CN104108727A - ZSM-11/SAPO-11 dual-structure molecular sieve and synthetic method thereof - Google Patents
ZSM-11/SAPO-11 dual-structure molecular sieve and synthetic method thereof Download PDFInfo
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Abstract
The invention relates to a ZSM-11/SAPO-11 dual-structure molecular sieve and a synthetic method thereof. The technical problems of single structure, small total amount of strong and weak acid sites and low catalytic activity of molecular sieve porous materials in the prior art are mainly solved. The ZSM-11/SAPO-11 dual-structure molecular sieve is characterized in that the ZSM-11/SAPO-11 dual-structure molecular sieve has two phases of ZSM-11 and SAPO-11, and the XRD pattern of the ZSM-11/SAPO-11 dual-structure molecular sieve has diffraction peaks in 2theta values of 7.85+/-0.05DEG, 8.55+/-0.1DEG, 9.53+/-0.02DEG, 11.93+/-0.1DEG, 13.35+/-0.1DEG, 14.66+/-0.05DEG, 15.75+/-0.1DEG, 18.38+/-0.1DEG, 20.25+/-0.05DEG, 21.07+/-0.1DEG, 22.66+/-0.1DEG, 23.34+/-0.1DEG, 23.83+/-0.1DEG, 26.70+/-0.02DEG, 27.94+/-0.1DEG, 29.92+/-0.05DEG, 31.83+/-0.1DEG, 35.18+/-0.1DEG, 36.07+/-0.05DEG, 38.04+/-0.1DEG, 45.11+/-0.1DEG. The problems are well solved, and the dual-structure molecular sieve can be used in the industrial production of methanol downstream products.
Description
Technical field
The present invention relates to a kind of ZSM-11/SAPO-11 binary structure zeolite and synthetic method thereof.
Background technology
Porous material is the solid compounds that a class has regular pore structure, the definition of pure according to the world in applied chemistry federation (IUPAC), porous material can be divided three classes by their bore dia: the material that aperture is less than 2 nm is poromerics (micropore materials); The material of aperture between 2 to 50 nm is mesoporous material (mesopore materials); The material that aperture is greater than 50 nm is large pore material (macropore materials), and zeolite molecular sieve belongs to poromerics.
Early stage zeolite refers to silico-aluminate, and it is by SiO
4tetrahedron and AlO
4tetrahedron is basic structural unit, and the class connecting and composing by bridging oxygen has the containing Microporous Compounds of cage type or pore passage structure.The forties in last century, Barrer etc. have synthesized the non-existent artificial zeolite of occurring in nature first in laboratory, after this enter more than ten years in, the people such as Milton, Breck and Sand adopt hydrothermal technique in silico-aluminate gel, to add basic metal or alkaline earth metal hydroxides, have synthesized A type, X-type, L-type and y-type zeolite and mordenite etc.; Nineteen sixties, along with the cationic introducing of organic bases, a series of brand new zeolite molecular sieves are produced out, as ZSM-n series (ZSM-1, ZSM-5, ZSM-11, ZSM-22, ZSM-48 etc.) zeolite molecular sieve, this molecular sieve analog has the advantages such as good catalytic activity, hydrothermal stability and higher erosion resistance, is widely used in the field such as refining of petroleum, fine chemistry industry, is the focus that people study for many years always.In numerous ZSM-n Series Molecules sieves, ZSM-5 is most widely used, it is the zeolite molecular sieve of Pentasil type two dimension pore canal system, is made up of oval ten-ring straight hole road (0. 54nm × 0. 56nm) and sinusoidal duct (0. 51nm × 0. 54nm).ZSM-5 zeolite has excellent catalytic performance, be widely used in the very important industrial chemical processes such as catalytic cracking, aromizing, alkylation, disproportionation, intersected by oval ten-ring two-dimensional direct duct (0. 51nm × 0. 55nm) that to form the attention rate that ZSM-11 molecular sieve obtains less and be all Pentasil type zeolite.
