CN111960430B - Synthetic method and application of high-crystallinity hierarchical-pore LSX zeolite molecular sieve - Google Patents
Synthetic method and application of high-crystallinity hierarchical-pore LSX zeolite molecular sieve Download PDFInfo
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- 239000010457 zeolite Substances 0.000 title claims abstract description 80
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 77
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 65
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 51
- 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 51
- 238000010189 synthetic method Methods 0.000 title description 2
- 238000003756 stirring Methods 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 42
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000001354 calcination Methods 0.000 claims abstract description 23
- 239000011780 sodium chloride Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 16
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 229910001388 sodium aluminate Inorganic materials 0.000 claims abstract description 10
- 238000001308 synthesis method Methods 0.000 claims abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 57
- 229910052681 coesite Inorganic materials 0.000 claims description 32
- 229910052906 cristobalite Inorganic materials 0.000 claims description 32
- 239000000377 silicon dioxide Substances 0.000 claims description 32
- 229910052682 stishovite Inorganic materials 0.000 claims description 32
- 229910052905 tridymite Inorganic materials 0.000 claims description 32
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 27
- 229910052593 corundum Inorganic materials 0.000 claims description 27
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 27
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- BOXDGARPTQEUBR-UHFFFAOYSA-N azane silane Chemical group N.[SiH4] BOXDGARPTQEUBR-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 abstract description 14
- 239000011148 porous material Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 19
- 239000000843 powder Substances 0.000 description 16
- 238000007789 sealing Methods 0.000 description 16
- 239000007787 solid Substances 0.000 description 16
- 238000000967 suction filtration Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- PYNUOAIJIQGACY-UHFFFAOYSA-N propylazanium;chloride Chemical compound Cl.CCCN PYNUOAIJIQGACY-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 4
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052665 sodalite Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- -1 ultrasonic treatment Chemical compound 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
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/205—Faujasite type, e.g. type X or Y using at least one organic template directing agent; Hexagonal faujasite; Intergrowth products of cubic and hexagonal faujasite
-
- 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/082—X-type faujasite
-
- B01J35/615—
-
- B01J35/617—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
Abstract
The invention discloses a synthesis method and application of a high-crystallinity hierarchical pore LSX zeolite molecular sieve. The method comprises the following steps: (1) dissolving sodium aluminate in water to obtain a solution A; (2) dissolving water glass in water to obtain a solution B; (3) adding NaCl into the solution A, fully stirring and mixing, continuously adding the solution B after mixing, fully stirring and mixing, then adding a template agent, and stirring to obtain a mixture; (4) and heating the mixture for reaction, washing, drying and calcining after the reaction to obtain the hierarchical pore LSX zeolite molecular sieve named MLSX. The application comprises the following steps: the high-crystallinity hierarchical-pore LSX zeolite molecular sieve is used in the glycerol hydrogenation reaction. According to the invention, different pore-forming templates are used in the hydrothermal synthesis process, the hierarchical pore LSX zeolite molecular sieve with controllable pore diameter and surface area is directly prepared, the synthesis method is simple, and the requirements on production equipment are not high; when the catalyst is used in the hydrogenation reaction of glycerol, the conversion rate of the glycerol and the selectivity of a target product are high.
Description
Technical Field
The invention relates to the field of inorganic nonmetallic materials, in particular to a synthesis method and application of a high-crystallinity hierarchical pore LSX zeolite molecular sieve.
Background
As an important catalytic material, the zeolite molecular sieve is widely applied to the fields of adsorption separation, sewage treatment, petrochemical industry and the like, but has long faced the challenges of difficult control of pore size, poor hydrothermal stability and the like. Research shows that the introduction of hierarchical pores can change the specific surface area of zeolite, enlarge the pore size, and increase the surface active sites of corresponding catalyst, so as to improve the activity and stability of the catalyst. However, the currently widely reported hierarchical pore zeolite molecular sieves are mainly limited to conventional zeolites such as ZSM-5, baste, Y and the like, and cannot meet the actual requirements of different catalytic reactions. Therefore, in order to further expand the practical application range of the zeolite catalyst and fully exert the unique advantages of the zeolite catalyst in the field of catalytic application, it is necessary to design and synthesize various types of hierarchical pore zeolite molecular sieves.
