CN103663489B - A kind of SAPO-44 molecular sieve and synthetic method thereof - Google Patents

A kind of SAPO-44 molecular sieve and synthetic method thereof Download PDF

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CN103663489B
CN103663489B CN201210363833.5A CN201210363833A CN103663489B CN 103663489 B CN103663489 B CN 103663489B CN 201210363833 A CN201210363833 A CN 201210363833A CN 103663489 B CN103663489 B CN 103663489B
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molecular sieve
sapo
silicone content
silicon
crystal
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CN103663489A (en
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田鹏
樊栋
刘中民
苏雄
张莹
杨越
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Dalian Institute of Chemical Physics of CAS
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    • 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
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    • 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

Abstract

The present invention relates to a kind of SAPO-44 molecular sieve and synthetic method thereof.It is characterized in that comprising template hexamethylene imine in this microporous molecular sieve, the slight Silicon-rich in molecular sieve crystal surface, the ratio of outside surface silicone content and the body phase silicone content of crystal is 1.50 ~ 1.01.This molecular sieve can be used as the catalyzer of acid catalyzed reaction and oxygen-containing compound conversion to produce olefine reaction after roasting in 400 ~ 700 DEG C of air.

Description

A kind of SAPO-44 molecular sieve and synthetic method thereof
Technical field
The invention belongs to SAPO molecular sieve art, 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 (USP4440871).This molecular sieve is a class crystalline silicoaluminophosphate salt, and its three dimensional skeletal structure is by PO 2 +, A1O 2 -and SiO 2tetrahedron is formed.Wherein SAPO-34 is class chabazite structure, and main aperture road is made up of eight annulus, and aperture is 0.38nm × 0.38nm.SAPO-34 molecular sieve, due to its suitable acidity and pore passage structure, presents excellent catalytic performance and receives 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, carries out in enclosed high pressure still.Synthesis 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 positive silicon ester, and there are activated alumina, pseudo-boehmite and aluminum alkoxide in aluminium source, and desirable silicon source and aluminium source are silicon sol and pseudo-boehmite; Phosphorus source generally adopts the phosphoric acid of 85%.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 has similar skeleton structure (CHA), but both exist some difference in XRD spectra.SAPO-44 adopts hexahydroaniline to synthesize as template usually.
Hexamethylene imine (HMI), in the synthesis of SAPO molecular sieve, is generally used as the structure directing agent synthesizing SAPO-35 molecular sieve.Chinese patent 200710175273.X reports and adopts HMI to be template synthesis SAPO-35.Initial synthesis mixture needs 35-100 DEG C 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 DEG C of crystallization 0.5-500h.SAPO-35 molecular sieve belongs to LEV structure, and it is formed by the order accumulation of two six-ring according to AABCCABBC.CHA structure is formed according to the accumulation of AABBCC order by two six-ring.Can see, structurally there is larger difference in both.The synthesis of usual SAPO molecular sieve needs organic amine/ammonium as structure directing agent, and a kind of organic amine can synthesize the molecular sieve of various structures under different conditions, and equally, a kind of molecular sieve can use multiple different organic amine to synthesize.But up to the present, the structure of organic amine and its association between the molecular sieve structure that generates of leading not be very clear.Although more investigator has carried out large quantifier elimination and trial in this respect, and also achieve some progress, want to accomplish that the prediction between structure directing agent and its molecular sieve structure generated is still very difficult.Most organic amine required for Zeolite synthesis is found all by experiment.
In the synthesis of SAPO molecular sieve, several investigator all reports the feature that synthesized molecular sieve has rich surface silicon.This is mainly generally acidity or weakly acidic pH due to the Primogel system of SAPO molecular sieve, and along with the carrying out of crystallization, phosphoric acid is consumed gradually, and (crystallization formation molecular sieve) causes the pH value of synthetic system constantly to increase.Silicon source existed with polymeric form form usually at the crystallization initial stage, because it has lower iso-electric point, along with the increase of synthetic system pH value, silicon oxide depolymerization can form the silicon species of oligomeric state gradually, thus the ratio making silicon participate in formation SAPO framework of molecular sieve increases, and causes the phenomenon of zeolite crystal surface Silicon-rich.Such as, we adopt in the research of diethylamine synthesis SAPO-34 in early stage and find silicon skewness in SAPO-34 molecular sieve crystal, from core to shell, its content increases progressively, and the ratio of outside surface silicone content (mol ratio Si/ (Si+Al+P)) and the body phase silicone content of crystal is at 1.41 (MicroporousandMesoporousMaterials, 2008,114 (1-3): 4163).Akolekar etc. are to finding in the research of SAPO-44 that the ratio of its surface silicon content and body phase silicone content is up to 6-10.(ColloidsandSurfacesA：PhysicochemicalandEngineeringAspects146(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 if to same SAPO molecular sieve, also can there is larger difference with the change of synthesis condition and template used in its surface-element composition and body phase composite.