Patent CN101348261A, B have reported the synthetic method of a kind of binderless ZSM-5-11 molecular sieve, and the method can simply be converted into binderless ZSM-5-11 molecular sieve by sial raw material comparatively easily.
Patent 201010536158.2, using EU-1 molecular sieve as crystal seed, has been reported a kind of preparation method of short period of time crystallization ZSM-5-11.
Patent 200810060621.2 utilizes microwave method can obtain in the short period of time the ZSM-11 molecular sieve that degree of crystallinity is higher.
SAPO-11 develops silicon aluminium phosphate Series Molecules sieve (SAPO-n as the eighties U.S. combinating carbide company in last century (UCC), n represents model) important a member, have unique one dimension ten-ring straight hole road (0.39nm × 0.63nm), topology is MEL.In the structure of SAPO-n, Si atom forms by SiO after replacing P in former AlPO or Al atom
4, AlO
4and PO
4the non-neutral framework of molecular sieve of tetrahedron composition, in the skeleton of this molecular sieve analog, silicon exists in two ways: (1) Si atom replaces a P atom; (2) 2 Siliciumatoms replace respectively pair of aluminum atom and phosphorus atom.
The traditional method of preparation SAPO-11 molecular sieve is that hydrothermal synthesis method is as US Patent No. P4440871, USP4701485, USP4943424 etc., reactant aluminium source is aluminum isopropylate or pseudo-boehmite, phosphorus source is phosphoric acid, what silicon source was conventional is acidic silicasol, conventional template is di-n-propylamine and Diisopropylamine, the shortcomings such as aforesaid method has the repetition of being difficult for, and formation Si district is more are unfavorable for the application of SAPO-11.
Chinese patent 00129373.7,200910081007.0 reported and in reactant, used Organic Alcohol, can prepare small particle size, SAPO-11 molecular sieve that cleanliness factor is high.
Up to now, about ZSM-11/SAPO-11 binary structure zeolite with and the document of synthetic method there is not yet report.
Summary of the invention
One of technical problem to be solved by this invention is the technical problem that single, the strong and weak acid site of the structure of molecular sieve porous material total amount is less, catalytic activity is not high, a kind of ZSM-11/SAPO-11 binary structure zeolite is provided, this molecular sieve tool pore passage structure complex distribution, strong and weak acid site total amount is more, the advantage that catalytic activity is higher.
Two of technical problem to be solved by this invention is the problems that do not relate to above-mentioned ZSM-11/SAPO-11 binary structure zeolite synthetic method in prior art, and a kind of preparation method of new ZSM-11/SAPO-11 binary structure zeolite is provided.
Three of technical problem to be solved by this invention is to provide the purposes of a kind of ZSM-11/SAPO-11 binary structure zeolite for the preparation of Downstream Products of Methanol.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of ZSM-11/SAPO-11 binary structure zeolite, it is characterized in that described ZSM-11/SAPO-11 binary structure zeolite has two kinds of thing phases of ZSM-11 and SAPO-11, its XRD diffracting spectrum is 7.85 ± 0.05 at 2 θ, 8.55 ± 0.1, 9.53 ± 0.02, 11.93 ± 0.1, 13.35 ± 0.1, 14.66 ± 0.05, 15.75 ± 0.1, 18.38 ± 0.1, 20.25 ± 0.05, 21.07 ± 0.1, 22.66 ± 0.1, 23.34 ± 0.1, 23.83 ± 0.1, 26.70 ± 0.02, 27.94 ± 0.1, 29.92 ± 0.05, 31.83 ± 0.1, 35.18 ± 0.1, 36.07 ± 0.05, 38.04 ± 0.1, there is diffraction peak in 45.11 ± 0.1 places.
