CN116002710A - SAPO-35/SAPO-5 intergrowth molecular sieve, preparation method and application thereof, and molecular sieve composition and application thereof - Google Patents
SAPO-35/SAPO-5 intergrowth molecular sieve, preparation method and application thereof, and molecular sieve composition and application thereof Download PDFInfo
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 216
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 213
- 239000000203 mixture Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 47
- JAJRRCSBKZOLPA-UHFFFAOYSA-M triethyl(methyl)azanium;hydroxide Chemical group [OH-].CC[N+](C)(CC)CC JAJRRCSBKZOLPA-UHFFFAOYSA-M 0.000 claims abstract description 40
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 34
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 33
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 26
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 238000003776 cleavage reaction Methods 0.000 claims abstract description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 78
- 238000002441 X-ray diffraction Methods 0.000 claims description 41
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 37
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 37
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 34
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000010703 silicon Substances 0.000 claims description 27
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 26
- 238000002425 crystallisation Methods 0.000 claims description 26
- 230000008025 crystallization Effects 0.000 claims description 26
- 239000011574 phosphorus Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000011148 porous material Substances 0.000 claims description 22
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 18
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- -1 aluminum alkoxide Chemical class 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000523 sample Substances 0.000 description 55
- 238000001228 spectrum Methods 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 238000009616 inductively coupled plasma Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 229910001220 stainless steel Inorganic materials 0.000 description 11
- 239000010935 stainless steel Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005336 cracking Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 241000269350 Anura Species 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910017119 AlPO Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 229940001007 aluminium phosphate Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000538 analytical sample Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
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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
- 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
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention belongs to the field of molecular sieves, and particularly discloses a SAPO-35/SAPO-5 intergrowth molecular sieve, a preparation method and application thereof, and a molecular sieve composition and application thereof. The SAPO-35/SAPO-5 (LEV/AFI) intergrowth molecular sieve has the following anhydrous chemical composition: (Al) x P y Si z )O 2 mR, wherein R is methyltriethylammonium hydroxide, x, y and z represent the mole fraction of the sum of the mole numbers of Al, P and Si, respectively, x=0.35 to 0.55, y=0.30 to 0.55, z=0.005 to 0.15, x+y+z=1, m is the mole fraction of R,m=0.005-0.05, the peak intensity of the characteristic peak belonging to the SAPO-5 (AFI) structure in the SAPO-35/SAPO-5 intergrowth molecular sieve is higher than the peak intensity of the characteristic peak belonging to the SAPO-35 (LEV) structure, the SAPO-5 molecular sieve accounts for 55-90% of the SAPO-35/SAPO-5 intergrowth molecular sieve, and the specific surface area of the intergrowth molecular sieve after calcination is 300-450 m 2 Per gram, the acid amount is 200-1000 mu mol/g. The molecular sieve of the invention is used for the cumene cleavage reaction. Has the advantages of high activity and high benzene selectivity.
Description
Technical Field
The invention relates to a SAPO-35/SAPO-5 intergrowth molecular sieve, a preparation method and application thereof, and a molecular sieve composition and application thereof.
Background
The aluminium phosphate molecular sieve (AlPO series molecular sieve) is a molecular sieve with skeleton formed by alternately connecting phosphorus-oxygen tetrahedron and aluminium-oxygen tetrahedron, and has no cation exchange performance and catalytic reaction performance because the molecular sieve skeleton is electrically neutral. Silicon is introduced into the framework of the aluminum phosphate molecular sieve, namely the SAPO series molecular sieve (US 4440871), the framework is negatively charged, and balance cations exist outside the framework, so that the aluminum phosphate molecular sieve has cation exchange performance and catalytic reaction performance. At present, SAPO series molecular sieves are widely applied in the fields of oil refining, petrochemical industry and the like, such as catalytic cracking, hydrocracking, isomerization, aromatic hydrocarbon alkylation and the like.
The topology structure of the SAPO-35 is a levant chabazite type (LEV), the space group is R-3m, the molecular sieve has eight-membered ring pore channels which are mutually intersected, the pore diameter is 0.36 multiplied by 0.48nm, the framework of the molecular sieve is formed by connecting LEV cages through single six-membered rings and double six-membered rings, and the pore channels have large micropore volume due to dodecahedral pores. The molecular sieve framework has two different T atom positions, one in the double six-membered ring and the other in the single six-membered ring, and the distribution ratio of the two positions is 2:1. The SAPO-35 molecular sieve is generally synthesized by adopting a hydrothermal or alcohol-thermal method and taking water or alcohol as a solvent, and a mixture consisting of an aluminum source, a silicon source, a phosphorus source, an organic structure directing agent and deionized water is synthesized in a reaction kettle under the self pressure. The choice of organic structure directing agent has a certain influence on the microstructure, elemental composition and morphology of the synthesized molecular sieve, and thus the catalytic performance thereof. The topology structure of the SAPO-5 molecular sieve is an AFI type, the framework structure of the SAPO-5 molecular sieve is a twelve-membered ring one-dimensional pore canal system formed by alternating two four-membered rings and six-membered rings, the aperture is 0.80nm, and the SAPO-5 molecular sieve belongs to a macroporous molecular sieve. Has unique catalytic performance and better catalytic performance in reactions such as m-xylene isomerization, n-hexane catalytic cracking and the like.
The molecular sieves of the LEV topological structure and the AFI topological structure have two pore diameter structural systems with different sizes, and the symbiotic composition of the two molecular sieves can influence the element distribution in pore channels of the molecular sieves.
CN103706394a discloses a submicron SAPO-5/SAPO-18 composite molecular sieve and a preparation method thereof, wherein only one type of medium strong acid center exists in the SAPO-5 molecular sieve with an AFI type structure, and the center of the L acid is most. SAPO-35 molecular sieves with LEV topology have strong and weak acids, so intergrowth molecular sieves with LEV topology and AFI topology can complement each other in acidity, possibly contributing to the performance of the catalyst.
Disclosure of Invention
The technical problem to be solved by the invention is to provide the SAPO-35/SAPO-5 intergrowth molecular sieve with adjustable composition proportion, adjustable specific surface area, adjustable micropore volume and adjustable acid quantity, and a preparation method of the SAPO-35/SAPO-5 intergrowth molecular sieve, which is simple and feasible to operate.
According to a first aspect of the present invention, there is provided a SAPO-35/SAPO-5 intergrowth molecular sieve,
the SAPO-35/SAPO-5 intergrowth molecular sieve has the following anhydrous chemical composition: (Al) x P y Si z )O 2 mR, wherein R is methyltriethylammonium hydroxide, x, y and z represent the mole fraction of the sum of the mole numbers of Al, P and Si, respectively, x=0.35 to 0.55, y=0.30 to 0.55, z=0.005 to 0.15, x+y+z=1, m is the mole fraction of R, m=0.005 to 0.05;
preferably, the SAPO-35/SAPO-5 intergrowth molecular sieve has an X-ray diffraction pattern including an AFI structure belonging to the SAPO-5 molecular sieve and an LEV structure belonging to the SAPO-35 molecular sieve as shown in the following table;
a: + -0.30 °, b: as a function of 2 theta.
In the present invention, vw, w, m, s, vs represents diffraction peak intensity, vw is very weak, w is weak, m is medium, s is strong, vs is very strong; generally, vw is less than 5%, w is 5% to 20%, m is 20% to 40% (20%, 40%) s is 40% to 70%, vs is greater than 70% (70%).
