CN103663489A - SAPO-44 (silicoaluminophosphate-44) molecular sieve and synthetic method thereof - Google Patents
SAPO-44 (silicoaluminophosphate-44) molecular sieve and synthetic method thereof Download PDFInfo
- Publication number
- CN103663489A CN103663489A CN201210363833.5A CN201210363833A CN103663489A CN 103663489 A CN103663489 A CN 103663489A CN 201210363833 A CN201210363833 A CN 201210363833A CN 103663489 A CN103663489 A CN 103663489A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- sapo
- silicon
- crystallization
- synthetic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to an SAPO-44 (silicoaluminophosphate-44) molecular sieve and a synthetic method thereof. The SAPO-44 molecular sieve is characterized by containing a template agent namely hexamethylene imine, the crystal surface of the molecular sieve is slightly rich in silicon, and the ratio of the outer surface silicon content to the bulk phase silicon content of crystals is 1.50-1.01. After being roasted in 400-700 DEG C air, the molecular sieve can be used as a catalyst for an acid-catalyzed reaction and a reaction for preparing olefin through oxygen-contained compound conversion.
Description
Technical field
The invention belongs to SAPO molecular sieve field, be specifically related to a kind of SAPO-44 molecular sieve and synthetic method thereof.
Background technology
1984, U.S. combinating carbide company (UCC) developed silicon aluminium phosphate series SAPO molecular sieve (USP 4440871).This molecular sieve is a class crystalline silicoaluminophosphate salt, and its three-dimensional framework structure is by PO
2 +, A1O
2 -and SiO
2tetrahedron forms.Wherein SAPO-34 is class chabazite structure, and main aperture road consists of eight annulus, and aperture is 0.38nm * 0.38nm.SAPO-34 molecular sieve is due to its suitable acidity and pore passage structure, presents excellent catalytic performance and receive much attention in preparing low carbon olefinic hydrocarbon with methanol (MTO) reaction.
SAPO-34 molecular sieve generally adopts hydrothermal synthesis method, take water as solvent, in enclosed high pressure still, carries out.Synthetic component comprises aluminium source, silicon source, phosphorus source, template and deionized water.What can be elected to be silicon source has silicon sol, active silica and a positive silicon ester, and there are activated alumina, pseudo-boehmite and aluminum alkoxide in aluminium source, and desirable Yu Lv source, silicon source is silicon sol and pseudo-boehmite; General 85% the phosphoric acid that adopts in phosphorus source.Conventional template comprises tetraethyl ammonium hydroxide (TEAOH), morpholine (MOR), piperidines (Piperidine), Isopropylamine (i-PrNH2), triethylamine (TEA), diethylamine (DEA), dipropyl amine etc. and their mixture.SAPO-44 and SAPO-34 have similar skeleton structure (CHA), but both exist some difference in XRD spectra.SAPO-44 adopts hexahydroaniline synthetic as template conventionally.
Hexamethylene imine (HMI), in SAPO molecular sieve synthetic, is generally used as the structure directing agent of synthetic SAPO-35 molecular sieve.Chinese patent 200710175273.X has reported that employing HMI is the synthetic SAPO-35 of template.Initial synthetic mixture need to be 35-100 ℃ of plastic, and synthetic ratio is (0.5-1.8) R: (0.05-2) SiO
2: 1Al
2o
3: (0.5-1.5) P
2o
5: (10-150) H
2o, in 150-210 ℃ of crystallization 0.5-500h.SAPO-35 molecular sieve belongs to LEV structure, and it is piled up and form according to the order of AABCCABBC by two six-rings.CHA structure is to be piled up and form according to AABBCC order by two six-rings.Can see, structurally there is larger difference in both.Conventionally the synthetic organic amine/ammonium that needs of SAPO molecular sieve is as structure directing agent, and a kind of organic amine can synthesize the molecular sieve of various structures under different conditions, same, and a kind of molecular sieve can use multiple different organic amine synthetic.But up to the present, the structure of organic amine and its association of leading between the molecular sieve structure generating not are very clear.Although more investigator has carried out a large amount of research and trial in this respect, and also obtained some progress, wanted to accomplish that the prediction between structure directing agent and its molecular sieve structure generating is still very difficult.The needed organic amine of most Zeolite synthesis is all found by experiment.
