CN103864096B - A kind of SAPO-35 molecular sieve and synthetic method thereof - Google Patents
A kind of SAPO-35 molecular sieve and synthetic method thereof Download PDFInfo
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- CN103864096B CN103864096B CN201210531580.8A CN201210531580A CN103864096B CN 103864096 B CN103864096 B CN 103864096B CN 201210531580 A CN201210531580 A CN 201210531580A CN 103864096 B CN103864096 B CN 103864096B
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Abstract
The invention provides a kind of SAPO-35 molecular sieve, its anhydrous chemical consists of: mR
1nCh
+(Si
xal
yp
z) O
2, wherein, R
1for hydramine, Ch
+for choline cation, be distributed in molecular sieve cage and duct; M is every mole of (Si
xal
yp
z) O
2the mole number of middle hydramine, n is every mole of (Si
xal
yp
z) O
2the mole number of middle choline cation, m=0 ~ 0.03, n=0.05 ~ 0.25; X, y, z represents the molar fraction of Si, Al, P respectively, and its scope is x=0.01 ~ 0.30 respectively, y=0.35 ~ 0.55, z=0.25 ~ 0.49, and x+y+z=1.The SAPO-35 molecular sieve of the present invention's synthesis can be used as the catalyzer of acid catalyzed reaction, as methanol to olefins reaction.The invention still further relates to this SAPO-35 molecular sieve at CH
4, CO
2, N
2the application of fractionation by adsorption aspect.
Description
Technical field
The invention belongs to SAPO molecular sieve art, be specifically related to a kind of SAPO-35 molecular sieve and synthetic method thereof.
Background technology
Aluminium phosphate molecular sieve is after Si-Al molecular sieve, the molecular sieve of new generation (US4310440) that UCC company of the U.S. invented in the early 1980s, the skeleton of this molecular sieve analog is alternately formed by connecting by phosphorus oxygen tetrahedron and aluminum-oxygen tetrahedron, because framework of molecular sieve is electric neutrality, so there is no cation exchange property and catalytic perfomance.
Silicon is introduced in aluminium phosphate molecular sieve skeleton, it is then silicoaluminophosphamolecular molecular sieves, i.e. SAPO Series Molecules sieve (US4440871), its framework of molecular sieve is made up of phosphorus oxygen tetrahedron, aluminum-oxygen tetrahedron and silicon-oxy tetrahedron, because skeleton is electronegative, there is balance cation to exist outside skeleton, therefore there is cation exchange property.When extraframework cation is H
+time, molecular sieve has acid sites, will have acid catalyzed reaction performance.SAPO molecular sieve as catalyzer active component likely for oil refining and field of petrochemical industry, as the conversion etc. of catalytic cracking, hydrocracking, isomerization, alkylating aromatic hydrocarbon, oxygenatedchemicals.
SAPO-35 is levyne type (LEV) molecular sieve, and have cross one another octatomic ring duct, aperture is
belong to small pore molecular sieve.The skeleton of SAPO-35 is that LEV cage is formed by connecting by single six-ring and two six-ring.Have the T atom site that two kinds different in skeleton, a kind of in two six-ring, another is in single six-ring, and the distribution proportion of these two kinds of positions is 2: 1.
SAPO-35 molecular sieve generally adopts hydro-thermal or alcohol thermal synthesis method, with water or alcohol for solvent, carries out in enclosed high pressure still, and synthesis component comprises aluminium source, silicon source, phosphorus source, structure directing agent and deionized water.Optional do silicon source have silicon sol, fumed silica, there are activated alumina, aluminum isopropylate, pseudo-boehmite and alkyl aluminum oxide in aluminium source, and phosphorus source generally adopts the phosphoric acid of 85%.The selection of structure directing agent can produce certain impact for the microstructure of synthesis of molecular sieve, elementary composition and pattern, and then affects its catalytic performance.