The data in the above tables are expressed as SAPO-35/SAPO-5 intergrowth molecular sieve at 2 theta (°) (a) At 7.40 d-spacing
11.941, relative intensity (I/I 0 X 100) is m-vs (medium strength) and the representation of the table is well known to those skilled in the art and the invention is not described here.
The SAPO-35/SAPO-5 intergrowth molecular sieve has unique chemical composition, adjustable composition proportion and adjustable acid amount, and has good industrial application prospect.
According to a preferred embodiment of the invention, x=0.38 to 0.52, y=0.38 to 0.52, z=0.01 to 0.15, x+y+z=1, m=0.01 to 0.05. The SAPO-35/SAPO-5 intergrowth molecular sieve has adjustable composition proportion and has better industrial application prospect.
According to a preferred embodiment of the present invention, the peak intensity of the characteristic peak belonging to the AFI structure of the SAPO-5 molecular sieve in the SAPO-35/SAPO-5 intergrowth molecular sieve is higher than the peak intensity of the characteristic peak belonging to the LEV structure of the SAPO-35 molecular sieve.
According to a preferred embodiment of the present invention, it is preferred that the SAPO-5 molecular sieve comprises 55 to 90 weight percent of the SAPO-35/SAPO-5 intergrowth molecular sieve. The SAPO-35/SAPO-5 intergrowth molecular sieve provided by the invention has an adjustable ratio of the SAPO-5 molecular sieve in the SAPO-35/SAPO-5 intergrowth molecular sieve, and has a better industrial application prospect.
The SAPO-35/SAPO-5 intergrowth molecular sieve with the structure and the composition of the invention can achieve the purposes of the invention, and has no special requirements on the preparation method, and according to a preferred embodiment of the invention, the invention provides a preparation method of the SAPO-35/SAPO-5 intergrowth molecular sieve, which comprises the following steps:
heating and crystallizing a mixture containing an aluminum source, a phosphorus source, a silicon source, methyl triethyl ammonium hydroxide and water, and performing post-treatment to obtain the SAPO-35/SAPO-5 intergrowth molecular sieve;
wherein the aluminum source is Al 2 O 3 Counting the phosphorus source by P 2 O 5 Meter, silicon source with SiO 2 Calculated by the mole ratio of the methyl triethyl ammonium hydroxide R and water, is Al 2 O 3 ：P 2 O 5 ：SiO 2 ：R：H 2 O＝1：0.65～1.40：0.02～0.65：0.60～1.45：28～100。
The invention provides a preparation method of an SAPO-35/SAPO-5 intergrowth molecular sieve, which is simple and feasible to operate, uses cheaper methyltriethylammonium hydroxide as an organic structure directing agent, and ensures that crystallization liquid is nearly neutral and post-treatment is simpler and more environment-friendly.
The crystallization can be carried out under near neutral conditions, and the pH value of the mixture is 5.5-8.0.
In the invention, the crystallization condition of the mixture is not particularly required, and conventional crystallization conditions can be used in the invention. According to a preferred embodiment of the invention, the crystallization conditions of the mixture comprise crystallization at 150 to 205 ℃ for 0.5 to 7 days, preferably at 155 to 200 ℃ for 0.5 to 6 days, more preferably at 160 to 195 ℃ for 0.75 to 5 days.
The process of the present invention may be carried out under non-seeded conditions, and for the present invention it is preferred that the mixture is free of seeds.
In the invention, the optional range of the usage amount of each substance is wider, and the usage amount can be adjusted according to the needs, according to the preferred embodiment of the invention, the aluminum source is made of Al 2 O 3 Counting the phosphorus source by P 2 O 5 Meter, silicon source with SiO 2 Calculated by the mole ratio of the methyl triethyl ammonium hydroxide R and water, is Al 2 O 3 ：P 2 O 5 ：SiO 2 ：R：H 2 O＝1：0.70～1.40：0.04～0.60：0.65～1.40：30～90。
In the invention, the optional types of the aluminum source, the phosphorus source and the silicon source have no special requirements, and common types can be used for the invention.
According to a preferred embodiment of the present invention, the aluminum source is at least one selected from the group consisting of pseudo-boehmite, aluminum alkoxide, aluminum salt, aluminum oxide and aluminum hydroxide, preferably pseudo-boehmite.
According to a preferred embodiment of the invention, the phosphorus source is selected from at least one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and organic phosphorus compounds, preferably phosphoric acid.
According to a preferred embodiment of the present invention, the silicon source is selected from at least one of silica sol, silica gel and ethyl orthosilicate, preferably silica sol.
In the present invention, the preparation method is post-treated after the crystallization step is completed, and the SAPO-35/SAPO-5 intergrowth molecular sieve can be separated from the obtained mixture by any post-treatment means conventionally known. Examples of the post-treatment method include a method of separating, filtering, washing, and drying a mixture obtained after the crystallization step is completed. Here, the filtering, washing and drying may be performed in any manner conventionally known in the art. As a specific example, as the filtration, for example, the obtained product mixture may be simply suction-filtered. The washing may be performed, for example, by washing with deionized water and/or ethanol 2 to 3 times. The drying temperature may be, for example, 40 to 110 ℃, and the drying time may be, for example, 4 to 24 hours. The drying may be performed under normal pressure or under reduced pressure.
According to the present invention, the molecular sieve prepared according to the foregoing method may also be calcined to remove the organic structure directing agent and moisture, if any, and the like. The calcination may be carried out in any manner conventionally known in the art, such as a calcination temperature of generally 300 to 800 ℃, preferably 400 to 650 ℃, and a calcination time of generally 1 to 10 hours, preferably 3 to 6 hours. In addition, the calcination is typically performed under an oxygen-containing atmosphere, such as air or an oxygen atmosphere.
The invention provides the SAPO-35/SAPO-5 intergrowth molecular sieve prepared by the preparation method.
As previously described, according to a preferred embodiment of the present invention, the SAPO-35/SAPO-5 intergrown molecular sieve has the following anhydrous chemical composition: (Al) x P y Si z )O 2 mR, wherein R is methyltriethylammonium hydroxide, x, y and z represent the mole fraction of the sum of the mole numbers of Al, P and Si, respectively, x=0.35 to 0.55, y=0.30 to 0.55, z=0.005 to 0.15, x+y+z=1, m is the mole fraction of R, m=0.005 to 0.05;
the SAPO-35/SAPO-5 intergrowth molecular sieve has an X-ray diffraction pattern comprising an AFI structure belonging to the SAPO-5 molecular sieve and an LEV structure belonging to the SAPO-35 molecular sieve as shown in the following table;
a: + -0.30 °, b: as a function of 2 theta.
According to a preferred embodiment of the invention, x=0.38 to 0.52, y=0.38 to 0.52, z=0.01 to 0.15, x+y+z=1, m=0.01 to 0.05.
According to a preferred embodiment of the present invention, the peak intensity of the characteristic peak belonging to the AFI structure of the SAPO-5 molecular sieve in the SAPO-35/SAPO-5 intergrowth molecular sieve is higher than the peak intensity of the characteristic peak belonging to the LEV structure of the SAPO-35 molecular sieve, and preferably the SAPO-5 molecular sieve accounts for 55 to 90 wt% of the SAPO-35/SAPO-5 intergrowth molecular sieve.