In SAPO molecular sieve synthetic, several investigators have all reported that the molecular sieve of synthesized has the feature of surperficial Silicon-rich.This is mainly that initial gelling system due to SAPO molecular sieve is generally acidity or closely neutral, and along with the carrying out of crystallization, phosphoric acid is consumed the constantly increase of pH value that (crystallization formation molecular sieve) causes synthetic system gradually.Silicon source existed with polymeric form form conventionally at the crystallization initial stage, because it has lower iso-electric point, increase along with synthetic system pH value, silicon oxide gradually depolymerization forms the silicon species of oligomeric state, thereby the ratio that makes silicon participate in formation SAPO framework of molecular sieve increases, and causes the phenomenon of zeolite crystal surface Silicon-rich.For example, we find silicon skewness in SAPO-34 molecular sieve crystal in the research that in earlier stage adopts the synthetic SAPO-34 of diethylamine, from core to shell, its content increases progressively, and outside surface silicone content (mol ratio Si/ (Si+Al+P)) with the ratio of the body phase silicone content of crystal at 1.41 (Microporous and Mesoporous Materials, 2008,114 (1-3): 4163).Akolekar etc. in the research of SAPO-44, find its surface silicon content with the ratio of body phase silicone content up to 6-10.(Colloids?and?Surfaces?A：Physicochemical?and?Engineering?Aspects?146(1999)375-386)。Generally speaking, SAPO molecular sieve all shows as the feature of grain surface Silicon-rich substantially, but it is worthy of note, even to same SAPO molecular sieve, its surface-element forms with body phase composite also can there is larger difference with the variation of synthesis condition and template used.
Conventionally in SAPO molecular sieve along with the increase of silicone content, the coordination environment of silicon can be also that multiple silicon environmental coexistence Si (nAl) (n=0-4) (allows the maximum list silicon dispersion amount of existence different different its skeletons of SAPO molecular sieve from initial simple Si (4Al) transition, see J.Phys.Chem., 1994,98,9614).The variation of silicon coordination environment causes its acid concentration and strength of acid to have greatly changed, and strength of acid has following order Si (Al) > Si (2Al) > Si (3Al) > Si (4Al).On the other hand, along with the appearance of silicon island in SAPO framework of molecular sieve, the corresponding acid site amount producing of each Siliciumatom reduces (during Si (4Al), be 1, during multiple silicon environment, be less than 1), that is to say, sour density reduces.It is contemplated that, as the SAPO molecular sieve of acid catalyst, if the skewness of silicon in zeolite crystal, its Acidity will be also inhomogeneous, must produce important impact to the catalytic performance of molecular sieve so.If the surperficial Silicon-rich of zeolite crystal, explanation is wanted relative complex near the silicon coordination environment in crystal grain shell region than inside.Weckhuysen etc. once reported in methanol to olefins reaction (MTO), first reaction is carried out in the nearly outer surface region of SAPO-34 crystal grain, carrying out along with reaction, larger carbon distribution material forms and stops up duct gradually, make the product diffusion difficulty of crystal grain inside increase (Chemistry-A European Journal, 2008,14,11320-11327; J.Catal., 2009,264,77-87).This also illustrates that the sour environment of zeolite crystal outside surface is even more important to catalyzed reaction simultaneously.The method of finding a kind of effective control molecular sieve surface Silicon-rich degree has great importance.
Summary of the invention
The object of the present invention is to provide a kind of SAPO-44 molecular sieve, this molecular sieve can be expressed as without hydrochemical compositions: mSDA (Si
xal
yp
z) O
2, wherein: SDA is hexamethylene imine; M represents every mole of (Si
xal
yp
z) O
2the mole number of corresponding organic amine, m=0.1～0.5; X, y, z represents respectively the molar fraction of Si, Al, P, and its scope is respectively x=0.01～0.60, y=0.2～0.60, z=0.2～0.60, and x+y+z=1.The slight Silicon-rich in this molecular sieve crystal surface, outside surface silicone content (Si/ (Si+Al+P) mol ratio) with the ratio of the body phase silicone content of crystal 1.50～1.01, preferably 1.40～1.02, more preferably 1.35～1.03, more preferably 1.30～1.03.It can be uniformly that silicon increases progressively from core to shell content in SAPO-44 molecular sieve crystal, can be also inhomogeneous.
Another object of the present invention is to provide a kind of synthetic method of SAPO-44 molecular sieve.
