CN105366687A - SAPO-34 molecular sieve with n-butylamine as template agent and synthetic method of SAPO-34 molecular sieve - Google Patents
SAPO-34 molecular sieve with n-butylamine as template agent and synthetic method of SAPO-34 molecular sieve Download PDFInfo
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- CN105366687A CN105366687A CN201410422598.3A CN201410422598A CN105366687A CN 105366687 A CN105366687 A CN 105366687A CN 201410422598 A CN201410422598 A CN 201410422598A CN 105366687 A CN105366687 A CN 105366687A
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- molecular sieve
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- nba
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- butyl amine
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Abstract
The invention provides an SAPO-34 molecular sieve. The SAPO-34 molecular sieve is characterized in that the anhydrous chemical composition is mNBA.(SixAlyPz)O2, wherein NBA is n-butylamine and is distributed in molecular sieve cages and porous channels, m indicates the mole number of n-butylamine in (SixAlyPz)O2 per mole and ranges from 0.05 to 0.30, x indicates the mole fraction of Si and ranges from 0.05-0.35, y indicates the mole fraction of Al and ranges from 0.35 to 0.55, z indicates the mole fraction of P and ranges from 0.25 to 0.45, and x+y+z=1. The Si-P-Al SAPO-34 molecular sieve synthesized through the method can serve as a catalyst for acid-catalyzed reactions like a methanol-to-olefin reaction. The invention further relates to application of the SAPO-34 molecular sieve in adsorption separation of CH4 and CO2.
Description
Technical field
The application belongs to SAPO molecular sieve art, is specifically related to a kind of SAPO-34 molecular sieve and synthetic method thereof.
Background technology
Low-carbon alkene, particularly ethene and propylene, be the basic organic of chemical industry, its demand is increasing.The production method of low-carbon alkene can be divided into two classes: a class is petroleum path, and a class is Non oil-based route.For petroleum path, there is price increase the short period of time, supplies unstable problem, has the problem that petroleum resources reserves are limited for a long time, and it is inadequate for therefore only carrying out increased low carbon olefine output by traditional petroleum path.Being with coal or Sweet natural gas for raw material is by the technological process of the low-carbon alkenes such as Methanol ethene, propylene by preparing light olefins from methanol (MethanoltoOlefine, be called for short MTO), is most promising Non oil-based route technique.Methyl alcohol abundance, cheap, solid raw material basis can be provided for MTO technique.The core technology of MTO technique is catalyzer, and having high reactivity, highly selective and good regenerability catalyzer is key point.
There is the aluminium silicophosphate molecular sieve SAPO-34 of CHA topological framework, the pore passage structure suitable due to it and Acidity, in methanol-to-olefins (MTO) reaction, present excellent catalytic performance.
SAPO-34 molecular sieve generally adopts hydrothermal synthesis method, take water as solvent, carries out in enclosed high pressure still.Synthesis component comprises aluminium source, silicon source, phosphorus source, structure directing agent and deionized water.The selection of structure directing agent can produce certain influence for the microstructure of synthesis of molecular sieve, elementary composition and pattern, and and then affects its catalytic performance.
The application take n-Butyl Amine 99 as structure directing agent first, has synthesized pure phase SAPO-34 molecular sieve under hydrothermal conditions.The SAPO-34 molecular sieve of preparation shows excellent catalytic performance and gas adsorption separation performance in catalyzed reaction.
Summary of the invention
According to an aspect of the application, provide a kind of SAPO-34 molecular sieve containing n-Butyl Amine 99, this molecular sieve as catalyzer methyl alcohol or dimethyl ether conversion be low-carbon alkene reaction in show excellent catalytic performance, in CH4/CO2 fractionation by adsorption, show good selectivity as adsorption separating agent.