In technique scheme, the weight percentage meter in ZSM-11/SAPO-11 binary structure zeolite, the weight percentage of ZSM-11 molecular sieve is 30 ~ 65%; The weight percentage of SAPO-11 is 35 ~ 70%.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of synthetic method of ZSM-11/SAPO-11 binary structure zeolite, comprises following steps:
A, taking raw materials used molar ratio as SiO
2/ Al
2o
3=5 ~ 5000, P
2o
5/ Al
2o
3=0.2 ~ 200, template T/Al
2o
3=1 ~ 500, solvent S/Al
2o
3=50 ~ 1000, a certain amount of aluminium source and solvent are formed to solution A, then solution A is divided into two parts is designated as solution A
1and solution A
2;
B, a part of silicon source, additive and the required organic formwork agent of preparation ZSM-11 are added to A
1in, stir 0.5 ~ 10 hour to obtain solution A
1';
C, phosphoric acid, remaining silicon source and the required organic formwork agent of synthetic SAPO-11 are added to A
2in solution, stir 0.5 ~ 10 hour, obtain solution A
2';
D, by solution A
1' and solution A
2' be placed in respectively at 80 ~ 120 DEG C hydrothermal treatment consists 12 ~ 48 hours, afterwards by solution A
1' and solution A
2' evenly mix, airtight stirring 0.5 ~ 24 hour, forms uniform crystallization mixture at 80 ~ 120 DEG C;
E, the crystallization mixture of above-mentioned steps d is placed in to 150 ~ 200 DEG C of crystallization 10 hours ~ 15 days, product after filtration, after washing 80 ~ 130 DEG C dry, be then warming up to 400 ~ 650 DEG C, constant temperature calcining 0.5 ~ 12 hour.
In technique scheme, preferred technical scheme, it is 5 ~ 95% that preparation ZSM-11 silicon used source accounts for total silicon source quality per-cent; It is 5 ~ 95% that preparation SAPO-11 silicon used source accounts for total silicon source quality per-cent.
Preferred technical scheme, aluminium used source be selected from aluminate, meta-aluminate, aluminium salt, aluminium oxyhydroxide, aluminium oxide compound or containing at least one in the mineral of aluminium; Silicon used source is selected from least one in organosilicon, soft silica, silicon sol, solid oxidation silicon, silica gel, diatomite or water glass; Additive is at least one in the halogen compound of basic metal or alkaline-earth metal.Preferred technical scheme, the required organic formwork agent of preparation ZSM-11 is organic amine, is selected from least one in 4-propyl bromide, TPAOH, tetraethylammonium bromide, tetraethyl ammonium hydroxide, Tetrabutyl amonium bromide, TBAH, triethylamine, n-Butyl Amine 99, di-n-propylamine, Diisopropylamine, quadrol or ethamine; Preferred technical scheme, the required organic formwork agent of preparation SAPO-11 is organic amine, is selected from least one in 4-propyl bromide, TPAOH, tetraethylammonium bromide, tetraethyl ammonium hydroxide, Tetrabutyl amonium bromide, TBAH, triethylamine, n-Butyl Amine 99, di-n-propylamine, Diisopropylamine, quadrol or ethamine; Solvent is deionized water.
Preferred technical scheme, raw materials used molar ratio is: SiO
2/ Al
2o
3=10 ~ 1000, P
2o
5/ Al
2o
3=0.5 ~ 50, template T/Al
2o
3=10 ~ 100, solvent S/Al
2o
3=50 ~ 500.
Preferred technical scheme, solution A in step a
1and solution A
2weight ratio be 0.1 ~ 10:1; In step b, to account for total silicon source quality per-cent be 15 ~ 85% in silicon used source; In step c, to account for total silicon source quality per-cent be 15 ~ 85% in silicon used source.
Preferred technical scheme, aluminium source be selected from aluminate, meta-aluminate, aluminium salt, aluminium oxyhydroxide, aluminium oxide compound or containing at least one in the mineral of aluminium; Silicon source is selected from least one in organosilicon, soft silica, silicon sol, solid oxidation silicon, silica gel, diatomite or water glass; Additive is at least one in basic metal or alkaline-earth metal halogen compound.