Along with the increase of silicone content in usual SAPO molecular sieve, the coordination environment of silicon can be also that multiple silicon environmental coexistence Si (nAl) (n=0-4) (allows the maximum single silicon dispersion amount difference existed different its skeletons of SAPO molecular sieve from initial simple Si (4Al) transition, see J.Phys.Chem., 1994,98,9614).The change 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 acid site amount that each Siliciumatom correspondence produces reduces (be 1 time Si (4Al), be less than 1 during multiple silicon environment), and that is, 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 uneven, so must produce important impact to the catalytic performance of molecular sieve.If the surperficial Silicon-rich of zeolite crystal, then illustrate that the silicon coordination environment near crystal grain housing region wants relative complex than inside.Weckhuysen etc. once reported in methanol to olefins reaction (MTO), first reaction is carried out in the nearly exterior surface area of SAPO-34 crystal grain, along with the carrying out of reaction, larger carbon distribution material is formed gradually and blocks duct, the product diffusion difficulty of intra-die is made to increase (Chemistry-AEuropeanJournal, 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.A kind of method finding 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 anhydrous chemical composition can be expressed as: 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 the molar fraction of Si, Al, P respectively, and its scope is x=0.01 ~ 0.60 respectively, y=0.2 ~ 0.60, z=0.2 ~ 0.60, and x+y+z=1.This slight Silicon-rich in molecular sieve crystal surface, the ratio of outside surface silicone content (Si/ (Si+Al+P) mol ratio) and the body phase silicone content of crystal is 1.50 ~ 1.01, preferably 1.40 ~ 1.02, more preferably 1.35 ~ 1.03, more preferably 1.30 ~ 1.03.It can be uniform that silicon increases progressively from core to shell content in SAPO-44 molecular sieve crystal, also can be uneven.
Another object of the present invention is the synthetic method providing a kind of SAPO-44 molecular sieve.
Another object of the present invention is to provide a kind of by aforesaid method synthesis SAPO-44 molecular sieve and acid catalyzed reaction catalyzer prepared therefrom or oxygen-containing compound conversion to produce olefine catalysts.
Another object of the present invention is to provide a kind of by aforesaid method synthesis SAPO-44 molecular sieve and adsorbent prepared therefrom.
Technical problem to be solved by this invention be directly with hexamethylene imine (hereinafter referred to as HMI) for structure directing agent, with conventional molecular sieve synthesize adopt phosphorus source, silicon source and aluminium source be for raw material, synthesize pure phase SAPO-44 molecular sieve under hydrothermal conditions, and the slight Silicon-rich in synthesized molecular sieve crystal surface, the ratio of outside surface silicone content (Si/ (Si+Al+P) mol ratio) and the body phase silicone content of crystal is 1.45 ~ 1.01.The present inventor found through experiments, and by adding a small amount of tensio-active agent in synthetic system, takes the method for variable temperature crystallization simultaneously, effectively can reduce the surperficial Silicon-rich degree of the SAPO-44 molecular sieve of synthesis.
