CN112694103A - Method for preparing high-crystallinity SAPO-5 molecular sieve by taking attapulgite as raw material - Google Patents
Method for preparing high-crystallinity SAPO-5 molecular sieve by taking attapulgite as raw material Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 87
- 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 87
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 56
- 229960000892 attapulgite Drugs 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000002994 raw material Substances 0.000 title claims abstract description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 48
- 239000011259 mixed solution Substances 0.000 claims description 40
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000012153 distilled water Substances 0.000 claims description 22
- 235000011007 phosphoric acid Nutrition 0.000 claims description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 239000012265 solid product Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000010335 hydrothermal treatment Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 30
- -1 polytetrafluoroethylene Polymers 0.000 description 20
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 description 18
- 229910001220 stainless steel Inorganic materials 0.000 description 18
- 239000010935 stainless steel Substances 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 238000006555 catalytic reaction Methods 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 241000269350 Anura Species 0.000 description 1
- 241000668854 Howardia biclavis Species 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000013265 porous functional material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Engineering & Computer Science (AREA)
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- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a method for preparing a high-crystallinity SAPO-5 molecular sieve by taking attapulgite as a raw material, which utilizes the attapulgite as a silicon source and a part of an aluminum source to prepare the high-crystallinity SAPO-5 molecular sieve by two-step hydrothermal treatment; the method reduces the synthesis cost of the SAPO-5 molecular sieve, and simultaneously converts cheap attapulgite into a molecular sieve functional material with high added value, so that the method has great economic value.
Description
Technical Field
The invention belongs to the field of fine chemical engineering and inorganic materials, and particularly relates to a method for preparing a high-crystallinity SAPO-5 molecular sieve by using attapulgite as a raw material.
Background
The attapulgite refers to a clay mineral which takes hydrated magnesium aluminum silicate as a main component and has a unique layer chain structure. In 1976, China discovers attapulgite ores in Liuhe small mountain of Jiangsu province and the like for the first time, and then discovers large-scale attapulgite ores in Suwan region, particularly mountain streams and Guanshan mountain areas of Ming City of Anhui province, and the proven ore reserves, the grades and the annual mining scale all occupy the top of the world. According to the estimation, the storage capacity of the attapulgite in China accounts for more than 50% of the total storage capacity of the whole world, and the attapulgite storage capacity is large and low in price. At present, the attapulgite is widely applied to the aspects of paint, drilling mud, edible oil decoloration and the like. However, the attapulgite clay has lower development and utilization level, monotonous attapulgite clay products and low added value. Therefore, the attapulgite is converted into a chemical product with high added value, and the method has great economic value and industrial prospect.
The molecular sieve is an important inorganic porous functional material, is widely applied to the fields of adsorption, catalysis, separation and the like due to the unique pore channel structure and adjustable composition, and has great value. At present, silicon and aluminum sources used in the synthesis process of molecular sieves are mainly industrial or chemically pure raw materials, such as white carbon black, silica sol, sodium aluminate and the like, and the cost of the raw materials is relatively high. If the attapulgite can be used as a silicon and aluminum source for synthesizing the molecular sieve, the attapulgite is converted into the molecular sieve, so that the synthesis cost of the molecular sieve can be reduced, the further development and utilization of the attapulgite are facilitated, and the method has important significance.