Preferred technical scheme, the organic formwork agent required for the preparation of ZSM-11 is organic amine, is selected from least one in 4-propyl bromide, TPAOH, tetraethylammonium bromide, tetraethyl ammonium hydroxide, Tetrabutyl amonium bromide, TBAH, triethylamine, n-Butyl Amine 99, di-n-propylamine, Diisopropylamine, quadrol or ethamine; Preferred technical scheme, the required organic formwork agent of preparation SAPO-11 is organic amine, and at least one solvent being selected from 4-propyl bromide, TPAOH, tetraethylammonium bromide, tetraethyl ammonium hydroxide, Tetrabutyl amonium bromide, TBAH, triethylamine, n-Butyl Amine 99, di-n-propylamine, Diisopropylamine, quadrol or ethamine is deionized water.
Preferred technical scheme, in step b, to account for total silicon source quality per-cent be 25 ~ 75% in silicon used source; In step c, to account for total silicon source quality per-cent be 25 ~ 75% in silicon used source, solution A in step a
1and solution A
2weight ratio be 0.2 ~ 5:1, preferred technical scheme, solution A
1and solution A
2weight ratio be 0.3 ~ 3:1.
For solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: ZSM-11/SAPO-11 binary structure zeolite is as catalyzer, the catalyzed reaction for Methanol for hydro carbons.
Binary structure zeolite provided by the invention has pore passage structure feature and the acidic character of two kinds of molecular sieves concurrently, and embodies good synergistic effect.The two-phase proportion changing in composite molecular screen by optimising and adjustment synthesis condition obtains having optimum pore passage structure and suitable acid binary structure zeolite, for the reaction process of methanol conversion hydrocarbon processed, within the scope of the appreciation condition of setting, methanol conversion is 100%, the once through yield of product iso-butylene and aromatic hydrocarbons reaches as high as 73.8%, in aromatic hydrocarbons, the selectivity of BTX can reach 60.6%, and catalyzer has satisfactory stability simultaneously, has obtained good technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
Synthesizing of ZSM-11/SAPO-11 binary structure zeolite
By the Tai-Ace S 150 [Al of 113.17g
2(SO
4)
318H
2o, purity>=98wt.%] be dissolved in 159.57mL water, be mixed and made into solution A, afterwards this solution is divided into two parts by mass fraction and is respectively 70% and 30%, be designated as solution A
1and solution A
2, A during 1425.6g acidic silicasol (40wt.%), the NaCl that accounts for reaction mass gross weight 3.2% and 51.92g TBAH (TBAOH, 50wt%) are dropped into
1, stir 0.5h and obtain solution A
1'; 12.7g phosphoric acid (85wt.%), 77.0g acidic silicasol (40wt.%) and 18.03g diethylamine (DEA) are dropped into A
2in solution, stir 1h and obtain solution A
2'; By solution A
1' and solution A
2' be placed in respectively hydrothermal treatment consists 18h at 90 DEG C, afterwards by solution A
1' and solution A
2' evenly mix airtight stirring 10h at 120 DEG C; Stir the mixture above-mentioned, then be placed in 150 DEG C of crystallization 15d, product after filtration, wash rear 110 DEG C of dry 5h, be then warming up to 400 DEG C, constant temperature calcining 12h both product, be designated as ZS-1.
[embodiment 2]
Synthesizing of ZSM-11/SAPO-11 binary structure zeolite
By the Tai-Ace S 150 [Al of 226.4g
2(SO
4)
318H
2o, purity>=98wt.%] be dissolved in 1074.66mL water, be mixed and made into solution A, afterwards this solution is divided into two parts by mass fraction and is respectively 60% and 40%, be designated as solution A
1and solution A
2, by 51.6g acidic silicasol (40wt.%), the NaCl that accounts for reaction mass gross weight 2.7% and MgCl
26H
2a during O and 249.2g TBAH (TBAOH, 50wt%) drop into
1, stir 10h and obtain solution A
1'; 30.55g phosphoric acid (85wt.%), 968.4g acidic silicasol (40wt.%) and 28.85g diethylamine (DEA) are dropped into A
2in solution, stir 10h and obtain solution A
2'; By solution A
1' and solution A
2' be placed in respectively hydrothermal treatment consists 24h at 80 DEG C, afterwards by solution A
1' and solution A
2' evenly mix 120 DEG C of airtight stirring 24h; Stir the mixture above-mentioned, then be placed in 200 DEG C of crystallization 10h, product after filtration, wash rear 80 DEG C of dry 8h, be then warming up to 550 DEG C, constant temperature calcining 9h both product, be designated as ZS-2.