Feature of the present invention is that preparation process is as follows:
A) by silicon source, aluminium source, phosphorus source, deionized water, tensio-active agent and SDA mixing, the initial gel mixture with following mol ratio is formed:
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 loading synthesis reactor, airtight, be warmed up to 190 ~ 230 DEG C of crystallization 1 ~ 15h at autogenous pressures;
C) crystallization temperature to 160 ~ 180 DEG C at autogenous pressures crystallization 1 ~ 15h is reduced;
D) after crystallization is complete, solid product, through centrifugation, with deionized water wash to neutral, namely obtains SAPO-44 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; Tensio-active agent is a kind of or several arbitrarily mixture in trimethyl ammonia chloride, tridecyl trimethyl ammonia chloride amine, tetradecyltrimethylammonium ammonia chloride, pentadecyl trimethyl ammonia chloride amine, cetyl trimethyl ammonia chloride, trimethyl amine bromide, tridecyl trimethylammonium amine bromide, tetradecyltrimethylammonium 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) in crystallization temperature be 195 ~ 225 DEG C, crystallization time is 1 ~ 12h, and preferred crystallization temperature is 211 ~ 225 DEG C, and crystallization time is 1 ~ 10h.
Described step c) in crystallization temperature be 165 ~ 175 DEG C, crystallization time is 3 ~ 12h.
The invention still further relates to a kind of catalyzer of acid catalyzed reaction, it obtains by above-mentioned SAPO-44 molecular sieve or according to SAPO-44 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-44 molecular sieve or according to SAPO-44 molecular sieve roasting in 400 ~ 700 DEG C of air of aforesaid method synthesis.
The invention still further relates to a kind of adsorbent, it obtains by above-mentioned SAPO-44 molecular sieve or according to SAPO-44 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 hexamethylene imine as the SAPO-44 molecular sieve of template, and there is the feature of the slight Silicon-rich of grain surface, the ratio of outside surface silicone content (mol ratio Si/ (Si+Al+P)) and the body phase silicone content of crystal is 1.50 ~ 1.01.
(2) the SAPO-44 molecular sieve prepared shows excellent 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
Body mutually elementary composition employing PANalyticalX ' PertPROX-raydiffractometer (XRF) measures, Cu target, K α source of radiation (λ=0.15418nm), voltage 40KV, electric current 100mA.
Surface-element composition XPS adopts x-ray photoelectron spectroscopy ThermoESCALAB250Xi to carry out measuring (with monochromatization AlK α for excitaton source), is that interior mark carrys out the charged of correcting sample surface with the Al2p=74.7eV of sample surfaces Al2O3.
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 proportion scale and crystallization condition are in table 1.Concrete blending process is as follows, by 16.4g phosphoric acid (H 3pO 4mass percentage 85%) mix with 30g deionized water, stir, then add 5.7g silicon sol (SiO 2mass percentage 30%), violent stirring 1h.21.5g hexamethylene imine HMI (mass percentage 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 3mass percentage 72.5%), 1.29g cetyl trimethylammonium bromide (CTAB) and the mixing of 20.9g deionized water stir evenly, join in mixture A, after airtight stirring 30min makes it mix, gel is transferred in stainless steel cauldron.The mol ratio 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 DEG C of dynamically lower crystallization 2h, is then cooled to 170 degree of crystallization 10h.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 CHA structure, and XRD data are in table 2.XRD result and the example 1 of embodiment 2-10 are close, and namely peak position is identical, and the relative peak intensities at each peak changes slightly difference with synthesis condition and ingredient proportion, fluctuate, show that synthetic product is SAPO-44 molecular sieve in ± 10% scope.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 list in table 1.The body phase element of embodiment 1 sample is Al 0.49p 0.40si 0.11.
Carry out CHN ultimate analysis to the former powder sample of embodiment 1, display C/N mol ratio is 6.05.CHN results of elemental analyses and XRF are measured the inorganic elements obtained and forms 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 13cMASNMR analyzes, and only finds the carbon resonance peak belonging to HMI, and does not observe the feature carbon resonance peak belonging to CTAB.These results illustrate that CTAB does not enter into final sintetics.
Table 1 Zeolite synthesis batching and crystallization condition table *
*: aluminium source is pseudo-boehmite (Al 2o 3mass percentage 72.5%), phosphorus source is phosphoric acid (H 3pO 4mass percentage 85%), silicon source is silicon sol (SiO 2mass percentage 30%); A: aluminium source is gama-alumina, Al 2o 3mass percentage 93%; B: tetraethoxysilane is silicon source; C: aluminium source is aluminum isopropylate; D: silicon source is fumed silica (SiO 2mass percentage 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 does XRD analysis, and result shows that product that embodiment 2-10 synthesizes has the constitutional features of SAPO-44, XRD 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.