According to a preferred embodiment of the invention, after calcination at 300 to 800 ℃, preferably 400 to 650 ℃, for 1 to 10 hours, preferably 3 to 6 hours: the specific surface area of the SAPO-35/SAPO-5 intergrowth molecular sieve is 300-450 m 2 /g。
According to a preferred embodiment of the invention, after calcination at 300 to 800 ℃, preferably 400 to 650 ℃, for 1 to 10 hours, preferably 3 to 6 hours: the total pore volume of the SAPO-35/SAPO-5 intergrowth molecular sieve is 0.20-0.50 cm 3 Preferably 0.20 to 0.45cm per gram 3 /g。
According to a preferred embodiment of the invention, after calcination at 300 to 800 ℃, preferably 400 to 650 ℃, for 1 to 10 hours, preferably 3 to 6 hours: the micropore volume of the SAPO-35/SAPO-5 intergrowth molecular sieve is 0.10-0.25 cm 3 Preferably 0.11 to 0.20cm per gram 3 /g。
According to a preferred embodiment of the invention, after calcination at 300 to 800 ℃, preferably 400 to 650 ℃, for 1 to 10 hours, preferably 3 to 6 hours: the acid amount of the SAPO-35/SAPO-5 intergrowth molecular sieve is 200-1000 mu mol/g, and preferably 300-900 mu mol/g.
The molecular sieve of the invention can be used alone or mixed with a binder or molded, and therefore, the invention provides a molecular sieve composition comprising the SAPO-35/SAPO-5 intergrowth molecular sieve of the invention and the binder.
The invention provides an application of the SAPO-35/SAPO-5 intergrowth molecular sieve or the molecular sieve composition as a catalyst in organic matter conversion reaction, preferably in cracking reaction, and particularly preferably in benzene preparation by cumene cracking reaction.
The molecular sieve of the invention is particularly suitable for application in organic matter conversion, for example in cumene cleavage reactions. Has the advantages of high activity and high benzene selectivity.
The invention provides an SAPO-35/SAPO-5 intergrowth molecular sieve, which has unique chemical composition, adjustable composition ratio of the two molecular sieves, adjustable acid amount and better industrial application prospect. The preparation method of the SAPO-35/SAPO-5 intergrowth molecular sieve is simple and feasible to operate, uses relatively low-cost methyltriethylammonium hydroxide as an organic structure directing agent, and the crystallization liquid is nearly neutral, and is relatively simple and environment-friendly in post-treatment.
Drawings
FIG. 1 is an X-ray diffraction pattern of the molecular sieve obtained in example 1;
FIG. 2 is an X-ray diffraction pattern of the molecular sieve obtained in example 2;
FIG. 3 is an X-ray diffraction pattern of the molecular sieve obtained in example 3;
FIG. 4 is an X-ray diffraction pattern of the molecular sieve obtained in example 4.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The following detailed description of embodiments of the invention is provided, but it should be noted that the scope of the invention is not limited by these embodiments, but is defined by the appended claims.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the meaning commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, definitions, will control.
When the specification derives materials, substances, methods, steps, devices, or elements and the like in the word "known to those skilled in the art", "prior art", or the like, such derived objects encompass those conventionally used in the art at the time of the application, but also include those which are not currently commonly used but which would become known in the art to be suitable for similar purposes.
According to a preferred embodiment of the present invention, the present invention provides a SAPO-35/SAPO-5 (LEV/AFI) intergrown molecular sieve having the following anhydrous chemical composition: (Al) x P y Si z )O 2 mR, wherein R is methyltriethylammonium hydroxide, x, y and z represent the mole fraction of the sum of the mole numbers of Al, P and Si, respectively, x=0.35 to 0.55, y=0.30 to 0.55, z=0.005 to 0.15, x+y+z=1, m is the mole fraction of R, m=0.005 to 0.05.
According to a preferred embodiment of the invention, in the chemical composition x=0.38 to 0.52, y=0.38 to 0.52, z=0.01 to 0.15, x+y+z=1, m=0.01 to 0.05.
According to a preferred embodiment of the present invention, the molecular sieve has an X-ray diffraction pattern comprising a structure belonging to the SAPO-5 molecular sieve (AFI) structure as shown in the following table,
a: + -0.30 °, b: as a function of 2 theta.
According to a preferred embodiment of the present invention, the molecular sieve has an X-ray diffraction pattern comprising a structure belonging to the SAPO-35 molecular sieve (LEV) structure as shown in the following table,
a: + -0.30 °, b: as a function of 2 theta.
According to a preferred embodiment of the present invention, the peak intensity of the characteristic peak belonging to the SAPO-5 (AFI) structure in the SAPO-35/SAPO-5 intergrowth molecular sieve is higher than the peak intensity of the characteristic peak belonging to the SAPO-35 (LEV) structure, and the SAPO-5 molecular sieve accounts for 55 to 90% of the SAPO-35/SAPO-5 intergrowth molecular sieve.
According to a preferred embodiment of the invention, after calcination at 300 to 800 ℃, preferably 400 to 650 ℃, for 1 to 10 hours, preferably 3 to 6 hours: the specific surface area of the SAPO-35/SAPO-5 intergrowth molecular sieve is 300-450 m 2 Per gram, the total pore volume is 0.20-0.50 cm 3 Preferably 0.20 to 0.45cm per gram 3 Per gram, the micropore volume is 0.10-0.25 cm 3 Preferably 0.11 to 0.20cm per gram 3 /g。
According to a preferred embodiment of the invention, after calcination at 300 to 800 ℃, preferably 400 to 650 ℃, for 1 to 10 hours, preferably 3 to 6 hours: the acid amount of the SAPO-35/SAPO-5 intergrowth molecular sieve is 200-1000 mu mol/g, and preferably 300-900 mu mol/g.
According to a preferred embodiment of the invention, the invention provides a preparation method of an SAPO-35/SAPO-5 intergrowth molecular sieve, comprising the following steps:
carrying out one-step heating crystallization treatment on a mixture formed by an aluminum source, a phosphorus source, a silicon source, methyl triethyl ammonium hydroxide and water, and carrying out post-treatment to obtain the SAPO-35/SAPO-5 intergrowth molecular sieve;
according to a preferred embodiment of the present invention, the aluminum source is made of Al 2 O 3 Counting the phosphorus source by P 2 O 5 Meter, silicon source with SiO 2 Calculated by mole ratio, the methyl triethyl ammonium hydroxide (R) and water are Al 2 O 3 ：P 2 O 5 ：SiO 2 ：R：H 2 O＝1：0.65～1.40：0.02～0.65：0.60～1.45：28～100。
According to a preferred embodiment of the present invention, the aluminum source is made of Al 2 O 3 Counting the phosphorus source by P 2 O 5 Meter, silicon source with SiO 2 Calculated by mole ratio, the methyl triethyl ammonium hydroxide (R) and water are Al 2 O 3 ：P 2 O 5 ：SiO 2 ：R：H 2 O＝1：0.70～1.40：0.04～0.60：0.65～1.40：30～90。
According to a preferred embodiment of the present invention, the aluminum source is at least one selected from the group consisting of pseudo-boehmite, aluminum alkoxide, aluminum salt, aluminum oxide, and aluminum hydroxide, the phosphorus source is at least one selected from the group consisting of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, and organic phosphorus compound, and the silicon source is at least one selected from the group consisting of silica sol, silica gel, and ethyl orthosilicate.
According to a preferred embodiment of the present invention, the aluminum source is at least one selected from the group consisting of pseudo-boehmite and aluminum isopropoxide, the phosphorus source is phosphoric acid, and the silicon source is a silica sol.