LSX is a low silicon-aluminum ratio X-type zeolite with a silicon-aluminum ratio of 1.0-1.1, and the unit cell structure of the low silicon-aluminum ratio X-type zeolite is a four-membered ring or a six-membered ring formed by connecting an aluminum tetrahedron and a silicon tetrahedron through an oxygen bridge. These multiple rings are then combined to form a beta cage and a sodalite cage, thus forming an octahedral zeolite cage. The octahedral zeolite cages are communicated with each other through twelve-membered rings to form the main pore canal of LSX zeolite, and the pore diameter is 0.9-1.0 nm. The related research on the hierarchical pore LSX zeolite molecular sieve is always quite short, and the reported preparation method has not ideal effect. Although traditional approaches for synthesizing hierarchical pore zeolite molecular sieves, such as ultrasonic treatment, alkali treatment and the like, can prepare the LSX zeolite containing a hierarchical pore structure to a certain extent, the LSX zeolite has low crystallinity, a small number of introduced mesopores and poor thermal stability, so that the service life of the corresponding catalyst is short, and the LSX zeolite is difficult to be widely applied to industrial production.
Disclosure of Invention
The invention aims to provide a simple synthesis method of a high-crystallinity hierarchical pore LSX zeolite molecular sieve.
The invention is realized by the following technical scheme:
a method for synthesizing a high-crystallinity hierarchical-pore LSX zeolite molecular sieve is characterized by comprising the following steps:
(1) dissolving sodium aluminate in water to obtain a solution A;
(2) dissolving water glass in water to obtain a solution B;
(3) adding NaCl into the solution A, fully stirring and mixing, continuously adding the solution B after mixing, fully stirring and mixing, then adding a template agent, and stirring to obtain a mixture;
(4) and heating the mixture for reaction, washing, drying and calcining after the reaction to obtain the hierarchical pore LSX zeolite molecular sieve. Named MLSX.
Further, the composition of the water glass in the step (2) is Na2O、SiO2And H2O。
Further, the composition of the water glass contains Na28.5% by mass of O and SiO2Has a mass content of 26.5% and H2The mass content of O is 65%.
Further, the template agent in the step (3) is any one of ammonium silane, hexadecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride, octadecyl dimethyl benzyl ammonium chloride and octadecyl dimethyl trimethyl silicone propyl ammonium chloride; the volume ratio of the template to the solution A is 20: (1-3).
Furthermore, the feeding molar ratio of each raw material in the synthesis method is Na2O：Al2O3：SiO2：H2O is (5.5-6.25): 1.0: (2.0-2.2): (80-130) wherein Na2O is a sodium source, and the mole number of the sodium source is sodium aluminate and waterThe sum of the molar amounts of the sodium elements contained in the glass and sodium chloride, Al2O3Is an aluminum source, the mole number of the aluminum source is the mole number of aluminum elements in sodium aluminate, SiO2The silicon source is the mole number of silicon elements in the water glass.
Furthermore, the feeding molar ratio of each raw material in the synthesis method is Na2O：Al2O3：SiO2：H2O is (5.5-6.25): 1.0: 2.2: (90-122).
Furthermore, the feeding molar ratio of each raw material in the synthesis method is Na2O：Al2O3：SiO2：H2Calculated as O, 5.85: 1.0: 2.2: (110-122).
Furthermore, the feeding molar ratio of each raw material in the synthesis method is Na2O：Al2O3：SiO2：H2Calculated as O, 5.85: 1.0: 2.2: 122.
further, the reaction in the step (4) is a hydrothermal reaction, the reaction temperature is 80-110 ℃, and the reaction time is 5-8 hours; the calcination temperature is 450 ℃, and the calcination time is 4 hours.
The application of the high-crystallinity hierarchical pore LSX zeolite molecular sieve is characterized in that the high-crystallinity hierarchical pore LSX zeolite molecular sieve is used in a glycerol hydrogenation reaction.