The SAPO-5 molecular sieve is a novel microporous molecular sieve material with a unique crystal structure, the pore diameter of the molecular sieve is 0.8nm, the framework presents electronegativity, the molecular sieve has moderate protonic acidity and has good thermal stability and hydrothermal stability, and the molecular sieve has huge application potential in catalytic reactions such as cracking reaction, alkylation reaction, aromatization reaction, isomerization reaction, MTO reaction and the like. The preparation of the SAPO-5 molecular sieve by using the attapulgite as the raw material has great significance for developing a synthesis method of the SAPO-5 molecular sieve and expanding the utilization range of the attapulgite. However, there are few reports related to the present. Chinese patent CN 109052428A discloses a method for preparing SAPO molecular sieve by using attapulgite as a raw material, which adopts a one-step hydrothermal method, and the SAPO-5 molecular sieve prepared by the method has low crystallinity or is easy to form a mixed crystal molecular sieve of SAPO-5 and other molecular sieves.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing a high-crystallinity SAPO-5 molecular sieve by taking attapulgite as a raw material, wherein the high-crystallinity SAPO-5 molecular sieve is synthesized by two-step hydrothermal treatment by taking the attapulgite as a silicon source and a part of an aluminum source; the method reduces the synthesis cost of the SAPO-5 molecular sieve, and simultaneously converts cheap attapulgite into a molecular sieve functional material with high added value, so that the method has great economic value.
The technical scheme adopted by the invention is as follows:
a method for preparing a high-crystallinity SAPO-5 molecular sieve by taking attapulgite as a raw material comprises the following steps:
(1) adding attapulgite and phosphoric acid into distilled water, uniformly mixing, carrying out hydrothermal reaction at 180-220 ℃ for 8-24 h, taking out, and cooling to obtain a mixed solution I;
(2) adding an aluminum source and triethylamine into the mixed solution I, violently stirring until the aluminum source and the triethylamine are uniformly mixed, carrying out hydrothermal reaction at 180-220 ℃ for 12-24 h, washing, filtering, drying and roasting the obtained solid product to obtain the high-crystallinity SAPO-5 molecular sieve.
Further, the mass ratio of the distilled water to the attapulgite to the aluminum source to the phosphoric acid to the triethylamine is 69.78: 2.77-4.15: 4.43-6.65: 10.66-16.00: 6.56-9.84.
In the step (2), the stirring speed of the vigorous stirring is more than 200 revolutions per minute.
In the step (2), the roasting condition is roasting for 4-8 hours at 500-600 ℃ in an air atmosphere.
The silicon content of the attapulgite is 50-70%, and the aluminum content is 6-15%.
The phosphoric acid is orthophosphoric acid with the content of more than or equal to 80 percent.
The aluminum source is one of pseudo-boehmite, aluminum hydroxide and aluminum oxide.
The invention also provides the SAPO-5 molecular sieve with high crystallinity, which is prepared by the preparation method and has high crystallinity without other mixed crystals.
The invention also provides application of the high-crystallinity SAPO-5 molecular sieve in catalyzing methanol to prepare olefin, and the high-crystallinity SAPO-5 molecular sieve has high catalytic efficiency when being used as a catalyst.
According to the invention, silicon and aluminum elements in the attapulgite are fully activated through two-step hydrothermal treatment, so that the silicon and aluminum elements can be used as a silicon source and a part of an aluminum source for synthesizing the SAPO-5 molecular sieve to fully participate in the crystallization of the SAPO-5 molecular sieve, and thus the high-crystallinity pure-phase SAPO-5 molecular sieve is synthesized.
Compared with the prior art, the invention has the following beneficial effects: the cheap and widely distributed natural clay mineral attapulgite is used for replacing a silicon source and part of an aluminum source synthesized by the SAPO-5 molecular sieve, so that the synthesis cost of the SAPO-5 molecular sieve is reduced, and the utilization range of the attapulgite is widened; the two-step hydrothermal treatment steps are simple and feasible; the prepared SAPO-5 molecular sieve has high crystallinity, good crystal form and excellent catalytic performance.
Drawings
FIG. 1 is an XRD spectrum of SAPO-5 molecular sieves obtained in example 1(A), example 2(B), comparative example 1(C) and comparative example 2 (D);
FIG. 2 is a scanning electron micrograph of SAPO-5 molecular sieve obtained in example 1;
FIG. 3 is a scanning electron micrograph of the SAPO-5 molecular sieve obtained in example 3;
FIG. 4 shows the results of the catalytic reaction of SAPO-5 molecular sieve obtained in example 1 as a catalyst for preparing olefin from methanol;
FIG. 5 shows the results of the catalytic reaction of SAPO-5 molecular sieve obtained in comparative example 1 as a catalyst for preparing olefin from methanol;
FIG. 6 shows the results of the catalytic reaction of SAPO-5 molecular sieve obtained in comparative example 2 as a catalyst for preparing olefin from methanol.
