CN108996518B - Hierarchical pore SAPO-11 molecular sieve and synthetic method and application thereof - Google Patents
Hierarchical pore SAPO-11 molecular sieve and synthetic method and application thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 166
- 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 165
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 76
- 238000010189 synthetic method Methods 0.000 title description 2
- 239000000843 powder Substances 0.000 claims abstract description 53
- 239000011148 porous material Substances 0.000 claims abstract description 43
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000011973 solid acid Substances 0.000 claims abstract description 12
- 238000001308 synthesis method Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 8
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 59
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 51
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 28
- 229940094933 n-dodecane Drugs 0.000 claims description 26
- 235000006408 oxalic acid Nutrition 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 16
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 11
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 3
- 239000001384 succinic acid Substances 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 68
- 239000010935 stainless steel Substances 0.000 description 68
- 239000002994 raw material Substances 0.000 description 37
- -1 SAPO-11 Chemical compound 0.000 description 36
- 239000007787 solid Substances 0.000 description 36
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 35
- 239000004810 polytetrafluoroethylene Substances 0.000 description 35
- 239000000376 reactant Substances 0.000 description 35
- 238000005303 weighing Methods 0.000 description 35
- 239000000047 product Substances 0.000 description 28
- 238000010298 pulverizing process Methods 0.000 description 27
- 239000003054 catalyst Substances 0.000 description 19
- 238000001228 spectrum Methods 0.000 description 19
- 239000002245 particle Substances 0.000 description 13
- 239000007790 solid phase Substances 0.000 description 13
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 7
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-UHFFFAOYSA-N 0.000 description 6
- SGVYKUFIHHTIFL-UHFFFAOYSA-N Isobutylhexyl Natural products CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 description 6
- VKPSKYDESGTTFR-UHFFFAOYSA-N isododecane Natural products CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- 238000002791 soaking Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010306 acid treatment Methods 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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- 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
-
- 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
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2767—Changing the number of side-chains
- C07C5/277—Catalytic processes
- C07C5/2775—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
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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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- 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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- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
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Abstract
The invention provides a hierarchical pore SAPO-11 molecular sieve and a synthesis method and application thereof, wherein the preparation method at least comprises the following steps: and (2) crushing and uniformly mixing SAPO-11 molecular sieve raw powder and solid acid to obtain a mixture, and reacting the mixture at the temperature of between 20 and 120 ℃ for 2 to 12 hours to obtain the hierarchical pore SAPO-11 molecular sieve. The SAPO-11 molecular sieve prepared by carrying out solid acid post-treatment on the SAPO-11 molecular sieve raw powder has a proper pore channel structure, namely a composite multi-stage pore channel, and is high in crystallinity; in addition, the catalytic performance of the hierarchical pore SAPO-11 molecular sieve after pore channel regulation is greatly improved. The method does not use water or other solvents in the treatment process, reduces the discharge of waste liquid, has low preparation cost and has potential economic and social values.
Description
Technical Field
The invention belongs to the field of synthesis of molecular sieves, and relates to a hierarchical pore SAPO-11 molecular sieve, a synthesis method and application thereof, in particular to a method for synthesizing the hierarchical pore SAPO-11 molecular sieve with a suitable pore structure by solid acid post-treatment and application of the molecular sieve.
Background
The molecular sieve has been widely noticed due to its excellent physicochemical properties, and has been widely used in the field of industrial catalysis due to its tunable acidity, high thermal stability, high hydrothermal stability and specific pore structure. The bifunctional catalyst prepared by compounding the noble metal/non-noble metal and the molecular sieve carrier is applied to the preparation process of the lubricating oil, and can effectively improve the yield of the lubricating oil base oil. Molecular sieves such as SAPO-11, SAPO-31, SAPO-34, ZSM-22, ZSM-23 and the like are subjected to long-chain alkane hydroisomerization reaction, so that the selectivity of the product can be improved. However, the prepared catalyst has the limitation on the conversion rate of raw materials or the selectivity of products in the reaction process due to the single pore channel structure of the molecular sieve, and the yield of the products can be further improved by adjusting the pore channel structure of the molecular sieve.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a hierarchical pore SAPO-11 molecular sieve, a synthesis method and an application thereof, which are used for solving the problem that the pore channel structure of the SAPO-11 molecular sieve prepared in the prior art is single.
