学物理研究所 | SAPO-34 molecular sieve adopting diglycol amine as template agent, and synthesis method thereof |
| CN103864087A (en) * | 2012-12-10 | 2014-06-18 | 中国科学院大连化学物理研究所 | SAPO-34 molecular sieve with N-methyldiethanolamine as template, and its synthetic method |
-
2014
- 2014-08-25 CN CN201410422598.3A patent/CN105366687B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4440871A (en) * | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
| CN101125665A (en) * | 2007-08-08 | 2008-02-20 | 华陆工程科技有限责任公司 | Method for preparing SAPO-34 molecular sieve by liquid phase crystallization method |
| CN103864097A (en) * | 2012-12-10 | 2014-06-18 | 中国科学院大连化学物理研究所 | SAPO-34 molecular sieve adopting diglycol amine as template agent, and synthesis method thereof |
| CN103864087A (en) * | 2012-12-10 | 2014-06-18 | 中国科学院大连化学物理研究所 | SAPO-34 molecular sieve with N-methyldiethanolamine as template, and its synthetic method |
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