CN104108727B - ZSM-11/SAPO-11 binary structure zeolite and synthetic method thereof - Google Patents
ZSM-11/SAPO-11 binary structure zeolite and synthetic method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of ZSM-11/SAPO-11 binary structure zeolite and synthetic method thereof, the structure mainly solving prior art Middle molecule sieve porous material is single, strong and weak acid site total amount is less, the technical problem that catalytic activity is not high, the present invention is by adopting a kind of ZSM-11/SAPO-11 binary structure zeolite, it is characterized in that described ZSM-11/SAPO-11 binary structure zeolite has ZSM-11 and SAPO-11 two kinds of thing phases, 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 the technical scheme of diffraction peak in 45.11 ± 0.1 places, solve the problems referred to above preferably, this binary structure zeolite can be used in the industrial production of Downstream Products of Methanol.
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, according to the world is pure and the definition of applied chemistry federation (IUPAC), porous material can be divided three classes by their bore dia: the material that aperture is less than 2nm is poromerics (microporematerials); The material of aperture between 2 to 50nm is mesoporous material (mesoporematerials); The material that aperture is greater than 50nm is large pore material (macroporematerials), 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 connected and composed 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 the lab, after this enter in more than ten years, the people such as Milton, Breck and Sand adopt hydrothermal technique in aluminosilicate gels, 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 introducing of organic base cation, a series of brand new zeolite molecular sieve is produced out, as ZSM-n series (ZSM-1, ZSM-5, ZSM-11, ZSM-22, ZSM-48 etc.) zeolite molecular sieve, this kind of molecular sieve has the advantages such as good catalytic activity, hydrothermal stability and higher erosion resistance, and be widely used in the field such as refining of petroleum, fine chemistry industry, be the focus that people study for many years always.In numerous ZSM-n Series Molecules sieve, ZSM-5 is most widely used, it is the zeolite molecular sieve of Pentasil type two-dimensional channel 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, and being all Pentasil type zeolite, to form by oval ten-ring two-dimensional direct duct (0.51nm × 0.55nm) intersecting the attention rate that ZSM-11 molecular sieve obtains less.
Patent CN101348261A, B report a kind of synthetic method of binderless ZSM-5-11 molecular sieve, and sial raw material conveniently can be simply converted into binderless ZSM-5-11 molecular sieve by the method.
Patent 201010536158.2, using EU-1 molecular sieve as crystal seed, reports a kind of preparation method of short period of time crystallization ZSM-5-11.
Patent 200810060621.2 utilizes microwave method can obtain the higher ZSM-11 molecular sieve of degree of crystallinity in the short period of time.
SAPO-11 is as developing silicon aluminium phosphate Series Molecules sieve (SAPO-n 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 is formed by SiO after replacing P or the Al atom in former AlPO
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 pair of aluminum atom and phosphorus atom respectively.
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, aforesaid method has and not easily repeats, and forms the application that the shortcomings such as Si district is more are unfavorable for SAPO-11.
Chinese patent 00129373.7,200910081007.0 reports and use Organic Alcohol in reactant, can prepare small particle size, SAPO-11 molecular sieve that cleanliness factor is high.
Up to now, about the document of ZSM-11/SAPO-11 binary structure zeolite and its synthetic method, there is not been reported.
Summary of the invention
One of technical problem to be solved by this invention is the technical problem that the structure of molecular sieve porous material single, strong and weak acid site total amount is less, catalytic activity is not high, a kind of ZSM-11/SAPO-11 binary structure zeolite is provided, this molecular sieve 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 not relating to above-mentioned ZSM-11/SAPO-11 binary structure zeolite synthetic method in prior art, provides a kind of preparation method of new ZSM-11/SAPO-11 binary structure zeolite.