According to a preferred embodiment of the invention, the pH of the mixture is between 5.5 and 8.0.
According to a preferred embodiment of the invention, the crystallization conditions of the mixture are from 0.5 to 7 days at 150 to 205 ℃, preferably from 0.5 to 6 days at 155 to 200 ℃, more preferably from 0.75 to 5 days at 160 to 195 ℃.
According to a preferred embodiment of the invention, the mixture is free of seeds.
According to a preferred embodiment of the present invention, there is provided a SAPO-35/SAPO-5 intergrown molecular sieve obtained by the above-described preparation method, the SAPO-35/SAPO-5 (LEV/AFI) intergrown molecular sieve having the following anhydrous chemical composition: (Al) x P y Si z )O 2 mR, wherein R is methyltriethylammonium hydroxide, x, y and z represent the mole fraction of the sum of the mole numbers of Al, P and Si, respectively, x=0.35 to 0.55, y=0.30 to 0.55, z=0.005 to 0.15, x+y+z=1, m is the mole fraction of R, m=0.005 to 0.05.
According to a preferred embodiment of the invention, in the chemical composition x=0.38 to 0.52, y=0.38 to 0.52, z=0.01 to 0.15, x+y+z=1, m=0.01 to 0.05.
According to a preferred embodiment of the present invention, the peak intensity of the characteristic peak belonging to the SAPO-5 (AFI) structure in the SAPO-35/SAPO-5 intergrowth molecular sieve is higher than the peak intensity of the characteristic peak belonging to the SAPO-35 (LEV) structure, and the SAPO-5 molecular sieve accounts for 55 to 90% of the SAPO-35/SAPO-5 intergrowth molecular sieve.
According to a preferred embodiment of the invention, the calcination is carried out at a temperature of 300 to 800 ℃, preferably 400 to 650 ℃, for 1 to 10 hours, preferably 3 to 6 hoursAnd (2) after that: the specific surface area of the SAPO-35/SAPO-5 intergrowth molecular sieve is 300-450 m 2 Per gram, the total pore volume is 0.20-0.50 cm 3 Preferably 0.20 to 0.45cm per gram 3 Per gram, the micropore volume is 0.10-0.25 cm 3 Preferably 0.11 to 0.20cm per gram 3 /g。
According to a preferred embodiment of the invention, after calcination at 300 to 800 ℃, preferably 400 to 650 ℃, for 1 to 10 hours, preferably 3 to 6 hours: the acid amount of the SAPO-35/SAPO-5 intergrowth molecular sieve is 200-1000 mu mol/g, and preferably 300-900 mu mol/g.
According to a preferred embodiment of the present invention, the present invention also provides a molecular sieve composition comprising the SAPO-35/SAPO-5 intergrown molecular sieve or the binder provided according to the present invention.
The invention provides an application of the SAPO-35/SAPO-5 intergrowth molecular sieve or the molecular sieve composition as a catalyst in organic matter conversion reaction, preferably in cracking reaction, and particularly preferably in benzene preparation by cumene cracking reaction.
The molecular sieve of the invention is particularly suitable for application in organic matter conversion, for example in cumene cleavage reactions. Has the advantages of high activity and high benzene selectivity.
The invention provides an SAPO-35/SAPO-5 intergrowth molecular sieve, which has unique chemical composition, adjustable composition ratio of the two molecular sieves, adjustable acid amount and better industrial application prospect. The preparation method of the SAPO-35/SAPO-5 intergrowth molecular sieve is simple and feasible to operate, uses relatively low-cost methyltriethylammonium hydroxide as an organic structure directing agent, and the crystallization liquid is nearly neutral, and is relatively simple and environment-friendly in post-treatment.
In the context of this specification, any matters or matters not mentioned are directly applicable to those known in the art without modification except as explicitly stated. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are all deemed to be part of the original disclosure or original description of the present invention, and should not be deemed to be a new matter which has not been disclosed or contemplated herein, unless such combination is clearly unreasonable by those skilled in the art.
In the context of this specification, a molecular sieve is referred to as a "precursor" before the materials (e.g., organic structure directing agent molecules, etc.) that fill the channels of the molecular sieve are not removed during synthesis of the molecular sieve, except for water and metal ions in the channels.
In the context of the present specification, the structure of a molecular sieve is determined by X-ray diffraction patterns (XRD) as determined by an X-ray powder diffractometer, using a Cu-ka radiation source, a nickel filter. Before the sample test, a Scanning Electron Microscope (SEM) is adopted to observe the crystallization condition of the molecular sieve sample, and the sample is confirmed to contain only one crystal, namely the molecular sieve sample is in a pure phase, and XRD test is carried out on the sample, so that no interference peak of other crystals exists in diffraction peaks in an XRD spectrogram.
In the context of the present specification, w, m, s, vs in the XRD data of the molecular sieve represents the diffraction peak intensity, w is weak, m is medium, s is strong, vs is very strong, as is well known to those skilled in the art. In general, w is less than 20; m is 20-40; s is 40-70; vs is greater than 70.
In the context of the present specification, including in the examples and comparative examples below, the molecular sieve X-ray powder diffractometer model Panalytical X PERPRO X-ray powder diffractometer, analysis of the phase of the sample, cuka radiation source
The scanning range of the nickel filter and 2 theta is 2-50 degrees, the operating voltage is 40KV, the current is 40mA, and the scanning speed is 10 degrees/min.
In the context of this specification, including in the examples and comparative examples below, the inductively coupled plasma atomic emission spectrometer (ICP) model number Varian 725-ES for molecular sieves, the analytical sample was dissolved in hydrofluoric acid to obtain the elemental content in moles.
In the context of the present specification, including in the examples and comparative examples below, the micropore volume, specific surface area of the molecular sieve are measured by the nitrogen physical adsorption and desorption method (BET method): the nitrogen physical adsorption and desorption isotherms of the molecular sieve are measured by a physical adsorption instrument (such as Micromeretic ASAP2020M physical adsorption instrument), and then calculated by a BET equation and a t-plot equation. The experimental conditions for the SAPO-35/SAPO-5 intergrowth molecular sieve are as follows: the temperature was measured at-169℃and the molecular sieves were heat treated for 6 hours in an air atmosphere at 550℃and then vacuum pre-treated for 4 hours at 350 ℃.
In the context of the present specification, including in the examples and comparative examples below, the acid amount of the molecular sieve employs NH 3 The TPD chemical adsorption-desorption curve is measured by adopting an AMI-3300 type instrument of Altamira company, the sample is activated for 1h at 550 ℃ before the test, ammonia gas is adsorbed for 20min at 100 ℃, and then desorption detection is carried out at 100-600 ℃.
In the context of the present specification, including in the examples and comparative examples below, the catalyst is used in the cumene cleavage reaction:
conversion of cumene = (molar amount of cumene fed-molar amount of cumene in the effluent product)/(molar amount of methanol fed) ×100%.
Benzene selectivity% = (molar amount of benzene in product)/(molar amount of aromatic hydrocarbon in product) ×100%.
Wherein the aromatic hydrocarbon in the product does not comprise raw material isopropylbenzene.
