CN103864096A - SAPO-35 molecular sieve and synthetic method thereof - Google Patents
SAPO-35 molecular sieve and synthetic method thereof Download PDFInfo
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Abstract
The invention provides an SAPO-35 molecular sieve having an anhydrous chemical composition of mR1.nCh<+>.(SixAlyPz)O2, wherein R1 is alcohol amine, and Ch<+> is choline cation and is distributed in a molecular sieve cage and pore passages; m is the number of moles of alcohol amine in each mole of (SixAlyPz)O2, n is the number of moles of the choline cation in each mole of (SixAlyPz)O2, m=0-0.03, and n=0.05-0.25; x, y and z respectively represent the molar fractions of Si, Al and P, the scopes of x, y and z are respectively x=0.01-0.30, y=0.35-0.55, z=0.25-0.49, and x+y+z=1. The synthesized SAPO-35 molecular sieve can be used as a catalyst for acid catalytic reactions, such as a reaction of preparing olefin from methanol. The invention also relates to an application of the SAPO-35 molecular sieve in adsorption and separation of CH4, CO2 and N2.
Description
Technical field
The invention belongs to SAPO molecular sieve field, 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, UCC company of the U.S. is at the molecular sieve of new generation (US4310440) of the invention 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, therefore there is no cation exchange property and catalytic perfomance.
In aluminium phosphate molecular sieve skeleton, introduce silicon, it is silicoaluminophosphamolecular molecular sieves, it is 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, skeleton has balance cation to exist outward, therefore has cation exchange property.When extraframework cation is H
+time, molecular sieve has acid sites, will have acid catalyzed reaction performance.SAPO molecular sieve as the active component of catalyzer likely for oil refining and field of petrochemical industry, as the conversion of catalytic cracking, hydrocracking, isomerization, alkylating aromatic hydrocarbon, oxygenatedchemicals etc.
SAPO-35 is levyne type (LEV) molecular sieve, has cross one another octatomic ring duct, and 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.In skeleton, have two kinds of different T atom sites, a kind of in two six-rings, 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, take water or alcohol as solvent, in enclosed high pressure still, carries out, and synthetic component comprises aluminium source, silicon source, phosphorus source, structure directing agent and deionized water.Optional do silicon source have silicon sol, a fumed silica, there are activated alumina, aluminum isopropylate, pseudo-boehmite and alkyl aluminum oxide in aluminium source, general 85% the phosphoric acid that adopts in phosphorus source.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, a kind of method of synthesizing SAPO-35 molecular sieve take rubane as template was disclosed in US440871 first.CN1299776A in 1999 discloses a kind of method of synthesizing SAPO-35 as template take hexamethylene imine (HMI) and hexanediamine (HDA).2005, in US2005/0090390, disclose a kind of in alcohol hot system take hexamethylene imine as template synthesizing high-crystallinity, the method for highly acid SAPO-35 molecular sieve.
The present invention adopts amine thermal means first, has synthesized pure phase SAPO-35 molecular sieve under the amine heat condition take choline cation as structure directing agent, take hydramine as solvent.The SAPO-35 molecular sieve of preparation shows good 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 without hydrochemical compositions is: 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 respectively the molar fraction of Si, Al, P, and its scope is respectively x=0.01～0.30, 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 N, N-dimethylethanolamine, N, any one in N-diethylethanolamine, trolamine, diethanolamine, tri-isopropanolamine, diisopropanolamine (DIPA), diglycolamine or several mixing arbitrarily.In this molecular sieve X-ray diffraction analysis result, at least contain diffraction peak as shown in the table:
Another object of the present invention is to provide a kind of synthetic method of SAPO-35 molecular sieve.
It is a kind of by the synthetic SAPO-35 molecular sieve of aforesaid method and acid catalyzed reaction catalyzer prepared therefrom and adsorbent that another object of the present invention is to provide.
Technical problem to be solved by this invention is take choline cation as structure directing agent, take phosphorus source that conventional Zeolite synthesis was adopted, He Lv source, silicon source is as raw material, synthetic pure phase SAPO-35 molecular sieve under the amine heat condition take hydramine as solvent.