To achieve the above and other related objects, the present invention provides a method for synthesizing a hierarchical pore SAPO-11 molecular sieve, the method at least comprising:
and (2) crushing and uniformly mixing SAPO-11 molecular sieve raw powder and solid acid to obtain a mixture, and reacting the mixture at the temperature of between 20 and 120 ℃ for 2 to 12 hours to obtain the hierarchical pore SAPO-11 molecular sieve.
As an optimized scheme of the synthesis method of the hierarchical pore SAPO-11 molecular sieve, the solid acid comprises one of oxalic acid, ethylenediamine tetraacetic acid, periodic acid and succinic acid. Because the SAPO-11 molecular sieve has a one-dimensional straight pore channel structure, the pore diameter data
After the acid treatment step of the present invention, Al-O bond, P-O bond or Si-O bond inside the crystal is broken, TO4The tetrahedral structure is destroyed; originally from TO4The space occupied by the tetrahedron is released to form the void. When the degree of acid treatment is increased but the SAPO-11 molecular sieve crystal structure is not collapsed, the internal or external cavities of the crystal are gradually enlarged, and the SAPO-11 molecular sieve gradually forms a mesoporous and macroporous pore channel structure.
As an optimized scheme of the synthesis method of the hierarchical pore SAPO-11 molecular sieve, the mass ratio of the solid acid to the SAPO-11 molecular sieve raw powder is 1: 5 to 1: 100, respectively.
As an optimized scheme of the synthesis method of the hierarchical pore SAPO-11 molecular sieve, the crushing and mixing comprises one of grinding and mixing and crushing and mixing by a mechanical crusher.
As an optimized scheme of the synthesis method of the hierarchical pore SAPO-11 molecular sieve, the mixture is reacted for 2 to 10 hours at the temperature of between 50 and 120 ℃.
The invention provides a hierarchical pore SAPO-11 molecular sieve synthesized by the synthesis method, wherein the synthesis method of the hierarchical pore SAPO-11 molecular sieve has an AEL crystal structure, and the pore size distribution of the hierarchical pore SAPO-11 molecular sieve is between 0.4nm and 100 nm.
The hierarchical pore SAPO-11 molecular sieve has a macroporous-microporous composite pore channel. Furthermore, the crystal grains of the multi-stage pore SAPO-11 molecular sieve are spherically stacked, and the crystal grains after being treated by the solid acid are loosely arranged.
As an optimized scheme of the hierarchical pore SAPO-11 molecular sieve, the pore size distribution of the hierarchical pore SAPO-11 molecular sieve is between 0.4nm and 50 nm.
As an optimized scheme of the multi-stage pore SAPO-11 molecular sieve, the BET specific surface area of the multi-stage pore SAPO-11 molecular sieve is between 100m2/g～400m2Between/g.
The ratio of the micropore volume to the mesopore volume of the hierarchical pore SAPO-11 molecular sieve is between 1 and 3.
The invention further provides a catalytic application of the hierarchical pore SAPO-11 molecular sieve in a n-dodecane hydroisomerization reaction.
As an optimized scheme of the catalytic application of the invention, the reaction temperature of the n-dodecane hydroisomerization reaction is between 260 and 400 ℃, the reaction pressure is between 0.1 and 2MPa, and the reaction space velocity is 0.1h-1～10h-1In the meantime.