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
Example 1
22.13 g deionized water, 11.96 g methyl triethylammonium hydroxide solution (40 wt% methyl triethylammonium hydroxide), 5.466 g pseudo-boehmite (Al-containing) 2 O 3 67.0 wt%), 8.28 g phosphoric acid (containing H) 3 PO 4 85% by weight) and 2.16 g of a silica sol (containing SiO 2 40 wt%) and uniformly mixing them, stirring them at room temperature for 3 hr to obtain a mixture, its pH value is 6.5, and the final material ratio (mole ratio) is:
P 2 O 5 /Al 2 O 3 ＝1.00
SiO 2 /Al 2 O 3 ＝0.40
R/Al 2 O 3 ＝1.00
H 2 O/Al 2 O 3 ＝52
the mixture was placed in a stainless steel reactor and crystallized by rotation at 180℃for 3 days. And after crystallization, centrifuging and washing for three times, and drying in a 110 ℃ oven to obtain XRD spectrum data of a sample, wherein the XRD spectrum data are shown in table 1 and figure 1, and the XRD spectrum data are the SAPO-35/SAPO-5 intergrowth molecular sieve with LEV and AFI type structures. Wherein the SAPO-5 molecular sieve accounts for 60 weight percent of the SAPO-35/SAPO-5 intergrowth molecular sieve. Measurement of phosphorus to aluminum molar ratio (P) of samples by inductively coupled plasma atomic emission spectrometry (ICP) 2 O 5 /Al 2 O 3 ) At 0.92, silicon to aluminum molar ratio (SiO 2 /Al 2 O 3 ) The molecular sieve had a chemical composition of (Al 0.48 P 0.44 Si 0.08 )O 2 ·0.02R。
TABLE 1
Roasting at 550 deg.c for 6 hr to obtain sample with specific surface area of 411 m 2 Per gram, micropore volume 0.13 cm 3 Per gram, total pore volume of 0.33 cm 3 /g. Sample warp NH 3 The total acid amount tested by TPD was 771. Mu. Mol/g.
Example 2
14.33 g deionized water, 15.04 g methyl triethylammonium hydroxide solution (40 wt% methyl triethylammonium hydroxide), 4.909 g pseudo-boehmite (Al-containing) 2 O 3 67.0 wt%), 7.81 g phosphoric acid (H-containing) 3 PO 4 85% by weight) and 2.91 g of silica sol (containing SiO) 2 40 wt%) and uniformly mixing them, stirring them at room temperature for 3 hr to obtain a mixture, its pH value is 6.5, and the final material ratio (mole ratio) is:
P 2 O 5 /Al 2 O 3 ＝1.05
SiO 2 /Al 2 O 3 ＝0.60
R/Al 2 O 3 ＝1.40
H 2 O/Al 2 O 3 ＝48
the mixture was placed in a stainless steel reactor and crystallized by rotation at 180℃for 3 days. And after crystallization, centrifuging and washing for three times, and drying in a 110 ℃ oven to obtain XRD spectrum data of a sample, wherein the XRD spectrum data are shown in table 2 and figure 2, and the XRD spectrum data are the SAPO-35/SAPO-5 intergrowth molecular sieve with LEV and AFI type structures. Wherein the SAPO-5 molecular sieve accounts for 65 weight percent of the SAPO-35/SAPO-5 intergrowth molecular sieve. Measurement of phosphorus to aluminum molar ratio (P) of samples by inductively coupled plasma atomic emission spectrometry (ICP) 2 O 5 /Al 2 O 3 ) At 0.93, silicon to aluminum molar ratio (SiO 2 /Al 2 O 3 ) At 0.56, the molecular sieve has a chemical composition of (Al 0.45 P 0.42 Si 0.13 )O 2 ·0.02R。
TABLE 2
Roasting at 550 deg.c for 6 hr to obtain sample with specific surface area of 389 m 2 Per gram, micropore volume 0.12 cm 3 Per gram, total pore volume of 0.30 cm 3 /g. Sample warp NH 3 The total acid amount tested by TPD was 826. Mu. Mol/g.
Example 3
22.25 g deionized water, 12.39 g methyl triethylammonium hydroxide solution (40 wt.% methyl triethylammonium hydroxide), 5.661 g pseudo-boehmite (Al-containing) 2 O 3 67.0 wt%), 8.58 g phosphoric acid (H-containing) 3 PO 4 85% by weight) and 1.12 g of silica sol (SiO-containing) 2 40 wt%) and uniformly mixing them, stirring them at room temperature for 3 hr to obtain a mixture, its pH value is 6.5, and the final material ratio (mole ratio) is:
P 2 O 5 /Al 2 O 3 ＝1.00
SiO 2 /Al 2 O 3 ＝0.20
R/Al 2 O 3 ＝1.00
H 2 O/Al 2 O 3 ＝50
the mixture was placed in a stainless steel reactor and crystallized by rotation at 180℃for 3 days. And after crystallization, centrifuging and washing for three times, and drying in a 110 ℃ oven to obtain XRD spectrum data of a sample, wherein the XRD spectrum data are shown in table 3 and figure 3, and the XRD spectrum data are the SAPO-35/SAPO-5 intergrowth molecular sieve with LEV and AFI type structures. Wherein the SAPO-5 molecular sieve accounts for 75 weight percent of the SAPO-35/SAPO-5 intergrowth molecular sieve. Measurement of phosphorus to aluminum molar ratio (P) of samples by inductively coupled plasma atomic emission spectrometry (ICP) 2 O 5 /Al 2 O 3 ) At 0.91, silicon to aluminum molar ratio (SiO 2 /Al 2 O 3 ) At 0.19, the molecular sieve has a chemical composition of (Al 0.50 P 0.45 Si 0.05 )O 2 ·0.03R。
TABLE 3 Table 3
Roasting at 550 deg.c for 6 hr to obtain sample with specific surface area of 386 m 2 Per gram, micropore volume 0.11 cm 3 Per gram, total pore volume of 0.31 cm 3 /g. Sample warp NH 3 The total acid amount tested by TPD was 568. Mu. Mol/g.
Example 4
7.98 g deionized water, 10.04 g methyl triethylammonium hydroxide solution (40 wt% methyl triethylammonium hydroxide), 4.585 g pseudoboehmite (Al-containing) 2 O 3 67.0 wt%), 6.95 g phosphoric acid (H-containing) 3 PO 4 85% by weight) and 0.45 g of silica sol (containing SiO 2 40 wt%) and uniformly mixing them, stirring them at room temperature for 3 hr to obtain a mixture, its pH value is 6.5, and the final material ratio (mole ratio) is:
P 2 O 5 /Al 2 O 3 ＝1.00
SiO 2 /Al 2 O 3 ＝0.10
R/Al 2 O 3 ＝1.00
H 2 O/Al 2 O 3 ＝31
the mixture was placed in a stainless steel reactor and crystallized by rotation at 180℃for 3 days. And after crystallization, centrifuging and washing for three times, and drying in a 110 ℃ oven to obtain XRD spectrum data of a sample, wherein the XRD spectrum data are shown in table 4 and figure 4, and the XRD spectrum data are the SAPO-35/SAPO-5 intergrowth molecular sieve with LEV and AFI type structures. Wherein the SAPO-5 molecular sieve accounts for 85 weight percent of the SAPO-35/SAPO-5 intergrowth molecular sieve. Measurement of phosphorus to aluminum molar ratio (P) of samples by inductively coupled plasma atomic emission spectrometry (ICP) 2 O 5 /Al 2 O 3 ) 1.05, silicon to aluminum molar ratio (SiO 2 /Al 2 O 3 ) At 0.11, the molecular sieve has a chemical composition of (Al 0.47 P 0.50 Si 0.03 )O 2 ·0.04R。
TABLE 4 Table 4
Roasting at 550 deg.c for 6 hr to obtain sample with specific surface area of 426 m 2 Per gram, micropore volume 0.11 cm 3 Per gram, total pore volume of 0.32 cm 3 /g. Sample warp NH 3 The total acid amount tested by TPD was 428. Mu. Mol/g.