Feature of the present invention is that preparation process is as follows:
A) hydramine, aluminium source, silicon source, phosphorus source, the compound that contains choline cation and deionized water are mixed according to a certain percentage, obtain having the initial gel mixture of following mole of proportioning:
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 pack Autoclaves for synthesis into, airtight, be warmed up to 150～220 ℃ of crystallization 5～120 hours under autogenous pressure;
C), after crystallization is complete, solid product, through centrifugation, to neutral, obtains SAPO-35 molecular sieve after being dried with deionized water wash.
Described step a) the silicon source in initial gel mixture is a kind of in silicon sol, active silica, positive silicon ester, metakaolin or several mixture arbitrarily; Aluminium source is a kind of or any several mixture in aluminium salt, activated alumina, aluminum alkoxide, metakaolin; Phosphorus source is a kind of or any several mixture in ortho-phosphoric acid, ammonium hydrogen phosphate, primary ammonium phosphate, Organophosphorous compounds or phosphorous oxides.Hydramine is N, N-dimethylethanolamine, N, any one in N-diethylethanolamine, trolamine, diethanolamine, tri-isopropanolamine, diisopropanolamine (DIPA), diglycolamine or arbitrarily several mixtures; The described choline cation Ch that contains
+compound be choline inorganic salt and/or choline organic salt.
Described step a) contains choline cation Ch in initial gel mixture
+compound be any one or any several mixture 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.
The crystallization process of described step in b) can static or dynamically under carry out.
The invention still further relates to a kind of catalyzer of acid catalyzed reaction, it is that synthetic SAPO-35 molecular sieve roasting in 400～700 ℃ of air obtains by above-mentioned SAPO-35 molecular sieve or according to aforesaid method.
The catalyzer that the invention still further relates to a kind of oxygen-containing compound conversion to produce olefine reaction, it is that synthetic SAPO-35 molecular sieve roasting in 400～700 ℃ of air obtains by above-mentioned SAPO-35 molecular sieve or according to aforesaid method.
The invention still further relates to a kind of for CH
4/ CO
2and N
2/ CO
2the sorbent material separating, it is that synthetic SAPO-35 molecular sieve roasting in 400～700 ℃ of air obtains by above-mentioned SAPO-35 molecular sieve or according to aforesaid method.
The beneficial effect that the present invention can produce comprises:
(1) obtained a kind of SAPO-35 molecular sieve take choline cation as template.
(2) adopt first amine thermal means to obtain SAPO-35 molecular sieve, for a new system has been opened up in the preparation of SAPO-35 molecular sieve.
(3) the SAPO-35 molecular sieve of preparing can be used as catalyzer and shows good catalytic performance for acid catalyzed reaction and oxygen-containing compound conversion to produce olefine reaction.
(4) the SAPO-35 molecular sieve of preparing can be used as CH
4/ CO
2and N
2/ CO
2the sorbent material separating.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph (SEM) of synthetic product in embodiment 1.
Embodiment:
The elementary composition Magix 2424X type ray fluorescence analysis instrument (XRF) that adopts Philips company is measured.
X-ray powder diffraction material phase analysis (XRD) adopts X ' the PertPRO X-ray diffractometer of Dutch PANalytical (PANalytical) company, Cu target, K α source of radiation (λ=0.15418nm), voltage 40KV, electric current 40mA.
SEM morphology analysis adopts the KYKY-AMRAY-1000B of Scientific Instrument Factory of C.A.S type scanning electronic microscope.
Nuclear magnetic resonance of carbon (
13c MAS MR) analyze the Infinity plus400WB solid state nmr wave spectrum analyzer that adopts Varian company of the U.S., with BBO MAS probe, magnetic manipulation field intensity is 9.4T.
The Vario EL Cube 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 embodiment.