The invention has the beneficial effects that:
the invention uses different types of template agents, directly synthesizes the LSX zeolite sieve with controllable aperture and surface area and high crystallinity and containing a hierarchical pore structure by a simple hydrothermal method, has simple synthesis method and low requirements on production equipment, and enterprises producing the zeolite molecular sieve can put into production by using the existing equipment.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Figure 1 is an XRD pattern of a hierarchical pore LSX zeolite molecular sieve synthesized under the action of different volumes of a template agent.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention
The following examples used the following starting materials and solutions:
the composition of water glass is as follows: SiO 22:6.865mol/L，Na2O:1.8444mol/L，H2O:49.8333mol/L；
Solution A: 2.5g of sodium aluminate (NaAlO)2) Dissolved to 20mL of H2Preparing in O;
solution B: dissolve 5.5mL of water glass to 8.5mL of H2And O is prepared.
In the following examples and comparative examples "molar ratio of materials Na2O：Al2O3：SiO2：H2In the expression of O', Na2O is a sodium source, the mole number of the sodium source is the sum of the mole numbers of sodium elements contained in sodium aluminate, water glass and sodium chloride, and Al is2O3The aluminum source is an aluminum source, the mole number of the aluminum source is the mole number of aluminum elements in the sodium aluminate, SiO2The silicon source is a silicon source, and the mole number of the silicon source is the mole number of silicon element in water glass in the water glass.
Methods for testing and calculating crystallinity (%): the crystallinity is measured using an X-ray diffractometer, and the formula is calculated: the crystallinity (diffraction peak intensity/total intensity) was 100%, and data was processed using the jade software.
SBET、SEXTAnd VEXTThe iso-texture data was measured by nitrogen adsorption using a physical adsorption apparatus.
Example 1
Taking the solution A, adding 6.75g of NaCl solid powder into the solution A, stirring for 0.5h, then slowly dropwise adding the solution B into the solution A, continuously stirring for 0.5h, then adding 1mL of hexadecyl trimethyl ammonium bromide (which is marked as a # 1 template agent) and stirring for 1 h to obtain a mixture; then the obtained mixture is moved into a reaction kettle for sealing and reacts for 7.0 hours at the temperature of 100 ℃; and then, carrying out suction filtration, washing and drying on a reaction sample, and calcining for 4 hours at 450 ℃ to obtain the hierarchical pore LSX zeolite molecular sieve. The molar ratio of each material in the embodiment is Na2O：Al2O3：SiO2：H2O is 5.85: 1.0: 2.2: 122. the crystallinity of the prepared hierarchical pore LSX zeolite sieve is shown in Table 1.
Example 2
Taking the solution A, adding 6.75g of NaCl solid powder into the solution A, stirring for 0.5h, then slowly dropwise adding the solution B into the solution A, continuously stirring for 0.5h, then adding 2mL of hexadecyl trimethyl ammonium bromide (which is marked as a # 1 template agent) and stirring for 1 h to obtain a mixture; then the obtained mixture is moved into a reaction kettle for sealing and reacts for 7.0 hours at the temperature of 100 ℃; and then, carrying out suction filtration, washing and drying on a reaction sample, and calcining for 4 hours at 450 ℃ to obtain the hierarchical pore LSX zeolite molecular sieve. The molar ratio of each material in the embodiment is Na2O：Al2O3：SiO2：H2O is 5.85: 1.0: 2.2: 122. the crystallinity of the prepared hierarchical pore LSX zeolite sieve is shown in Table 1.
Example 3
Taking the solution A, adding 6.75g of NaCl solid powder into the solution A, stirring for 0.5h, then slowly dropwise adding the solution B into the solution A, continuously stirring for 0.5h, then adding 3mL of hexadecyl trimethyl ammonium bromide (which is marked as a # 1 template agent) and stirring for 1 h to obtain a mixture; then the obtained mixture is moved into a reaction kettle for sealing and reacts for 7.0 hours at the temperature of 100 ℃; then, after the reaction sample is filtered, washed and dried, the reaction sample is calcined for 4 hours at the temperature of 450 ℃ to obtainHierarchical pore LSX zeolite molecular sieve. The molar ratio of each material in the embodiment is Na2O：Al2O3：SiO2：H2O is 5.85: 1.0: 2.2: 122. the crystallinity of the prepared hierarchical pore LSX zeolite sieve is shown in Table 1.