1984, in US440871, make public for the first time a kind of method taking rubane as template and synthesize SAPO-35 molecular sieve.Within 1999, CN1299776A discloses a kind of method being template synthesis SAPO-35 with hexamethylene imine (HMI) and hexanediamine (HDA).2005, disclose a kind of in US2005/0090390 was the method for template synthesizing high-crystallinity, highly acid SAPO-35 molecular sieve with hexamethylene imine in alcohol hot system.
The present invention adopts amine thermal means first, is being structure directing agent, has synthesized pure phase SAPO-35 molecular sieve under the amine heat condition that is solvent with hydramine with choline cation.The SAPO-35 molecular sieve of preparation shows excellent catalytic performance and gas adsorption separation performance in catalyzed reaction.
Summary of the invention
The object of the present invention is to provide a kind of SAPO-35 molecular sieve, this molecular sieve anhydrous chemical consists of: mR
1nCh
+(Si
xal
yp
z) O
2, wherein: R
1for hydramine, Ch
+for choline cation, be distributed in molecular sieve cage and duct; M is every mole of (Si
xal
yp
z) O
2the mole number of middle hydramine, m=0 ~ 0.03; N is every mole of (Si
xal
yp
z) O
2the mole number of middle choline cation, n=0.05 ~ 0.25; X, y, z represents the molar fraction of Si, Al, P respectively, and its scope is x=0.01 ~ 0.30 respectively, y=0.35 ~ 0.55, z=0.25 ~ 0.49, and x+y+z=1; Preferable range is x=0.05 ~ 0.20, y=0.38 ~ 0.52, z=0.30 ~ 0.48, and x+y+z=1.Hydramine R
1for any one in N, N-dimethylethanolamine, N, N-diethylethanolamine, trolamine, diethanolamine, tri-isopropanolamine, diisopropanolamine (DIPA), diglycolamine or mixing several arbitrarily.At least containing diffraction peak as shown in the table in this molecular sieve X-ray diffraction analysis result:
Another object of the present invention is the synthetic method providing a kind of SAPO-35 molecular sieve.
Another object of the present invention is to provide a kind of SAPO-35 molecular sieve of being synthesized by aforesaid method and acid catalyzed reaction catalyzer prepared therefrom and adsorbent.
Technical problem to be solved by this invention take choline cation as structure directing agent, with conventional molecular sieve synthesize adopt phosphorus source, silicon source and aluminium source for raw material, under the amine heat condition being solvent with hydramine, synthesize pure phase SAPO-35 molecular sieve.
Feature of the present invention is that preparation process is as follows:
A) hydramine, aluminium source, silicon source, phosphorus source, compound containing choline cation and deionized water are mixed according to a certain percentage, obtain the initial gel mixture with following mol ratio:
SiO
2/Al
2O
3＝0.01～1.5；
P
2O
5/Al
2O
3＝0.5～3；
H
2O/Al
2O
3＝3～20；
Ch
+/ Al
2o
3=0.01 ~ 3, wherein Ch
+for choline cation;
R
1/ Al
2o
3=3 ~ 30, wherein R
1for hydramine;
B) by step a) gained initial gel mixture load Autoclaves for synthesis, airtight, be warmed up to 150 ~ 220 DEG C of crystallization 5 ~ 120 hours at autogenous pressures;
C) after crystallization is complete, solid product, through centrifugation, with deionized water wash to neutral, namely obtains SAPO-35 molecular sieve after drying.
The silicon source of described step a) in initial gel mixture is a kind of or several arbitrarily mixture in silicon sol, active silica, positive silicon ester, metakaolin; Aluminium source is a kind of or several arbitrarily mixture in aluminium salt, activated alumina, aluminum alkoxide, metakaolin; Phosphorus source is a kind of or several arbitrarily mixture in ortho-phosphoric acid, ammonium hydrogen phosphate, primary ammonium phosphate, Organophosphorous compounds or phosphorous oxides.Hydramine is any one or mixtures several arbitrarily in N, N-dimethylethanolamine, N, N-diethylethanolamine, trolamine, diethanolamine, tri-isopropanolamine, diisopropanolamine (DIPA), diglycolamine; Described containing choline cation Ch
+compound be choline inorganic salt and/or choline organic salt.