As mentioned above, the multi-stage pore SAPO-11 molecular sieve of the invention, the synthesis method and the application thereof, the synthesis method at least comprises the following steps: and (2) crushing and uniformly mixing SAPO-11 molecular sieve raw powder and solid acid to obtain a mixture, and reacting the mixture at the temperature of between 20 and 120 ℃ for 2 to 12 hours to obtain the hierarchical pore SAPO-11 molecular sieve. The SAPO-11 molecular sieve prepared by carrying out solid acid post-treatment on the SAPO-11 molecular sieve raw powder has a proper pore channel structure, namely a composite multi-stage pore channel, and is high in crystallinity; in addition, the catalytic performance of the hierarchical pore SAPO-11 molecular sieve catalyst after pore channel regulation is also greatly improved. The method does not use water or other solvents in the treatment process, reduces the discharge of waste liquid, has low preparation cost and has potential economic and social values.
Drawings
FIG. 1 is an XRD spectrum of the SAPO-11 molecular sieve raw powder of the invention.
FIG. 2 is a scanning electron micrograph of the SAPO-11 molecular sieve raw powder of the invention.
FIG. 3 is the nitrogen adsorption and desorption isotherm of the SAPO-11 molecular sieve raw powder of the invention.
FIG. 4 is an XRD spectrum of a multi-stage pore SAPO-11 molecular sieve of example 1 of the invention.
FIG. 5 is a scanning electron micrograph of the multi-stage pore SAPO-11 molecular sieve of example 1 of the invention.
FIG. 6 is an XRD spectrum of a multi-stage pore SAPO-11 molecular sieve of example 2 of the invention.
FIG. 7 is a SEM image of the multi-stage SAPO-11 molecular sieve in example 2 of the invention.
FIG. 8 is an XRD spectrum of a multi-stage pore SAPO-11 molecular sieve of example 3 of the invention.
FIG. 9 is a SEM image of the multi-stage SAPO-11 molecular sieve in example 3 of the invention.
FIG. 10 is an XRD spectrum of a multi-stage pore SAPO-11 molecular sieve of example 4 of the invention.
FIG. 11 is a SEM photograph of the multi-stage SAPO-11 molecular sieve in example 4 of the invention.
FIG. 12 is an XRD spectrum of a multi-stage pore SAPO-11 molecular sieve of example 5 of the invention.
FIG. 13 is a SEM of the multi-stage SAPO-11 molecular sieve of example 5.
FIG. 14 is an XRD spectrum of a multi-stage pore SAPO-11 molecular sieve of example 6 of the invention.
FIG. 15 is a SEM of the multi-stage SAPO-11 molecular sieve of example 6 of the invention.
FIG. 16 is an XRD spectrum of a multi-stage pore SAPO-11 molecular sieve of example 7 of the invention.
FIG. 17 is a SEM of the multi-stage SAPO-11 molecular sieve of example 7 of the invention.
FIG. 18 is an XRD spectrum of a multi-stage pore SAPO-11 molecular sieve of example 10 of the invention.
FIG. 19 is a SEM of the multi-stage SAPO-11 molecular sieve of example 10.
FIG. 20 is a nitrogen adsorption desorption isotherm of the multi-stage pore SAPO-11 molecular sieve of example 10 of the invention.
FIG. 21 is an XRD spectrum of a multi-stage pore SAPO-11 molecular sieve of example 14 of the invention.
FIG. 22 is a SEM of the multi-stage SAPO-11 molecular sieve of example 14.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and its several details are capable of modifications and variations in various respects, all without departing from the spirit of the invention.
Example 1
Weighing 10g of laboratory-synthesized SAPO-11 molecular sieve raw powder (shown in figure 1 as XRD spectrogram of the raw powder and figure 2 as SEM picture of the raw powder) and 0.1g of solid-phase oxalic acid, adding into a pulverizer, and pulverizing to uniformly mix the solid reactants. And then transferring the raw materials into a stainless steel autoclave with a 100ml polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 6 hours at 100 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
FIG. 4 is the XRD spectrum of the product, which shows that the product is a typical AEL structure with better relative crystallinity
FIG. 5 is SEM scanning electron micrograph of the product, which shows that the product is spherical particles with particle size of 6-10 μm stacked by lamellar crystals, and the surface has a small amount of fallen crystals compared with the original powder.