Detailed Description
For the purpose of enhancing understanding of the present invention, the present invention will be described in further detail with reference to specific examples, which are provided for illustration only and are not intended to limit the scope of the present invention.
Example 1
A method for preparing a high-crystallinity SAPO-5 molecular sieve by taking attapulgite as a raw material comprises the following steps:
(1) adding 3.46g of attapulgite and 14.21g of phosphoric acid with the content of 85% into 69.78g of distilled water, uniformly mixing, transferring to a stainless steel reaction kettle with a polytetrafluoroethylene lining, treating at 220 ℃ for 24 hours, taking out, and cooling to obtain a first mixed solution;
(2) adding 5.54g of pseudo-boehmite and 7.26g of triethylamine into the mixed solution I, violently stirring at 300 r/min until the mixture is uniformly mixed to obtain a mixed solution II, then transferring the mixed solution II into a stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallizing for 24h at 220 ℃, washing the obtained solid product to be neutral by using distilled water, filtering, drying, and roasting for 6h at 550 ℃ to obtain the high-crystallinity SAPO-5 molecular sieve, wherein XRD (X-ray diffraction) diagrams and SEM (scanning electron microscope) diagrams of which are respectively shown in figures 1(A) and 2.
The XRD spectrogram as shown in fig. 1(a) shows that the obtained sample is a pure-phase SAPO-5 molecular sieve, and the peak intensity of the XRD spectrogram reflects that the crystallinity of the SAPO-5 molecular sieve prepared in this example is high, which is equivalent to the crystallinity of the SAPO-5 molecular sieve prepared by using chemically pure raw materials in the conventional method (comparative example 1), and no other mixed crystals are generated; the SEM chart shown in FIG. 2 shows that the obtained sample is hexagonal columnar crystal, which is consistent with the morphology of the SAPO-5 molecular sieve.
Example 2
A method for preparing a high-crystallinity SAPO-5 molecular sieve by taking attapulgite as a raw material comprises the following steps:
(1) adding 2.77g of attapulgite and 16.00g of phosphoric acid with the content of 80% into 69.78g of distilled water, uniformly mixing, then transferring into a stainless steel reaction kettle with a polytetrafluoroethylene lining, treating for 16 hours at 180 ℃, taking out, and cooling to obtain a mixed solution I;
(2) adding 4.43g of aluminum oxide and 7.26g of triethylamine into the mixed solution I, violently stirring at 260 revolutions per minute until the mixture is uniformly mixed to obtain a mixed solution II, then transferring the mixed solution II into a stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallizing for 16 hours at 180 ℃, washing the obtained solid product to be neutral by using distilled water, filtering, drying, and roasting for 8 hours at 500 ℃ to obtain the high-crystallinity SAPO-5 molecular sieve, wherein an XRD (X-ray diffraction) diagram of the high-crystallinity SAPO-5 molecular sieve is shown in figure 1(B), and the obtained sample is the pure-phase SAPO-5 molecular sieve which is high in crystallinity and free of other miscellaneous crystals.
Example 3
A method for preparing a high-crystallinity SAPO-5 molecular sieve by taking attapulgite as a raw material comprises the following steps:
(1) adding 4.05g of attapulgite and 10.66g of 90% phosphoric acid into 69.78g of distilled water, uniformly mixing, then transferring to a stainless steel reaction kettle with a polytetrafluoroethylene lining, treating at 220 ℃ for 20 hours, taking out, and cooling to obtain a first mixed solution;
(2) adding 6.65g of aluminum hydroxide and 6.56g of triethylamine into the mixed solution I, violently stirring at 350 r/min until the mixture is uniformly mixed to obtain a mixed solution II, then transferring the mixed solution II into a stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallizing at 200 ℃ for 24h, washing the obtained solid product with distilled water to be neutral, filtering, drying, and roasting at 600 ℃ for 4h to obtain the high-crystallinity SAPO-5 molecular sieve, wherein SEM pictures of the SAPO-5 molecular sieve are respectively shown in figure 3, and the obtained sample is a hexagonal columnar crystal and is consistent with the shape of the SAPO-5 molecular sieve.