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 ZSM-11 and SAPO-11 two kinds of thing phases, 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 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, with raw materials used molar ratio be: 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 solution A, then solution A is divided into two parts and is designated as solution A
1and solution A
2;
B, organic formwork agent needed for a part of silicon source, additive and preparation ZSM-11 is added A
1in, stir 0.5 ~ 10 hour to obtain solution A
1';
C, by phosphoric acid, remaining silicon source and synthesis SAPO-11 needed for organic formwork agent add A
2in solution, stir 0.5 ~ 10 hour, obtain solution A
2';
D, by solution A
1' and solution A
2' be placed in 80 ~ 120 DEG C respectively at hydrothermal treatment consists 12 ~ 48 hours, afterwards by solution A
1' and solution A
2' Homogeneous phase mixing, at 80 ~ 120 DEG C, airtight stirring 0.5 ~ 24 hour, forms uniform crystallization mixture;
E, the crystallization mixture of above-mentioned steps d is placed in 150 ~ 200 DEG C of crystallization 10 hours ~ 15 days, product after filtration, 80 ~ 130 DEG C of dryings after washing, 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, at least one that aluminium source used is selected from aluminate, meta-aluminate, aluminium salt, the oxyhydroxide of aluminium, the oxide compound of aluminium or contains in the mineral of aluminium; Silicon source used 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 organic formwork agent of preparation needed for 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 organic formwork agent of preparation needed for 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, silicon source used accounts for total silicon source quality per-cent is 15 ~ 85%; In step c, silicon source used accounts for total silicon source quality per-cent is 15 ~ 85%.
Preferred technical scheme, at least one that aluminium source is selected from aluminate, meta-aluminate, aluminium salt, the oxyhydroxide of aluminium, the oxide compound of aluminium or contains 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, be organic amine for the preparation of the organic formwork agent needed for ZSM-11, 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; Preferred technical scheme, the organic formwork agent of preparation needed for SAPO-11 is organic amine, and at least one solvent be 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, silicon source used accounts for total silicon source quality per-cent is 25 ~ 75%; In step c, silicon source used accounts for total silicon source quality per-cent is 25 ~ 75%, 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 as catalyzer, for the catalyzed reaction of 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 binary structure zeolite with optimum pore passage structure and suitable acidity is obtained by the optimising and adjustment synthesis condition two-phase proportion changed in composite molecular screen, for the reaction process of methanol conversion hydrocarbon, 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, achieves good technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
The synthesis 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 be divided into two parts by mass fraction and be respectively 70% and 30%, be designated as solution A
1and solution A
2, by 1425.6g acidic silicasol (40wt.%), account for reaction mass gross weight 3.2% NaCl and 51.92g TBAH (TBAOH, 50wt%) drop in A
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 90 DEG C respectively at hydrothermal treatment consists 18h, afterwards by solution A
1' and solution A
2' Homogeneous phase mixing, 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]
The synthesis 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 be divided into two parts by mass fraction and be respectively 60% and 40%, be designated as solution A
1and solution A
2, by 51.6g acidic silicasol (40wt.%), NaCl and MgCl accounting for reaction mass gross weight 2.7%
26H
2a during O and 249.2g TBAH (TBAOH, 50wt%) drops 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 80 DEG C respectively at hydrothermal treatment consists 24h, afterwards by solution A
1' and solution A
2' Homogeneous phase mixing, 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]
The synthesis of ZSM-11/SAPO-11 binary structure zeolite
By the aluminum nitrate [Al (NO of 187.7g
3)
39H
2o] be dissolved in 3280.43mL water, be mixed and made into solution A, afterwards this solution be divided into two parts by mass fraction and be respectively 50% and 50%, be designated as solution A
1and solution A
2, by 53.03g acidic silicasol (40wt.%), KCl and CaCl accounting for reaction mass gross weight 3.5%
22H
2a during O and 524.35g TBAH (TBAOH, 50wt%) drops 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 120 DEG C respectively at hydrothermal treatment consists 0.5h, afterwards by solution A
1' and solution A
2' Homogeneous phase mixing, 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]