Example 2
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 0.1g of solid-phase oxalic acid, adding into a pulverizer, and pulverizing to uniformly mix solid reactants. And then transferring the raw materials into a 100ml stainless steel autoclave with a polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 12 hours at 100 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Fig. 6 is an XRD spectrum of the product, which can be seen as a typical AEL structure with better crystallinity.
FIG. 7 is SEM photograph showing the product, and it can be seen that the product has spherical particles with a particle size of 6-10 μm stacked from plate-like crystals, and the surface of the product is more exfoliated than that of the crystals shown in FIG. 2 of example 1.
Example 3
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 0.15g of solid oxalic acid, adding into a pulverizer, and pulverizing to uniformly mix solid reactants. And then transferring the raw materials into a stainless steel autoclave with a 100ml polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 6 hours at 100 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Fig. 8 is an XRD spectrum of the product, which can be seen as a typical AEL structure with better crystallinity.
FIG. 9 is an SEM scanning electron micrograph of a product.
Example 4
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 0.2g of solid-phase oxalic acid, adding into a pulverizer, and pulverizing to uniformly mix solid reactants. And then transferring the raw materials into a stainless steel autoclave with a 100ml polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 2 hours at 100 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Fig. 10 is an XRD spectrum of the product, which can be seen as a typical AEL structure with better crystallinity.
FIG. 11 is an SEM scanning electron micrograph of a product.
Example 5
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 0.25g of solid-phase oxalic acid, adding into a pulverizer, and pulverizing to uniformly mix solid reactants. And then transferring the raw materials into a stainless steel autoclave with a 100ml polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 10 hours at 100 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Fig. 12 is an XRD spectrum of the product, which can be seen as a typical AEL structure with better crystallinity.
FIG. 13 is an SEM scanning electron micrograph of a product.
Example 6
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 0.3g of solid-phase ethylenediamine tetraacetic acid, adding into a grinder for grinding, and uniformly mixing solid reactants. And then transferring the raw materials into a 100ml stainless steel autoclave with a polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 12 hours at 100 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Fig. 14 is an XRD spectrum of the product, which can be seen as a typical AEL structure with better crystallinity.
FIG. 15 is an SEM scanning electron micrograph of a product.
Example 7
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 0.5g of solid-phase oxalic acid, adding into a pulverizer, and pulverizing to uniformly mix solid reactants. And then transferring the raw materials into a 100ml stainless steel autoclave with a polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 6 hours at 50 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Fig. 16 is an XRD spectrum of the product, which can be seen as a typical AEL structure with better crystallinity.
FIG. 17 is an SEM scanning electron micrograph of a product.
Example 8
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 1g of solid-phase oxalic acid, adding into a pulverizer, and pulverizing to uniformly mix solid reactants. And then transferring the raw materials into a 100ml stainless steel autoclave with a polytetrafluoroethylene lining, putting the autoclave into an oven, and reacting for 2h at 120 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Example 9
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 1g of solid-phase oxalic acid, adding into a pulverizer, and pulverizing to uniformly mix solid reactants. And then transferring the raw materials into a 100ml stainless steel autoclave with a polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 4 hours at 120 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Example 10
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 1g of solid-phase oxalic acid, adding into a pulverizer, and pulverizing to uniformly mix solid reactants. And then transferring the raw materials into a 100ml stainless steel autoclave with a polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 6 hours at 120 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Fig. 18 is an XRD spectrum of the product, which can be seen as a typical AEL structure with better crystallinity.
FIG. 19 is a SEM scanning electron micrograph showing that the product is a spherical particle having a particle size of 6 to 10 μm and stacked from plate-like crystals, and the crystals dropped off more from the surface of the product, and oxalic acid and AlO of SAPO-11 molecular sieve4、PO4、SiO4The tetrahedron reacts to cause the original compact crystal to generate defects and cavities on the surface and in the crystal, so that the SAPO-11 molecular sieve with hierarchical pores is formed.