Described SAPO-34 molecular sieve anhydrous chemical composition can represent that chemical constitution is:
mNBA·(Si
xAl
yP
z)O
2；
Wherein, NBA is n-Butyl Amine 99, is distributed in molecular sieve cage and duct; M is every mole of (Si
xal
yp
z) O
2the mole number of middle n-Butyl Amine 99 template, m=0.05 ~ 0.30; X, y, z represents the molar fraction of Si, Al, P respectively, and its scope is x=0.05 ~ 0.35 respectively, y=0.35 ~ 0.55, z=0.25 ~ 0.45, and x+y+z=1.Preferably, in described SAPO-34 molecular sieve anhydrous chemical composition, the span upper limit of m is optionally from 0.3,0.25,0.24,0.23,0.22 or 0.20, and lower value is optionally from 0.10,0.12,0.13,0.16,0.17,0.18 or 0.19; The upper limit of x span is optionally from 0.23,0.22,0.21,0.20,0.19, and lower limit is optionally from 0.10,0.11,0.14,0.15; The upper limit of y span is optionally from 0.5,0.49,0.48,0.47,0.46, and lower limit is optionally from 0.40,0.41,0.42,0.43,0.44,0.45; The upper limit of z span is optionally from 0.40,0.39,0.37,0.35, and lower limit is optionally from 0.30,0.31,032,0.33,0.34; And x+y+z=1.Further preferably, in described SAPO-34 molecular sieve anhydrous chemical composition, x=0.10 ~ 0.30, y=0.35 ~ 0.50, z=0.25 ~ 0.40, and x+y+z=1.
Preferably, described SAPO-34 molecular sieve X ray diffracting spectrum is at least containing diffraction peak as shown in table 1:
Table 1
According to the another aspect of the application, provide the synthetic method of described SAPO-34 molecular sieve, it is characterized in that, at least comprise following steps:
A) deionized water, silicon source, aluminium source, phosphorus source and n-Butyl Amine 99 are mixed according to a certain percentage, obtain the initial gel mixture with following mol ratio:
SiO
2/Al
2O
3＝0.1～1.5；
P
2O
5/Al
2O
3＝0.5～1.5；
H
2O/Al
2O
3＝10～200；
NBA/Al
2o
3=0.5 ~ 8; Wherein, NBA is n-Butyl Amine 99;
B) by step a) gained initial gel mixture loading Autoclaves for synthesis, airtight, be warmed up to 160 ~ 240 DEG C, at autogenous pressures crystallization 5 ~ 72 hours;
C) after crystallization is complete, solid product, after separation, washing, drying, obtains described SAPO-34 molecular sieve.
In described step Primogel a), the mole number in silicon source is with SiO
2molar basis; The mole number in aluminium source is with Al
2o
3meter; The mole number in phosphorus source is with P
2o
5molar basis.
Preferably, described step a) in silicon source to be selected from silicon sol, active silica, positive silicon ester, metakaolin one at least.
Preferably, described step a) in aluminium source be selected from least one in aluminium salt, activated alumina, aluminum alkoxide, metakaolin.
Preferably, described step a) in phosphorus source be selected from least one in ortho-phosphoric acid, ammonium hydrogen phosphate, primary ammonium phosphate, Organophosphorous compounds or phosphorous oxides.
Preferably, described step is a) in initial gel mixture, SiO
2/ Al
2o
3the molar ratio upper limit optionally from 1.5,1.2,0.8, lower limit is optionally from 0.3,0.4,0.5,0.6.
Preferably, described step is a) in initial gel mixture, P
2o
5/ Al
2o
3the molar ratio upper limit optionally from 1.5,1.3,1.2, lower limit is optionally from 0.5,0.9,1.
Preferably, described step is a) in initial gel mixture, H
2o/Al
2o
3the molar ratio upper limit optionally from 200,180,160,120, lower limit is optionally from 20,33,67,80; Further preferably, H
2o/Al
2o
3molar ratio is 65 ~ 200; Still more preferably, H
2o/Al
2o
3molar ratio is 101 ~ 200.
Preferably, described step is a) in initial gel mixture, NBA/Al
2o
3the molar ratio upper limit is optionally from 6,5,4.5,4,3,2.5,2, and lower limit is optionally from 0.8,1,1.2,1.5; Further preferably, NBA/Al
2o
3molar ratio is 1.5 ~ 5.0, further preferably, and NBA/Al
2o
3molar ratio is 2.0 ~ 4.0.