Example 4
A method for preparing a high-crystallinity SAPO-5 molecular sieve by taking attapulgite as a raw material comprises the following steps:
(1) adding 4.15g of attapulgite and 12.66g of phosphoric acid with 85% content into 69.78g of distilled water, uniformly mixing, then transferring into a stainless steel reaction kettle with a polytetrafluoroethylene lining, treating at 180 ℃ for 24 hours, taking out, and cooling to obtain a mixed solution I;
(2) adding 6.60g of aluminum hydroxide and 9.84g of triethylamine into the mixed solution I, violently stirring at 300 revolutions per minute until the mixture is uniformly mixed to obtain a mixed solution II, then transferring the mixed solution II into a stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallizing for 16 hours at 180 ℃, washing the obtained solid product to be neutral by using distilled water, filtering, drying, and roasting for 5 hours at 580 ℃ to obtain the high-crystallinity SAPO-5 molecular sieve.
Example 5
A method for preparing a high-crystallinity SAPO-5 molecular sieve by taking attapulgite as a raw material comprises the following steps:
(1) adding 3.69g of attapulgite and 13.40g of phosphoric acid with the content of 85% into 69.78g of distilled water, uniformly mixing, transferring to a stainless steel reaction kettle with a polytetrafluoroethylene lining, treating at 190 ℃ for 12 hours, taking out, and cooling to obtain a mixed solution I;
(2) adding 5.25g of pseudo-boehmite and 8.15g of triethylamine into the mixed solution I, violently stirring at 360 revolutions per minute until the pseudo-boehmite and the triethylamine are uniformly mixed to obtain a mixed solution II, then transferring the mixed solution II into a stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallizing for 20 hours at 210 ℃, washing the obtained solid product to be neutral by using distilled water, filtering, drying, and roasting for 6 hours at 530 ℃ to obtain the high-crystallinity SAPO-5 molecular sieve.
Example 6
A method for preparing a high-crystallinity SAPO-5 molecular sieve by taking attapulgite as a raw material comprises the following steps:
(1) adding 2.89g of attapulgite and 15.50g of phosphoric acid with the content of 85% into 69.78g of distilled water, uniformly mixing, transferring to a stainless steel reaction kettle with a polytetrafluoroethylene lining, treating at 180 ℃ for 8 hours, taking out, and cooling to obtain a mixed solution I;
(2) adding 6.38g of aluminum oxide and 7.58g of triethylamine into the mixed solution I, violently stirring at 400 rpm until the mixture is uniformly mixed to obtain a mixed solution II, then transferring the mixed solution II into a stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallizing for 24 hours at 210 ℃, washing the obtained solid product to be neutral by using distilled water, filtering, drying, and roasting for 5 hours at 550 ℃ to obtain the high-crystallinity SAPO-5 molecular sieve.
Example 7
A method for preparing a high-crystallinity SAPO-5 molecular sieve by taking attapulgite as a raw material comprises the following steps:
(1) adding 3.15g of attapulgite and 10.96g of phosphoric acid with the content of 95% into 69.78g of distilled water, uniformly mixing, then transferring into a stainless steel reaction kettle with a polytetrafluoroethylene lining, treating for 24 hours at 220 ℃, taking out, and cooling to obtain a mixture (1);
(2) adding 6.50g of aluminum hydroxide and 8.12g of triethylamine into the mixed solution I, violently stirring at 340 rpm until the mixture is uniformly mixed to obtain a mixed solution II, then transferring the mixed solution II into a stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallizing at 180 ℃ for 12 hours, washing the obtained solid product with distilled water to be neutral, filtering, drying, and roasting at 520 ℃ for 8 hours to obtain the high-crystallinity SAPO-5 molecular sieve.
