CN108187736A - Gibbsite@SAPO molecular sieves compound and preparation method with nucleocapsid and the application in catalysis methanol alkene - Google Patents
Gibbsite@SAPO molecular sieves compound and preparation method with nucleocapsid and the application in catalysis methanol alkene Download PDFInfo
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P30/40—Ethylene production
Abstract
The invention discloses the gibbsite@SAPO molecular sieves compound with nucleocapsid and preparation method and the applications in catalysis methanol alkene.It is using gibbsite as core, SAPO 34 is the nucleocapsid of shell, the feature that gibbsite and SAPO 34 coexist is presented in the XRD diffraction spectrograms of the compound, wherein 2 θ for belonging to gibbsite characteristic peak are located at the intensity at 18.3 ° of ± 0.10 ° of peaks and belong to 2 θ of 34 characteristic peaks of SAPO to be located at the intensity ratio at 18.05 ° of ± 0.10 ° of peaks be 0.2~10.The catalyst containing the gibbsite@SAPO molecular sieve compounds with nucleocapsid of the present invention is for methanol to olefins reaction with high olefin selectivity and reaction service life.
Description
Technical field
The present invention relates to a kind of molecular screen composites for catalysis methanol alkene, are furtherly to be related to a kind of tool
There are the gibbsite@SAPO molecular sieve compounds of nucleocapsid.
Background technology
Methanol-to-olefins (MTO) technology is the key technology in the New Coal Chemical Industry that new century China gives priority to,
Diversification of the conventional petroleum route so as to fulfill olefin feedstock can be substituted, has been carried out large-scale industrial application at present.
A kind of important catalyst that MTO technologies use is silicoaluminophosphate (SAPO) family molecular sieves.The molecular sieve is by U.S. UCC
Company invents in the early 1980s, and skeleton is made of phosphorus oxygen tetrahedron, aluminum-oxygen tetrahedron and oxygen-octahedron, bone
Frame is negatively charged, can be used as solid acid catalyst in the reactions such as hydrocarbon cracking, isomerization and dehydration of alcohols.Wherein there are eight yuan of oxygen
Small pore SAPO molecular sieves such as SAPO-34, SAPO-18 of annular aperture (about 4 angstroms of diameter) etc. are widely used in MTO catalyst.In recent years,
Researcher is constantly working to be promoted the performance of MTO catalyst.
In the prior art, usually all it is to synthesize that there is dual structure feature or dual by modulation silicon source and Template Types
The molecular screen material of duct feature come improve MTO reaction selectivity, but the prior art exist select expensive starting materials, prepared
The factors such as journey complexity, therefore still have room for improvement.
Invention content
An object of the present invention is to provide a kind of at low cost, activity height, three with nucleocapsid of excellent catalytic effect
Diaspore@SAPO molecular sieve compounds.
The second object of the present invention is to provide a kind of system of the gibbsite@SAPO molecular sieve compounds with nucleocapsid
Preparation Method.
The third object of the present invention is to provide a kind of gibbsite@SAPO molecular sieves compound with nucleocapsid and is urging
Change the application in methanol-to-olefins.
The technical solution adopted by the present invention is：Gibbsite@SAPO molecular sieve compounds with nucleocapsid, are with three
Diaspore is core, and SAPO-34 is shell, the obtained gibbsite@SAPO molecular sieve compounds with nucleocapsid；Described three
The x-ray diffraction pattern of diaspore SAPO molecular sieve compound has at least one diffraction maximum in such as the following table 1 in each range：
Table 1
| 2θ | Relative intensity |
| 9.45-9.65 | s-vs |
| 16.0-16.2 | w-m |
| 17.95-18.15 | w-s |
| 18.20-18.40 | w-s |
| 20.55-20.9 | m-vs |
| 24.95-25.4 | w-s |
| 30.5-30.7 | w-s |
W, m, s, vs represent the relative ratio of diffraction peak intensity and most strong diffraction maximum respectively in table 1, and w is for 0~20%, m
20~60%, s are that 60~80%, vs is 80~100%.