Another object of the present invention is to provide a kind of and synthesizes SAPO-44 molecular sieve and acid catalyzed reaction catalyzer prepared therefrom or oxygen-containing compound conversion to produce olefine catalysts by aforesaid method.
Another object of the present invention is to provide a kind of and synthesizes SAPO-44 molecular sieve and adsorbent prepared therefrom by aforesaid method.
Technical problem to be solved by this invention is that directly to take hexamethylene imine (hereinafter to be referred as HMI) be structure directing agent, take phosphorus source, the He Lv source, silicon source that conventional Zeolite synthesis was adopted is raw material, synthetic pure phase SAPO-44 molecular sieve under hydrothermal condition, and the slight Silicon-rich in the molecular sieve crystal of synthesized surface, outside surface silicone content (Si/ (Si+Al+P) mol ratio) with the ratio of the body phase silicone content of crystal 1.45～1.01.The inventor found through experiments, and by add a small amount of tensio-active agent in synthetic system, takes the method for variable temperature crystallization simultaneously, can effectively reduce the surperficial Silicon-rich degree of synthetic SAPO-44 molecular sieve.
Feature of the present invention is that preparation process is as follows:
A) silicon source, aluminium source, phosphorus source, deionized water, tensio-active agent and SDA are mixed, form the initial gel mixture with following mole of proportioning:
SiO
2/Al
2O
3＝0.01～1；
P
2O
5/Al
2O
3＝0.5～1.5；
H
2O/Al
2O
3＝30～130；
SDA/Al
2O
3＝2.0～6；
BM/Al
2O
3＝0.01～0.10；
Wherein SDA is hexamethylene imine, and BM is tensio-active agent;
B) by step a) gained initial gel mixture pack synthesis reactor into, airtight, be warmed up to 190～230 ℃ of crystallization 1～15h under autogenous pressure;
C) reduce crystallization temperature to 160～180 crystallization 1～15h ℃ under autogenous pressure;
D), after crystallization is complete, solid product, through centrifugation, to neutral, obtains SAPO-44 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; Tensio-active agent is a kind of or any several mixture in dodecyl trimethylammonium ammonia chloride, tridecyl trimethylammonium ammonia chloride, tetradecyl trimethylammonium ammonia chloride, pentadecyl trimethylammonium ammonia chloride, cetyl trimethyl ammonia chloride, dodecyl trimethylammonium amine bromide, tridecyl trimethylammonium amine bromide, tetradecyl trimethylammonium amine bromide, pentadecyl trimethylammonium amine bromide, hexadecyl trimethyl ammonium bromide.
Described step is SDA and Al in initial gel mixture a)
2o
3molar ratio be SDA/Al
2o
3=2.5～5.0, more preferably SDA/Al
2o
3=3.0～4.5.
Described step is H in initial gel mixture a)
2o and Al
2o
3molar ratio be H
2o/Al
2o
3=35～100.
Described step is BM and Al in initial gel mixture a)
2o
3molar ratio be BM/Al
2o
3=0.03～0.08.
Described step b) crystallization temperature in is 195～225 ℃, and crystallization time is 1～12h, and preferred crystallization temperature is 211～225 ℃, and crystallization time is 1～10h.
Described step c) crystallization temperature in is 165～175 ℃, and crystallization time is 3～12h.
The invention still further relates to a kind of catalyzer of acid catalyzed reaction, it is that synthetic SAPO-44 molecular sieve roasting in 400～700 ℃ of air obtains by above-mentioned SAPO-44 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-44 molecular sieve roasting in 400～700 ℃ of air obtains by above-mentioned SAPO-44 molecular sieve or according to aforesaid method.
The invention still further relates to a kind of adsorbent, it is that synthetic SAPO-44 molecular sieve roasting in 400～700 ℃ of air obtains by above-mentioned SAPO-44 molecular sieve or according to aforesaid method.
The beneficial effect that the present invention can produce comprises:
(1) obtain a kind of SAPO-44 molecular sieve that hexamethylene imine is template of take, and there is the feature of the slight Silicon-rich of grain surface, outside surface silicone content (mol ratio Si/ (Si+Al+P)) with the ratio of the body phase silicone content of crystal 1.50～1.01.
(2) the SAPO-44 molecular sieve of preparing shows good catalytic performance and gas adsorption separation performance in catalyzed reaction.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph (SEM) of synthetic product in the embodiment of the present invention 1.