FIG. 20 is a nitrogen adsorption-desorption isotherm of the product, with a total pore volume of 0.153cm3Per g, micropore volume of 0.076cm3Per g, the mesoporous volume is 0.077cm3The ratio of the micropore volume to the mesopore volume is 1.01. FIG. 3 is a nitrogen adsorption and desorption isotherm of SAPO-11 raw powder showing that the product is a hierarchical pore SAPO-11 molecular sieve with a total pore volume of 0.205cm3Per g, micropore volume of 0.088cm3(g) the mesoporous volume is 0.117cm3The ratio of the micropore volume to the mesopore volume is 1.33. Comparing the difference of the ratio of the micropore volume to the mesopore volume, the pore structure of the hierarchical pore SAPO-11 molecular sieve is adjusted after the oxalic acid treatment.
Example 11
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 1g of solid-phase oxalic acid, adding into a pulverizer, and pulverizing to uniformly mix solid reactants. And then transferring the raw materials into a 100ml stainless steel autoclave with a polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 8 hours at 120 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Example 12
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 1g of solid-phase oxalic acid, adding into a pulverizer, and pulverizing to uniformly mix solid reactants. And then transferring the raw materials into a 100ml stainless steel autoclave with a polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 10 hours at 120 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Example 13
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 1g of solid-phase oxalic acid, adding into a pulverizer, and pulverizing to uniformly mix solid reactants. And then transferring the raw materials into a 100ml stainless steel autoclave with a polytetrafluoroethylene lining, putting the autoclave into an oven, and reacting for 12 hours at 120 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Example 14
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 2g of solid-phase oxalic acid, adding into a pulverizer, and pulverizing to uniformly mix solid reactants. And then transferring the raw materials into a stainless steel autoclave with a 100ml polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 6 hours at 100 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Fig. 21 is an XRD spectrum of the product, which can be seen as a typical AEL structure with better crystallinity.
FIG. 22 is an SEM scanning electron micrograph of a product.
Example 15
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 1g of ethylenediamine tetraacetic acid, adding into a grinder for grinding, and uniformly mixing solid reactants. And then transferring the raw materials into a 100ml stainless steel autoclave with a polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 6 hours at the temperature of 20 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Example 16
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 1g of periodic acid, adding into a pulverizer, and pulverizing to uniformly mix solid reactants. And then transferring the raw materials into a 100ml stainless steel autoclave with a polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 6 hours at the temperature of 20 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Example 17
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 1g of succinic acid, adding into a pulverizer, and pulverizing to uniformly mix solid reactants. And then transferring the raw materials into a 100ml stainless steel autoclave with a polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 6 hours at the temperature of 20 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Example 18
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 1g of ethylenediamine tetraacetic acid, adding into a grinder for grinding, and uniformly mixing solid reactants. And then transferring the raw materials into a 100ml stainless steel autoclave with a polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 6 hours at the temperature of 60 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Example 19
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 1g of periodic acid, adding into a pulverizer, and pulverizing to uniformly mix solid reactants. And then transferring the raw materials into a 100ml stainless steel autoclave with a polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 6 hours at the temperature of 60 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Example 20
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 1g of succinic acid, adding into a pulverizer, and pulverizing to uniformly mix solid reactants. And then transferring the raw materials into a 100ml stainless steel autoclave with a polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 6 hours at the temperature of 60 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Example 21
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 1g of ethylenediamine tetraacetic acid, adding into a grinder for grinding, and uniformly mixing solid reactants. And then transferring the raw materials into a stainless steel autoclave with a 100ml polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 6 hours at 100 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Example 22
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 1g of periodic acid, adding into a pulverizer, and pulverizing to uniformly mix solid reactants. And then transferring the raw materials into a stainless steel autoclave with a 100ml polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 6 hours at 100 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Example 23