Further, in the present invention, there is the gibbsite@SAPO molecular sieve compounds of nucleocapsid, the compound
XRD diffraction spectrograms are presented the feature that gibbsite and SAPO-34 coexist, and in x-ray diffraction pattern, 2 θ are located at 18.3 ° ± 0.10 °
The intensity for belonging to the characteristic peak of gibbsite is located at the intensity of 18.05 ° of ± 0.10 ° of characteristic peaks for belonging to SAPO-34 with 2 θ
The ratio between be 0.2~10.
Further, the above-mentioned gibbsite@SAPO molecular sieve compounds with nucleocapsid, x-ray diffraction pattern
In, the intensity that 2 θ are located at 18.3 ° of ± 0.10 ° of characteristic peaks for belonging to gibbsite is belonged to 2 θ positioned at 18.05 ° ± 0.10 °
The intensity ratio of the characteristic peak of SAPO-34 is 0.3~5.
The preparation method of gibbsite@SAPO molecular sieve compounds with nucleocapsid, includes the following steps：5~
At 60 DEG C, silicon source, silicon source, phosphorus source, organic formwork agent, crystallization conditioning agent and water are mixed into plastic, are heated to 80~250 DEG C, from
Under raw pressure, hydrothermal crystallizing reacts 1~100h；The silicon source is gibbsite or gibbsite and boehmite, Bao Shui
One or two or more kinds of mixing in aluminium stone, aluminium hydroxide and activated alumina.
Further, above-mentioned preparation method, the silicon source are Ludox, silica gel, waterglass, silester and silicic acid
The mixing of one or more of methyl esters；The phosphorus source is phosphoric acid, metaphosphoric acid, aluminum phosphate, aluminium dihydrogen phosphate, di(2-ethylhexyl)phosphate
The mixing of one or more of hydrogen ammonium, diammonium hydrogen phosphate and ammonium phosphate；The organic formwork agent is morpholine, diethyl
The mixing of one or more of amine, triethylamine, tetraethyl ammonium hydroxide and di-n-propylamine；The crystallization conditioning agent is
The mixing of one or more of glycerine, the tert-butyl alcohol, polyethylene glycol and isopropanol.
Further, above-mentioned preparation method, silicon source, phosphorus source, silicon source, organic formwork agent, crystallization conditioning agent and water according to
Al2O3:P2O5:SiO2:Organic formwork agent:Crystallization conditioning agent:Water meter, mol ratio 1:(0.5~2):(0.01~0.8):
(0.1~5):(0.01~1):(10~150).
Further, the gibbsite@SAPO molecular sieves compound with nucleocapsid in the synthesis process, mixes
Using in terms of gel butt 0.1~10% molecular screen composite itself product can be added in plastic as crystal seed.The hydro-thermal is brilliant
Change reaction process known to existing technical staff, single hop crystallization may be used, multistage temperature progress can also be divided into, with two sections
For crystallization, the low temperature crystallized temperature of first segment can be divided into for 80~150 DEG C, crystallization time is 3~72h, second segment high temperature crystallization
Temperature is 150~250 DEG C, and crystallization time is 1~96h.After the completion of crystallization, slurries are filtered to obtain molecular screen composite filter cake.
This filter cake optionally can be after drying, roasting removing organic matter, and supply catalyst preparation is used.
Application of the gibbsite@SAPO molecular sieves compound in catalysis methanol alkene with nucleocapsid.Be with
The above-mentioned gibbsite@SAPO molecular sieves compound with nucleocapsid is active constituent and inorganic oxide binder and glues
Soil is mixed and made into catalyst, for catalysis methanol alkene.
Further, catalyst provided by the invention, by weight percentage with following composition：5~90% have core
Gibbsite@SAPO molecular sieves compound, 5~50% inorganic oxide binder and 5~70% clay of shell structure.
Further, the inorganic oxide binder is selected from Aluminum sol, Ludox, aluminium oxide, silica, phosphoric acid
The mixing of one or more of aluminium or amorphous silica-alumina.
Further, the clay is one or more of kaolin, more water and soil, montmorillonite or diatomite
Mixing.