[embodiment 3]
Synthesizing of ZSM-11/SAPO-11 binary structure zeolite
By the aluminum nitrate of 187.7g [Al (NO
3)
39H
2o] be dissolved in 3280.43mL water, be mixed and made into solution A, afterwards this solution is divided into two parts by mass fraction and is respectively 50% and 50%, be designated as solution A
1and solution A
2, by 53.03g acidic silicasol (40wt.%), the KCl that accounts for reaction mass gross weight 3.5% and CaCl
22H
2a during O and 524.35g TBAH (TBAOH, 50wt%) drop into
1, stir 5h and obtain solution A
1'; 81.84g phosphoric acid (85wt.%), 300.48g acidic silicasol (40wt.%) and 204.83g triethylamine (TEA) are dropped into A
2in solution, stir 3h and obtain solution A
2'; By solution A
1' and solution A
2' be placed in respectively hydrothermal treatment consists 0.5h at 120 DEG C, afterwards by solution A
1' and solution A
2' evenly mix 120 DEG C of airtight stirring 0.5h; Stir the mixture above-mentioned, then be placed in 165 DEG C of crystallization 7d, product after filtration, wash rear 80 DEG C of dry 9h, be then warming up to 650 DEG C, constant temperature calcining 9h both product, be designated as ZS-3.
[embodiment 4]
Synthesizing of ZSM-11/SAPO-11 binary structure zeolite
By the aluminum nitrate of 285.23g [Al (NO
3)
39H
2o] be dissolved in 4713.25mL water, be mixed and made into solution A, afterwards this solution is divided into two parts by mass fraction and is respectively 45% and 55%, be designated as solution A
1and solution A
2, by 1162.81g acidic silicasol (40wt.%), the NaCl that accounts for reaction mass gross weight 1.5% and CaCl
22H
2a during O and 1245.8g TBAH (TBAOH, 50wt%) drop into
1, stir 12h and obtain solution A
1'; 132.86g phosphoric acid (85wt.%), 387.61g acidic silicasol (40wt.%) and 363.8g triethylamine (TEA) are dropped into A
2in solution, stir 12h and obtain solution A
2'; By solution A
1' and solution A
2' be placed in respectively hydrothermal treatment consists 6h at 105 DEG C, afterwards by solution A
1' and solution A
2' evenly mix 120 DEG C of airtight stirring 3h; Stir the mixture above-mentioned, then be placed in 185 DEG C of crystallization 3d, product after filtration, wash rear 110 DEG C of dry 9h, be then warming up to 650 DEG C, constant temperature calcining 10h both product, be designated as ZS-4.
[embodiment 5]
Synthesizing of ZSM-11/SAPO-11 binary structure zeolite
By the sodium metaaluminate [NaAlO of 245.1g
2] be dissolved in 2608.1mL water, be mixed and made into solution A, afterwards this solution is divided into two parts by mass fraction and is respectively 42% and 58%, be designated as solution A
1and solution A
2, by 12.11g white carbon black (SiO
2, 99wt.%), account for KCl and the MgCl of reaction mass gross weight 0.73%
26H
2a during O and 412.6g TBAH (TBABr) drop into
1, stir 12h and obtain solution A
1'; By 516.51g phosphoric acid (85wt.%), 10.1g white carbon black (SiO
2, 99wt.%) and 791.6g di-n-propylamine (DPA) input A
2in solution, stir 12h and obtain solution A
2'; By solution A
1' and solution A
2' be placed in respectively hydrothermal treatment consists 9h at 105 DEG C, afterwards by solution A
1' and solution A
2' evenly mix 120 DEG C of airtight stirring 3h; Stir the mixture above-mentioned, then be placed in 170 DEG C of crystallization 6d, product after filtration, wash rear 120 DEG C of dry 6h, be then warming up to 550 DEG C, constant temperature calcining 8h both product, be designated as ZS-5.