Embodiment 1
Each feed molar ratio and crystallization condition are in table 1.Concrete blending process is as follows, by pseudo-boehmite (Al
2o
3quality percentage composition 72.5%) and N, N-ehtylethanolamine (quality percentage composition 99%) mix and blend, then adds silicon sol (SiO
2quality percentage composition 30.04%), stir, then by phosphoric acid (H
3pO
4quality percentage composition 85%) dropwise add, stir, then add water, finally add choline chloride 60, stir and make gel, gel is transferred in stainless steel cauldron.Reactor is put into after baking oven to temperature programming to 200 ℃ dynamically lower crystallization 48h.After crystallization finishes, solid product is centrifugal, and washing, after drying, obtains former powder in 100 ℃ 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, and data results and table 2 approach, and peak position is identical with shape, fluctuates in ± 10% scope according to the variation peak Relative Peak intensity of synthesis condition, shows that synthetic product has the feature of SAPO-35 structure.
The former powder sample of embodiment 1-7 is carried out
13c MAS NMR analyzes, by with choline cation and hydramine
13the contrast of C MAS NMR standard spectrogram is found to contain choline cation and corresponding hydramine in sample simultaneously, according to carrying out quantitative analysis in two kinds of peculiar NMR peaks that do not overlap of material, determines both ratios.
Adopt XRF analysis zeolite product body mutually elementary composition, the former powder sample of embodiment 1-7 is carried out to CHN ultimate analysis.Comprehensive CHN ultimate analysis, XRF and
13c MAS NMR analytical results, the composition that obtains 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, by N, N-diethylethanolamine changes trolamine into.Synthetic sample does XRD analysis, and result shows that synthetic product XRD result and table 2 approach, and peak position is identical with shape, and each peak Relative Peak intensity fluctuates in ± 10% scope, shows that synthetic product has the feature of SAPO-35 structure.
Former powder sample is carried out
13c MAS NMR analyzes, and result shows, wherein only contains the characteristic resonances peak of choline.
Embodiment 21
The synthetic sample 3g that gets respectively embodiment 1-20, puts into plastic beaker, adds the hydrofluoric acid solution of 3ml 40% to dissolve framework of molecular sieve under ice-water bath condition, then adds 15ml tetracol phenixin to dissolve organism wherein.By organism ICS-3000 chromatography of ions, positively charged ion column type is CS12A, analyzes composition, shows and wherein all contains 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
The sample that embodiment 1 is obtained passes into air roasting 4 hours at 600 ℃, then compressing tablet, be crushed to 20～40 orders.Take 1.0g sample and pack fixed-bed reactor into, carry out MTO reaction evaluating.At 550 ℃, logical nitrogen activation 1 hour, is then cooled to 400 ℃ and reacts.Methyl alcohol is carried by nitrogen, and nitrogen flow rate is 40ml/min, methyl alcohol weight space velocity 4.0h
-1.Reaction product is analyzed (Varian3800, fid detector, capillary column PoraPLOTQ-HT) by online gas-chromatography.The results are shown in table 3.
The preparing olefin by conversion of methanol reaction result of table 3 sample
Embodiment 23
The sample that embodiment 4 is obtained is as CO
2sorbent material.The adsorption isothermal line of sample is to measure 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%).For fear of in molecular sieve due to the impact on absorption test of the water of physical adsorption, sample is carrying out before thermoisopleth test, at 600 ℃, pass into air roasting 4 hours, then in ASAP2020, be further processed, treatment condition are, under utmost point low vacuum (5 × 10-3mmHg), rise to 350 ℃ with the temperature rise rate of 1 ℃/min, keep 8 hours.Control the temperature of gas adsorption with water bath with thermostatic control (precision: positive and negative 0.05 ℃), adsorption temp 298K.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 calculating take this is CO
2/ CH
4=10.5, CO
2/ N
2=13.5.Sample after adsorption experiment room temperature on ASAP2020 device is vacuumized and processed after 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 under condition as mild as a dove, regenerate.
Claims (12)
1. a SAPO-35 molecular sieve, is characterized in that, described molecular sieve has following without hydrochemical compositions: 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=0～0.03;
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 respectively the molar fraction of Si, Al, P, and its scope is respectively x=0.01～0.30, 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 N, N-dimethylethanolamine, N, any one in N-diethylethanolamine, trolamine, diethanolamine, tri-isopropanolamine, diisopropanolamine (DIPA), diglycolamine or several mixing arbitrarily.