Example 4
Taking the solution A, adding 6.75g of NaCl solid powder into the solution A, stirring for 0.5h, slowly dropwise adding the solution B into the solution A, continuously stirring for 0.5h, then adding 1mL of octadecyl dimethyl benzyl ammonium chloride (which is marked as a No. 5 template agent) and stirring for 1 h to obtain a mixture; then the obtained mixture is moved into a reaction kettle for sealing and reacts for 7.0 hours at the temperature of 100 ℃; and then, carrying out suction filtration, washing and drying on a reaction sample, and calcining for 4 hours at 450 ℃ to obtain the hierarchical pore LSX zeolite molecular sieve. The molar ratio of each material in the embodiment is Na2O：Al2O3：SiO2：H2O is 5.85: 1.0: 2.2: 122. the crystallinity of the prepared hierarchical pore LSX zeolite sieve is shown in Table 1.
Example 5
Taking the solution A, adding 6.75g of NaCl solid powder into the solution A, stirring for 0.5h, slowly dropwise adding the solution B into the solution A, continuously stirring for 0.5h, adding 2mL of octadecyl dimethyl benzyl ammonium chloride (which is marked as a No. 5 template agent), and stirring for 1 h to obtain a mixture; then the obtained mixture is moved into a reaction kettle for sealing and reacts for 7.0 hours at the temperature of 100 ℃; and then, carrying out suction filtration, washing and drying on a reaction sample, and calcining for 4 hours at 450 ℃ to obtain the hierarchical pore LSX zeolite molecular sieve. The molar ratio of each material in the embodiment is Na2O：Al2O3：SiO2：H2O is 5.85: 1.0: 2.2: 122. the crystallinity of the prepared hierarchical pore LSX zeolite sieve is shown in Table 1.
Example 6
Taking the solution A, adding 6.75g of NaCl solid powder into the solution A, stirring for 0.5h, slowly dropwise adding the solution B into the solution A, continuously stirring for 0.5h, adding 3mL of octadecyl dimethyl benzyl ammonium chloride (which is marked as a No. 5 template agent), and stirring for 1 h to obtain a mixture; the resulting mixture is then transferred to the reactionSealing the reaction kettle, and reacting for 7.0 hours at 100 ℃; and then, carrying out suction filtration, washing and drying on a reaction sample, and calcining for 4 hours at 450 ℃ to obtain the hierarchical pore LSX zeolite molecular sieve. The molar ratio of each material in the embodiment is Na2O：Al2O3：SiO2：H2O is 5.85: 1.0: 2.2: 122. the crystallinity of the prepared hierarchical pore LSX zeolite sieve is shown in Table 1.
Example 7
Taking the solution A, adding 6.75g of NaCl solid powder into the solution A, stirring for 0.5h, then slowly dropwise adding the solution B into the solution A, continuously stirring for 0.5h, then adding 1mL of octadecyl trimethyl ammonium chloride (which is marked as 7# template agent) and stirring for 1 h to obtain a mixture; then the obtained mixture is moved into a reaction kettle for sealing and reacts for 7.0 hours at the temperature of 100 ℃; and then, carrying out suction filtration, washing and drying on a reaction sample, and calcining for 4 hours at 450 ℃ to obtain the hierarchical pore LSX zeolite molecular sieve. The molar ratio of each material in the embodiment is Na2O：Al2O3：SiO2：H2O is 5.85: 1.0: 2.2: 122. the crystallinity of the prepared hierarchical pore LSX zeolite sieve is shown in Table 1.
Example 8
Taking the solution A, adding 6.75g of NaCl solid powder into the solution A, stirring for 0.5h, then slowly dropwise adding the solution B into the solution A, continuously stirring for 0.5h, then adding 2mL of octadecyl trimethyl ammonium chloride (which is marked as 7# template agent) and stirring for 1 h to obtain a mixture; then the obtained mixture is moved into a reaction kettle for sealing and reacts for 7.0 hours at the temperature of 100 ℃; and then, carrying out suction filtration, washing and drying on a reaction sample, and calcining for 4 hours at 450 ℃ to obtain the hierarchical pore LSX zeolite molecular sieve. The molar ratio of each material in the embodiment is Na2O：Al2O3：SiO2：H2O is 5.85: 1.0: 2.2: 122. the crystallinity of the prepared hierarchical pore LSX zeolite sieve is shown in Table 1.