Example 5
14.34 g deionized water, 10.55 g methyltriethylammonium hydroxide solution (40 wt.% methyl triethylammonium hydroxide), 5.355 g pseudo-boehmite (Al-containing) 2 O 3 67.0 wt%), 9.33 g phosphoric acid (H-containing) 3 PO 4 85% by weight) and 0.42 g of silica sol (containing SiO 2 40 wt.%) and uniformly mixing them, stirring them at room temperature for 3 hr so as to obtain the invented mixture pThe H value is 6.5, and the final material proportion (molar ratio) is:
P 2 O 5 /Al 2 O 3 ＝1.15
SiO 2 /Al 2 O 3 ＝0.08
R/Al 2 O 3 ＝0.90
H 2 O/Al 2 O 3 ＝38
the mixture was placed in a stainless steel reactor and crystallized by rotation at 190℃for 1.5 days. And after crystallization, centrifuging and washing for three times, and drying in a 110 ℃ oven to obtain XRD spectrum data of a sample, wherein the XRD spectrum data of the sample are shown in table 5, and the sample is the SAPO-35/SAPO-5 intergrowth molecular sieve with LEV and AFI type structures. Wherein the SAPO-5 molecular sieve accounts for 80 weight percent of the SAPO-35/SAPO-5 intergrowth molecular sieve. Measurement of phosphorus to aluminum molar ratio (P) of samples by inductively coupled plasma atomic emission spectrometry (ICP) 2 O 5 /Al 2 O 3 ) 1.13, silicon to aluminum molar ratio (SiO 2 /Al 2 O 3 ) At 0.07, the molecular sieve had a chemical composition of (Al 0.46 P 0.52 Si 0.02 )O 2 ·0.04R。
TABLE 5
Roasting at 550 deg.c for 6 hr to obtain sample with specific surface area of 428 m 2 Per gram, micropore volume 0.11 cm 3 Per gram, total pore volume of 0.30 cm 3 /g. Sample warp NH 3 The total acid amount tested by TPD was 379. Mu. Mol/g.
Example 6
14.69 g deionized water, 14.77 g methyl triethylammonium hydroxide solution (40 wt% methyl triethylammonium hydroxide), 5.192 g pseudo-boehmite (Al-containing) 2 O 3 67.0 wt%), 9.83 g phosphoric acid (H-containing) 3 PO 4 85% by weight) and 0.51 g of silica sol (containing SiO) 2 40 wt%) and uniformly mixing them, stirring them at room temperature for 3 hr to obtain a mixture, its pH value is 6.5, and the final material ratio (mole ratio) is:
P 2 O 5 /Al 2 O 3 ＝1.25
SiO 2 /Al 2 O 3 ＝0.10
R/Al 2 O 3 ＝1.30
H 2 O/Al 2 O 3 ＝44
the mixture was placed in a stainless steel reactor and crystallized by rotation at 185℃for 2 days. And after crystallization, centrifuging and washing for three times, and drying in a 110 ℃ oven to obtain XRD spectrum data of a sample, wherein the XRD spectrum data of the sample are shown in table 6, and the sample is the SAPO-35/SAPO-5 intergrowth molecular sieve with LEV and AFI type structures. Wherein the SAPO-5 molecular sieve accounts for 85 weight percent of the SAPO-35/SAPO-5 intergrowth molecular sieve. Measurement of phosphorus to aluminum molar ratio (P) of samples by inductively coupled plasma atomic emission spectrometry (ICP) 2 O 5 /Al 2 O 3 ) 1.22, silicon to aluminum molar ratio (SiO 2 /Al 2 O 3 ) At 0.09, the molecular sieve has a chemical composition of (Al 0.44 P 0.54 Si 0.02 )O 2 ·0.04R。
TABLE 6
Roasting at 550 deg.c for 6 hr to obtain sample with specific surface area of 379 m 2 Per gram, micropore volume 0.11 cm 3 Per gram, total pore volume of 0.32 cm 3 /g. Sample warp NH 3 The total acid amount tested by TPD was 414. Mu. Mol/g.
Example 7
24.31 g deionized water, 15.49 g methyltriethylammonium hydroxide solution (40 wt% methyl triethylammonium hydroxide), 5.661 g pseudo-boehmite (Al containing) 2 O 3 67.0 wt%), 8.15 g phosphoric acid (H-containing) 3 PO 4 85% by weight) and 1.40 g of a silica sol (containing SiO) 2 40% by weight) Uniformly mixing, stirring at room temperature for 3 hours to obtain a mixture, wherein the pH value of the mixture is 6.5, and the final material ratio (molar ratio) is as follows:
P 2 O 5 /Al 2 O 3 ＝0.95
SiO 2 /Al 2 O 3 ＝0.25
R/Al 2 O 3 ＝1.25
H 2 O/Al 2 O 3 ＝56
the mixture was placed in a stainless steel reactor and crystallized by rotation at 175℃for 3 days. And after crystallization, centrifuging and washing for three times, and drying in a 110 ℃ oven to obtain XRD spectrum data of a sample, wherein the XRD spectrum data of the sample are shown in table 7, and the sample is the SAPO-35/SAPO-5 intergrowth molecular sieve with LEV and AFI type structures. Wherein the SAPO-5 molecular sieve accounts for 80 weight percent of the SAPO-35/SAPO-5 intergrowth molecular sieve. Measurement of phosphorus to aluminum molar ratio (P) of samples by inductively coupled plasma atomic emission spectrometry (ICP) 2 O 5 /Al 2 O 3 ) At 0.88, silicon to aluminum molar ratio (SiO 2 /Al 2 O 3 ) 0.23, the chemical composition of the molecular sieve is (Al 0.50 P 0.44 Si 0.06 )O 2 ·0.03R。
TABLE 7
Roasting at 550 deg.c for 6 hr to obtain sample with specific surface area of 430 m 2 Per gram, micropore volume 0.13 cm 3 Per gram, total pore volume of 0.35 cm 3 /g. Sample warp NH 3 The total acid amount tested by TPD was 481. Mu. Mol/g.
Example 8
33.68 g deionized water, 15.46 g methyltriethylammonium hydroxide solution (containing 40 wt.% methyltriethylammonium hydroxide), 6.141 g pseudo-boehmite (containing Al) 2 O 3 67.0 wt%), 7.91 g phosphoric acid (H-containing) 3 PO 4 85% by weight) and 1.82 g of a silica sol (containing SiO) 2 40 wt%) and uniformly mixing them, stirring them at room temperature for 3 hr to obtain a mixture, mixingThe pH value of the product is 6.5, and the final material proportion (molar ratio) is as follows:
P 2 O 5 /Al 2 O 3 ＝0.85
SiO 2 /Al 2 O 3 ＝0.30
R/Al 2 O 3 ＝1.15
H 2 O/Al 2 O 3 ＝65
the mixture was placed in a stainless steel reactor and crystallized by rotation at 170℃for 3 days. And after crystallization, centrifuging and washing for three times, and drying in a 110 ℃ oven to obtain XRD spectrum data of a sample, wherein the XRD spectrum data of the sample are shown in table 8, and the sample is the SAPO-35/SAPO-5 intergrowth molecular sieve with LEV and AFI type structures. Wherein the SAPO-5 molecular sieve accounts for 75 weight percent of the SAPO-35/SAPO-5 intergrowth molecular sieve. Measurement of phosphorus to aluminum molar ratio (P) of samples by inductively coupled plasma atomic emission spectrometry (ICP) 2 O 5 /Al 2 O 3 ) At 0.85, silicon to aluminum molar ratio (SiO 2 /Al 2 O 3 ) 0.28, the molecular sieve has a chemical composition of (Al 0.50 P 0.43 Si 0.07 )O 2 ·0.03R。
TABLE 8
Roasting at 550 deg.c for 6 hr to obtain sample with specific surface area of 426 m 2 Per gram, micropore volume 0.11 cm 3 Per gram, total pore volume of 0.31 cm 3 /g. Sample warp NH 3 The total acid amount tested by TPD was 649. Mu. Mol/g.