Table 1
[embodiment 6～15]
According to the method for embodiment 5, raw materials used as shown in table 2, control and react the different proportionings (table 3) of selecting materials, synthesize respectively ZSM-11/SAPO-11 binary structure zeolite, in material, the ratio of ZSM-11 and SAPO-11 is in table 4.
Table 2
Table 3
[embodiment 16]
The application of ZSM-11/SAPO-11 binary structure zeolite in methanol conversion hydrocarbon reaction processed
Get the synthetic ZS-1 molecular sieve of embodiment 1, carry out ammonium with 5wt% ammonium nitrate solution at 80 DEG C and exchange 3 hours.Product after filtration, washing, dry after 3 hours at 130 DEG C, then repeat an ammonium exchange, after filtration, dry after 3 hours at washing, 130 DEG C, at 550 DEG C, roasting 3 hours, makes Hydrogen coexisting molecular sieve, then compressing tablet, break into pieces, sieve, get 12～20 object particles for subsequent use, be designated as M
1.Taking methyl alcohol as raw material, be the fixed-bed reactor of 15 millimeters with diameter, at 450 DEG C, mass space velocity 1.5h
-1, check and rate under the pressure condition that is 0.02MPa, iso-butylene mass yield reaches 22.4%, aromatic hydrocarbons mass yield reaches 51.4%, in aromatic hydrocarbons, the selectivity of BTX, up to 60.6%, has obtained good technique effect.
Table 4
| Sample number into spectrum | ZSM-11 content (% by weight) | SAPO-11 content (% by weight) |
| ZS-6 | 65 | 35 |
| ZS-7 | 54 | 46 |
| ZS-8 | 31 | 69 |
| ZS-9 | 43 | 57 |
| ZS-10 | 30 | 70 |
| ZS-11 | 46 | 54 |
| ZS-12 | 59 | 41 |
| ZS-13 | 56 | 44 |
| ZS-14 | 68 | 32 |
| ZS-15 | 49 | 51 |
[embodiment 17]
Get the synthetic ZS-2 molecular sieve of embodiment 2, adopt the catalyzer side of the preparation method of embodiment 16 to make catalyzer, be designated as M
2.Taking methyl alcohol as raw material, be the fixed-bed reactor of 15 millimeters with diameter, at 400 DEG C, mass space velocity 2.5h
-1, check and rate under the pressure condition that is 1MPa, iso-butylene mass yield reaches 26.7%, aromatic hydrocarbons mass yield reaches 42.4%, in aromatic hydrocarbons, the selectivity of BTX reaches 52.1%.
[embodiment 18]
Get the synthetic ZS-3 molecular sieve of embodiment 3, adopt the catalyzer side of the preparation method of embodiment 16 to make catalyzer, be designated as M
3.Taking methyl alcohol as raw material, be the fixed-bed reactor of 15 millimeters with diameter, at 350 DEG C, mass space velocity 3.0h
-1, check and rate under the pressure condition that is 2MPa, iso-butylene mass yield reaches 24.2%, aromatic hydrocarbons mass yield reaches 38.4%, in aromatic hydrocarbons, the selectivity of BTX reaches 46.3%.
[embodiment 19]
Get the synthetic ZS-4 molecular sieve of embodiment 4, adopt the catalyzer side of the preparation method of embodiment 16 to make catalyzer, be designated as M
4.Taking methyl alcohol as raw material, be the fixed-bed reactor of 15 millimeters with diameter, at 500 DEG C, mass space velocity 0.5h
-1, check and rate under the pressure condition that is 4MPa, iso-butylene mass yield reaches 31.9%, aromatic hydrocarbons mass yield reaches 43.4%, in aromatic hydrocarbons, the selectivity of BTX reaches 38.1%.