Example 9
Taking the solution A, adding 6.75g NaCl solid powder, stirring for 0.5h, slowly adding the solution B dropwise, continuing to stir for 0.5h, and then adding 3mL eighteenAlkyl trimethyl ammonium chloride (which is marked as 7# template) is stirred for 1 hour to obtain a mixture; then the obtained mixture is moved into a reaction kettle for sealing and reacts for 7.0 hours at the temperature of 100 ℃; and then, carrying out suction filtration, washing and drying on a reaction sample, and calcining for 4 hours at 450 ℃ to obtain the hierarchical pore LSX zeolite molecular sieve. The molar ratio of each material in the embodiment is Na2O：Al2O3：SiO2：H2O is 5.85: 1.0: 2.2: 122. the crystallinity of the prepared hierarchical pore LSX zeolite sieve is shown in Table 1.
Example 10
Taking the solution A, adding 6.75g of NaCl solid powder into the solution A, stirring for 0.5h, then slowly dropwise adding the solution B into the solution A, continuously stirring for 0.5h, then adding 1mL of octadecyl dimethyl trimethyl silicone propyl ammonium chloride (recorded as DM-3010 template) and stirring for 1 h to obtain a mixture; then the obtained mixture is moved into a reaction kettle for sealing and reacts for 7.0 hours at the temperature of 100 ℃; and then, carrying out suction filtration, washing and drying on a reaction sample, and calcining for 4 hours at 450 ℃ to obtain the hierarchical pore LSX zeolite molecular sieve. The molar ratio of each material in the embodiment is Na2O：Al2O3：SiO2：H2O is 5.85: 1.0: 2.2: 122. the crystallinity of the prepared hierarchical pore LSX zeolite sieve is shown in Table 1.
Example 11
Taking the solution A, adding 6.75g of NaCl solid powder into the solution A, stirring for 0.5h, then slowly dropwise adding the solution B into the solution A, continuously stirring for 0.5h, then adding 2mL of octadecyl dimethyl trimethyl silicone propyl ammonium chloride (recorded as DM-3010 template) and stirring for 1 h to obtain a mixture; then the obtained mixture is moved into a reaction kettle for sealing and reacts for 7.0 hours at the temperature of 100 ℃; and then, carrying out suction filtration, washing and drying on a reaction sample, and calcining for 4 hours at 450 ℃ to obtain the hierarchical pore LSX zeolite molecular sieve. The molar ratio of each material in the embodiment is Na2O：Al2O3：SiO2：H2O is 5.85: 1.0: 2.2: 122. the crystallinity of the prepared hierarchical pore LSX zeolite sieve is shown in Table 1.
Example 12
Taking the solution A, adding 6.75g of NaCl solid powder into the solution A, stirring for 0.5h, then slowly dropwise adding the solution B into the solution A, continuously stirring for 0.5h, then adding 3mL of octadecyl dimethyl trimethyl silicone propyl ammonium chloride (recorded as DM-3010 template) and stirring for 1 h to obtain a mixture; then the obtained mixture is moved into a reaction kettle for sealing and reacts for 7.0 hours at the temperature of 100 ℃; and then, carrying out suction filtration, washing and drying on a reaction sample, and calcining for 4 hours at 450 ℃ to obtain the hierarchical pore LSX zeolite molecular sieve. The molar ratio of each material in the embodiment is Na2O：Al2O3：SiO2：H2O is 5.85: 1.0: 2.2: 122. the crystallinity of the prepared hierarchical pore LSX zeolite sieve is shown in Table 1.
Example 13
Taking the solution A, adding 6.75g of NaCl solid powder into the solution A, stirring for 0.5h, then slowly dropwise adding the solution B into the solution A, continuously stirring for 0.5h, then adding 1mL of ammonium silane (marked as 3# template) and stirring for 1 h to obtain a mixture; then the obtained mixture is moved into a reaction kettle for sealing and reacts for 7.0 hours at the temperature of 100 ℃; and then, carrying out suction filtration, washing and drying on a reaction sample, and calcining for 4 hours at 450 ℃ to obtain the hierarchical pore LSX zeolite molecular sieve. The molar ratio of each material in the embodiment is Na2O：Al2O3：SiO2：H2O is 5.85: 1.0: 2.2: 122. the crystallinity of the prepared hierarchical pore LSX zeolite sieve is shown in Table 1.