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 1g of succinic acid, adding into a pulverizer, and pulverizing to uniformly mix solid reactants. And then transferring the raw materials into a stainless steel autoclave with a 100ml polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 6 hours at 100 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Example 24
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 0.5g of ethylenediamine tetraacetic acid, adding into a grinder for grinding, and uniformly mixing solid reactants. And then transferring the raw materials into a 100ml stainless steel autoclave with a polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 6 hours at 120 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Example 25
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 1g of periodic acid, adding into a pulverizer, and pulverizing to uniformly mix solid reactants. And then transferring the raw materials into a 100ml stainless steel autoclave with a polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 6 hours at 120 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Example 26
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 1g of succinic acid, adding into a pulverizer, and pulverizing to uniformly mix solid reactants. And then transferring the raw materials into a 100ml stainless steel autoclave with a polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 6 hours at 120 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Example 27
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 0.2g of ethylenediamine tetraacetic acid, adding into a grinder for grinding, and uniformly mixing solid reactants. And then transferring the raw materials into a stainless steel autoclave with a 100ml polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 2 hours at 100 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Example 28
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 0.5g of periodic acid, adding into a pulverizer, and pulverizing to uniformly mix solid reactants. And then transferring the raw materials into a stainless steel autoclave with a 100ml polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 2 hours at 100 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Example 29
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 1g of succinic acid, adding into a pulverizer, and pulverizing to uniformly mix solid reactants. And then transferring the raw materials into a stainless steel autoclave with a 100ml polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 2 hours at 100 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Example 30
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 0.5g of ethylenediamine tetraacetic acid, adding into a grinder for grinding, and uniformly mixing solid reactants. And then transferring the raw materials into a 100ml stainless steel autoclave with a polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 8 hours at 100 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Example 31
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 1g of periodic acid, adding into a pulverizer, and pulverizing to uniformly mix solid reactants. And then transferring the raw materials into a 100ml stainless steel autoclave with a polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 8 hours at 100 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Example 32
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 0.5g of succinic acid, adding into a pulverizer, and pulverizing to uniformly mix solid reactants. And then transferring the raw materials into a 100ml stainless steel autoclave with a polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 8 hours at 100 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Example 33
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 1g of ethylenediamine tetraacetic acid, adding into a grinder for grinding, and uniformly mixing solid reactants. And then transferring the raw materials into a 100ml stainless steel autoclave with a polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 12 hours at 100 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Example 34
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 1g of periodic acid, adding into a pulverizer, and pulverizing to uniformly mix solid reactants. And then transferring the raw materials into a 100ml stainless steel autoclave with a polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 12 hours at 100 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Example 35
Weighing 10g of laboratory synthesized SAPO-11 molecular sieve raw powder and 0.1g of succinic acid, adding into a pulverizer, and pulverizing to uniformly mix solid reactants. And then transferring the raw materials into a 100ml stainless steel autoclave with a polytetrafluoroethylene lining, putting the stainless steel autoclave into an oven, and reacting for 12 hours at 100 ℃ to obtain the hierarchical pore SAPO-11 molecular sieve.
Example 36
Soaking 0.5 wt% of Pt in the SAPO-11 molecular sieve catalyst with the hierarchical pore structure obtained in the example 1, tabletting, sieving particles with 20-40 meshes, and carrying out n-dodecane hydroisomerization reaction in a fixed bed reactor, wherein the reaction temperature is 320 ℃, the reaction pressure is 0.2MPa, and the reaction space velocity is 1.13h-1The volume ratio of hydrogen to n-dodecane was 1200: 1.