Embodiment
The mutually elementary composition employing of body PANalytical X ' Pert PRO X-ray diffractometer (XRF) measures, Cu target, K α source of radiation (λ=0.15418nm), voltage 40KV, electric current 100mA.
Surface-element forms XPS and adopts x-ray photoelectron spectroscopy Thermo ESCALAB250Xi to measure (the monochromatization AlK α of take is excitaton source), and the Al2p=74.7eV of sample surfaces Al2O3 of take carrys out the charged of correcting sample surface as interior mark.
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 proportion scale and crystallization condition are in Table 1.Concrete blending process is as follows, by 16.4g phosphoric acid (H
3pO
4quality percentage composition 85%) mix with 30g deionized water, stir, then add 5.7g silicon sol (SiO
2quality percentage composition 30%), violent stirring 1h.21.5g hexamethylene imine HMI (quality percentage composition 99%) is joined in mixture above, airtight and stir 30min to obtain a uniform mixture, be designated as A.In addition by 10g pseudo-boehmite (Al
2o
3quality percentage composition 72.5%), 1.29g cetyl trimethylammonium bromide (CTAB) and the mixing of 20.9g deionized water stir evenly, and join in mixture A, after airtight stirring 30min mixes it, gel are transferred in stainless steel cauldron.Mole proportioning of each component of synthetic system is 3.0HMI: 0.4SiO
2: 1Al
2o
3: 1P
2o
5: 0.05CTAB: 50H
2o.
Synthesis reactor is warmed up to 230 ℃ of dynamically lower crystallization 2h, is then cooled to 170 degree crystallization 10h.After crystallization finishes, solid product is centrifugal, and washing, after drying, obtains former powder in 100 ℃ of air.Sample is done XRD analysis, and result shows that synthetic product has the feature of CHA structure, and XRD data are in Table 2.The XRD result of embodiment 2-10 and example 1 approach, and peak position is identical, and Relative Peak intensity synthesis condition and the ingredient proportion at each peak change slightly difference, and in ± 10% scope, fluctuation, shows that synthetic product is SAPO-44 molecular sieve.The scanning electron microscope of sample the results are shown in Figure 1.
Adopt XPS mutually elementary composition with body with the surface of XRF analysis zeolite product, outside surface silicone content and body phase silicone content ratio are listed in table 1.The body phase element of embodiment 1 sample is Al
0.49p
0.40si
0.11.
The former powder sample of embodiment 1 is carried out to CHN ultimate analysis, show that C/N mol ratio is 6.05.CHN results of elemental analyses and XRF are measured to the inorganic elements obtaining and form normalization method, what obtain molecular screen primary powder consists of 0.17HMI (Si
0.11al
0.49p
0.40) O
2.
Former powder sample is carried out
13c MASNMR analyzes, and only finds to belong to the carbon resonance peak of HMI, and does not observe the feature carbon resonance peak that belongs to CTAB.These presentation of results CTAB does not enter into final sintetics.
Table 1 Zeolite synthesis batching and crystallization condition table *
*: aluminium source is pseudo-boehmite (Al
2o
3quality percentage composition 72.5%), phosphorus source is phosphoric acid (H
3pO
4quality percentage composition 85%), silicon source is silicon sol (SiO
2quality percentage composition 30%); A: aluminium source is gama-alumina, Al
2o
3quality percentage composition 93%; B: tetraethoxysilane is silicon source; C: aluminium source is aluminum isopropylate; D: silicon source is fumed silica (SiO
2quality percentage composition 93%); E:BM is tensio-active agent, the BM of embodiment 1 to 5 is CTAB, the BM of embodiment 6-9 is respectively ten dimethyl trimethyl ammonium chlorides, ten trimethylammonium trimethylammonium amine bromides, ten tetramethyl-trimethyl ammonium chlorides, ten pentamethyl-trimethyl ammonium chlorides and ten hexamethyl trimethyl ammonium chlorides, the BM of embodiment 10 is the mixture of ten dimethyl trimethylammonium amine bromides and CTAB, molar ratio 1/1.
The XRD result of table 2 embodiment 1 sample
Embodiment 2-10
Concrete proportion scale and crystallization condition are in Table 1, and concrete blending process is with embodiment 1.
Synthetic sample is done XRD analysis, and result shows that the synthetic product of embodiment 2-10 has the constitutional features of SAPO-44, and XRD data results and table 2 approach, and peak position is identical with shape, according to the variation peak Relative Peak intensity of synthesis condition, in ± 10% scope, fluctuates.