Described step a) in initial gel mixture containing choline cation Ch
+compound be any one or mixtures several arbitrarily in choline chloride 60, phosphorylcholine, choline citrate, bursine.
Described step is SiO in initial gel mixture a)
2/ Al
2o
3mol ratio be preferably 0.1 ~ 1.0.
Described step is P in initial gel mixture a)
2o
5/ Al
2o
3mol ratio be preferably 0.7 ~ 2.0.
Described step is H in initial gel mixture a)
2o/Al
2o
3mol ratio be preferably 8 ~ 17.
Described step is Ch in initial gel mixture a)
+/ Al
2o
3mol ratio be preferably 0.42 ~ 2.0.
Described step is hydramine/Al in initial gel mixture a)
2o
3mol ratio be preferably 6.0 ~ 15.
Described step b) in crystallization process can static or dynamically under carry out.
The invention still further relates to a kind of catalyzer of acid catalyzed reaction, it obtains by above-mentioned SAPO-35 molecular sieve or according to SAPO-35 molecular sieve roasting in 400 ~ 700 DEG C of air of aforesaid method synthesis.
The invention still further relates to the catalyzer of a kind of oxygen-containing compound conversion to produce olefine reaction, it obtains by above-mentioned SAPO-35 molecular sieve or according to SAPO-35 molecular sieve roasting in 400 ~ 700 DEG C of air of aforesaid method synthesis.
The invention still further relates to a kind of for CH
4/ CO
2and N
2/ CO
2the sorbent material be separated, it obtains by above-mentioned SAPO-35 molecular sieve or according to SAPO-35 molecular sieve roasting in 400 ~ 700 DEG C of air of aforesaid method synthesis.
The beneficial effect that the present invention can produce comprises:
(1) obtaining a kind of take choline cation as the SAPO-35 molecular sieve of template.
(2) adopt amine thermal means to obtain SAPO-35 molecular sieve first, the preparation for SAPO-35 molecular sieve opens a new system.
(3) the SAPO-35 molecular sieve prepared can be used as catalyzer for showing good catalytic performance in acid catalyzed reaction and oxygen-containing compound conversion to produce olefine reaction.
(4) the SAPO-35 molecular sieve prepared can be used as CH
4/ CO
2and N
2/ CO
2the sorbent material be separated.
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 (
13cMASMR) 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 present invention is described in detail, but the present invention is not limited to these embodiments.
Embodiment 1
Each feed molar ratio and crystallization condition are in table 1.Concrete blending process is as follows, by pseudo-boehmite (Al
2o
3mass percentage 72.5%) and N, N-ehtylethanolamine (mass percentage 99%) mix and blend, then add silicon sol (SiO
2mass percentage 30.04%), stir, then by phosphoric acid (H
3pO
4mass percentage 85%) dropwise add, stir, then add water, finally add choline chloride 60, stir and make gel, gel is transferred in stainless steel cauldron.After reactor is put into baking oven, temperature programming is to 200 DEG C of dynamic lower crystallization 48h.After crystallization terminates, solid product is centrifugal, washing, after drying, obtains former powder in 100 DEG C of air.Sample does XRD analysis, and result shows that synthetic product has the feature of SAPO-35 structure, and XRD data are in table 2.
Table 1 Zeolite synthesis batching and crystallization condition table *
The XRD result of table 2 embodiment 1 sample
Embodiment 2-19
Concrete proportion scale and crystallization condition are in table 1, and concrete blending process is with embodiment 1.Synthetic sample does XRD analysis, data results and table 2 close, namely peak position is identical with shape, and the change peak relative peak intensities according to synthesis condition fluctuates in ± 10% scope, shows that synthetic product has the feature of SAPO-35 structure.