Example 37
Soaking 0.5 wt% of Pt in the SAPO-11 molecular sieve catalyst with the hierarchical pore structure obtained in the example 2, tabletting, sieving particles with 20-40 meshes, and carrying out n-dodecane hydroisomerization reaction in a fixed bed reactor, wherein the reaction temperature is 320 ℃, the reaction pressure is 0.1MPa, and the reaction space velocity is 1.13h-1The volume ratio of hydrogen to n-dodecane was 1200: 1.
Example 38
The SAPO-11 molecular sieve catalyst with the hierarchical pore structure obtained in the example 3 is soaked with 0.5 wt% of Pd, and after tabletting, particles with 20-40 meshes are sieved to carry out n-dodecane hydroisomerization reaction in a fixed bed reactor, wherein the reaction temperature is 320 ℃, the reaction pressure is 0.2MPa, and the reaction space velocity is 1.13h-1Of hydrogen with n-dodecaneThe volume ratio was 1200: 1.
Example 39
The SAPO-11 molecular sieve catalyst with the hierarchical pore structure obtained in the example 4 is soaked with 0.5 wt% of Pd, and after tabletting, particles with 20-40 meshes are sieved to carry out n-dodecane hydroisomerization reaction in a fixed bed reactor, wherein the reaction temperature is 320 ℃, the reaction pressure is 0.2MPa, and the reaction space velocity is 1.13h-1The volume ratio of hydrogen to n-dodecane was 1200: 1.
Example 40
Soaking 0.5 wt% of Pt in the SAPO-11 molecular sieve catalyst with the hierarchical pore structure obtained in the example 5, tabletting, sieving particles with 20-40 meshes, and carrying out n-dodecane hydroisomerization reaction in a fixed bed reactor, wherein the reaction temperature is 320 ℃, the reaction pressure is 0.2MPa, and the reaction space velocity is 1.13h-1The volume ratio of hydrogen to n-dodecane was 1200: 1.
EXAMPLE 41
Soaking 0.5 wt% of Pt in the SAPO-11 molecular sieve catalyst with the hierarchical pore structure obtained in the example 6, tabletting, sieving particles with 20-40 meshes, and carrying out n-dodecane hydroisomerization reaction in a fixed bed reactor, wherein the reaction temperature is 320 ℃, the reaction pressure is 0.2MPa, and the reaction space velocity is 1.13h-1The volume ratio of hydrogen to n-dodecane was 1200: 1.
Example 42
Soaking 0.5 wt% of Pt in the SAPO-11 molecular sieve catalyst with the hierarchical pore structure obtained in the example 7, tabletting, sieving particles with 20-40 meshes, and carrying out n-dodecane hydroisomerization reaction in a fixed bed reactor, wherein the reaction temperature is 320 ℃, the reaction pressure is 0.2MPa, and the reaction space velocity is 1.13h-1The volume ratio of hydrogen to n-dodecane was 1200: 1.
Example 43
The SAPO-11 molecular sieve catalyst with the hierarchical pore structure obtained in the example 10 is soaked with 0.5 wt% of Pt, tabletted, and then sieved to obtain particles with 20-40 meshes, and n-dodecane hydroisomerization reaction is carried out in a fixed bed reactor, wherein the reaction temperature is 320 ℃, the reaction pressure is 2MPa, and the reaction space velocity is 1.13h-1Hydrogen to n-dodecane volume ratio of 1200:1. The results are shown in Table 1.
Example 44
The SAPO-11 molecular sieve catalyst with the hierarchical pore structure obtained in the example 14 is soaked with 0.5 wt% of Pt, tableted and sieved to obtain particles with 20-40 meshes, and n-dodecane hydroisomerization reaction is carried out in a fixed bed reactor, wherein the reaction temperature is 320 ℃, the reaction pressure is 2MPa, and the reaction space velocity is 1.13h-1The volume ratio of hydrogen to n-dodecane was 1200: 1. The results are shown in Table 2.