[embodiment 20]
Get the synthetic ZS-5 molecular sieve of embodiment 5,, adopt the catalyzer side of the preparation method of embodiment 16 to make catalyzer, be designated as M
5.Taking methyl alcohol as raw material, be the fixed-bed reactor of 15 millimeters with diameter, at 500 DEG C, mass space velocity 5.0h
-1, check and rate under the pressure condition that is 1.5MPa, iso-butylene mass yield reaches 20.7%, aromatic hydrocarbons mass yield reaches 28.4%, in aromatic hydrocarbons, the selectivity of BTX reaches 32.8%.
[embodiment 21]
The acid of ZSM-11/SAPO-11 binary structure zeolite measures examination
Get the synthetic ZS-3 molecular sieve of embodiment 3, by the method for embodiment 16, make Hydrogen ZSM-11/SAPO-11 binary structure zeolite.Measure the desorption curve of ammonia with temperature programmed desorption(TPD) device, use desorption temperature strong, weak acid position to represent strength of acid.The ammonia that desorption goes out, after chromatogram, with excessive dilution heat of sulfuric acid absorption, then carries out back titration with standard solution of sodium hydroxide, calculates thus the acid amount of tested molecular sieve.Measurement result is as table 5.
[comparative example 1]
The β zeolite that the silica alumina ratio of getting the production of Shanghai Petroleum Chemical Engineering Institute is 39.9, measures its acidity by the method for embodiment 21, and result is as shown in table 5.
[comparative example 2]
The ZSM-5 molecular sieve that the silica alumina ratio of getting the production of Shanghai Petroleum Chemical Engineering Institute is 20.8, measures its acidity by the method for embodiment 21, and result is as shown in table 5.
[comparative example 3]
The mordenite molecular sieve that the silica alumina ratio of getting the production of Shanghai Petroleum Chemical Engineering Institute is 22.6, measures its acidity by the method for embodiment 21, and result is as shown in table 5.
Table 5
Claims (10)
1. a ZSM-11/SAPO-11 binary structure zeolite, it is characterized in that described ZSM-11/SAPO-11 binary structure zeolite has two kinds of thing phases of ZSM-11 and SAPO-11, its XRD diffracting spectrum is 7.85 ± 0.05 at 2 θ, 8.55 ± 0.1, 9.53 ± 0.02, 11.93 ± 0.1, 13.35 ± 0.1, 14.66 ± 0.05, 15.75 ± 0.1, 18.38 ± 0.1, 20.25 ± 0.05, 21.07 ± 0.1, 22.66 ± 0.1, 23.34 ± 0.1, 23.83 ± 0.1, 26.70 ± 0.02, 27.94 ± 0.1, 29.92 ± 0.05, 31.83 ± 0.1, 35.18 ± 0.1, 36.07 ± 0.05, 38.04 ± 0.1, there is diffraction peak in 45.11 ± 0.1 places.
2. ZSM-11/SAPO-11 binary structure zeolite according to claim 1, is characterized in that the weight percentage in ZSM-11/SAPO-11 binary structure zeolite, and in described binary structure zeolite, the weight percentage of ZSM-11 molecular sieve is 30 ~ 65%; The weight percentage of SAPO-11 is 35 ~ 70%.