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 list in table 1.The body phase element of embodiment 10 sample is Al 0.50p 0.42si 0.08.
Carry out CHN ultimate analysis to the former powder sample of embodiment 2-10, display C/N mol ratio is in 6.0 ± 0.05 fluctuations.CHN results of elemental analyses and XRF are measured the inorganic elements obtained and forms normalization method, the composition obtaining 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 13cMASNMR analyzes, and only finds the carbon resonance peak belonging to HMI, and does not observe the feature carbon resonance peak belonging to CTAB.These results illustrate that CTAB does not enter into final sintetics.
Embodiment 11
The synthetic sample 3g of Example 1-10, 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 organism GC-MS being analyzed composition display wherein contained is hexamethylene imine.
Embodiment 12
The synthetic sample of Example 1, epoxy resin cure, then polishing on polishing machine, utilizes the line sweep pattern of SEM-EDX, and the crystal face chosen close to crystal core carries out the compositional analysis from core to shell.Result shows, and the Si/Al atomic ratio of crystal kernel area is about 0.19, and the Si/Al atomic ratio near surf zone is about 0.28.
(SEM is shown as water chestnut side's bodily form looks to the synthetic sample of Example 10, grain size 1-5 μm), epoxy resin cure, then polishing on polishing machine, utilize the line sweep pattern of SEM-EDX, the crystal face chosen close to crystal core carries out the compositional analysis from core to shell.Result shows, and the Si/Al atomic ratio of crystal kernel area is about 0.14, and the Si/Al atomic ratio near surf zone is about 0.21.
Comparative example 1
Concrete proportion scale and blending process are with embodiment 10.Crystallization condition becomes 215 DEG C of crystallization 13h.
Synthetic sample is through XRD analysis, and result shows with table 2 close, and namely 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 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 diffraction peak heights the strongest in comparative example 1 sample XRD spectra, I 1', I 2' and I 3' be three diffraction peak heights the strongest 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 with table 2 close, and namely 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 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 DEG C of crystallization 5h simultaneously.
Synthetic sample is through XRD analysis, and result shows with table 2 close, and namely 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 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
Sample embodiment 9 obtained is used as propylene adsorbs agent.The adsorption isothermal line of sample measures on the ASAP2020 of Micromeritics company of the U.S..Adsorbed gas is propylene (99.99%) and propane (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).The adsorptive capacity of result show sample to propylene and propane is respectively 2.0 and 1.0mmol/g (when pressure is 101kPa).The adsorption selectivity calculated with this is propylene/propane=2.0.
After sample after adsorption experiment room temperature on ASAP2020 device being vacuumized process 30min, carry out again adsorption isothermal line and measure, the adsorptive capacity of sample to propylene and propane is respectively 2.05 and 1.1mmol/g (when pressure is 101kPa).Interpret sample has good regenerability, can regenerate under condition as mild as a dove.
Embodiment 14
Sample embodiment 10 and comparative example 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 ethanol dehydration reaction evaluation.At 550 DEG C, logical nitrogen activation 1 hour, is then cooled to 260 DEG C and reacts.Ethanol is carried by nitrogen, and nitrogen flow rate is 60ml/min, ethanol weight space velocity 2.0h -1.Reaction product is undertaken analyzing (Varian3800, fid detector, capillary column PoraPLOTQ-HT) by online gas-chromatography.Result shows, and the transformation efficiency of embodiment 10 sample is 100%, and ethylene selectivity is 100%.The transformation efficiency of comparative example 1 sample is 72%, and ethylene selectivity is 89%, simultaneously containing hydro carbons by products such as methane in product.
Embodiment 15
Sample embodiment 10 and comparative example 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 450 DEG C and reacts.With pump charging 60wt% methanol aqueous solution, methanol weight air speed 2.5h -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
* the highest during 100% methanol conversion (ethene+propylene) selectivity.

Claims (18)

1. a SAPO-44 molecular sieve, is characterized in that this molecular sieve anhydrous chemical composition is expressed as: 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 the molar fraction of Si, Al, P respectively, and its scope is x=0.01 ~ 0.60 respectively, y=0.2 ~ 0.60, z=0.2 ~ 0.60, and x+y+z=1;
The slight Silicon-rich in wherein said molecular sieve crystal surface, outside surface silicone content is 1.50 ~ 1.01 with the ratio of the body phase silicone content of crystal, and wherein silicone content is the mol ratio of Si/ (Si+Al+P).