Example 8
A method for preparing a high-crystallinity SAPO-5 molecular sieve by taking attapulgite as a raw material comprises the following steps:
(1) adding 3.50g of attapulgite and 16.00g of phosphoric acid with the content of 85% into 69.78g of distilled water, uniformly mixing, then transferring into a stainless steel reaction kettle with a polytetrafluoroethylene lining, treating for 16h at 190 ℃, taking out, and cooling to obtain a mixture (1);
(2) adding 5.00g of aluminum oxide and 6.60g of triethylamine into the mixed solution I, violently stirring at 300 revolutions per minute until the mixture is uniformly mixed to obtain a mixed solution II, then transferring the mixed solution II into a stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallizing for 24 hours at 190 ℃, washing the obtained solid product to be neutral by using distilled water, filtering, drying, and roasting for 6 hours at 540 ℃ to obtain the high-crystallinity SAPO-5 molecular sieve.
Comparative example 1
A method for preparing an SAPO-5 molecular sieve by using gas-phase silicon dioxide as a silicon source and pseudo-boehmite as an aluminum source by adopting a traditional method comprises the following steps:
2.42g of fumed silica, 6.06g of pseudo-boehmite, 14.21g of phosphoric acid with the content of 85 percent and 7.26g of triethylamine are added into 69.78g of distilled water, stirred vigorously for 4 hours, then transferred into a stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallized at 220 ℃ for 48 hours, the obtained solid product is washed to be neutral by distilled water, filtered, dried and roasted at 550 ℃ for 6 hours to obtain the SAPO-5 molecular sieve, and the XRD diagram of the SAPO-5 molecular sieve is shown as figure 1 (C).
Comparative example 2
A method for preparing SAPO-5 molecular sieve by taking attapulgite as a raw material (repeat patent CN 109052428A example 3) comprises the following steps:
(1) 2.3g of phosphoric acid is dissolved in 5.4g of deionized water and is stirred uniformly; adding 1.36g of pseudo-boehmite, and stirring for 2h to obtain a mixed solution A;
(2) dissolving 2.1g of Diethylamine (DEA) in 5.4g of deionized water, stirring uniformly, adding 0.4g of attapulgite, and stirring for 2h to obtain a mixed solution B;
(3) gradually dropwise adding the mixed solution B into the mixed solution A, and stirring at room temperature for 4 hours to obtain a mixed solution C;
(4) transferring the mixed solution C into a stainless steel reaction kettle with a polytetrafluoroethylene lining for aging for 24 hours, then putting the mixture into a homogeneous reactor, and crystallizing at the constant temperature of 205 ℃ for 48 hours; cooling to room temperature, filtering, centrifugally washing for 3-5 times, and drying the obtained solid at 110 ℃ for 12 hours;
(5) the above crystallized product was calcined in a muffle furnace at 520 ℃ for 5 hours to remove the template, and a XRD pattern of the SAPO-5 molecular sieve was obtained as shown in FIG. 1(D), which indicates that the obtained product is not a pure phase SAPO-5 molecular sieve, but a mixture of SAPO-5 molecular sieve, SAPO-34 molecular sieve and palygorskite, and that the crystallinity of the SAPO-5 molecular sieve is not high, and is only about 30% relative to that of example 1 of the present invention.
Application example 1
The SAPO-5 molecular sieves prepared in example 1, comparative example 1 and comparative example 2 were used as catalysts to perform catalytic reactions for producing olefins from methanol, and their catalytic effects were evaluated as catalysts.