Further, but it is not limited to this as follows for the preparation method of the catalyst：Synthesis had into nucleocapsid
Gibbsite@SAPO molecular sieve compounds it is direct or it is fired removing organic matter after powder, with inorganic oxide binder,
Clay adds water mashing to be uniformly mixed, and then the spray-dried grain size that is made is 10~200 microns of microballoon, then through 400~
800 DEG C, 0.1~8h roasts to obtain high abrasion microspherical catalyst.
Further, the gibbsite@SAPO molecular sieves compound with nucleocapsid is in catalysis methanol alkene
Application, method is as follows：Using fluidized-bed reactor, the gibbsite@SAPO molecular sieve compounds with nucleocapsid are loaded on
In fluidized-bed reactor, reaction temperature is 300~700 DEG C, and reaction pressure is 0.01~1MPa, methanol Feed space velocities for 0.01~
10h-1。
Gibbsite@SAPO molecular sieve compounds of the present invention with nucleocapsid, inorganic skeleton after baking
With following chemical composition：(SixAlyPz)O2, wherein：X, y, z represents the molar fraction of Si, Al, P, range difference respectively
It is x=0.01~0.28, y=0.35~0.55, z=0.28~0.50, and x+y+z=1.
Catalyst provided by the invention can be used for methanol-to-olefins reaction process.For example, the first using fluidized-bed reactor
Alcohol olefine reaction, reaction temperature are 300~700 DEG C, and reaction pressure is 0.01~1MPa, methanol Feed space velocities for 0.01~
10h-1。
The beneficial effects of the invention are as follows：
The present invention has found according to test of many times, the silicon source type of SAPO-34 molecular sieves is synthesized by control, and with reference to crystallization
Conditioning agent regulates and controls its activity in crystallization, can obtain the molecular sieve with dual structure feature and dual pore size distribution and answer
Object is closed, these can find out from XRD diagram and SEM photograph, and XRD diagram has gibbsite and the characteristic diffraction peak of SAPO-34 concurrently, and
Visible molecular screen composite complete crystallization in SEM photograph, without amorphous substance, plane of crystal has larger aperture macropore, shows
Synthetic product is crystalline composites, is not mechanical impurity.And such molecular screen composite has suitable silica content
And distribution, that is, the content in acid site in being sieved with regulatory molecule and distribution.This molecular screen composite is because with suitable for acid
Property and the dual pore size distribution of the micropore conducive to solid tumor, macropore, in methanol-to-olefins reaction process, turn with high methanol
Change activity, it is possible to reduce the probability of the secondary responses such as hydrogen migration occurs for the primary first-order equations such as light olefin product, so as to improve light olefin
Yield.
The present invention, by three water containing the present invention with nucleocapsid for selecting suitable binder and preparation process preparation
The abrasion performance microspherical catalyst of aluminium stone@SAPO molecular sieve compounds, applied to MTO devices, it is possible to reduce catalyst consumption reduces
Production cost.
Description of the drawings
Fig. 1 is the XRD diagram for the gibbsite@SAPO molecular sieve compounds with nucleocapsid that embodiment 1 synthesizes.
Fig. 2 is the XRD diagram for the gibbsite@SAPO molecular sieve compounds with nucleocapsid that embodiment 2 synthesizes.
Fig. 3 is the XRD diagram for the gibbsite@SAPO molecular sieve compounds with nucleocapsid that embodiment 3 synthesizes.
Fig. 4 is the XRD diagram for the SAPO-34 molecular sieves that comparative example 1 synthesizes.
Fig. 5 is the scanning electron microscope for the gibbsite@SAPO molecular sieve compounds with nucleocapsid that embodiment 2 synthesizes
(SEM) photo.
Specific embodiment
The present invention is further described with example below, but the present invention is not restricted by the embodiments.