Preferably, described step b) in crystallization process can carry out in static state, also can dynamically carry out.
In the application, described crystallization process carries out in the quiescent state, refers in crystallization process, and the synthesis reactor that initial gel mixture is housed is statically placed in baking oven, and does not stir the mixture in synthesis reactor.
In the application, described crystallization process carries out in a dynamic state, refers to that the synthesis reactor that initial gel mixture is housed is in crystallization process, is in nonstatic state, as upset, rotation etc.; Or in crystallization process, the mixture of synthesis reactor inside is stirred.
Preferably, described step b) in crystallization temperature range limit optionally from 240 DEG C, 225 DEG C, lower limit is optionally from 180 DEG C, 190 DEG C, 200 DEG C, 205 DEG C, 215 DEG C; Further preferably, described step b) in crystallization temperature scope be 190 ~ 240 DEG C; Still more preferably, described step b) in crystallization temperature scope be 211 ~ 240 DEG C.In crystallization process, temperature can change in 160 ~ 240 DEG C or above-mentioned arbitrary preferred range, also can be stabilized in a certain temperature in 160 ~ 240 DEG C or above-mentioned arbitrary preferred range.Preferably, in crystallization process, crystallization temperature rangeability in 160 ~ 240 DEG C or above-mentioned arbitrary preferred range is no more than 10 DEG C; Further preferably, crystallization temperature is stabilized in a certain value in 160 ~ 240 DEG C or above-mentioned arbitrary preferred range.
Preferably, described step b) in crystallization time range limit optionally from 72 hours, 60 hours, 48 hours, lower limit is optionally from 15 hours, 24 hours, 36 hours.
According to the another aspect of the application, provide a kind of catalyzer of acid catalyzed reaction, it obtains by above-mentioned SAPO-34 molecular sieve and/or according to SAPO-34 molecular sieve roasting in 400 ~ 700 DEG C of air of aforesaid method synthesis.
According to the another aspect of the application, provide the catalyzer that a kind of oxygen-containing compound conversion to produce olefine reacts, it obtains by above-mentioned SAPO-34 molecular sieve and/or according to SAPO-34 molecular sieve roasting in 400 ~ 700 DEG C of air of aforesaid method synthesis.
According to the another aspect of the application, provide a kind of CH
4/ CO
2adsorption and separation material, it obtains by above-mentioned SAPO-34 molecular sieve and/or according to SAPO-34 molecular sieve roasting in 400 ~ 700 DEG C of air of aforesaid method synthesis.
The beneficial effect that technical scheme described in the application can produce comprises:
(1) a kind of SAPO-34 molecular sieve containing n-Butyl Amine 99 is obtained.
(2) the SAPO-34 molecular sieve prepared is show excellent catalytic performance in low-carbon alkene reaction at methyl alcohol or dimethyl ether conversion.
(3) the SAPO-34 molecular sieve prepared, in the reaction of ethanol dehydration ether, shows good ethanol conversion and ether selectivity.
(4) the SAPO-34 molecular sieve prepared is at CH
4/ CO
2good selectivity is showed in fractionation by adsorption.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph (SEM) of synthetic product in embodiment 1.
Embodiment
Magix2424X type ray fluorescence analysis instrument (XRF) of elementary composition employing Philips company measures.
X-ray powder diffraction material phase analysis (XRD) adopts X ' the PertPROX x ray diffractometer x of Dutch PANalytical (PANalytical) company, Cu target, K α source of radiation (λ=0.15418nm), voltage 40KV, electric current 40mA.
SEM morphology analysis adopts Scientific Instrument Factory of C.A.S KYKY-AMRAY-1000B type scanning electronic microscope.
Nuclear magnetic resonance of carbon (
13cMASNMR) analyze the Infinityplus400WB solid state nmr wave spectrum analyzer adopting Varian company of the U.S., use BBOMAS probe, magnetic manipulation field intensity is 9.4T.
The VarioELCube elemental analyser that CHN ultimate analysis adopts Germany to manufacture.
Below by embodiment in detail the application is described in detail, but the application is not limited to these embodiments.