The specific experimental process is as follows: preparing each SAPO-5 molecular sieve sample into particles of 20-40 meshesLoading into fixed bed reactor, loading catalyst 0.2g, reacting at 400 deg.C, nitrogen as carrier gas at flow rate of 30mL/min, continuously feeding methanol into reaction tube via micro sample injection pump, and reacting at mass airspeed of 2h-1The product composition was analyzed on-line using a gas chromatograph (Agilent 1790, FID detector, HP-PLOTQ capillary column).
The catalytic reaction result of the SAPO-5 molecular sieve prepared in example 1 as a catalyst is shown in fig. 4, and it can be seen from the graph that the conversion rate of methanol catalyzed by the catalyst is still maintained above 80% after 200min of reaction, and the selectivity of low carbon olefin is 56.2% after 20min of reaction.
The results of the catalytic reaction of the SAPO-5 molecular sieve prepared in comparative example 1 as a catalyst are shown in fig. 5, which shows that the conversion rate of methanol catalyzed by the catalyst can be maintained above 80% only within 80min of reaction, and the selectivity of low carbon olefin is 53.2% at 20min of reaction.
The catalytic reaction result of the SAPO-5 molecular sieve prepared in the comparative example 2 as the catalyst is shown in FIG. 6, which shows that the conversion rate of the catalyst catalyzing methanol can be maintained above 80% only within 20min of reaction, and the selectivity of the low-carbon olefin is 43.9% at 20min of reaction.
The embodiment and the comparative example in the invention show that the high-crystallinity pure-phase SAPO-5 molecular sieve prepared by the invention has better catalytic performance in the catalytic reaction of methanol to olefin by taking attapulgite as the raw material, and has wider application prospect compared with the comparative example.
The above detailed description of the process for preparing a high crystallinity SAPO-5 molecular sieve based on attapulgite is illustrative and not restrictive with reference to the examples, and several examples are set forth in the scope of the invention as defined, therefore variations and modifications thereof without departing from the general inventive concept are intended to be within the scope of the present invention.
Claims (7)
1. A method for preparing a high-crystallinity SAPO-5 molecular sieve by taking attapulgite as a raw material is characterized by comprising the following steps:
(1) adding attapulgite and phosphoric acid into distilled water, uniformly mixing, carrying out hydrothermal reaction at 180-220 ℃ for 8-24 h, taking out, and cooling to obtain a mixed solution I;
(2) adding an aluminum source and triethylamine into the mixed solution I, violently stirring until the aluminum source and the triethylamine are uniformly mixed, carrying out hydrothermal reaction at 180-220 ℃ for 12-24 h, washing, filtering, drying and roasting the obtained solid product to obtain the high-crystallinity SAPO-5 molecular sieve.
2. The method according to claim 1, wherein the mass ratio of the distilled water to the attapulgite to the aluminum source to the phosphoric acid to the triethylamine is 69.78: 2.77-4.15: 4.43-6.65: 10.66-16.00: 6.56-9.84.
3. The method according to claim 1, wherein in the step (2), the roasting is carried out for 4-8 hours at 500-600 ℃ under an air atmosphere.
4. The method of claim 1, wherein the attapulgite has a silicon content of 50% to 70% and an aluminum content of 6% to 15%.
5. The method according to claim 1, wherein the phosphoric acid is orthophosphoric acid having a content of 80% or more.
6. The method of claim 1, wherein the aluminum source is one of pseudoboehmite, aluminum hydroxide, and aluminum oxide.
7. The SAPO-5 molecular sieve with high crystallinity prepared by the method of any one of claims 1 to 6.
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Inventor after: Li Xingyang Inventor after: Zhang Dandan Inventor after: Zhu Haipeng Inventor after: Li Qingqing Inventor after: Pan Meng Inventor after: Lou Shuyuan Inventor after: Wei Xueling Inventor after: Shi Zhisheng Inventor before: Pan Meng Inventor before: Lou Shuyuan Inventor before: Li Xing Inventor before: Wei Xueling Inventor before: Shi Zhisheng Inventor before: Li Xingyang |