Embodiment 1 has the gibbsite@SAPO molecular sieve compounds of nucleocapsid
By 284.8 grams of phosphoric acid (85 heavy % phosphoric acid, chemically pure reagent) and 421 grams of deionized water mashing, it is slowly added to 93 grams
Gibbsite (65 heavy %Al2O3, Shandong Aluminum Co., Ltd. production) and 84 grams of boehmite (72 heavy %Al2O3, Shandong Aluminum Co., Ltd. production),
1h is vigorously stirred, adds 356.5 grams of triethylamines (chemically pure reagent) of organic formwork agent and 68.4 grams of tetraethyl ammonium hydroxide water
Solution (25.3 heavy %TEAOH, the production of Jiangsu Kent new material), adds in 47 grams of polyethylene glycol 400s (chemically pure reagent), adds
23.5 grams of alkaline silica sol (30 heavy %SiO2, the production of Qingdao Ge Ruide new materials), 1h is vigorously stirred, is uniformly mixed, gained slurry
Liquid is formed with following molar ratio, Al2O3：P2O5：SiO2：Triethylamine：Tetraethyl ammonium hydroxide：Polyethylene glycol 400：Water=1：
1.05：0.1：3：0.1：0.1：40.Raw slurry is moved into the stainless steel water thermal crystallisation kettle of sealing, in 175 DEG C and spontaneous pressure
Crystallization 72h is rotated under power.Crystallization product is isolated in filtered after the completion of crystallization, washing, and dry in 100 DEG C of baking ovens to get
To the gibbsite@SAPO molecular sieve compounds with nucleocapsid, it is denoted as A.
The x-ray diffraction pattern of gained sample is as shown in Figure 1.2 θ are located at 18.29 ° of characteristic peaks for belonging to gibbsite
Intensity is 3.55 with the 2 θ intensity ratios for being located at 18.1 ° of characteristic peaks for belonging to SAPO-34.
Embodiment 2 has the gibbsite@SAPO molecular sieve compounds of nucleocapsid
By 298.4 grams of phosphoric acid and 297 grams of deionized water mashing, it is slowly added to 130 grams of gibbsites and 50.4 grams is intended thin water
Aluminium stone, is vigorously stirred 1h, adds 237.6 grams of triethylamines of organic formwork agent and 205.7 grams of tetraethyl ammonium hydroxide aqueous solutions, adds
Enter 23.5 grams of polyethylene glycol 400s, add 47.1 grams of alkaline silica sols, be vigorously stirred 1h, be uniformly mixed, gained slurries have with
Lower molar ratio composition, Al2O3：P2O5：SiO2：Triethylamine：Tetraethyl ammonium hydroxide：Polyethylene glycol 400：Water=1：1.1：0.2：2：
0.3：0.05：40.Raw slurry is moved into the stainless steel water thermal crystallisation kettle of sealing, crystallization is rotated for 24 hours, then rise to 175 at 120 DEG C
DEG C and self-generated pressure under rotation crystallization 60h.Filtered after the completion of crystallization, washing isolates crystallization product, and in 100 DEG C of baking ovens
Drying is denoted as B to get the gibbsite@SAPO molecular sieve compounds with nucleocapsid.
The x-ray diffraction pattern of gained sample is as shown in Figure 2.2 θ are located at 18.28 ° of characteristic peaks for belonging to gibbsite
Intensity is 1.96 with the 2 θ intensity ratios for being located at 18.13 ° of characteristic peaks for belonging to SAPO-34.Its scanning electron microscope pattern such as Fig. 5 institutes
Show, as seen from Figure 5, gained molecular screen composite is cubic crystal, is SAPO-34 crystal typical case's patterns, has no other classes
Type material morphology.And there are many macropore ducts among SAPO-34 crystal faces, it is seen that this compound crystal is tied with dual duct
Structure.Since this compound contains there are two types of crystal type, with reference to SEM patterns and crystallization process it is believed that this is multiple in XRD diffraction patterns
Solvate crystal is that gibbsite nucleus is embedded in kernel by SAPO-34 molecular sieve shells to be formed.