Example 14
Taking the solution A, adding 6.75g of NaCl solid powder into the solution A, stirring for 0.5h, then slowly dropwise adding the solution B into the solution A, continuously stirring for 0.5h, then adding 2mL of ammonium silane (marked as 3# template) and stirring for 1 h to obtain a mixture; then the obtained mixture is moved into a reaction kettle for sealing and reacts for 7.0 hours at the temperature of 100 ℃; and then, carrying out suction filtration, washing and drying on a reaction sample, and calcining for 4 hours at 450 ℃ to obtain the hierarchical pore LSX zeolite molecular sieve. The molar ratio of each material in the embodiment is Na2O：Al2O3：SiO2：H2O is 5.85: 1.0: 2.2: 122. the crystallinity of the prepared hierarchical pore LSX zeolite sieve,see table 1 for details.
Example 15
Taking the solution A, adding 6.75g of NaCl solid powder into the solution A, stirring for 0.5h, then slowly dropwise adding the solution B into the solution A, continuously stirring for 0.5h, then adding 3mL of ammonium silane (marked as 3# template) and stirring for 1 h to obtain a mixture; then the obtained mixture is moved into a reaction kettle for sealing and reacts for 7.0 hours at the temperature of 100 ℃; and then, carrying out suction filtration, washing and drying on a reaction sample, and calcining for 4 hours at 450 ℃ to obtain the hierarchical pore LSX zeolite molecular sieve. The molar ratio of each material in the embodiment is Na2O：Al2O3：SiO2：H2O is 5.85: 1.0: 2.2: 122. the crystallinity of the prepared hierarchical pore LSX zeolite sieve is shown in Table 1.
Comparative example 1
Taking the solution A, adding 6.75g of NaCl solid powder into the solution A, stirring for 0.5h, then slowly dropwise adding the solution B into the solution A, continuously stirring for 0.5h, then transferring the obtained mixture into a reaction kettle, sealing, and reacting for 7.0 h at 100 ℃; and then, carrying out suction filtration, washing and drying on a reaction sample, and calcining for 4 hours at 450 ℃ to obtain the hierarchical pore LSX zeolite molecular sieve. The molar ratio of each material in the embodiment is Na2O：Al2O3：SiO2：H2O is 5.85: 1.0: 2.2: 122. the crystallinity of the prepared hierarchical pore LSX zeolite (LSX) is shown in Table 1; (no templating agent was added in comparative example 1).
Test example 1
The above examples 1-15 and comparative example 1 were tested by an X-ray diffractometer to obtain the XRD patterns of the hierarchical pore LSX zeolite molecular sieves prepared by adding different volumes of the # 3 template as shown in fig. 1.
Table 1 shows the crystallinity and structural properties of the sieves of the multigraded pore LSX zeolites prepared in comparative example 1 and examples 1-15 above:
examples 13-15 were set up to compare the effect of adding different volumes of # 3 template on the synthesis of a hierarchical pore LSX zeolite molecular sieve, the XRD patterns of comparative example 1 and examples 13-15 were analyzed (figure 1), and from the crystallinity and XRD patterns of table 1 we can see that the crystallinity of the prepared hierarchical pore LSX zeolite molecular sieve decreases slightly as the volume of the template increases. As can be seen from the data of nitrogen adsorption in Table 1, when the volume of the template added is 3mL, the specific surface area is slightly reduced to some extent, but the pore size is obviously increased, so 3mL of the 3# template is selected to be added.
Application example 1
The sieves of the multi-stage pore LSX zeolites prepared in example 12, example 15 and comparative example 1 above were tested for catalytic performance in the hydrogenation of glycerol:
preparation of the catalyst: taking the classified sieve samples of the hierarchical pore LSX zeolite prepared in the above example 12, example 15 and comparative example 1 as catalyst carriers, respectively, and introducing metal species according to 5% of the mass of the carriers by an isometric impregnation method, wherein the metal precursor is mainly nitrate (nickel nitrate is selected in the application example 1); drying the soaked sample in air at room temperature overnight, then drying in an oven at 80-120 ℃, and finally calcining at 450 ℃ for 4 hours to obtain catalysts Ni/MLSX-DM-3010 (obtained by loading the molecular sieve prepared in example 12 with nickel), Ni/MLSX-3# (obtained by loading the molecular sieve prepared in example 15 with nickel), and Ni/LSX (obtained by loading the molecular sieve prepared in comparative example 1 with nickel), respectively; the catalyst needs to be subjected to reduction treatment before use: the prepared catalyst is screened to a target mesh number and then reduced for 4 hours at 400 ℃ in a high-pressure reaction kettle in a hydrogen atmosphere.