Embodiment 1
Each feed molar proportion scale, crystallization condition are in table 2.Concrete blending process is as follows, by 15.10g pseudo-boehmite (Al
2o
3mass percentage 67.5%) and 120g deionized water mix rear dropping 23.06g phosphoric acid (H
3pO
4mass percentage 85%), add 6g active silica after stirring, finally add 14.6g n-Butyl Amine 99, stir and make gel, gel is transferred in stainless steel cauldron.The mol ratio of each component of synthetic system is:
2.0NBA:1.0SiO
2:1.0Al
2O
3:1.0P
2O
5:66.7H
2O。
After reactor is put into baking oven, temperature programming is to 200 DEG C of dynamic lower crystallization 24h.After crystallization terminates, solid product is centrifugal, washing, after drying, obtains described SAPO-34 sieve sample in 100 DEG C of air.
Table 2 Zeolite synthesis batching, crystallization condition and gained sample sets submeter *
Embodiment 2 ~ 19
Concrete proportion scale and crystallization condition are in table 2, and concrete blending process is with embodiment 1.
Embodiment 20 sample structure and compositional analysis
Adopt the sample of X-ray powder diffraction to embodiment 1-19 to characterize, result shows, and embodiment 1 ~ 19 gained sample all has the constitutional features of SAPO-34 molecular sieve.With embodiment 1 gained sample for Typical Representative, its XRD diffraction data result is as shown in table 3.X-ray powder diffraction data result and the table 3 of embodiment 2 ~ 19 gained sample are close, and namely peak position is identical with shape, and the change peak relative peak intensities according to synthesis condition fluctuates in ± 10% scope.
Adopt the inorganic and organic composition of XRF and CHN ultimate analysis embodiment 1 ~ 19 gained sample, the results are shown in Table the data that in 2, " the elementary composition analysis result of product " arranges.
Embodiment 1 ~ 19 gained sample is carried out
13cMASNMR analyzes, by with n-Butyl Amine 99
13cMASNMR standard spectrogram contrasts, and finds the resonance peak only having n-Butyl Amine 99 in sample.
The XRD result of table 3 embodiment 1 sample
Embodiment 21
Embodiment 1 gained sample is passed into air roasting 4 hours at 550 DEG C, then compressing tablet, crushing and screening to 20 ~ 40 order.Take 5.0g sample and add the tank reactor that 30ml ethanol is housed, carry out ethanol dehydration reaction.Temperature of reaction is set in 150 stills, reacts and carries out under whipped state.Reaction result shows, and ethanol conversion can reach 95%, and in product, ether selectivity is 90%.
Embodiment 22
Embodiment 1 gained sample is passed into air roasting 4 hours at 550 DEG C, then compressing tablet, crushing and screening to 20 ~ 40 order.Take 1.0g sample and load fixed-bed reactor, carry out MTO reaction evaluating.At 550 DEG C, logical nitrogen activation 1 hour, is then cooled to 450 DEG C and reacts.Methyl alcohol is carried by nitrogen, and nitrogen flow rate is 60ml/min, methanol weight air speed 2.0h
-1.Reaction product is undertaken analyzing (Varian3800, fid detector, capillary column PoraPLOTQ-HT) by online gas-chromatography.Result is shown in table 4.
The preparing olefin by conversion of methanol reaction result of table 4 sample
Embodiment 23
Sample embodiment 1 obtained passes into air roasting 4 hours at 550 DEG C.CO
2, CH
4adsorption isothermal line recorded by MicrometricsASAP2020 device.The sample degassed pre-treatment of 350 shape 4 hours under vacuum conditions before measuring.Absorption test constant temperature is attached 25, and pressure is 101kPa.
The CO of table 5 sample
2/ CH
4fractionation by adsorption result
Although the application with preferred embodiment openly as above; but be not for limiting claim; any those skilled in the art are under the prerequisite not departing from the application's design; can make some possible variations and amendment, the scope that therefore protection domain of the application should define with the application's claim is as the criterion.