Adopt XPS mutually elementary composition with body with the surface of XRF analysis zeolite product, outside surface silicone content and body phase silicone content ratio are listed in table 1.The body phase element of embodiment 10 samples is Al
0.50p
0.42si
0.08.
The former powder sample of embodiment 2-10 is carried out to CHN ultimate analysis, show that C/N mol ratio is in 6.0 ± 0.05 fluctuations.CHN results of elemental analyses and XRF are measured to the inorganic elements composition normalization method obtaining, and the composition that obtains molecular screen primary powder is followed successively by 0.12HMI (Si
0.07al
0.49p
0.43) O
2, 0.13HMI (Si
0.10al
0.55p
0.35) O
2, 0.14HMI (Si
0.05al
0.53p
0.42) O
2, 0.15HMI (Si
0.14al
0.47p
0.39) O
2, 0.16HMI (Si
0.21al
0.40p
0.39) O
2, 0.20HMI (Si
0.28al
0.38p
0.34) O
2, 0.18HMI (Si
0.10al
0.48p
0.42) O
2, 0.16HMI (Si
0.11al
0.49p
0.40) O
2, 0.17HMI (Si
0.08al
0.50p
0.42) O
2.
The former powder sample of embodiment 2-10 is carried out
13c MASNMR analyzes, and only finds to belong to the carbon resonance peak of HMI, and does not observe the feature carbon resonance peak that belongs to CTAB.These presentation of results CTAB does not enter into final sintetics.
Embodiment 11
The synthetic sample 3g that gets respectively embodiment 1-10, 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.Organism is analyzed to form with GC-MS and show that wherein contained organism is hexamethylene imine.
Embodiment 12
Get the synthetic sample of embodiment 1, epoxy resin cure, then polishing on polishing machine, utilizes the line sweep pattern of SEM-EDX, chooses the crystal face that approaches crystal core and carries out the compositional analysis from core to shell.Result demonstration, the Si/Al atomic ratio of crystal kernel area is about 0.19, and the Si/Al atomic ratio of close surf zone is about 0.28.
(SEM is shown as water chestnut side's bodily form looks to get the synthetic sample of embodiment 10, grain size 1-5 μ m), epoxy resin cure, then polishing on polishing machine, utilize the line sweep pattern of SEM-EDX, choose the crystal face that approaches crystal core and carry out the compositional analysis from core to shell.Result demonstration, the Si/Al atomic ratio of crystal kernel area is about 0.14, and the Si/Al atomic ratio of close surf zone is about 0.21.
Comparative example 1
Concrete proportion scale and blending process are with embodiment 10.Crystallization condition becomes 215 ℃ of crystallization 13h.
Synthetic sample is through XRD analysis, and result shows to approach with table 2, and peak position is identical with peak shape, shows that synthetic product has the feature of SAPO-44 structure.The relative crystallinity of sample and embodiment 1 sample are in a ratio of 89% (embodiment 1 sample degree of crystallinity is defined as 100%).
Relative crystallinity=(I
1+ I
2+ I
3) * 100%/(I
1'+I
2'+I
3') (I
1, I
2and I
3for three the strongest diffraction peak heights in comparative example 1 sample XRD spectra, I
1', I
2' and I
3' be three the strongest diffraction peak heights in embodiment 1 sample XRD spectra.)
Adopt XPS mutually elementary composition with body with the surface of XRF analysis zeolite product, the body phase element of comparative example 1 sample is Al
0.50p
0.40si
0.10.Outside surface silicone content and body phase silicone content ratio Si
outside surface/ Si
body phase=2.5.
Comparative example 2
Concrete proportion scale and blending process, with embodiment 10, save adding of tensio-active agent.
Synthetic sample is through XRD analysis, and result shows to approach with table 2, and peak position is identical with peak shape, shows that synthetic product has the feature of SAPO-44 structure.The relative crystallinity of sample and embodiment 1 sample are in a ratio of 95% (embodiment 1 sample degree of crystallinity is defined as 100%).
Adopt XPS mutually elementary composition with body with the surface of XRF analysis zeolite product, outside surface silicone content and body phase silicone content ratio Si
outside surface/ Si
body phase=2.0.
Comparative example 3
Concrete proportion scale and blending process, with embodiment 10, save adding of tensio-active agent, and crystallization process becomes 215 ℃ of crystallization 5h simultaneously.