The former powder sample of embodiment 1-7 is carried out
13cMASNMR analyzes, by with choline cation and hydramine
13cMASNMR standard spectrogram contrasts, and finds that, simultaneously containing choline cation and corresponding hydramine in sample, foundation two kinds of peculiar NMR peaks do not overlapped of material carry out quantitative analysis, determine both ratios.
Adopt XRF analysis zeolite product body mutually elementary composition, CHN ultimate analysis is carried out to the former powder sample of embodiment 1-7.Comprehensive CHN ultimate analysis, XRF and
13cMASNMR analytical results, the composition obtaining molecular screen primary powder is followed successively by:
0.01N, N-diethylethanolamine 0.10Ch
+(Si
0.12al
0.49p
0.39) O
2
0.02N, N-diethylethanolamine 0.08Ch
+(Si
0.07al
0.53p
0.40) O
2,
0.03N, N-diethylethanolamine 0.05Ch
+(Si
0.17al
0.46p
0.37) O
2,
0.013N, N-diethylethanolamine 0.17Ch
+(Si
0.14al
0.47p
0.39) O
2,
0.005 trolamine 0.19Ch
+(Si
0.11al
0.50p
0.39) O
2,
0.008 trolamine 0.23Ch
+(Si
0.13al
0.46p
0.41) O
2,
0.014N, N-diethylethanolamine 0.19Ch
+(Si
0.15al
0.47p
0.38) O
2.
Embodiment 20
Concrete proportion scale and crystallization condition are in table 1, and concrete blending process is with embodiment 1.Only change N, N-diethylethanolamine into trolamine.Synthetic sample does XRD analysis, result show synthetic product XRD result and table 2 close, namely peak position is identical with shape, and each peak relative peak intensities fluctuates in ± 10% scope, shows that synthetic product has the feature of SAPO-35 structure.
Former powder sample is carried out
13cMASNMR analyzes, and result shows, the characteristic resonances peak wherein only containing choline.
Embodiment 21
The synthetic sample 3g of Example 1-20, puts into plastic beaker respectively, and the hydrofluoric acid solution adding 3ml40% under ice-water bath condition dissolves framework of molecular sieve, then adds 15ml tetracol phenixin dissolving organism wherein.Organism is used ICS-3000 chromatography of ions, positively charged ion column type is CS12A, analyzes composition, and display is wherein all containing choline cation.
Comparative example 1 (adding without choline cation compound in synthetic system)
Concrete proportion scale, blending process and crystallization condition, with embodiment 1, no longer add choline chloride 60 in synthesized gel rubber.Synthetic sample does XRD analysis, and result shows that synthetic product XRD result is the characteristic peak of SAPO-34.
Embodiment 22
Sample embodiment 1 obtained passes into air roasting 4 hours at 600 DEG C, then compressing tablet, be crushed to 20 ~ 40 orders.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 400 DEG C and reacts.Methyl alcohol is carried by nitrogen, and nitrogen flow rate is 40ml/min, methanol weight air speed 4.0h
-1.Reaction product is undertaken analyzing (Varian3800, fid detector, capillary column PoraPLOTQ-HT) by online gas-chromatography.Result is shown in table 3.