Example 9
40.30 g deionized water, 13.38 g methyltriethylammonium hydroxide solution (containing 40 wt.% methyltriethylammonium hydroxide), 5.558 g pseudo-boehmite (containing Al) 2 O 3 67.0 wt%), 8.84 g phosphoric acid (containing H) 3 PO 4 85% by weight) and 1.92 g of silica sol (SiO-containing) 2 40 wt%) and uniformly mixing them, stirring them at room temperature for 3 hr to obtain a mixture, its pH value is 6.5, and the final material ratio (mole ratio) is:
P 2 O 5 /Al 2 O 3 ＝1.05
SiO 2 /Al 2 O 3 ＝0.35
R/Al 2 O 3 ＝1.10
H 2 O/Al 2 O 3 ＝80
the mixture was placed in a stainless steel reactor and crystallized by rotation at 165℃for 4 days. And after crystallization, centrifuging and washing for three times, and drying in a 110 ℃ oven to obtain XRD spectrum data of a sample, wherein the XRD spectrum data of the sample are shown in table 9, and the sample is the SAPO-35/SAPO-5 intergrowth molecular sieve with LEV and AFI type structures. Wherein the SAPO-5 molecular sieve accounts for 80 weight percent of the SAPO-35/SAPO-5 intergrowth molecular sieve. Measurement of phosphorus to aluminum molar ratio (P) of samples by inductively coupled plasma atomic emission spectrometry (ICP) 2 O 5 /Al 2 O 3 ) 1.01, silicon to aluminum molar ratio (SiO 2 /Al 2 O 3 ) 0.32, the molecular sieve has a chemical composition of (Al 0.46 P 0.47 Si 0.07 )O 2 ·0.03R。
TABLE 9
Roasting at 550 deg.c for 6 hr to obtain sample with specific surface area of 418 m 2 Per gram, micropore volume 0.14 cm 3 Per gram, total pore volume of 0.36 cm 3 /g. Sample warp NH 3 The total acid amount tested by TPD was 692. Mu. Mol/g.
Example 10
43.13 g deionized water, 10.74 g methyl triethyl ammonium hydroxide solution (containing methyl triethyl hydroxide)Ammonium 40 wt%), 6.133 g pseudo-boehmite (containing Al) 2 O 3 67.0 wt%), 6.97 g phosphoric acid (containing H) 3 PO 4 85% by weight) and 3.03 g of a silica sol (containing SiO) 2 40 wt%) and uniformly mixing them, stirring them at room temperature for 3 hr to obtain a mixture, its pH value is 6.5, and the final material ratio (mole ratio) is:
P 2 O 5 /Al 2 O 3 ＝0.75
SiO 2 /Al 2 O 3 ＝0.50
R/Al 2 O 3 ＝0.80
H 2 O/Al 2 O 3 ＝75
the mixture was placed in a stainless steel reactor and crystallized by rotation at 165℃for 4 days. And after crystallization, centrifuging and washing for three times, and drying in a 110 ℃ oven to obtain XRD spectrum data of a sample, wherein the XRD spectrum data of the sample are shown in table 10, and the sample is the SAPO-35/SAPO-5 intergrowth molecular sieve with LEV and AFI type structures. Wherein the SAPO-5 molecular sieve accounts for 65 weight percent of the SAPO-35/SAPO-5 intergrowth molecular sieve. Measurement of phosphorus to aluminum molar ratio (P) of samples by inductively coupled plasma atomic emission spectrometry (ICP) 2 O 5 /Al 2 O 3 ) At 0.78, silicon to aluminum molar ratio (SiO 2 /Al 2 O 3 ) At 0.46, the molecular sieve has a chemical composition of (Al 0.50 P 0.39 Si 0.11 )O 2 ·0.02R。
Table 10
Roasting at 550 deg.c for 6 hr to obtain sample with specific surface area 398 m 2 Per gram, micropore volume 0.12 cm 3 Per gram, total pore volume of 0.28 cm 3 /g. Sample warp NH 3 The total acid amount tested by TPD was 702. Mu. Mol/g.
Example 11
32.89 g deionized water, 9.35 g methyl triethylammonium hydroxide solution (40 wt.% methyl triethylammonium hydroxide), 6.103 g pseudo-boehmite (Al-containing) 2 O 3 67.0 wt%), 9.25 g phosphoric acid (H-containing) 3 PO 4 85% by weight) and 2.41 g of silica sol (containing SiO) 2 40 wt%) and uniformly mixing them, stirring them at room temperature for 3 hr to obtain a mixture, its pH value is 6.5, and the final material ratio (mole ratio) is:
P 2 O 5 /Al 2 O 3 ＝1.00
SiO 2 /Al 2 O 3 ＝0.40
R/Al 2 O 3 ＝0.70
H 2 O/Al 2 O 3 ＝60
the mixture was placed in a stainless steel reactor and crystallized by rotation at 160℃for 5 days. And after crystallization, centrifuging and washing for three times, and drying in a 110 ℃ oven to obtain XRD spectrum data of a sample, wherein the XRD spectrum data of the sample are shown in table 11, and the sample is the SAPO-35/SAPO-5 intergrowth molecular sieve with LEV and AFI type structures. Wherein the SAPO-5 molecular sieve accounts for 75 weight percent of the SAPO-35/SAPO-5 intergrowth molecular sieve. Measurement of phosphorus to aluminum molar ratio (P) of samples by inductively coupled plasma atomic emission spectrometry (ICP) 2 O 5 /Al 2 O 3 ) At 0.96, silicon to aluminum molar ratio (SiO 2 /Al 2 O 3 ) At 0.37, the molecular sieve has a chemical composition of (Al 0.47 P 0.45 Si 0.08 )O 2 ·0.02R。
TABLE 11
Roasting at 550 deg.c for 6 hr to obtain sample with specific surface area of 383 m 2 Per gram, micropore volume 0.12 cm 3 Per gram, total pore volume of 0.35 cm 3 /g. Sample warp NH 3 The total acid amount tested by TPD was 477. Mu. Mol/g.
Examples 12 to 22
The molecular sieves synthesized in examples 1 to 11 were calcined at 550℃for 6 hours to obtain H-type SAPO-35/SAPO-5 molecular sieves, respectively.