Synthetic sample is through XRD analysis, and result shows to approach with table 2, and peak position is identical with peak shape, shows that synthetic product has the feature of SAPO-44 structure.The relative crystallinity of sample and embodiment 1 sample are in a ratio of 75% (embodiment 1 sample degree of crystallinity is defined as 100%).
Adopt XPS mutually elementary composition with body with the surface of XRF analysis zeolite product, outside surface silicone content and body phase silicone content ratio Si
outside surface/ Si
body phase=1.8.
Embodiment 13
The sample that embodiment 9 is obtained is as propylene sorbent material.On the ASAP2020 of the adsorption isothermal line Shi U.S. Micromeritics company of sample, measure.Adsorbed gas is propylene (99.99%) and propane (99.99%).For fear of in molecular sieve due to the impact on absorption test of the water of physical adsorption, sample is before carrying out 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), with the temperature rise rate of 1 ℃/min, rise to 350 ℃, keep 8 hours.With water bath with thermostatic control (precision: positive and negative 0.05 ℃), control the temperature of gas adsorption, adsorption temp 298K.Result show sample is respectively 2.0 and 1.0mmol/g (when pressure is 101kPa) to the adsorptive capacity of propylene and propane.Take this adsorption selectivity calculating is propylene/propane=2.0.
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 respectively 2.05 and 1.1mmol/g (when pressure is 101kPa) to the adsorptive capacity of propylene and propane.Interpret sample has good regenerability, can under condition as mild as a dove, regenerate.
Embodiment 14
The sample that embodiment 10 and comparative example 1 are 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 ethanol dehydration reaction evaluation.At 550 ℃, logical nitrogen activation is 1 hour, is then cooled to 260 ℃ and reacts.Ethanol is carried by nitrogen, and nitrogen flow rate is 60ml/min, ethanol weight space velocity 2.0h
-1.Reaction product is analyzed (Varian3800, fid detector, capillary column PoraPLOT Q-HT) by online gas-chromatography.Result demonstration, the transformation efficiency of embodiment 10 samples is 100%, ethylene selectivity is 100%.The transformation efficiency of comparative example 1 sample is 72%, and ethylene selectivity is 89%, contains the hydro carbons by products such as methane in product simultaneously.
Embodiment 15
The sample that embodiment 10 and comparative example 1 are 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 is 1 hour, is then cooled to 450 ℃ and reacts.With pump charging 60wt% methanol aqueous solution, methyl alcohol weight space velocity 2.5h
-1.Reaction product is analyzed (Varian3800, fid detector, capillary column PoraPLOT Q-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
* the highest during 100% methanol conversion (ethene+propylene) selectivity.
Claims (14)
1. a SAPO-44 molecular sieve, is characterized in that this molecular sieve is expressed as without hydrochemical compositions: mSDA (Si
xal
yp
z) O
2, wherein:
SDA is hexamethylene imine;
M represents every mole of (Si
xal
yp
z) O
2the mole number of corresponding organic amine, m=0.1～0.5;
X, y, z represents respectively the molar fraction of Si, Al, P, and its scope is respectively x=0.01～0.60, y=0.2～0.60, z=0.2～0.60, and x+y+z=1.
2. SAPO-44 molecular sieve according to claim 1, it is characterized in that, the slight Silicon-rich in molecular sieve crystal surface, outside surface silicone content with the ratio of the body phase silicone content of crystal 1.50～1.01, be preferably 1.40～1.02, more preferably 1.35～1.03, be more preferably 1.30～1.03, wherein silicone content is the mol ratio of Si/ (Si+Al+P).
3. SAPO-44 molecular sieve according to claim 1, is characterized in that, it is uniform that silicon increases progressively from core to shell content in SAPO-44 molecular sieve crystal.
4. SAPO-44 molecular sieve according to claim 1, is characterized in that, it is inhomogeneous that silicon increases progressively to shell content from core in SAPO-44 molecular sieve crystal.