Embodiment 3 has the gibbsite@SAPO molecular sieve compounds of nucleocapsid
By 298.4 grams of phosphoric acid and 605 grams of deionized water mashing, it is slowly added to 93 grams of gibbsites and 84 grams is intended thin water aluminium
Stone is vigorously stirred 1h, adds compound 166.4 grams of triethylamines of organic formwork agent, 82 grams of morpholines (chemically pure reagent) and 68.4 grams
Tetraethyl ammonium hydroxide aqueous solution adds in 17.4 grams of tert-butyl alcohols (chemically pure reagent), adds 70.6 grams of acidic silicasols (25
Weight %SiO2, the production of Qingdao Ge Ruide new materials), 1h is vigorously stirred, is uniformly mixed, gained slurries have following molar ratio group
Into Al2O3：P2O5：SiO2：Triethylamine：Morpholine：Tetraethyl ammonium hydroxide：Polyethylene glycol 400：Water=1：1.1：0.25：1.4：
0.8：0.1：0.2：42.Raw slurry immigration is sealed in stainless steel water thermal crystallisation kettle, crystallization 12h is rotated, then rise at 140 DEG C
175 DEG C rotate crystallization for 24 hours under self-generated pressure.Crystallization product is isolated in filtered after the completion of crystallization, washing, and in 100 DEG C of bakings
It is dried in case to get the gibbsite@SAPO molecular sieve compounds with nucleocapsid, is denoted as C.
The x-ray diffraction pattern of gained sample is as shown in Figure 3.2 θ are located at 18.29 ° of characteristic peaks for belonging to gibbsite
Intensity is 0.69 with the 2 θ intensity ratios for being located at 18.12 ° of characteristic peaks for belonging to SAPO-34.
Comparative example 1
Contrast test is set according to the charge ratio of embodiment 2, difference lies in do not add gibbsite and crystallization conditioning agent
Polyethylene glycol.
By 298.4 grams of phosphoric acid and 499 grams of deionized water mashing, 168.7 grams of boehmites are slowly added to, are vigorously stirred
1h adds 237.6 grams of triethylamines of organic formwork agent and 205.7 grams of tetraethyl ammonium hydroxide aqueous solutions, adds 47.1 grams of alkali
Property Ludox, be vigorously stirred 1h, be uniformly mixed, gained slurries have following molar ratio composition, Al2O3：P2O5：SiO2：Triethylamine：
Tetraethyl ammonium hydroxide：Water=1：1.1：0.2：2：0.3：40.Raw slurry is moved into the stainless steel water thermal crystallisation kettle of sealing,
120 DEG C of rotation crystallization for 24 hours, then rise to rotation crystallization 60h under 175 DEG C and self-generated pressure.Filtered after the completion of crystallization, washing separation
Go out crystallization product, and dried in 100 DEG C of baking ovens to get to molecular screen primary powder product, be denoted as DB.
The x-ray diffraction pattern of gained sample is as shown in Figure 4.The result shows that gained sample is SAPO-34 molecular sieves, 2 θ
Salt free ligands peak is spent in 18.28 °.
By embodiment 1-3 and comparative example 1 as it can be seen that the present invention uses the aluminium hydroxide with gibbsite structure as aluminium
Source, by crystallization precursor liquid and the precise controlling of crystallization condition, synthesis has two paracrystalline organizations of gibbsite and SAPO-34,
And with the crystalline composites of the high SAPO-34 embedding gibbsite cores of the regular pattern of cube, crystallinity.
Embodiment 4
Gibbsite@SAPO molecular sieve compound A with nucleocapsid prepared by embodiment 1, by 600 DEG C of roastings
After 4h, cooling obtains roasting powder.
With 380 grams of deionized waters by 137 grams of kaolin (China Kaolin Co., Ltd's product, 81 heavy % of solid content) and 214 grams
Aluminum sol (Al2O321 heavy % of content, Laiwu is glad to reach chemical products) it is beaten uniformly, it adds in 145 grams of fired embodiments 1 and prepares
The gibbsite@SAPO molecular sieve compound A with nucleocapsid, homogeneous stirs evenly, and obtains slurries, slurries are through small spraying
Drier is molded, and thus obtained microsphere roasts 4h in Muffle furnace at 600 DEG C, cools down to obtain catalyst sample C-A.The catalyst contains 48
The kaolinite of the gibbsite@SAPO molecular sieve compounds A with nucleocapsid of weight %, the Aluminum sol of 15 weight % and 37 weight %
Soil.