Taking the calcined H-type SAPO-35/SAPO-5 molecular sieve powder sample, and breakingScreening 0.5 g of 20-40 mesh particle size part after crushing, and placing the particle size part into a fixed bed reactor for cumene cracking reaction, wherein the reaction conditions are as follows: the reaction temperature is 300-350 ℃, the reaction pressure is normal pressure, and the weight airspeed of the isopropylbenzene is 2-4 h -1 The specific reaction conditions for each example are shown in Table 12. The products were analyzed by Shimadzu GC-2014 gas chromatograph for catalyst activity and product selectivity as shown in Table 12.
Table 12 catalyst performance results for examples 12-22 and comparative example 3
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (13)
1. A SAPO-35/SAPO-5 intergrowth molecular sieve is characterized in that,
the SAPO-35/SAPO-5 intergrowth molecular sieve has the following anhydrous chemical composition: (Al) x P y Si z )O 2 mR, wherein R is methyltriethylammonium hydroxide, x, y and z represent the mole fraction of the sum of the mole numbers of Al, P and Si, respectively, x=0.35 to 0.55, y=0.30 to 0.55, z=0.005 to 0.15, x+y+z=1, m is the mole fraction of R, and m=0.005 to 0.05.
2. The SAPO-35/SAPO-5 intergrowth molecular sieve of claim 1, wherein x = 0.38 to 0.52, y = 0.38 to 0.52, z = 0.01 to 0.15, x+y+z = 1, m = 0.01 to 0.05.
3. The SAPO-35/SAPO-5 intergrowth molecular sieve of claim 1 or 2, wherein,
the peak intensity of the characteristic peak belonging to the AFI structure of the SAPO-5 molecular sieve in the SAPO-35/SAPO-5 intergrowth molecular sieve is higher than that of the characteristic peak belonging to the LEV structure of the SAPO-35 molecular sieve;
preferably, the SAPO-5 molecular sieve accounts for 55 to 90 weight percent of the SAPO-35/SAPO-5 intergrowth molecular sieve.
4. The SAPO-35/SAPO-5 intergrowth molecular sieve according to any of the claim 1-3, wherein,
the SAPO-35/SAPO-5 intergrowth molecular sieve has an X-ray diffraction pattern comprising an AFI structure belonging to the SAPO-5 molecular sieve and an LEV structure belonging to the SAPO-35 molecular sieve as shown in the following table;
a: + -0.30 °, b: as a function of 2 theta.
5. The preparation method of the SAPO-35/SAPO-5 intergrowth molecular sieve is characterized by comprising the following steps of:
heating and crystallizing a mixture containing an aluminum source, a phosphorus source, a silicon source, methyl triethyl ammonium hydroxide and water, and performing post-treatment to obtain the SAPO-35/SAPO-5 intergrowth molecular sieve;
wherein the aluminum source is Al 2 O 3 Counting the phosphorus source by P 2 O 5 Meter, silicon source with SiO 2 Calculated by the mole ratio of the methyl triethyl ammonium hydroxide R and water, is Al 2 O 3 ：P 2 O 5 ：SiO 2 ：R：H 2 O＝1：0.65～1.40：0.02～0.65：0.60～1.45：28～100。
6. The preparation method according to claim 5, wherein,
the pH value of the mixture is 5.5-8.0; and/or
The crystallization conditions of the mixture include crystallization at 150 to 205 ℃ for 0.5 to 7 days, preferably at 155 to 200 ℃ for 0.5 to 6 days, more preferably at 160 to 195 ℃ for 0.75 to 5 days; and/or
The mixture is free of seeds;
the post-treatment comprises the following steps: separating, washing, drying and optionally roasting.
7. The preparation method according to claim 5 or 6, wherein,
the aluminum source is Al 2 O 3 Counting the phosphorus source by P 2 O 5 Meter, silicon source with SiO 2 Calculated by the mole ratio of the methyl triethyl ammonium hydroxide R and water, is Al 2 O 3 ：P 2 O 5 ：SiO 2 ：R：H 2 O=1: 0.70 to 1.40:0.04 to 0.60:0.65 to 1.40: 30-90; and/or
The aluminum source is at least one selected from pseudo-boehmite, aluminum alkoxide, aluminum salt, aluminum oxide and aluminum hydroxide, preferably pseudo-boehmite; and/or
The phosphorus source is at least one selected from phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and organic phosphorus compounds, preferably phosphoric acid; and/or
The silicon source is at least one selected from silica sol, silica gel and ethyl orthosilicate, preferably silica sol.
8. The SAPO-35/SAPO-5 intergrown molecular sieve prepared by the method of any one of claims 5 to 7.
9. The SAPO-35/SAPO-5 intergrowth molecular sieve of claim 8, wherein,
the SAPO-35/SAPO-5 intergrowth molecular sieve has the following anhydrous chemical composition: (Al) x P y Si z )O 2 mR, wherein R is methyltriethylammonium hydroxide, x, y and z represent the mole fraction of the sum of the mole numbers of Al, P and Si, respectively, x=0.35 to 0.55, y=0.30 to 0.55, z=0.005 to 0.15, x+y+z=1, m is the mole fraction of R, m=0.005 to 0.05;
preferably, the SAPO-35/SAPO-5 intergrowth molecular sieve has an X-ray diffraction pattern including an AFI structure belonging to the SAPO-5 molecular sieve and an LEV structure belonging to the SAPO-35 molecular sieve as shown in the following table;
a: + -0.30 °, b: as a function of 2 theta.
10. The SAPO-35/SAPO-5 intergrowth molecular sieve of claim 8 or 9, wherein,
x=0.38 to 0.52, y=0.38 to 0.52, z=0.01 to 0.15, x+y+z=1, m=0.01 to 0.05; and/or
The peak intensity of the characteristic peak belonging to the AFI structure of the SAPO-5 molecular sieve in the SAPO-35/SAPO-5 intergrowth molecular sieve is higher than the peak intensity of the characteristic peak belonging to the LEV structure of the SAPO-35 molecular sieve, and the SAPO-5 molecular sieve preferably accounts for 55 to 90 weight percent of the SAPO-35/SAPO-5 intergrowth molecular sieve.
11. The SAPO-35/SAPO-5 intergrowth molecular sieve according to any of the claims 8-10, wherein,
after calcination at 300-800 ℃, preferably 400-650 ℃, for 1-10 hours, preferably 3-6 hours:
the specific surface area of the SAPO-35/SAPO-5 intergrowth molecular sieve is 300-450 m 2 /g; and/or
The pore volume of the SAPO-35/SAPO-5 intergrowth molecular sieve is 0.20-0.50 cm 3 Preferably 0.20 to 0.45cm per gram 3 /g; and/or
The micropore volume of the SAPO-35/SAPO-5 intergrowth molecular sieve is 0.10-0.25 cm 3 Preferably 0.11 to 0.20cm per gram 3 /g; and/or
The acid amount of the SAPO-35/SAPO-5 intergrowth molecular sieve is 200-1000 mu mol/g, and preferably 300-900 mu mol/g.
12. A molecular sieve composition comprising the SAPO-35/SAPO-5 intergrown molecular sieve of any one of claims 1 to 4 and 8 to 11 and a binder.
13. Use of the SAPO-35/SAPO-5 intergrown molecular sieve according to any one of claims 1 to 4 and 8 to 11 or the molecular sieve composition according to claim 12 as a catalyst in organic conversion reactions, preferably in cleavage reactions, particularly preferably in the preparation of benzene by cumene cleavage reactions.
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| CN104340985A (en) * | 2013-07-30 | 2015-02-11 | 中国科学院大连化学物理研究所 | Method for preparing small granulated SAPO molecular sieve, product prepared through method, and use of product |
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