The synthesis of ZSM-11/SAPO-11 binary structure zeolite
By the aluminum nitrate [Al (NO of 285.23g
3)
39H
2o] be dissolved in 4713.25mL water, be mixed and made into solution A, afterwards this solution be divided into two parts by mass fraction and be respectively 45% and 55%, be designated as solution A
1and solution A
2, by 1162.81g acidic silicasol (40wt.%), NaCl and CaCl accounting for reaction mass gross weight 1.5%
22H
2a during O and 1245.8g TBAH (TBAOH, 50wt%) drops 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 105 DEG C respectively at hydrothermal treatment consists 6h, afterwards by solution A
1' and solution A
2' Homogeneous phase mixing, 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]
The synthesis 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 be divided into two parts by mass fraction and be 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 MgCl of reaction mass gross weight 0.73%
26H
2a during O and 412.6g TBAH (TBABr) drops 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) drop into A
2in solution, stir 12h and obtain solution A
2'; By solution A
1' and solution A
2' be placed in 105 DEG C respectively at hydrothermal treatment consists 9h, afterwards by solution A
1' and solution A
2' Homogeneous phase mixing, 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 reaction and to select materials different ratio (table 3), synthesize ZSM-11/SAPO-11 binary structure zeolite respectively, 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
The ZS-1 molecular sieve that Example 1 synthesizes, carries out ammonium with 5wt% ammonium nitrate solution at 80 DEG C and exchanges 3 hours.Product after filtration, washing, at 130 DEG C after dry 3 hours, then repeat an ammonium and exchange, after filtration, washing, at 130 DEG C after dry 3 hours, roasting 3 hours at 550 DEG C, obtained 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, is the fixed-bed reactor of 15 millimeters with diameter, at 450 DEG C, mass space velocity 1.5h
-1, pressure is check and rate under the condition of 0.02MPa, iso-butylene mass yield reaches 22.4%, and aromatics quality yield reaches 51.4%, and in aromatic hydrocarbons, the selectivity of BTX is up to 60.6%, achieves 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]
The ZS-2 molecular sieve of the 2-in-1 one-tenth of Example, adopts catalyst preparing side's method of embodiment 16 to obtain catalyzer, is designated as M
2.Taking methyl alcohol as raw material, is the fixed-bed reactor of 15 millimeters with diameter, at 400 DEG C, mass space velocity 2.5h
-1, pressure is check and rate under the condition of 1MPa, iso-butylene mass yield reaches 26.7%, and aromatics quality yield reaches 42.4%, and in aromatic hydrocarbons, the selectivity of BTX reaches 52.1%.
[embodiment 18]
The ZS-3 molecular sieve that Example 3 synthesizes, adopts catalyst preparing side's method of embodiment 16 to obtain catalyzer, is designated as M
3.Taking methyl alcohol as raw material, is the fixed-bed reactor of 15 millimeters with diameter, at 350 DEG C, mass space velocity 3.0h
-1, pressure is check and rate under the condition of 2MPa, iso-butylene mass yield reaches 24.2%, and aromatics quality yield reaches 38.4%, and in aromatic hydrocarbons, the selectivity of BTX reaches 46.3%.
[embodiment 19]
The ZS-4 molecular sieve that Example 4 synthesizes, adopts catalyst preparing side's method of embodiment 16 to obtain catalyzer, is designated as M
4.Taking methyl alcohol as raw material, is the fixed-bed reactor of 15 millimeters with diameter, at 500 DEG C, mass space velocity 0.5h
-1, pressure is check and rate under the condition of 4MPa, iso-butylene mass yield reaches 31.9%, and aromatics quality yield reaches 43.4%, and in aromatic hydrocarbons, the selectivity of BTX reaches 38.1%.
[embodiment 20]
The ZS-5 molecular sieve that Example 5 synthesizes, adopt catalyst preparing side's method of embodiment 16 to obtain catalyzer, be designated as M
5.Taking methyl alcohol as raw material, is the fixed-bed reactor of 15 millimeters with diameter, at 500 DEG C, mass space velocity 5.0h
-1, pressure is check and rate under the condition of 1.5MPa, iso-butylene mass yield reaches 20.7%, and aromatics quality yield reaches 28.4%, and in aromatic hydrocarbons, the selectivity of BTX reaches 32.8%.
[embodiment 21]
The acid of ZSM-11/SAPO-11 binary structure zeolite measures examination
The ZS-3 molecular sieve that Example 3 synthesizes, by the method for embodiment 16, obtained Hydrogen ZSM-11/SAPO-11 binary structure zeolite.Measure the desorption curve of ammonia with temperature programmed desorption(TPD) device, represent strength of acid with desorption temperature that is strong, weak acid position.The ammonia that desorption goes out, after chromatogram, absorbs with excessive dilution heat of sulfuric acid, then carries out back titration with standard solution of sodium hydroxide, calculate the acid amount of tested molecular sieve thus.Measurement result is as table 5.