3. the synthetic method of ZSM-11/SAPO-11 binary structure zeolite claimed in claim 1, comprises following several step:
A, taking raw materials used molar ratio as SiO
2/ Al
2o
3=5 ~ 5000, P
2o
5/ Al
2o
3=0.2 ~ 200, template T/Al
2o
3=1 ~ 500, solvent S/Al
2o
3=50 ~ 1000, a certain amount of aluminium source and solvent are formed to solution A, then solution A is divided into two parts is designated as solution A
1and solution A
2;
B, a part of silicon source, additive and the required organic formwork agent of preparation ZSM-11 are added to A
1in, stir 0.5 ~ 10 hour to obtain solution A
1';
C, phosphoric acid, remaining silicon source and the required organic formwork agent of synthetic SAPO-11 are added to A
2in solution, stir 0.5 ~ 10 hour, obtain solution A
2';
D, by solution A
1' and solution A
2' be placed in respectively at 80 ~ 120 DEG C hydrothermal treatment consists 12 ~ 48 hours, afterwards by solution A
1' and solution A
2' evenly mix, airtight stirring 0.5 ~ 24 hour, forms uniform crystallization mixture at 80 ~ 120 DEG C;
E, the crystallization mixture of above-mentioned steps d is placed in to 150 ~ 200 DEG C, crystallization 10 hours ~ 15 days, product after filtration, after washing 80 ~ 130 DEG C dry, be then warming up to 400 ~ 650 DEG C, constant temperature calcining 0.5 ~ 12 hour.
4. the synthetic method of ZSM-11/SAPO-11 binary structure zeolite according to claim 3, is characterized in that raw materials used molar ratio is: SiO
2/ Al
2o
3=10 ~ 1000, P
2o
5/ Al
2o
3=0.5 ~ 50, template T/Al
2o
3=10 ~ 100, solvent S/Al
2o
3=50 ~ 500.
5. the synthetic method of ZSM-11/SAPO-11 binary structure zeolite according to claim 3, is characterized in that solution A in step a
1and solution A
2weight ratio be 0.1 ~ 10:1; In step b, to account for total silicon source quality per-cent be 5 ~ 95% in silicon used source; In step c, to account for total silicon source quality per-cent be 5 ~ 95% in silicon used source.
6. the synthetic method of ZSM-11/SAPO-11 binary structure zeolite according to claim 3, aluminium source be selected from aluminate, meta-aluminate, aluminium salt, aluminium oxyhydroxide, aluminium oxide compound or containing at least one in the mineral of aluminium; Silicon source is selected from least one in organosilicon, soft silica, silicon sol, solid oxidation silicon, silica gel, diatomite or water glass; Additive is at least one in basic metal or alkaline-earth metal halogen compound.
7. the synthetic method of ZSM-11/SAPO-11 binary structure zeolite according to claim 3, it is characterized in that for the preparation of the required organic formwork agent of ZSM-11 be organic amine, be selected from least one in 4-propyl bromide, TPAOH, tetraethylammonium bromide, tetraethyl ammonium hydroxide, Tetrabutyl amonium bromide, TBAH, triethylamine, n-Butyl Amine 99, di-n-propylamine, Diisopropylamine, quadrol or ethamine; The required organic formwork agent of preparation SAPO-11 is organic amine, is selected from least one in 4-propyl bromide, TPAOH, tetraethylammonium bromide, tetraethyl ammonium hydroxide, Tetrabutyl amonium bromide, TBAH, triethylamine, n-Butyl Amine 99, di-n-propylamine, Diisopropylamine, quadrol or ethamine; Solvent is deionized water.
8. the synthetic method of ZSM-11/SAPO-11 binary structure zeolite according to claim 3, is characterized in that solution A in step a
1and solution A
2weight ratio be 0.2 ~ 5:1; In step b, to account for total silicon source quality per-cent be 15 ~ 85% in silicon used source; In step c, to account for total silicon source quality per-cent be 15 ~ 85% in silicon used source.
9. the synthetic method of ZSM-11/SAPO-11 binary structure zeolite according to claim 3, is characterized in that solution A in step a
1and solution A
2weight ratio be 0.3 ~ 3:1; In step b, to account for total silicon source quality per-cent be 25 ~ 75% in silicon used source; In step c, to account for total silicon source quality per-cent be 25 ~ 75% in silicon used source.
10. the reaction for Methanol hydro carbons as catalyzer of the ZSM-11/SAPO-11 binary structure zeolite described in claim 1 or 2.
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