The preparing olefin by conversion of methanol reaction result of table 3 sample
Embodiment 23
Sample embodiment 4 obtained is used as CO
2sorbent material.The adsorption isothermal line of sample measures on the ASAP2020 of Micromeritics company of the U.S..Adsorbed gas is CO
2(99.99%), CH
4and N (99.99%)
2(99.99%).Because the water of physical adsorption is on the impact of absorption test in molecular sieve, sample is before carrying out thermoisopleth test, air roasting is passed into 4 hours at 600 DEG C, then be further processed in ASAP2020, treatment condition are, under pole low vacuum (5 × 10-3mmHg), rise to 350 DEG C with the temperature rise rate of 1 DEG C/min, keep 8 hours.The temperature of gas adsorption is controlled, adsorption temp 298K with water bath with thermostatic control (precision: positive and negative 0.05 DEG C).Sample is to CO
2, CH
4and N
2adsorptive capacity be respectively 3.79,0.36 and 0.28mmol/g (when pressure is 101kPa).The adsorption selectivity calculated with this is CO
2/ CH
4=10.5, CO
2/ N
2=13.5.After sample after adsorption experiment room temperature on ASAP2020 device being vacuumized process 30min, carry out again adsorption isothermal line and measure, sample is to CO
2, CH
4and N
2adsorptive capacity be respectively 3.78,0.38 and 0.30mmol/g (when pressure is 101kPa), interpret sample has good regenerability, can regenerate under condition as mild as a dove.
Claims (12)
1. a SAPO-35 molecular sieve, is characterized in that, described molecular sieve is made up of following anhydrous chemical: mR
1nCh
+(Si
xal
yp
z) O
2, wherein:
R
1for hydramine, m is every mole of (Si
xal
yp
z) O
2the mole number of middle hydramine, m=0.005 ~ 0.03;
Ch
+for choline cation, n is every mole of (Si
xal
yp
z) O
2the mole number of middle choline cation, n=0.05 ~ 0.25;
X, y, z represents the molar fraction of Si, Al, P respectively, and its scope is x=0.01 ~ 0.30 respectively, y=0.35 ~ 0.55, z=0.25 ~ 0.49, and x+y+z=1.
2. SAPO-35 molecular sieve according to claim 1, is characterized in that, X ray diffracting spectrum has diffraction peak with upper/lower positions:
。
3. SAPO-35 molecular sieve according to claim 1, it is characterized in that, described hydramine is any one or mixing several arbitrarily in N, N-dimethylethanolamine, N, N-diethylethanolamine, trolamine, diethanolamine, tri-isopropanolamine, diisopropanolamine (DIPA), diglycolamine.
4. synthesize a method for SAPO-35 molecular sieve according to claim 1, it is characterized in that, adopt amine thermal means, synthesis step is as follows:
A) hydramine, aluminium source, silicon source, phosphorus source, compound containing choline cation and deionized water are mixed according to a certain percentage, obtain the initial gel mixture with following mol ratio:
SiO
2/Al
2O
3＝0.01～1.5；
P
2O
5/Al
2O
3＝0.5～3；
H
2O/Al
2O
3＝3～20；
Ch
+/ Al
2o
3=0.01 ~ 3, wherein Ch
+for choline cation;
R
1/ Al
2o
3=3 ~ 30, wherein R
1for hydramine;
B) by step a) gained initial gel mixture load Autoclaves for synthesis, airtight, be warmed up to 150 ~ 220 DEG C of crystallization 5 ~ 120 hours at autogenous pressures;
C) after crystallization is complete, solid product, through being separated, with deionized water wash to neutral, namely obtains SAPO-35 molecular sieve after drying.
5. in accordance with the method for claim 4, it is characterized in that, the silicon source of described step a) in initial gel mixture is a kind of or several arbitrarily mixture in silicon sol, active silica, positive silicon ester, metakaolin; Aluminium source is a kind of or several arbitrarily mixture in aluminium salt, activated alumina, aluminum alkoxide, metakaolin; Phosphorus source is a kind of or several arbitrarily mixture in ortho-phosphoric acid, ammonium hydrogen phosphate, primary ammonium phosphate, Organophosphorous compounds or phosphorous oxides; Hydramine is any one or mixtures several arbitrarily in N, N-dimethylethanolamine, N, N-diethylethanolamine, trolamine, diethanolamine, tri-isopropanolamine, diisopropanolamine (DIPA), diglycolamine; Described containing choline cation Ch
+compound be choline inorganic salt and/or choline organic salt.