2. SAPO-44 molecular sieve according to claim 1, it is characterized in that, the slight Silicon-rich in described molecular sieve crystal surface, outside surface silicone content is 1.40 ~ 1.02 with the ratio of the body phase silicone content of crystal, and wherein silicone content is the mol ratio of Si/ (Si+Al+P).
3. SAPO-44 molecular sieve according to claim 1, it is characterized in that, the slight Silicon-rich in described molecular sieve crystal surface, outside surface silicone content is 1.35 ~ 1.03 with the ratio of the body phase silicone content of crystal, and wherein silicone content is the mol ratio of Si/ (Si+Al+P).
4. SAPO-44 molecular sieve according to claim 1, it is characterized in that, the slight Silicon-rich in described molecular sieve crystal surface, outside surface silicone content is 1.30 ~ 1.03 with the ratio of the body phase silicone content of crystal, and wherein silicone content is the mol ratio of Si/ (Si+Al+P).
5. 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.
6. SAPO-44 molecular sieve according to claim 1, is characterized in that, it is uneven that silicon increases progressively from core to shell content in SAPO-44 molecular sieve crystal.
7. synthesize a method for molecular sieve described in claim 1, said method comprising the steps of:
A) by silicon source, aluminium source, phosphorus source, deionized water, tensio-active agent and SDA mixing, the initial gel mixture with following mol ratio is formed:
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 loading synthesis reactor, airtight, be warmed up to 190 ~ 230 DEG C of crystallization 1 ~ 15h at autogenous pressures;
C) crystallization temperature to 160 ~ 180 DEG C at autogenous pressures crystallization 1 ~ 15h is reduced;
D) after crystallization is complete, solid product, through centrifugation, with deionized water wash to neutral, namely obtains SAPO-44 molecular sieve after drying.
8. in accordance with the method for claim 7, 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; Tensio-active agent is a kind of or several arbitrarily mixture in trimethyl ammonia chloride, tridecyl trimethyl ammonia chloride amine, tetradecyltrimethylammonium ammonia chloride, pentadecyl trimethyl ammonia chloride amine, cetyl trimethyl ammonia chloride, trimethyl amine bromide, tridecyl trimethylammonium amine bromide, tetradecyltrimethylammonium amine bromide, pentadecyl trimethylammonium amine bromide, hexadecyl trimethyl ammonium bromide.
9. in accordance with the method for claim 7, 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.
10. in accordance with the method for claim 7, it is characterized in that, described step is SDA and Al in initial gel mixture a) 2o 3molar ratio be SDA/Al 2o 3=3.0 ~ 4.5.
11. in accordance with the method for claim 7, 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.
12. in accordance with the method for claim 7, 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.
13. in accordance with the method for claim 7, it is characterized in that, described step b) in crystallization temperature be 195 ~ 225 DEG C, crystallization time is 1 ~ 12h.
14. in accordance with the method for claim 7, it is characterized in that, described step b) in crystallization temperature be 211 ~ 225 DEG C, crystallization time is 1 ~ 10h.
15. in accordance with the method for claim 7, it is characterized in that, described step c) in crystallization temperature be 165 ~ 175 DEG C, crystallization time is 3 ~ 12h.
The catalyzer of 16. 1 kinds of acid catalyzed reactions, is characterized in that, SAPO-44 molecular sieve roasting in 400 ~ 700 DEG C of air of the SAPO-44 molecular sieve according to any one of claim 1-6 or either method synthesis according to claim 7-15 obtains.
The catalyzer of 17. 1 kinds of oxygen-containing compound conversion to produce olefine reactions, it is characterized in that, SAPO-44 molecular sieve roasting in 400 ~ 700 DEG C of air of the SAPO-44 molecular sieve according to any one of claim 1-6 or either method synthesis according to claim 7-15 obtains.
18. 1 kinds of adsorbents, is characterized in that, SAPO-44 molecular sieve roasting in 400 ~ 700 DEG C of air of the SAPO-44 molecular sieve according to any one of claim 1-6 or either method synthesis according to claim 7-15 obtains.
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