Embodiment 5
Gibbsite@SAPO molecular sieve compound B with nucleocapsid prepared by embodiment 2, by 550 DEG C of roastings
After 8h, cooling obtains roasting powder.
With 300 grams of deionized waters by 145 grams of kaolin and 240 grams of acidic silicasol (SiO225 heavy % of content, Qingdao lattice are auspicious
Moral product) it is beaten uniform, prepared by the fired embodiments 2 of 123 grams of the addition gibbsite@SAPO molecules with nucleocapsid
Sieve compound B, homogeneous stirs evenly, and obtains slurries, and slurries are molded through disk-type spray dryer, thus obtained microsphere in Muffle furnace
600 DEG C of roasting 1h, cool down to obtain catalyst sample C-B.The catalyst contains the gibbsite@with nucleocapsid of 41 weight %
The kaolin of SAPO molecular sieve compound B, the Ludox of 20 weight % and 39 weight %.
Embodiment 6
With 380 grams of deionized waters that 167 grams of kaolin and 171 grams of Aluminum sol mashing are uniform, 154 grams of addition is dried solid
Gibbsite@SAPO molecular sieve compound C with nucleocapsid prepared by the embodiment 3 that content is 80 weight %, homogeneous stirring
Uniformly, slurries are obtained, slurries are molded through disk-type spray dryer, and thus obtained microsphere roasts 6h in Muffle furnace at 600 DEG C, cools down to urge
Agent sample C-C.The catalyst contains the gibbsite@SAPO molecular sieve compounds C with nucleocapsid of 43 weight %, and 12
The kaolin of the Aluminum sol of weight % and 45 weight %.
Comparative example 2
Molecular screen primary powder product DB prepared by comparative example 1 after 550 DEG C roast 8h, cools down to obtain roasting powder.
With 300 grams of deionized waters that 145 grams of kaolin and 240 grams of acidic silicasol mashing are uniform, 123 grams of addition is fired
The SAPO-34 molecular sieve DB that prepare of comparative example 1, homogeneous stirs evenly, and obtains slurries, and slurries are molded through disk-type spray dryer,
Thus obtained microsphere roasts 1h in Muffle furnace at 600 DEG C, cools down to obtain catalyst sample C-DB.The catalyst contains 41 weight %'s
The kaolin of SAPO-34 molecular sieves DB, the Ludox of 20 weight % and 39 weight %.
7 catalyst of embodiment and the MTO catalytic performances of comparative catalyst
The MTO reactivity worth of catalyst is evaluated using fixed-bed micro-reactor device, and experiment condition is：Catalyst loads
It measures as 2.0g, reaction temperature setting value is 450 DEG C, and reaction pressure is normal pressure, and the weight space velocity of first alcohol and water is respectively 2h-1With
2h-1.Gas method is taken to collect the gas dosing volume that MTO reactions generate using draining in reaction evaluating, using chromatographic
Gas forms；Using gas chromatograph for determination methanol content after water-phase product metering after gas-liquid separation, thus calculate methanol and turn
Rate and product distribution.The methanol matter of every gram of catalyst processing when wherein catalyst life is defined as methanol conversion less than 95%
Amount.Ethylene and propylene light olefins product yield are that the carbonaceous amount being made of in the ethylene and propylene that calculate gas accounts for charging methanol
The percentage of carbonaceous amount.Gained evaluation result is shown in Table 2.
Table 2
| Catalyst | Catalyst life/(g methanol/g catalyst) | Ethylene carbon base absorption rate/weight % | Propylene carbon base absorption rate/weight % |
| 4 C-A of embodiment | 6.9 | 41.5 | 41.2 |
| 5 C-B of embodiment | 7.3 | 42.7 | 41.4 |
| 6 C-C of embodiment | 6.8 | 42.2 | 40.9 |
| 2 C-DB of comparative example | 6.0 | 40.6 | 39.2 |
As can be seen from Table 2, using the MTO reaction service life obtained by catalyst of the present invention and the comparison catalysis of Light olefin products yield ratio
Agent is significantly improved, this is conducive to reduce catalyst use cost in MTO industrial practices.