4. a method for synthetic SAPO-35 molecular sieve claimed in claim 1, is characterized in that, adopts amine thermal means, and synthesis step is as follows:
A) hydramine, aluminium source, silicon source, phosphorus source, the compound that contains choline cation and deionized water are mixed according to a certain percentage, obtain having the initial gel mixture of following mole of proportioning:
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 pack Autoclaves for synthesis into, airtight, be warmed up to 150～220 ℃ of crystallization 5～120 hours under autogenous pressure;
C), after crystallization is complete, solid product, through separating, to neutral, obtains SAPO-35 molecular sieve after being dried with deionized water wash.
5. in accordance with the method for claim 4, it is characterized in that, described step a) the silicon source in initial gel mixture is a kind of in silicon sol, active silica, positive silicon ester, metakaolin or several mixture arbitrarily; Aluminium source is a kind of or any several mixture in aluminium salt, activated alumina, aluminum alkoxide, metakaolin; Phosphorus source is a kind of or any several mixture in ortho-phosphoric acid, ammonium hydrogen phosphate, primary ammonium phosphate, Organophosphorous compounds or phosphorous oxides; Hydramine is N, N-dimethylethanolamine, N, any one in N-diethylethanolamine, trolamine, diethanolamine, tri-isopropanolamine, diisopropanolamine (DIPA), diglycolamine or arbitrarily several mixtures; The described choline cation Ch that contains
+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) contains choline cation Ch in initial gel mixture
+compound be any one or any several mixture in choline chloride 60, phosphorylcholine, choline citrate, bursine.
7. it is characterized in that in accordance with the method for claim 4, the crystallization process of described step in b) 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, according to the SAPO-35 molecular sieve described in claim 1-3 any one or according to either method described in claim 4-9, synthetic SAPO-35 molecular sieve roasting in 400～700 ℃ of air obtains.
The catalyzer of 11. 1 kinds of oxygen-containing compound conversion to produce olefine reactions, it is characterized in that, according to the SAPO-35 molecular sieve described in claim 1-3 any one or according to either method described in claim 4-9, synthetic SAPO-35 molecular sieve roasting in 400～700 ℃ of air obtains.
12. 1 kinds for CH
4/ CO
2and N
2/ CO
2the sorbent material separating, is characterized in that, synthetic SAPO-35 molecular sieve roasting in 400～700 ℃ of air obtains according to the SAPO-35 molecular sieve described in claim 1-3 any one or according to either method described in claim 4-9.
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| CN105347356A (en) * | 2014-08-18 | 2016-02-24 | 中国科学院大连化学物理研究所 | SAPO-44 molecular sieve and synthesis method thereof |
| CN105439170A (en) * | 2014-08-18 | 2016-03-30 | 中国科学院大连化学物理研究所 | SAPO-35 molecular sieve and synthetic method thereof |
| CN108928832A (en) * | 2017-05-22 | 2018-12-04 | 中国石油化工股份有限公司 | Preparation method without germanium IWR zeolite molecular sieve |
| 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 |
| CN109502604A (en) * | 2017-09-15 | 2019-03-22 | 中国科学院大连化学物理研究所 | A method of preparing the Y type molecular sieve of high silica alumina ratio |
| CN110642262A (en) * | 2019-11-15 | 2020-01-03 | 广西师范大学 | Method for synthesizing SAPO-35 molecular sieve by using double templates |
| 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 |
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| CN105439170A (en) * | 2014-08-18 | 2016-03-30 | 中国科学院大连化学物理研究所 | SAPO-35 molecular sieve and synthetic method thereof |
| 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 |
| CN108928832A (en) * | 2017-05-22 | 2018-12-04 | 中国石油化工股份有限公司 | Preparation method without germanium IWR zeolite molecular sieve |
| 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 |
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| CN109502604A (en) * | 2017-09-15 | 2019-03-22 | 中国科学院大连化学物理研究所 | A method of preparing the Y type molecular sieve of high silica alumina ratio |
| 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 |
| 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 |
| CN110642262A (en) * | 2019-11-15 | 2020-01-03 | 广西师范大学 | Method for synthesizing SAPO-35 molecular sieve by using double templates |
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