Mixing the reduced catalyst with glycerol and water, stirring for 10 molecules at room temperature, putting into a reaction kettle, sealing, and repeatedly introducing hydrogen for three times to remove redundant air in the kettle and check the air tightness of the reactor. The specific reaction conditions are as follows: 5.0g of glycerol, 0.5g of metal-supported catalyst, 75mL of H2O, reaction temperature of 200 ℃, reaction time of 8 hours, 2MPa H2The stirring speed during the reaction was 600 rpm.
Table 2 shows the activity comparison of the hydrogenation of glycerol on different catalysts
It can be seen from table 2 that the high-crystallinity hierarchical pore LSX zeolite molecular sieve is synthesized by adding the pore-forming template agent, and is used in the glycerol hydrogenation reaction to improve the conversion rate of glycerol and the selectivity of the corresponding target product.
The above-mentioned preferred embodiments of the present invention are provided for illustration only and not for the purpose of limiting the invention. Obvious variations or modifications of the present invention are within the scope of the present invention.
Claims (7)
1. A method for synthesizing a high-crystallinity hierarchical-pore LSX zeolite molecular sieve is characterized by comprising the following steps:
(1) dissolving sodium aluminate in water to obtain a solution A;
(2) dissolving water glass in water to obtain a solution B;
(3) adding NaCl into the solution A, fully stirring and mixing, continuously adding the solution B after mixing, fully stirring and mixing, then adding a template agent, and stirring to obtain a mixture;
(4) heating the mixture for reaction, washing, drying and calcining after the reaction to obtain the hierarchical pore LSX zeolite molecular sieve;
in the step (3), the template agent is ammonium silane; the volume ratio of the template to the solution A is (1-3): 20;
in the synthesis method, the feeding molar ratio of each raw material is Na2O：Al2O3：SiO2：H2O is (5.5-6.25): 1.0: (2.0-2.2): (80-130) wherein Na2O is a sodium source, and the mole number of the sodium source is sodium contained in sodium aluminate, water glass and sodium chlorideSum of the moles of the elements, Al2O3The aluminum source is an aluminum source, the mole number of the aluminum source is the mole number of aluminum elements in the sodium aluminate, SiO2The silicon source is a silicon source, and the mole number of the silicon source is the mole number of silicon element in water glass in the water glass;
the hierarchical pore LSX zeolite molecular sieve is used in the glycerol hydrogenation reaction.
2. The method for synthesizing a high crystallinity hierarchical pore LSX zeolite molecular sieve according to claim 1, wherein the composition of said water glass in step (2) is Na2O、SiO2And H2O。
3. The method for synthesizing a high crystallinity hierarchical pore LSX zeolite molecular sieve of claim 2 wherein the composition of said water glass is Na28.5% by mass of O and SiO2Has a mass content of 26.5% and H2The mass content of O is 65%.
4. The method for synthesizing a high crystallinity hierarchical pore LSX zeolite molecular sieve according to claim 1, wherein the molar ratio of each raw material fed in the method is Na2O：Al2O3：SiO2：H2O is (5.5-6.25): 1.0: 2.2: (90-122).
5. The method for synthesizing a high crystallinity hierarchical pore LSX zeolite molecular sieve according to claim 1, wherein the molar ratio of each raw material fed in the method is Na2O：Al2O3：SiO2：H2Calculated as O, 5.85: 1.0: 2.2: (110-122).
6. The method for synthesizing a high crystallinity hierarchical pore LSX zeolite molecular sieve according to claim 1, wherein the molar ratio of each raw material fed in the method is Na2O：Al2O3：SiO2：H2Calculated as O, 5.85: 1.0：2.2：122。
7. The method for synthesizing the LSX zeolite molecular sieve with high crystallinity and hierarchical pores as claimed in claim 1, wherein the reaction in step (4) is hydrothermal reaction at 80-110 ℃ for 5-8 hours; the calcination temperature is 450 ℃ and the calcination time is 4 hours.
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