6. in accordance with the method for claim 4, it is characterized in that, described step a) in initial gel mixture containing choline cation Ch
+compound be any one or mixtures several arbitrarily in choline chloride 60, phosphorylcholine, choline citrate, bursine.
7. it is characterized in that in accordance with the method for claim 4, described step b) in crystallization process static or dynamically under carry out.
8. in accordance with the method for claim 4, it is characterized in that, described step is Ch in initial gel mixture a)
+/ Al
2o
3=0.42 ~ 2.0.
9. in accordance with the method for claim 4, it is characterized in that, described step is hydramine R in initial gel mixture a)
1/ Al
2o
3=6.0 ~ 15.
10. a catalyzer for acid catalyzed reaction, is characterized in that, SAPO-35 molecular sieve roasting in 400 ~ 700 DEG C of air of the SAPO-35 molecular sieve according to any one of claim 1-3 or either method synthesis according to claim 4-9 obtains.
The catalyzer of 11. 1 kinds of oxygen-containing compound conversion to produce olefine reactions, it is characterized in that, SAPO-35 molecular sieve roasting in 400 ~ 700 DEG C of air of the SAPO-35 molecular sieve according to any one of claim 1-3 or either method synthesis according to claim 4-9 obtains.
12. 1 kinds for CH
4/ CO
2and N
2/ CO
2the sorbent material be separated, is characterized in that, SAPO-35 molecular sieve roasting in 400 ~ 700 DEG C of air of the SAPO-35 molecular sieve according to any one of claim 1-3 or either method synthesis according to claim 4-9 obtains.
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| CN105347356B (en) * | 2014-08-18 | 2017-08-25 | 中国科学院大连化学物理研究所 | A kind of molecular sieves of SAPO 44 and its synthetic method |
| CN105439170B (en) * | 2014-08-18 | 2017-12-19 | 中国科学院大连化学物理研究所 | A kind of molecular sieves of SAPO 35 and its synthetic method |
| CN108928832B (en) * | 2017-05-22 | 2020-08-07 | 中国石油化工股份有限公司 | Preparation method of germanium-free IWR zeolite molecular sieve |
| CN109502604B (en) * | 2017-09-15 | 2021-12-21 | 中国科学院大连化学物理研究所 | Method for preparing Y-type molecular sieve with high silicon-aluminum ratio |
| WO2019051774A1 (en) * | 2017-09-15 | 2019-03-21 | 中国科学院大连化学物理研究所 | Method for preparing y-type molecular sieve with high silicon-to-aluminum ratio |
| CN112569898A (en) * | 2019-09-30 | 2021-03-30 | 中国科学院大连化学物理研究所 | Adsorbent and preparation method and application thereof |
| CN110642262B (en) * | 2019-11-15 | 2021-08-03 | 广西师范大学 | Method for synthesizing SAPO-35 molecular sieve by using double templates |
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| US4440871A (en) * | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
| CN1656048A (en) * | 2002-05-22 | 2005-08-17 | 埃克森美孚化学专利公司 | Method for adding heat to a reactor system used to convert oxygenates to olefins |
| CN101397143A (en) * | 2007-09-28 | 2009-04-01 | 中国石油化工股份有限公司 | Method for synthesizing SAPO-35 molecular sieve |
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| US4440871A (en) * | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
| CN1656048A (en) * | 2002-05-22 | 2005-08-17 | 埃克森美孚化学专利公司 | Method for adding heat to a reactor system used to convert oxygenates to olefins |
| CN101397143A (en) * | 2007-09-28 | 2009-04-01 | 中国石油化工股份有限公司 | Method for synthesizing SAPO-35 molecular sieve |
| CN102530987A (en) * | 2010-12-29 | 2012-07-04 | 中国科学院大连化学物理研究所 | Solvent thermal synthesis method of SAPO (silicoaluminophosphate) molecular sieve and catalyst prepared by SAPO molecular sieve |
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