Claims (10)
1. with nucleocapsid gibbsite@SAPO molecular sieve compounds, which is characterized in that be using gibbsite as core,
SAPO-34 is shell, the obtained gibbsite@SAPO molecular sieve compounds with nucleocapsid；The gibbsite@SAPO
The x-ray diffraction pattern of molecular screen composite has at least one diffraction maximum in following each range：
2. the gibbsite@SAPO molecular sieve compounds according to claim 1 with nucleocapsid, it is characterised in that：
In x-ray diffraction pattern, 2 θ are located at the intensity of 18.3 ° of ± 0.10 ° of characteristic peaks for belonging to gibbsite and 2 θ be located at 18.05 ° ±
The intensity ratio of 0.10 ° of characteristic peak for belonging to SAPO-34 is 0.2~10.
3. the gibbsite@SAPO molecular sieve compounds according to claim 2 with nucleocapsid, it is characterised in that：
In x-ray diffraction pattern, 2 θ are located at the intensity of 18.3 ° of ± 0.10 ° of characteristic peaks for belonging to gibbsite and 2 θ be located at 18.05 ° ±
The intensity ratio of 0.10 ° of characteristic peak for belonging to SAPO-34 is 0.3~5.
4. the preparation method of the gibbsite@SAPO molecular sieve compounds described in claim 1 with nucleocapsid, feature
It is, includes the following steps：At 5~60 DEG C, silicon source, silicon source, phosphorus source, organic formwork agent, crystallization conditioning agent and water are mixed
Plastic is heated to 80~250 DEG C, and hydrothermal crystallizing reacts 1~100h；The silicon source is thin for gibbsite or gibbsite and plan
One or two or more kinds of mixing in diaspore, boehmite, aluminium hydroxide and activated alumina.
5. preparation method according to claim 4, which is characterized in that the silicon source be Ludox, silica gel, waterglass,
The mixing of one or more of silester and methyl silicate；The phosphorus source is phosphoric acid, metaphosphoric acid, aluminum phosphate, phosphorus
The mixing of one or more of acid dihydride aluminium, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate；The organic formwork
Agent is the mixing of one or more of morpholine, diethylamine, triethylamine, tetraethyl ammonium hydroxide and di-n-propylamine；It is described
Crystallization conditioning agent be one or more of glycerine, the tert-butyl alcohol, polyethylene glycol and isopropanol mixing.
6. the gibbsite@SAPO molecular sieves compound described in claim 1 with nucleocapsid is in catalysis methanol alkene
In application.
7. application according to claim 6, which is characterized in that be with it is described in claim 1 with nucleocapsid three
Diaspore@SAPO molecular sieves compound is mixed and made into catalyst for active constituent and inorganic oxide binder and clay, is used for
Catalysis methanol alkene.
8. application according to claim 7, which is characterized in that the catalyst, by weight percentage composition are：5~
The 90% gibbsite@SAPO molecular sieves compound with nucleocapsid, 5~50% inorganic oxide binder and 5~
70% clay.
9. application according to claim 7, which is characterized in that the inorganic oxide binder is selected from Aluminum sol, silicon
The mixing of one or more of colloidal sol, aluminium oxide, silica, aluminum phosphate or amorphous silica-alumina；The clay is
The mixing of one or more of kaolin, more water and soil, montmorillonite or diatomite.
10. application according to claim 7, which is characterized in that method is as follows：Using fluidized-bed reactor, reaction temperature
It it is 300~700 DEG C, reaction pressure is 0.01~1MPa, and methanol Feed space velocities are 0.01~10h-1。
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| CN105668589A (en) * | 2016-04-21 | 2016-06-15 | 北京化工大学 | Method for preparing SAPO-11 molecular sieve with high crystallinity |
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| CN101676247A (en) * | 2008-09-19 | 2010-03-24 | 中国石油化工股份有限公司 | Method for preparing low carbon olefin |
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