[comparative example 1]
The silica alumina ratio getting the production of Shanghai Petroleum Chemical Engineering Institute is the β zeolite of 39.9, and measure its acidity by the method for embodiment 21, result is as shown in table 5.
[comparative example 2]
The silica alumina ratio getting the production of Shanghai Petroleum Chemical Engineering Institute is the ZSM-5 molecular sieve of 20.8, and measure its acidity by the method for embodiment 21, result is as shown in table 5.
[comparative example 3]
The silica alumina ratio getting the production of Shanghai Petroleum Chemical Engineering Institute is the mordenite molecular sieve of 22.6, and measure its acidity by the method for embodiment 21, result is as shown in table 5.
Table 5
Claims (9)
1. a ZSM-11/SAPO-11 binary structure zeolite, it is characterized in that described ZSM-11/SAPO-11 binary structure zeolite has ZSM-11 and SAPO-11 two kinds of thing phases, 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,
Wherein, 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%.
2. the synthetic method of ZSM-11/SAPO-11 binary structure zeolite according to claim 1, comprises following several step:
A, with raw materials used molar ratio be: 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 solution A, then solution A is divided into two parts and is designated as solution A
1and solution A
2;
B, organic formwork agent needed for a part of silicon source, additive and preparation ZSM-11 is added A
1in, stir 0.5 ~ 10 hour to obtain solution A
1'; Described additive is at least one in basic metal or alkaline-earth metal halogen compound;
C, by phosphoric acid, remaining silicon source and synthesis SAPO-11 needed for organic formwork agent add A
2in solution, stir 0.5 ~ 10 hour, obtain solution A
2';
D, by solution A
1' and solution A
2' be placed in 80 ~ 120 DEG C respectively at hydrothermal treatment consists 12 ~ 48 hours, afterwards by solution A
1' and solution A
2' Homogeneous phase mixing, at 80 ~ 120 DEG C, airtight stirring 0.5 ~ 24 hour, forms uniform crystallization mixture;
E, the crystallization mixture of above-mentioned steps d is placed in 150 ~ 200 DEG C, crystallization 10 hours ~ 15 days, product after filtration, 80 ~ 130 DEG C of dryings after washing, be then warming up to 400 ~ 650 DEG C, constant temperature calcining 0.5 ~ 12 hour.
3. the synthetic method of ZSM-11/SAPO-11 binary structure zeolite according to claim 2, 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.
4. the synthetic method of ZSM-11/SAPO-11 binary structure zeolite according to claim 2, is characterized in that solution A in step a
1and solution A
2weight ratio be 0.1 ~ 10:1; In step b, silicon source used accounts for total silicon source quality per-cent is 5 ~ 95%; In step c, silicon source used accounts for total silicon source quality per-cent is 5 ~ 95%.
5. the synthetic method of ZSM-11/SAPO-11 binary structure zeolite according to claim 2, aluminium source is selected from aluminate, meta-aluminate, the oxyhydroxide of aluminium, the oxide compound of aluminium 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.
6. the synthetic method of ZSM-11/SAPO-11 binary structure zeolite according to claim 2, it is characterized in that for the preparation of the organic formwork agent needed for 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 organic formwork agent of preparation needed for 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.
7. the synthetic method of ZSM-11/SAPO-11 binary structure zeolite according to claim 2, is characterized in that solution A in step a
1and solution A
2weight ratio be 0.2 ~ 5:1; In step b, silicon source used accounts for total silicon source quality per-cent is 15 ~ 85%; In step c, silicon source used accounts for total silicon source quality per-cent is 15 ~ 85%.
8. the synthetic method of ZSM-11/SAPO-11 binary structure zeolite according to claim 2, is characterized in that solution A in step a
1and solution A
2weight ratio be 0.3 ~ 3:1; In step b, silicon source used accounts for total silicon source quality per-cent is 25 ~ 75%; In step c, silicon source used accounts for total silicon source quality per-cent is 25 ~ 75%.
9. ZSM-11/SAPO-11 binary structure zeolite according to claim 1 is used in the reaction of Methanol hydro carbons as catalyzer.
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