5. a method for molecular sieve described in synthetic claim 1, said method comprising the steps of:
A) silicon source, aluminium source, phosphorus source, deionized water, tensio-active agent and SDA are mixed, form the initial gel mixture with following mole of proportioning:
SiO
2/A1
2O
3＝0.01～1；
P
2O
5/Al
2O
3＝0.5～1.5；
H
2O/Al
2O
3＝30～130；
SDA/Al
2O
3＝2.0～6；
BM/Al
2O
3＝0.01～0.10；
Wherein SDA is hexamethylene imine, and BM is tensio-active agent;
B) by step a) gained initial gel mixture pack synthesis reactor into, airtight, be warmed up to 190～230 ℃ of crystallization 1～15h under autogenous pressure;
C) reduce crystallization temperature to 160～180 crystallization 1～15h ℃ under autogenous pressure;
D), after crystallization is complete, solid product, through centrifugation, to neutral, obtains SAPO-44 molecular sieve after being dried with deionized water wash.
6. in accordance with the method for claim 5, 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; Tensio-active agent is a kind of or any several mixture in dodecyl trimethylammonium ammonia chloride, tridecyl trimethylammonium ammonia chloride, tetradecyl trimethylammonium ammonia chloride, pentadecyl trimethylammonium ammonia chloride, cetyl trimethyl ammonia chloride, dodecyl trimethylammonium amine bromide, tridecyl trimethylammonium amine bromide, tetradecyl trimethylammonium amine bromide, pentadecyl trimethylammonium amine bromide, hexadecyl trimethyl ammonium bromide.
7. in accordance with the method for claim 5, it is characterized in that, described step is SDA and Al in initial gel mixture a)
2o
3molar ratio be SDA/Al
2o
3=2.5～5.0, be preferably 3.0～4.5.
8. in accordance with the method for claim 5, it is characterized in that, described step is H in initial gel mixture a)
2o and Al
2o
3molar ratio be H
2o/Al
2o
3=35～100.
9. in accordance with the method for claim 5, it is characterized in that, described step is BM and Al in initial gel mixture a)
2o
3molar ratio be BM/Al
2o
3=0.03～0.08.
10. in accordance with the method for claim 5, it is characterized in that described step b) in crystallization temperature be 195～225 ℃, be preferably 211～225 ℃, crystallization time is 1～12h, is preferably 1～10h.
11. in accordance with the method for claim 5, it is characterized in that, described step c) in crystallization temperature be 165～175 ℃, crystallization time is 3～12h.
The catalyzer of 12. 1 kinds of acid catalyzed reactions, is characterized in that, according to the SAPO-44 molecular sieve described in claim 1-4 any one or according to either method described in claim 5-11, synthetic SAPO-44 molecular sieve roasting in 400～700 ℃ of air obtains.
The catalyzer of 13. 1 kinds of oxygen-containing compound conversion to produce olefine reactions, it is characterized in that, according to the SAPO-44 molecular sieve described in claim 1-4 any one or according to either method described in claim 5-11, synthetic SAPO-44 molecular sieve roasting in 400～700 ℃ of air obtains.
14. 1 kinds of adsorbents, is characterized in that, according to the SAPO-44 molecular sieve described in claim 1-4 any one or according to either method described in claim 5-11, synthetic SAPO-44 molecular sieve roasting in 400～700 ℃ of air obtains.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210363833.5A CN103663489B (en) | 2012-09-26 | 2012-09-26 | A kind of SAPO-44 molecular sieve and synthetic method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210363833.5A CN103663489B (en) | 2012-09-26 | 2012-09-26 | A kind of SAPO-44 molecular sieve and synthetic method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103663489A true CN103663489A (en) | 2014-03-26 |
| CN103663489B CN103663489B (en) | 2015-11-18 |
Family
ID=50302396
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210363833.5A Active CN103663489B (en) | 2012-09-26 | 2012-09-26 | A kind of SAPO-44 molecular sieve and synthetic method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103663489B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104743574B (en) * | 2014-11-26 | 2017-03-29 | 济南大学 | A kind of preparation method of 44 micro porous molecular sieve of high-purity SAPO |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296914A (en) * | 1999-11-17 | 2001-05-30 | 中国石油化工集团公司 | Process for synthesizing molecular sieve (MCM-22) with special crystal structure |