Comparative example
Taking SAPO-11 molecular sieve raw powder synthesized in a laboratory as a catalyst, dipping 0.5 wt% of Pt, tabletting, sieving 20-40 mesh particles, and carrying out n-dodecane hydroisomerization reaction in a fixed bed reactor, wherein the reaction temperature is 320 ℃, the reaction pressure is 0.1MPa, and the reaction space velocity is 1.13h-1The volume ratio of hydrogen to n-dodecane was 1200: 1. The results are shown in tables 1 and 2, wherein Table 1 shows the hydroisomerization performance at 320 ℃ for n-dodecane of example 7 and the catalyst of comparative example, and Table 2 shows the hydroisomerization performance at 320 ℃ for n-dodecane of example 10 and the catalyst of comparative example.
TABLE 1
| Example 7 | Comparative example | |
| N-dodecane conversion (%) | 70.19 | 67.23 |
| Yield of isododecane (%) | 59.44 | 55.34 |
| Isododecane selectivity (%) | 84.68 | 82.32 |
TABLE 2
| Example 10 | Comparative example | |
| N-dodecane conversion (%) | 92.53 | 67.23 |
| Yield of isododecane (%) | 80.13 | 55.34 |
| Isododecane selectivity (%) | 86.60 | 82.32 |
Note: table 1 and table 2 select the analytical data of the reaction product of the catalyst at a reaction temperature of 320 ℃, and the catalyst performance is the best.
As can be seen from tables 1 and 2, in the hydroisomerization of n-dodecaneWhen the reaction temperature is 280-360 ℃ and the space velocity of the raw material is 0.1-10 h-1When the reaction pressure is 0.1-2 MPa, compared with the SAPO-11 molecular sieve of a comparative example, the multi-stage pore SAPO-11 molecular sieve catalyst after pore channel adjustment provided by the invention can enable the conversion rate of n-dodecane to be as high as 92.53%, which shows that the multi-stage pore SAPO-11 molecular sieve catalyst after pore channel adjustment has high activity; the isododecane selectivity (82.32%) in example 8 was significantly increased compared to the comparative example raw powder (67.23%), and the isododecane yield (80.13%) was significantly increased compared to the comparative example raw powder (55.34%).
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (6)
1. A hierarchical pore SAPO-11 molecular sieve, characterized by: the hierarchical pore SAPO-11 molecular sieve has an AEL crystal structure, the pore size distribution is between 0.4nm and 100nm, crystal grains are stacked in a spherical manner and are loosely arranged, the BET specific surface area is 100m2/g～400m2The ratio of the micropore volume to the mesopore volume is between 1 and 3, and the hierarchical pore SAPO-11 molecular sieve is obtained by the following synthesis method: the method comprises the steps of crushing and uniformly mixing SAPO-11 molecular sieve raw powder and solid acid to obtain a mixture, reacting the mixture at the temperature of 20-120 ℃ for 2-12 h to obtain the hierarchical pore SAPO-11 molecular sieve, wherein the mass ratio of the solid acid to the SAPO-11 molecular sieve raw powder is 1: 5 to 1: 100, respectively.
2. The multi-stage pore SAPO-11 molecular sieve of claim 1, characterized in that: the solid acid comprises one of oxalic acid, ethylene diamine tetraacetic acid, periodic acid and succinic acid.
3. The multi-stage pore SAPO-11 molecular sieve of claim 1, characterized in that: the crushing and mixing includes one of grinding and mixing and crushing and mixing by a mechanical crusher.
4. The multi-stage pore SAPO-11 molecular sieve of claim 1, characterized in that: reacting the mixture for 2 to 10 hours at the temperature of between 50 and 120 ℃.
5. The catalytic application of the hierarchical pore SAPO-11 molecular sieve as described in any one of claims 1 to 4 in n-dodecane hydroisomerization reaction.
6. The catalytic application according to claim 5, characterized in that: the reaction temperature of the n-dodecane hydroisomerization reaction is between 260 and 400 ℃, the reaction pressure is between 0.1 and 2MPa, and the reaction space velocity is 0.1h-1～10h-1In the meantime.
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