Claims (10)
1. a SAPO-34 molecular sieve, is characterized in that, described molecular sieve anhydrous chemical composition is expressed as:
mNBA(Si
xAl
yP
z)O
2，
Wherein, NBA is n-Butyl Amine 99; M is every mole of (Si
xal
yp
z) O
2the mole number of middle n-Butyl Amine 99, m=0.05 ~ 0.30; X, y, z represents the molar fraction of Si, Al, P respectively, and its scope is x=0.05 ~ 0.35 respectively, y=0.35 ~ 0.55, z=0.25 ~ 0.45, and x+y+z=1.
2. SAPO-34 molecular sieve according to claim 1, is characterized in that, in the anhydrous chemical composition of described SAPO-34 molecular sieve, and x=0.10 ~ 0.30, y=0.35 ~ 0.50, z=0.25 ~ 0.40, and x+y+z=1.
3. SAPO-34 molecular sieve according to claim 1, is characterized in that, the X ray diffracting spectrum of described SAPO-34 molecular sieve at least has diffraction peak with upper/lower positions:
4. synthesize a method for SAPO-34 molecular sieve described in claim 1, it is characterized in that, at least comprise following steps:
A) deionized water, silicon source, aluminium source, phosphorus source and n-Butyl Amine 99 are mixed according to a certain percentage, obtain the initial gel mixture with following mol ratio:
SiO
2/Al
2O
3＝0.10～1.5；
P
2O
5/Al
2O
3＝0.5～1.5；
H
2O/Al
2O
3＝10～200；
NBA/Al
2o
3=0.5 ~ 8; NBA is n-Butyl Amine 99;
B) by step a) gained initial gel mixture loading Autoclaves for synthesis, airtight, be warmed up to 160 ~ 240 DEG C, at autogenous pressures crystallization 5 ~ 72 hours;
C) after crystallization is complete, solid product, after separation, washing, drying, obtains described SAPO-34 molecular sieve.
5. in accordance with the method for claim 4, it is characterized in that, described step is NBA/Al in initial gel mixture a)
2o
3molar ratio is 1.5 ~ 5.0, is preferably 2.0 ~ 4.0; Described step is H in initial gel mixture a)
2o/Al
2o
3molar ratio is 65 ~ 200, is preferably 101 ~ 200.
6. in accordance with the method for claim 4, it is characterized in that, described step b) in crystallization process static or dynamically under carry out.
7. in accordance with the method for claim 4, it is characterized in that, described step b) in crystallization temperature be 190 ~ 240 DEG C, be preferably 211 ~ 240 DEG C.
8. a catalyzer for acid catalyzed reaction, is characterized in that, SAPO-34 molecular sieve roasting in 400 ~ 700 DEG C of air of the SAPO-34 molecular sieve according to any one of claims 1 to 3 and/or method synthesis according to any one of claim 4 ~ 7 obtains.
9. the catalyzer of an oxygen-containing compound conversion to produce olefine reaction, it is characterized in that, SAPO-34 molecular sieve roasting in 400 ~ 700 DEG C of air of the SAPO-34 molecular sieve according to any one of claims 1 to 3 and/or method synthesis according to any one of claim 4-7 obtains.
10. a CH
4/ CO
2adsorption and separation material, is characterized in that, SAPO-34 molecular sieve roasting in 400 ~ 700 DEG C of air of the SAPO-34 molecular sieve according to any one of claims 1 to 3 and/or method synthesis according to any one of claim 4 ~ 7 obtains.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111825102A (en) * | 2019-04-18 | 2020-10-27 | 中国科学院大连化学物理研究所 | Dry glue conversion synthesis method of high-silicon Y molecular sieve |
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| 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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2014
- 2014-08-25 CN CN201410422598.3A patent/CN105366687B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111825102A (en) * | 2019-04-18 | 2020-10-27 | 中国科学院大连化学物理研究所 | Dry glue conversion synthesis method of high-silicon Y molecular sieve |
| CN111825102B (en) * | 2019-04-18 | 2022-03-22 | 中国科学院大连化学物理研究所 | Dry glue conversion synthesis method of high-silicon Y molecular sieve |
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