| CN1308019A (en) * | 1999-12-30 | 2001-08-15 | 中国科学院大连化学物理研究所 | Porous metal-silicon aluminium phosphate molecular sieve and its synthesis process |
| CN102557072A (en) * | 2010-12-29 | 2012-07-11 | 中国科学院大连化学物理研究所 | Solvothermal synthesis method of silicoaluminophosphate (SAPO)-34 molecular sieve and catalytic agent prepared by using solvothermal synthesis method |
-
2012
- 2012-09-26 CN CN201210363833.5A patent/CN103663489B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296914A (en) * | 1999-11-17 | 2001-05-30 | 中国石油化工集团公司 | Process for synthesizing molecular sieve (MCM-22) with special crystal structure |
| CN1308019A (en) * | 1999-12-30 | 2001-08-15 | 中国科学院大连化学物理研究所 | Porous metal-silicon aluminium phosphate molecular sieve and its synthesis process |
| CN102557072A (en) * | 2010-12-29 | 2012-07-11 | 中国科学院大连化学物理研究所 | Solvothermal synthesis method of silicoaluminophosphate (SAPO)-34 molecular sieve and catalytic agent prepared by using solvothermal synthesis method |
Non-Patent Citations (2)
| Title |
|---|
| ALBUQUERQUE A.ET AL.: "Synthesis of SAPO-34 from the lamellar ALPO-kanemite", 《STUDIES IN SURFACE SCIENCE AND CATALYSIS》 * |
| HELOISE O. PASTORE ET AL.: "Reaction at Interfaces: The Silicoaluminophosphate Molecular Sieve CAL-1", 《J. PHYS. CHEM. C》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN104743574B (en) * | 2014-11-26 | 2017-03-29 | 济南大学 | A kind of preparation method of 44 micro porous molecular sieve of high-purity SAPO |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103663489B (en) | 2015-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5982064B2 (en) | SAPO-34 molecular sieve and synthesis method thereof | |
| CN101743061B (en) | The preparation method of SAPO (SAPO) molecular sieve, the catalyst containing described molecular sieve and use the catalytic dehydration method of described catalyst | |
| CN103663490B (en) | A kind of SAPO-34 molecular sieve and synthetic method thereof | |
| US9499409B2 (en) | Metal silicoaluminophosphate molecular sieve with RHO framework structure, and method for preparing the same | |
| CN103787371B (en) | A kind of preparation method of submicron SAPO-18 molecular sieve | |
| CN103663492B (en) | A kind of SAPO-34 molecular sieve and synthetic method thereof | |
| CN101195492B (en) | Method for synthesizing SAPO-11 and SAPO-34 molecular sieve with diethylamine as template agent | |
| CN103663491A (en) | Synthesis method of silicoaluminophosphate (SAPO) molecular sieve with CHA structure and catalyst prepared thereby | |
| JP6006879B2 (en) | SAPO-34 molecular sieve and synthesis method thereof | |
| CN103011195B (en) | One-step preparation method for hydrogen type multistage pore molecular sieve with SAPO-5 and SAPO-34 symbiosis | |
| CN104828842B (en) | A kind of preparation method of the composite molecular screen of SAPO 5 and 34 symbiosis of SAPO | |
| CN111659251A (en) | Low-cost hierarchical pore SAPO-34 molecular sieve and preparation method and application thereof | |
| CN103482646A (en) | Metal-doped silicoaluminophosphate molecular sieve with RHO skeleton structure and preparation method thereof | |
| CN103864096B (en) | A kind of SAPO-35 molecular sieve and synthetic method thereof | |
| CN101195491A (en) | Method for hoisting degree of silicon entering SAPO-34 molecular sieve framework in synthesized gel rubber | |
| CN105731484B (en) | A kind of synthetic method of the middle molecular sieves of micropore SAPO 34 | |
| CN106032282A (en) | Preparation method and applications of mordenite having mesopores and micropores | |
| JP2016505492A (en) | SAPO-34 molecular sieve using diglycolamine as template agent and synthesis method thereof | |
| CN103663483B (en) | A kind of synthetic method of SAPO-34 molecular sieve and catalyzer prepared therefrom | |
| CN103663489B (en) | A kind of SAPO-44 molecular sieve and synthetic method thereof | |
| CN105439170A (en) | SAPO-35 molecular sieve and synthetic method thereof | |
| CN103864087A (en) | SAPO-34 molecular sieve with N-methyldiethanolamine as template, and its synthetic method | |
| CN105347356B (en) | A kind of molecular sieves of SAPO 44 and its synthetic method | |
| CN103864097B (en) | A kind of take diglycolamine as SAPO-34 molecular sieve and the synthetic method thereof of template | |
| CN111056562B (en) | SAPO-34 molecular sieve, synthetic method and application thereof, and method for preparing olefin from methanol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |