CN111097493B - Preparation method of mesoporous molecular sieve - Google Patents
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- CN111097493B CN111097493B CN201811248682.2A CN201811248682A CN111097493B CN 111097493 B CN111097493 B CN 111097493B CN 201811248682 A CN201811248682 A CN 201811248682A CN 111097493 B CN111097493 B CN 111097493B
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 310
- 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 310
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 117
- 239000003513 alkali Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 159
- 239000011259 mixed solution Substances 0.000 claims description 155
- 239000000243 solution Substances 0.000 claims description 72
- 239000001257 hydrogen Substances 0.000 claims description 71
- 229910052739 hydrogen Inorganic materials 0.000 claims description 71
- 238000003756 stirring Methods 0.000 claims description 64
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 35
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 25
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 15
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 14
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 34
- 238000006243 chemical reaction Methods 0.000 description 188
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 180
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 92
- 238000001179 sorption measurement Methods 0.000 description 67
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 62
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 51
- 239000003054 catalyst Substances 0.000 description 51
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 48
- 239000000523 sample Substances 0.000 description 47
- 229910052757 nitrogen Inorganic materials 0.000 description 45
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 30
- 238000004817 gas chromatography Methods 0.000 description 30
- 239000010453 quartz Substances 0.000 description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 30
- 238000001228 spectrum Methods 0.000 description 27
- 239000013078 crystal Substances 0.000 description 23
- 238000003795 desorption Methods 0.000 description 22
- 239000000376 reactant Substances 0.000 description 16
- 239000011541 reaction mixture Substances 0.000 description 16
- 239000000758 substrate Substances 0.000 description 16
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 15
- 150000002431 hydrogen Chemical class 0.000 description 15
- 239000007791 liquid phase Substances 0.000 description 15
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 15
- 230000035484 reaction time Effects 0.000 description 15
- 239000007789 gas Substances 0.000 description 14
- 239000012071 phase Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- QCWXDVFBZVHKLV-UHFFFAOYSA-N 1-tert-butyl-4-methylbenzene Chemical compound CC1=CC=C(C(C)(C)C)C=C1 QCWXDVFBZVHKLV-UHFFFAOYSA-N 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- PWATWSYOIIXYMA-UHFFFAOYSA-N Pentylbenzene Chemical group CCCCCC1=CC=CC=C1 PWATWSYOIIXYMA-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 4
- AXHVNJGQOJFMHT-UHFFFAOYSA-N 1-tert-butyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C(C)(C)C AXHVNJGQOJFMHT-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical group [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- 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
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
-
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/38—Base treatment
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Abstract
The invention relates to a preparation method of a mesoporous molecular sieve, which mainly solves the problems of low mesoporous order degree, low sample solid yield, low crystallinity and the like in the existing alkali treatment method for preparing the mesoporous molecular sieve. The invention solves the problem well by adopting the scheme that the molecular sieve is contacted with the ordered mesoporous guiding agent solution in advance and then is subjected to alkali treatment, thereby achieving the purposes of improving the internal mesoporous order of the mesoporous molecular sieve and improving the solid yield and the crystallinity of the sample.
Description
Technical Field
The invention belongs to the technical field of catalytic chemistry and chemical engineering, and particularly relates to a preparation method of a mesoporous molecular sieve.
Background
The zeolite molecular sieve has regular pore canal structure and is prepared from SiO 4 Tetrahedra and AlO 4 Three-dimensional crystals formed by connecting tetrahedra through a common oxygen bridge have negative charges due to the existence of four-coordinated Al in the framework, and are formed as protons H + When the negative charge of the framework is balanced, an acidic active center is formed at the framework Al, and the unique structure enables the zeolite molecular sieve to rapidly develop in the catalytic field.
The aperture of the artificially synthesized molecular sieve is generally smaller than 1.0nm, and only small-size molecules can enter the pore canal of the molecular sieve, so that the molecular sieve is widely applied in the aspects of adsorption separation and shape selective catalysis due to the special property. However, for the reaction process of large molecules, mass transfer is limited by the small-size pore channel structure, and reaction substrates are difficult to enter the pore channels of the molecular sieve to contact with active sites, so that the activity of the catalyst is reduced and carbon deposition is easy to induce. To overcome this disadvantage, researchers have made extensive efforts to introduce mesopores inside microporous molecular sieves to increase catalyst activity or extend service life by shortening the mass transfer path or exposing more accessible active sites.
Among them, alkali treatment is a method that is simply and effectively capable of introducing mesopores inside a microporous molecular sieve, and has been successfully applied to MFI (micro.meso.mate, 2004, 69:29-34), MTW (micro.meso.mate, 2006, 97:97-106), MOR (j.catalyst, 2007, 251:21), BEA (micro.meso.mate, 2008, 114:93-102), AST (angel.chem.int.ed., 2008, 47:7913-7917), FER (j.cat, 2009, 265:170-180), MWW (cat.lett, 2009, 127:296-303), IFR (appl.cat.a, 2008, 338:100-113), STF (top.cat, 2010, 53:273-282), CHA (micro.meso.mate, 2010, 132), fas (touch.main, 2010-132), and so on (touch.340, etc.), and to be applied to molecular sieves of (micro.mat.main, etc. that are in topology of, which is called "book" (j.cat.) (c.mat, 35, 35:296-303), and so on).
Although the inorganic alkali treatment method is easy to introduce mesopores into the microporous molecular sieve, the problems of disorder of the medium Kong Zaluan in the mesoporous molecular sieve, poor order degree, low sample yield, low crystallinity and the like are easily caused.
Disclosure of Invention
The invention aims to solve the technical problems that the mesoporous molecular sieve prepared by the prior art has poor internal mesoporous order, low sample solid yield, low crystallinity and the like. The invention solves the problem well by adopting the scheme of alkali treatment after the molecular sieve is contacted with the ordered mesoporous guiding agent in advance, thereby achieving the purposes of improving the internal mesoporous order of the mesoporous molecular sieve and simultaneously improving the solid yield and the crystallinity of the sample.
The invention is realized in the following way:
the preparation method of the mesoporous molecular sieve comprises the steps of mixing and contacting the molecular sieve with an ordered mesoporous guiding agent to obtain a mixed solution A, adding an inorganic alkali solution B into the mixed solution A to obtain a mixed solution C, washing the mixed solution C, and drying to obtain the mesoporous molecular sieve.
In the above technical solution, preferably, the ordered mesoporous guiding agent has a structural formula:
wherein R is 1 Is one of hydrogen, methyl, ethyl, propyl or isopropyl, R 2 Is one of hydrogen, methyl, ethyl, propyl or isopropyl, R 3 Is one of hydrogen, methyl, ethyl, propyl or isopropyl, R 4 Is one of hydrogen, methyl, ethyl, propyl or isopropyl, R 5 Is one of hydrogen, methyl, ethyl, propyl or isopropyl. And at least three groups of R1, R2, R3, R4 and R5 are simultaneously hydrogen. The ordered mesoporous guiding agent is one or a mixture of a plurality of kinds; by a means ofThe mesoporous molecular sieve is Beta molecular sieve or MOR molecular sieve.
In the above technical solution, preferably, R 1 ，R 5 ，R 3 ，R 4 Is hydrogen, R 2 Is a non-hydrogen group; or R is 1 ，R 5 ，R 2 ，R 4 Is hydrogen, R 3 Is a non-hydrogen group; or R is 1 ，R 4 ，R 5 Is hydrogen, R 2 And R is 3 Is a non-hydrogen group; or R is 1 ，R 3 ，R 5 ，R 2 And R is 4 Is hydrogen.
In the above technical solution, preferably, R 1 ，R 3 ，R 4 ，R 5 Is hydrogen, R 2 Is methyl; or R is 1 ，R 3 ，R 4， R 5 Is hydrogen, R 2 Is ethyl; or R is 1 ，R 3 ，R 4 ，R 5 Is hydrogen, R 2 Is propyl; or R is 1 ，R 2 ，R 4 ，R 5 Is hydrogen, R 3 Is propyl; or R is 1 ，R 2 ，R 4 ，R 5 Is hydrogen, R 3 Is propyl; or R is 1 ，R 2 ，R 3 ，R 4 ，R 5 Is hydrogen; or R is 1 ，R 4 ，R 5 Is hydrogen, R 2 And R is 3 Is ethyl.
In the above technical scheme, preferably, the ordered mesoporous guiding agent and SiO in the molecular sieve 2 The molar ratio of (2) is 0.02:1-0.15:1; preferably, the ordered mesoporous guide agent and SiO in the molecular sieve 2 The molar ratio of (2) is 0.025:1-0.10:1.
In the above technical scheme, preferably, after the mixed solution A is obtained, stirring the mixed solution A for 5min-120min; more preferably, the stirring time of the mixed solution A is 10min-90min.
In the above technical scheme, preferably, after the mixed solution A is obtained, stirring the mixed solution A, wherein the stirring temperature of the mixed solution A is 20-100 ℃; more preferably, the stirring temperature is 30-80 ℃.
In the above technical solution, preferably, the inorganic base includes at least one selected from sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, ammonium hydroxide, ammonium carbonate, and ammonium bicarbonate.
In the above technical scheme, preferably, the molar concentration of the inorganic alkali solution B is 0.15-1.0M; more preferably, the inorganic alkaline solution B concentration is 0.2 to 0.5M.
In the above technical scheme, preferably, the inorganic alkali solution B and SiO in the molecular sieve 2 The mass ratio of (2) is 5:1-40:1; more preferably, the mass ratio of the inorganic alkali solution B to the molecular sieve is 10:1-30:1.
In the above technical scheme, preferably, after the mixed solution C is obtained, stirring the mixed solution C for 5min-120min; more preferably, the stirring time of the mixed solution C is 10min-90min.
In the above technical scheme, preferably, after the mixed solution C is obtained, stirring the mixed solution C at a stirring temperature of 20-90 ℃; more preferably, the stirring temperature of the mixed solution C is 25-80 ℃.
Preferably, the molecular sieve is a molecular sieve for removing the organic template agent after roasting, including but not limited to Na type and NH type 4 Form or H molecular sieve, wherein the silicon-aluminum atom ratio is greater than or equal to 20.
In the invention, the solid yield of the mesoporous molecular sieve is calculated by the mass of the mesoporous molecular sieve solid obtained after alkali treatment and the mass of the microporous molecular sieve solid before treatment, the mass of the mesoporous molecular sieve solid obtained after alkali treatment is marked as M1, and the mass of the microporous molecular sieve solid before treatment is marked as M0, so that the solid yield of the mesoporous molecular sieve is 100 percent.
The crystallinity of the mesoporous molecular sieve is calculated by peak area integral values at the positions of 2Theta angles of 7.8 degrees and 22.4 degrees in a Beta molecular sieve XRD spectrogram, the peak area integral values at the positions of 2Theta angles of 7.8 degrees and 22.4 degrees in the mesoporous Beta molecular sieve XRD spectrogram obtained after alkali treatment are marked as S1, the peak area integral values at the positions of 2Theta angles of 7.8 degrees and 22.4 degrees in the microporous Beta molecular sieve XRD spectrogram before treatment are marked as S0, and then the crystallinity of the mesoporous molecular sieve is = (S1/S0) 100%.
The crystallinity of the mesoporous molecular sieve is calculated from the integrated values of peak areas at 2Theta angles of 9.7 degrees, 19.7 degrees, 22.4 degrees, 25.7 degrees and 31.0 degrees in the XRD spectrum of the MOR molecular sieve. The sum of peak area integral values at the angles of 2Theta, 19.7 degrees, 22.4 degrees, 25.7 degrees and 31.0 degrees in the XRD spectrum of the mesoporous MOR molecular sieve obtained after alkali treatment is marked as S1, and the sum of peak area integral values at the angles of 9.7 degrees, 19.7 degrees, 22.4 degrees, 25.7 degrees and 31.0 degrees in the XRD spectrum of the microporous MOR molecular sieve before treatment is marked as S0, so that the crystallinity of the mesoporous molecular sieve is = (S1/S0) =.100%.
Testing the catalyst for N at liquid nitrogen temperature using BEL-MAX specific surface and pore size analyzer manufactured by BELSORP Co., japan 2 Adsorption and desorption isotherms and mesoporous pore volume. Firstly, the sample is subjected to vacuum pretreatment at 80 ℃ for 5 hours to remove water, then is subjected to vacuum pretreatment at 300 ℃ for 5 hours to remove organic impurities, and after the pretreatment is finished, a sample tube is connected to the device to start isothermal line test.
The invention adopts the technical scheme that the molecular sieve is contacted with the ordered mesoporous guiding agent in advance, the ordered mesoporous guiding agent enters the pore canal of the molecular sieve, and then the alkali treatment is carried out, so that the simple and efficient alkali treatment process is realized, a large number of mesopores are introduced into the microporous molecular sieve, the mesopores in the obtained mesoporous molecular sieve are distributed in a radial manner, the order of the mesopores in the obtained mesoporous molecular sieve is high, the sample yield is high, and the crystallinity is high.
After the mesoporous Beta molecular sieve obtained by the invention is exchanged into a hydrogen form, the mesoporous Beta molecular sieve shows higher conversion rate in a liquid phase Friedel-crafts acylation reaction, the reaction is carried out in a round bottom flask provided with a spherical condenser tube, and the reaction equation is as follows:
the specific reaction conditions are as follows: the catalyst consumption is 100 mg, the reaction substrate anisole is 5.22 g, acetic anhydride is 0.51 g, the reaction temperature is 70 ℃ and the reaction time is 30 minutes. After the reaction was completed, the catalyst was cooled and separated, and the reaction mixture was analyzed by gas chromatography (Agilent 5820) equipped with FID probe, and the catalytic performance of the catalyst was calibrated by the conversion of acetic anhydride.
After the MOR mesoporous molecular sieve is exchanged into a hydrogen form, the MOR mesoporous molecular sieve shows higher conversion rate in the reaction of catalyzing toluene and tertiary butyl alcohol gas phase synthesis of the tertiary butyl toluene. The specific reaction conditions are as follows: 2g of catalyst is filled in a quartz reaction tube, a mixed solution of toluene and tertiary butanol is pumped into an evaporator through a micro plunger pump, reactants are gasified and enter the quartz reaction tube, the reaction temperature is 180 ℃, the mass ratio of raw material toluene to tertiary butanol is 2:1, the feeding volume airspeed is 4 mL/(g.h), after the reaction is finished, the mixture is cooled and collected, the mixture of the reaction liquid is analyzed by gas chromatography (Agilent 5820) provided with a FID detector, and the catalytic performance of the catalyst is calibrated according to the toluene conversion rate and the selectivity of the tertiary butyl toluene.
Drawings
FIG. 1 is an XRD spectrum of a mesoporous Beta molecular sieve prepared by the invention.
FIG. 2 is a graph showing isothermal adsorption and desorption of nitrogen gas of the mesoporous Beta molecular sieve prepared by the invention.
FIG. 3 is a TEM photograph of the mesoporous Beta molecular sieve prepared according to the present invention.
FIG. 4 is a TEM photograph of the mesoporous Beta molecular sieve prepared in comparative example 1.
FIG. 5 is an XRD spectrum of a mesoporous MOR molecular sieve prepared according to the invention.
Fig. 6 is a nitrogen adsorption-desorption isothermal curve of the mesoporous MOR molecular sieve prepared by the invention.
FIG. 7 is a TEM photograph of a mesoporous MOR molecular sieve prepared according to the present invention.
FIG. 8 is a TEM photograph of the mesoporous MOR molecular sieve prepared in comparative example 4.
Detailed Description
[ example 1 ]
10 grams of Beta molecular sieve and 0.413 grams of ordered mesoporous directing agent (wherein R 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Methyl) to obtain a mixed solution A, stirring at 80deg.C for 10min, adding 100 g of 0.2M sodium hydroxide solution to the mixed solution A to obtain a mixed solution C, stirring at 25deg.C for 90min, and stirringCentrifuging, washing and drying to obtain the mesoporous Beta molecular sieve. Wherein, the ordered mesoporous guiding agent and SiO in the Beta molecular sieve 2 The molar ratio of sodium hydroxide solution to SiO in the Beta molecular sieve is 0.025:1 2 The mass ratio of (2) is 10:1. The XRD spectrum of the mesoporous Beta molecular sieve is shown in figure 1, and shows stronger diffraction peaks which are attributed to BEA topological structures. The isothermal curve of nitrogen adsorption and desorption is shown in figure 2, and is a mixed nitrogen adsorption curve of type I and type IV, and the high specific pressure area in 0.4-0.99 is multi-layer adsorption, which shows that the sample after alkali treatment contains abundant mesopores, and the mesopore volume is 0.46cm 3 And/g. The calculated solid yield of the mesoporous Beta molecular sieve is 90 percent, and the crystallinity is 95 percent. TEM pictures show in figure 3 that mesoporous channels are uniform and orderly, the mesoporous channels are cylindrical, and the mesoporous channels are distributed in a divergent manner from the center to the periphery of the crystal, so that the three-dimensional space connectivity is good. The conversion rate of the mesoporous Beta molecular sieve in the liquid phase Friedel-crafts acylation reaction is 70%. The reaction conditions are as follows: the reaction was carried out in a round-bottomed flask equipped with a bulb-type condenser in an amount of 100 mg of catalyst, 5.22 g of anisole as the substrate, 0.51 g of acetic anhydride, at a reaction temperature of 70℃and for a reaction time of 30 minutes. After the reaction was completed, the catalyst was cooled and separated, and the reaction mixture was analyzed by gas chromatography (Agilent 5820) equipped with FID probe.
[ example 2 ]
10 g of Beta molecular sieve and 1.887 g of ordered mesoporous directing agent (wherein R 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Ethyl) to obtain a mixed solution A, stirring the mixed solution A at 30 ℃ for 90min, adding 400 g of 0.5M sodium hydroxide solution into the mixed solution A to obtain a mixed solution C, stirring the mixed solution C at 80 ℃ for 10min, centrifuging, washing and drying to obtain the mesoporous Beta molecular sieve. Wherein, the ordered mesoporous guiding agent and SiO in the Beta molecular sieve 2 The molar ratio of the sodium hydroxide solution to the SiO in the Beta molecular sieve is 0.1:1 2 The mass ratio of (2) is 40:1. The XRD spectrum of the mesoporous Beta molecular sieve is shown in figure 1, and shows stronger diffraction peaks which are attributed to BEA topological structures. The isothermal curve of nitrogen adsorption and desorption is shown in figure 2, and is a mixed nitrogen adsorption curve of type I and type IV, and is high in 0.4-0.99The specific pressure area is multi-layer adsorption, which shows that the alkali treated sample contains abundant mesopores with the pore volume of 0.44cm 3 And/g. The calculated solid yield of the mesoporous Beta molecular sieve is 85 percent, and the crystallinity is 92 percent. TEM pictures show in figure 3 that mesoporous channels are uniform and orderly, the mesoporous channels are cylindrical, and the mesoporous channels are distributed in a divergent manner from the center to the periphery of the crystal, so that the three-dimensional space connectivity is good. The conversion rate of the mesoporous Beta molecular sieve in the liquid phase Friedel-crafts acylation reaction is 65%. The reaction conditions are as follows: the reaction was carried out in a round-bottomed flask equipped with a bulb-type condenser in an amount of 100 mg of catalyst, 5.22 g of anisole as the substrate, 0.51 g of acetic anhydride, at a reaction temperature of 70℃and for a reaction time of 30 minutes. After the reaction was completed, the catalyst was cooled and separated, and the reaction mixture was analyzed by gas chromatography (Agilent 5820) equipped with FID probe.
[ example 3 ]
10 g of Beta molecular sieve and 1.177 g of ordered mesoporous directing agent (wherein R 1 ，R 4 ，R 5 Is hydrogen; r is R 2 ,R 3 Ethyl) to obtain a mixed solution A, stirring the mixed solution A at 50 ℃ for 60min, adding 300 g of 0.3M sodium hydroxide solution into the mixed solution A to obtain a mixed solution C, stirring the mixed solution C at 60 ℃ for 30min, centrifuging, washing and drying to obtain the mesoporous Beta molecular sieve. Wherein, the ordered mesoporous guiding agent and SiO in the Beta molecular sieve 2 The molar ratio of the sodium hydroxide solution to the SiO in the Beta molecular sieve is 0.05:1 2 The mass ratio of (2) is 30:1. The XRD spectrum of the mesoporous Beta molecular sieve is shown in figure 1, and shows stronger diffraction peaks which are attributed to BEA topological structures. The isothermal curve of nitrogen adsorption and desorption is shown in figure 2, and is a mixed nitrogen adsorption curve of type I and type IV, and the high specific pressure area in 0.4-0.99 is multi-layer adsorption, which shows that the sample after alkali treatment contains abundant mesopores, and the mesopore volume is 0.50cm 3 And/g. The calculated solid yield of the mesoporous Beta molecular sieve is 84 percent, and the crystallinity is 90 percent. TEM pictures show in figure 3 that mesoporous channels are uniform and orderly, the mesoporous channels are cylindrical, and the mesoporous channels are distributed in a divergent manner from the center to the periphery of the crystal, so that the three-dimensional space connectivity is good. The conversion rate of the mesoporous Beta molecular sieve in the liquid phase Friedel-crafts acylation reaction is 65%. The reaction conditions are as follows: the reaction was carried out in a round-bottomed flask equipped with a bulb-type condenser in an amount of 100 mg of catalyst, 5.22 g of anisole as the substrate, 0.51 g of acetic anhydride, at a reaction temperature of 70℃and for a reaction time of 30 minutes. After the reaction was completed, the catalyst was cooled and separated, and the reaction mixture was analyzed by gas chromatography (Agilent 5820) equipped with FID probe.
[ example 4 ]
10 grams of Beta molecular sieve and 0.848 grams of ordered mesoporous directing agent (wherein R 1 ，R 2 ，R 4 ，R 5 Is hydrogen; r is R 3 Propyl) is uniformly mixed to obtain a mixed solution A, 300 g of 0.2M sodium hydroxide solution is added into the mixed solution A after stirring for 120min at 80 ℃ to obtain a mixed solution C, and the mixed solution C is centrifuged, washed and dried after stirring for 30min at 60 ℃ to obtain the mesoporous Beta molecular sieve. Wherein, the ordered mesoporous guiding agent and SiO in the Beta molecular sieve 2 The molar ratio of the sodium hydroxide solution to the SiO in the Beta molecular sieve is 0.04:1 2 The mass ratio of (2) is 30:1. The XRD spectrum of the mesoporous Beta molecular sieve is shown in figure 1, and shows stronger diffraction peaks which are attributed to BEA topological structures. The isothermal curve of nitrogen adsorption and desorption is shown in figure 2, and is a mixed nitrogen adsorption curve of type I and type IV, and the high specific pressure area in 0.4-0.99 is multi-layer adsorption, which shows that the sample after alkali treatment contains abundant mesopores, and the mesopore volume is 0.46cm 3 And/g. The calculated solid yield of the mesoporous Beta molecular sieve is 84 percent, and the crystallinity is 93 percent. TEM pictures show in figure 3 that mesoporous channels are uniform and orderly, the mesoporous channels are cylindrical, and the mesoporous channels are distributed in a divergent manner from the center to the periphery of the crystal, so that the three-dimensional space connectivity is good. The conversion rate of the mesoporous Beta molecular sieve in the liquid phase Friedel-crafts acylation reaction is 62%. The reaction conditions are as follows: the reaction was carried out in a round-bottomed flask equipped with a bulb-type condenser in an amount of 100 mg of catalyst, 5.22 g of anisole as the substrate, 0.51 g of acetic anhydride, at a reaction temperature of 70℃and for a reaction time of 30 minutes. After the reaction was completed, the catalyst was cooled and separated, and the reaction mixture was analyzed by gas chromatography (Agilent 5820) equipped with FID probe.
[ example 5 ]
Will 10 g Beta molecular sieve and 0.568 g ordered mesoporous directing agent (wherein R 1 ，R 2 ，R 3 ，R 4 ，R 5 All of which are hydrogen) are uniformly mixed to obtain a mixed solution A, stirring the mixed solution A at 80 ℃ for 60min, adding 300 g of 0.2M sodium hydroxide solution into the mixed solution A to obtain a mixed solution C, stirring the mixed solution C at 60 ℃ for 30min, centrifuging, washing and drying to obtain the mesoporous Beta molecular sieve. Wherein, the ordered mesoporous guiding agent and SiO in the Beta molecular sieve 2 The molar ratio of the sodium hydroxide solution to the SiO in the Beta molecular sieve is 0.04:1 2 The mass ratio of (2) is 30:1. The XRD spectrum of the mesoporous Beta molecular sieve is shown in figure 1, and shows stronger diffraction peaks which are attributed to BEA topological structures. The isothermal curve of nitrogen adsorption and desorption is shown in figure 2, and is a mixed nitrogen adsorption curve of type I and type IV, and the high specific pressure area in 0.4-0.99 is multi-layer adsorption, which shows that the sample after alkali treatment contains abundant mesopores, and the mesopore volume is 0.52cm 3 And/g. The calculated solid yield of the mesoporous Beta molecular sieve is 86 percent, and the crystallinity is 91 percent. TEM pictures show in figure 3 that mesoporous channels are uniform and orderly, the mesoporous channels are cylindrical, and the mesoporous channels are distributed in a divergent manner from the center to the periphery of the crystal, so that the three-dimensional space connectivity is good. The conversion rate of the mesoporous Beta molecular sieve in the liquid phase Friedel-crafts acylation reaction is 66%. The reaction conditions are as follows: the reaction was carried out in a round-bottomed flask equipped with a bulb-type condenser in an amount of 100 mg of catalyst, 5.22 g of anisole as the substrate, 0.51 g of acetic anhydride, at a reaction temperature of 70℃and for a reaction time of 30 minutes. After the reaction was completed, the catalyst was cooled and separated, and the reaction mixture was analyzed by gas chromatography (Agilent 5820) equipped with FID probe.
[ example 6 ]
10 grams of Beta molecular sieve and 0.848 grams of ordered mesoporous directing agent (wherein R 1 ，R 2 ，R 4 ，R 5 Is hydrogen; r is R 3 Isopropyl) to obtain a mixed solution A, stirring the mixed solution A at 80 ℃ for 120min, adding 300 g of 0.2M sodium hydroxide solution into the mixed solution A to obtain a mixed solution C, stirring the mixed solution C at 60 ℃ for 30min, centrifuging, washing and drying to obtain the mesoporous Beta molecular sieve. Wherein, the ordered mesoporous guiding agent and SiO in the Beta molecular sieve 2 Molar of (2)The ratio of the sodium hydroxide solution to the SiO in the Beta molecular sieve is 0.04:1 2 The mass ratio of (2) is 30:1. The XRD spectrum of the mesoporous Beta molecular sieve is shown in figure 1, and shows stronger diffraction peaks which are attributed to BEA topological structures. The isothermal curve of nitrogen adsorption and desorption is shown in figure 2, and is a mixed nitrogen adsorption curve of type I and type IV, and the high specific pressure area in 0.4-0.99 is multi-layer adsorption, which shows that the sample after alkali treatment contains abundant mesopores, and the mesopore volume is 0.50cm 3 And/g. The calculated solid yield of the mesoporous Beta molecular sieve is 82 percent, and the crystallinity is 91 percent. TEM pictures show in figure 3 that mesoporous channels are uniform and orderly, the mesoporous channels are cylindrical, and the mesoporous channels are distributed in a divergent manner from the center to the periphery of the crystal, so that the three-dimensional space connectivity is good. The conversion rate of the mesoporous Beta molecular sieve in the liquid phase Friedel-crafts acylation reaction is 60%. The reaction conditions are as follows: the reaction was carried out in a round-bottomed flask equipped with a bulb-type condenser in an amount of 100 mg of catalyst, 5.22 g of anisole as the substrate, 0.51 g of acetic anhydride, at a reaction temperature of 70℃and for a reaction time of 30 minutes. After the reaction was completed, the catalyst was cooled and separated, and the reaction mixture was analyzed by gas chromatography (Agilent 5820) equipped with FID probe.
[ example 7 ]
10 g of Beta molecular sieve, 0.377 g of ordered mesoporous directing agent 1 (wherein R 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Ethyl) and 0.331 g of ordered mesoporous directing agent 1 (wherein R 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Methyl) to obtain a mixed solution A, stirring the mixed solution A at 80 ℃ for 120min, adding 400 g of 0.2M sodium hydroxide solution into the mixed solution A to obtain a mixed solution C, stirring the mixed solution C at 60 ℃ for 60min, centrifuging, washing and drying to obtain the mesoporous Beta molecular sieve. Wherein, siO in ordered mesoporous guiding agent 1 and Beta molecular sieve 2 The mol ratio of (2) is 0.02:1, and the ordered mesoporous guiding agent is 2, and SiO in the Beta molecular sieve is the same as that of the Beta molecular sieve 2 The molar ratio of the sodium hydroxide solution to the SiO in the Beta molecular sieve is 0.02:1 2 The mass ratio of (2) is 40:1. The XRD spectrum of the mesoporous Beta molecular sieve is shown in figure 1, and shows stronger diffraction peaks which are attributed to BEA topological structures. Nitrogen gas absorption and desorptionThe isothermal curve is shown in figure 2, and is an I-type and IV-type mixed nitrogen adsorption curve, and the high specific pressure area is multi-layer adsorption in 0.4-0.99, which shows that the sample after alkali treatment contains a large amount of rich mesopores, and the mesopore volume is 0.50cm 3 And/g. Calculated, the solid yield of the mesoporous Beta molecular sieve is 85%, and the crystallinity is 90%. TEM pictures show in figure 3 that mesoporous channels are uniform and orderly, the mesoporous channels are cylindrical, and the mesoporous channels are distributed in a divergent manner from the center to the periphery of the crystal, so that the three-dimensional space connectivity is good. The conversion rate of the mesoporous Beta molecular sieve in the liquid phase Friedel-crafts acylation reaction is 65%. The reaction conditions are as follows: the reaction was carried out in a round-bottomed flask equipped with a bulb-type condenser in an amount of 100 mg of catalyst, 5.22 g of anisole as the substrate, 0.51 g of acetic anhydride, at a reaction temperature of 70℃and for a reaction time of 30 minutes. After the reaction was completed, the catalyst was cooled and separated, and the reaction mixture was analyzed by gas chromatography (Agilent 5820) equipped with FID probe.
[ example 8 ]
10 g of Beta molecular sieve, 0.165 g of ordered mesoporous directing agent 1 (wherein R 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Methyl), 0.189 grams of ordered mesoporous directing agent 2 (where R is 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Ethyl) and 0.212 gram of ordered mesoporous directing agent 3 (wherein R 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Propyl) is uniformly mixed to obtain a mixed solution A, 300 g of 0.2M potassium hydroxide solution is added into the mixed solution A after stirring for 120min at 80 ℃ to obtain a mixed solution C, and the mixed solution C is centrifuged, washed and dried after stirring for 30min at 60 ℃ to obtain the mesoporous Beta molecular sieve. Wherein, siO in ordered mesoporous guiding agent 1 and Beta molecular sieve 2 The mol ratio of (2) is 0.01:1, and the ordered mesoporous guiding agent is 2, and SiO in the Beta molecular sieve is the same as that of the Beta molecular sieve 2 The mol ratio of (3) is 0.01:1, and the ordered mesoporous guiding agent is 3, and SiO in the Beta molecular sieve is the same as that of the Beta molecular sieve 2 The molar ratio of the sodium hydroxide solution to the SiO in the Beta molecular sieve is 0.01:1 2 The mass ratio of (2) is 30:1. The XRD spectrum of the mesoporous Beta molecular sieve is shown in figure 1, and shows stronger diffraction peaks which are attributed to BEA topological structures. Nitrogen gasThe adsorption-desorption isothermal curve is shown in figure 2, and is an I-type and IV-type mixed nitrogen adsorption curve, and the high specific pressure region in 0.4-0.99 is multi-layer adsorption, which shows that the alkali treated sample contains abundant mesopores with the mesopore volume of 0.52cm 3 And/g. The calculated solid yield of the mesoporous Beta molecular sieve is 88 percent, and the crystallinity is 90 percent. TEM pictures show in figure 3 that mesoporous channels are uniform and orderly, the mesoporous channels are cylindrical, and the mesoporous channels are distributed in a divergent manner from the center to the periphery of the crystal, so that the three-dimensional space connectivity is good. The conversion rate of the mesoporous Beta molecular sieve in the liquid phase Friedel-crafts acylation reaction is 68%. The reaction conditions are as follows: the reaction was carried out in a round-bottomed flask equipped with a bulb-type condenser in an amount of 100 mg of catalyst, 5.22 g of anisole as the substrate, 0.51 g of acetic anhydride, at a reaction temperature of 70℃and for a reaction time of 30 minutes. After the reaction was completed, the catalyst was cooled and separated, and the reaction mixture was analyzed by gas chromatography (Agilent 5820) equipped with FID probe.
[ example 9 ]
10 g of Beta molecular sieve, 0.165 g of ordered mesoporous directing agent 1 (wherein R 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Methyl), 0.189 grams of ordered mesoporous directing agent 2 (where R is 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Ethyl) and 0.424 gram of ordered mesoporous directing agent 3 (wherein R 3 ，R 4 ，R 5 Is hydrogen; r is R 1 Is methyl, R 2 Ethyl) to obtain a mixed solution A, stirring the mixed solution A at 80 ℃ for 120min, adding 300 g of 0.5M ammonium hydroxide solution into the mixed solution A to obtain a mixed solution C, stirring the mixed solution C at 60 ℃ for 30min, centrifuging, washing and drying to obtain the mesoporous Beta molecular sieve. Wherein, siO in ordered mesoporous guiding agent 1 and Beta molecular sieve 2 The mol ratio of (2) is 0.01:1, and the ordered mesoporous guiding agent is 2, and SiO in the Beta molecular sieve is the same as that of the Beta molecular sieve 2 The mol ratio of (3) is 0.01:1, and the ordered mesoporous guiding agent is 3, and SiO in the Beta molecular sieve is the same as that of the Beta molecular sieve 2 The molar ratio of the sodium hydroxide solution to the SiO in the Beta molecular sieve is 0.02:1 2 The mass ratio of (2) is 30:1. The XRD spectrum of the mesoporous Beta molecular sieve is shown in figure 1, and shows stronger diffraction peaks which are attributed to BEA topological structures.The isothermal curve of nitrogen adsorption and desorption is shown in figure 2, and is a mixed nitrogen adsorption curve of type I and type IV, and the high specific pressure area in 0.4-0.99 is multi-layer adsorption, which shows that the sample after alkali treatment contains abundant mesopores, and the mesopore volume is 0.50cm 3 And/g. The calculated solid yield of the mesoporous Beta molecular sieve is 88 percent, and the crystallinity is 94 percent. TEM pictures show in figure 3 that mesoporous channels are uniform and orderly, the mesoporous channels are cylindrical, and the mesoporous channels are distributed in a divergent manner from the center to the periphery of the crystal, so that the three-dimensional space connectivity is good. The conversion rate of the mesoporous Beta molecular sieve in the liquid phase Friedel-crafts acylation reaction is 72 percent. The reaction conditions are as follows: the reaction was carried out in a round-bottomed flask equipped with a bulb-type condenser in an amount of 100 mg of catalyst, 5.22 g of anisole as the substrate, 0.51 g of acetic anhydride, at a reaction temperature of 70℃and for a reaction time of 30 minutes. After the reaction was completed, the catalyst was cooled and separated, and the reaction mixture was analyzed by gas chromatography (Agilent 5820) equipped with FID probe.
[ example 10 ]
10 g of Beta molecular sieve, 0.165 g of ordered mesoporous directing agent 1 (wherein R 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Methyl), 0.189 grams of ordered mesoporous directing agent 2 (where R is 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Ethyl), 0.212 grams of ordered mesoporous directing agent 3 (wherein R 3 ，R 4 ，R 5 Is hydrogen; r is R 1 Is methyl, R 2 Ethyl) and 0.189 grams of ordered mesoporous directing agent 4 (wherein R 3 ，R 4 ，R 5 Is hydrogen; r is R 1 Is methyl, R 2 Methyl) to obtain a mixed solution A, stirring the mixed solution A at 80 ℃ for 120min, adding 300 g of 0.5M sodium carbonate solution into the mixed solution A to obtain a mixed solution C, stirring the mixed solution C at 80 ℃ for 60min, centrifuging, washing and drying to obtain the mesoporous Beta molecular sieve. Wherein, siO in ordered mesoporous guiding agent 1 and Beta molecular sieve 2 The mol ratio of (2) is 0.01:1, and the ordered mesoporous guiding agent is 2, and SiO in the Beta molecular sieve is the same as that of the Beta molecular sieve 2 The mol ratio of (3) is 0.01:1, and the ordered mesoporous guiding agent is 3, and SiO in the Beta molecular sieve is the same as that of the Beta molecular sieve 2 The molar ratio of the ordered mesoporous guide agent 4 and Beta molecules is 0.01:1SiOin sieve 2 The molar ratio of the sodium hydroxide solution to the SiO in the Beta molecular sieve is 0.01:1 2 The mass ratio of (2) is 30:1. The XRD spectrum of the mesoporous Beta molecular sieve is shown in figure 1, and shows stronger diffraction peaks which are attributed to BEA topological structures. The isothermal curve of nitrogen adsorption and desorption is shown in figure 2, and is a mixed nitrogen adsorption curve of type I and type IV, and the high specific pressure area in 0.4-0.99 is multi-layer adsorption, which shows that the sample after alkali treatment contains abundant mesopores, and the mesopore volume is 0.52cm 3 And/g. The calculated solid yield of the mesoporous Beta molecular sieve is 84 percent, and the crystallinity is 95 percent. TEM pictures show in figure 3 that mesoporous channels are uniform and orderly, the mesoporous channels are cylindrical, and the mesoporous channels are distributed in a divergent manner from the center to the periphery of the crystal, so that the three-dimensional space connectivity is good. The conversion rate of the mesoporous Beta molecular sieve in the liquid phase Friedel-crafts acylation reaction is 70%. The reaction conditions are as follows: the reaction was carried out in a round-bottomed flask equipped with a bulb-type condenser in an amount of 100 mg of catalyst, 5.22 g of anisole as the substrate, 0.51 g of acetic anhydride, at a reaction temperature of 70℃and for a reaction time of 30 minutes. After the reaction was completed, the catalyst was cooled and separated, and the reaction mixture was analyzed by gas chromatography (Agilent 5820) equipped with FID probe.
[ example 11 ]
10 g of Beta molecular sieve, 0.377 g of ordered mesoporous directing agent 1 (wherein R 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Ethyl) and 0.377 g of ordered mesoporous directing agent 2 (wherein R 1 ，R 3 ，R 5 Is hydrogen; r is R 2 ，R 4 Methyl) to obtain a mixed solution A, stirring the mixed solution A at 80 ℃ for 120min, adding 300 g of 0.2M sodium hydroxide solution into the mixed solution A to obtain a mixed solution C, stirring the mixed solution C at 60 ℃ for 30min, centrifuging, washing and drying to obtain the mesoporous Beta molecular sieve. Wherein, siO in ordered mesoporous guiding agent 1 and Beta molecular sieve 2 The mol ratio of (2) is 0.02:1, and the ordered mesoporous guiding agent is 2, and SiO in the Beta molecular sieve is the same as that of the Beta molecular sieve 2 The molar ratio of the sodium hydroxide solution to the SiO in the Beta molecular sieve is 0.02:1 2 The mass ratio of (2) is 30:1. The XRD spectrum of the mesoporous Beta molecular sieve is shown in figure 1, and shows stronger attribution to BEA topologyDiffraction peaks of the flutter structure. The isothermal curve of nitrogen adsorption and desorption is shown in figure 2, and is a mixed nitrogen adsorption curve of type I and type IV, and the high specific pressure area in 0.4-0.99 is multi-layer adsorption, which shows that the sample after alkali treatment contains abundant mesopores, and the mesopore volume is 0.54cm 3 And/g. Calculated, the solid yield of the mesoporous Beta molecular sieve is 85%, and the crystallinity is 96%. TEM pictures show in figure 3 that mesoporous channels are uniform and orderly, the mesoporous channels are cylindrical, and the mesoporous channels are distributed in a divergent manner from the center to the periphery of the crystal, so that the three-dimensional space connectivity is good. The conversion rate of the mesoporous Beta molecular sieve in the liquid phase Friedel-crafts acylation reaction is 72 percent. The reaction conditions are as follows: the reaction was carried out in a round-bottomed flask equipped with a bulb-type condenser in an amount of 100 mg of catalyst, 5.22 g of anisole as the substrate, 0.51 g of acetic anhydride, at a reaction temperature of 70℃and for a reaction time of 30 minutes. After the reaction was completed, the catalyst was cooled and separated, and the reaction mixture was analyzed by gas chromatography (Agilent 5820) equipped with FID probe.
Comparative example 1
In comparison to example 11, the ordered mesoporous directing agent was not used, and the steps were performed as follows:
uniformly mixing 10 g of Beta molecular sieve and 300 g of 0.2M sodium hydroxide solution, stirring at 60 ℃ for 30min, centrifuging, washing and drying to obtain the mesoporous Beta molecular sieve. Wherein, the sodium hydroxide solution and SiO in the Beta molecular sieve 2 The mass ratio of (2) is 30:1. The calculated solid yield of the mesoporous Beta molecular sieve is 45 percent, and the crystallinity is 60 percent. As shown in FIG. 4, compared with the TEM photograph of the sample obtained in example 11 (FIG. 3), the mesoporous channels are disordered and irregular in shape, and the mesoporous volume is 0.24cm 3 And/g. The conversion rate of the mesoporous Beta molecular sieve in the liquid phase Friedel-crafts acylation reaction is 35%. The reaction conditions are as follows: the reaction was carried out in a round-bottomed flask equipped with a bulb-type condenser in an amount of 100 mg of catalyst, 5.22 g of anisole as the substrate, 0.51 g of acetic anhydride, at a reaction temperature of 70℃and for a reaction time of 30 minutes. After the reaction was completed, the catalyst was cooled and separated, and the reaction mixture was analyzed by gas chromatography (Agilent 5820) equipped with FID probe.
Comparative example 2
In comparison with example 11, the alkali treatment is carried out by directly and uniformly mixing the Beta molecular sieve, the ordered mesoporous directing agent solution and the sodium hydroxide solution without adopting the scheme of pre-contacting the Beta molecular sieve with the ordered mesoporous directing agent solution and then carrying out alkali treatment, and the specific implementation steps are as follows:
10 g of Beta molecular sieve, 0.377 g of ordered mesoporous directing agent 1 (wherein R 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Ethyl) and 0.377 g of ordered mesoporous directing agent 2 (wherein R 1 ，R 3 ，R 5 Is hydrogen; r is R 2 ，R 4 Methyl) is added into 300 g of 0.2M sodium hydroxide solution to obtain a mixed solution, and the mixed solution is stirred at 60 ℃ for 30min, and then is centrifuged, washed and dried to obtain the mesoporous Beta molecular sieve. Wherein, siO in ordered mesoporous guiding agent 1 and Beta molecular sieve 2 The mol ratio of (2) is 0.02:1, and the ordered mesoporous guiding agent is 2, and SiO in the Beta molecular sieve is the same as that of the Beta molecular sieve 2 The molar ratio of the sodium hydroxide solution to the SiO in the Beta molecular sieve is 0.02:1 2 The mass ratio of (2) is 30:1. Calculated, the solid yield of the mesoporous Beta molecular sieve is 70%, the crystallinity is 72%, and the mesoporous volume is 0.28cm 3 And/g. The conversion rate of the mesoporous Beta molecular sieve in the liquid phase Friedel-crafts acylation reaction is 55%. The reaction conditions are as follows: the reaction was carried out in a round-bottomed flask equipped with a bulb-type condenser in an amount of 100 mg of catalyst, 5.22 g of anisole as the substrate, 0.51 g of acetic anhydride, at a reaction temperature of 70℃and for a reaction time of 30 minutes. After the reaction was completed, the catalyst was cooled and separated, and the reaction mixture was analyzed by gas chromatography (Agilent 5820) equipped with FID probe.
[ comparative example 3 ]
Compared with the embodiment 11, the treatment temperature and time of the mixed solution C are respectively changed to 170 ℃ and 30min, and the specific implementation steps are as follows:
10 g of Beta molecular sieve, 0.377 g of ordered mesoporous directing agent 1 (wherein R 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Ethyl) and 0.377 g of ordered mesoporous directing agent 2 (wherein R 1 ，R 3 ，R 5 Is hydrogen; r is R 2 ，R 4 Methyl) to obtain a mixed solution A, stirring the mixed solution A at 80 ℃ for 120min, adding 300 g of 0.2M sodium hydroxide solution into the mixed solution A to obtain a mixed solution C, stirring the mixed solution C at 170 ℃ for 30min, centrifuging, washing and drying to obtain the mesoporous Beta molecular sieve. Wherein, siO in ordered mesoporous guiding agent 1 and Beta molecular sieve 2 The mol ratio of (2) is 0.02:1, and the ordered mesoporous guiding agent is 2, and SiO in the Beta molecular sieve is the same as that of the Beta molecular sieve 2 The molar ratio of the sodium hydroxide solution to the SiO in the Beta molecular sieve is 0.02:1 2 The mass ratio of (2) is 30:1. Calculated, the solid yield of the mesoporous Beta molecular sieve is 15%, the crystallinity is 20%, the solid yield and the crystallinity of the sample are very low, and the mesoporous volume is only 0.15cm 3 And/g. The conversion rate of the mesoporous Beta molecular sieve in the liquid phase Friedel-crafts acylation reaction is 18%. The reaction conditions are as follows: the reaction was carried out in a round-bottomed flask equipped with a bulb-type condenser in an amount of 100 mg of catalyst, 5.22 g of anisole as the substrate, 0.51 g of acetic anhydride, at a reaction temperature of 70℃and for a reaction time of 30 minutes. After the reaction was completed, the catalyst was cooled and separated, and the reaction mixture was analyzed by gas chromatography (Agilent 5820) equipped with FID probe.
[ example 12 ]
10 grams of MOR molecular sieve and 0.413 grams of ordered mesoporous directing agent (wherein R 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Methyl) to obtain a mixed solution A, stirring the mixed solution A at 80 ℃ for 10min, adding 100 g of 0.2M sodium hydroxide solution into the mixed solution A to obtain a mixed solution C, stirring the mixed solution C at 25 ℃ for 90min, centrifuging, washing and drying to obtain the mesoporous MOR molecular sieve. Wherein, the ordered mesoporous guiding agent and SiO in MOR molecular sieve 2 The molar ratio of sodium hydroxide solution to SiO in MOR molecular sieve is 0.025:1 2 The mass ratio of (2) is 10:1. The XRD spectrum of the obtained mesoporous MOR molecular sieve is shown in figure 5, and shows stronger diffraction peaks which are attributed to BEA topological structures. The isothermal curve of nitrogen adsorption and desorption is shown in figure 6, and is a mixed nitrogen adsorption curve of type I and type IV, and the high specific pressure area in 0.4-0.99 is multi-layer adsorption, which shows that the sample after alkali treatment contains abundant mesopores, and the mesopore volume is 0.46cm 3 And/g. Calculated, mesoporousThe yield of MOR molecular sieve solid is 90% and the crystallinity is 95%. TEM pictures show in figure 7 that mesoporous channels are uniform and orderly, the mesoporous channels are cylindrical, and the mesoporous channels are distributed in a divergent manner from the center to the periphery of the crystal, so that the three-dimensional space connectivity is good. The mesoporous MOR molecular sieve has the toluene conversion rate of 35% and the selectivity of 80% in the reaction of catalyzing the synthesis of toluene and tertiary butyl alcohol gas phase into tertiary butyl toluene. The specific reaction conditions are as follows: 1.5g of catalyst is filled in a quartz reaction tube, a mixed solution of toluene and tertiary butanol is pumped into an evaporator through a micro plunger pump, reactants are gasified and enter the quartz reaction tube, the reaction temperature is 180 ℃, the mass ratio of raw materials toluene and tertiary butanol is 2:1, the feeding volume airspeed is 4.2 mL/(g.h), after the reaction is finished, the mixture is cooled and collected, and the mixture is analyzed by gas chromatography (Agilent 5820) provided with a FID detector.
[ example 13 ]
10 g MOR molecular sieve and 1.887 g ordered mesoporous directing agent (wherein R 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Ethyl) to obtain a mixed solution A, stirring the mixed solution A at 30 ℃ for 90min, adding 400 g of 0.5M sodium hydroxide solution into the mixed solution A to obtain a mixed solution C, stirring the mixed solution C at 80 ℃ for 10min, centrifuging, washing and drying to obtain the mesoporous MOR molecular sieve. Wherein, the ordered mesoporous guiding agent and SiO in MOR molecular sieve 2 The molar ratio of sodium hydroxide solution to SiO in MOR molecular sieve is 0.1:1 2 The mass ratio of (2) is 40:1. The XRD spectrum of the obtained mesoporous MOR molecular sieve is shown in figure 5, and shows stronger diffraction peaks which are attributed to BEA topological structures. The isothermal curve of nitrogen adsorption and desorption is shown in figure 6, and is a mixed nitrogen adsorption curve of type I and type IV, and the high specific pressure area in 0.4-0.99 is multi-layer adsorption, which shows that the sample after alkali treatment contains abundant mesopores, and the mesopore volume is 0.44cm 3 And/g. Calculated, the solid yield of the mesoporous MOR molecular sieve is 85%, and the crystallinity is 92%. TEM pictures show in figure 7 that mesoporous channels are uniform and orderly, the mesoporous channels are cylindrical, and the mesoporous channels are distributed in a divergent manner from the center to the periphery of the crystal, so that the three-dimensional space connectivity is good. The mesoporous MOR molecular sieve is used for catalyzing toluene and tertiary butanol to be combined The toluene conversion in the p-tert-butyltoluene reaction was 37%, and the selectivity to p-tert-butyltoluene was 82%. The specific reaction conditions are as follows: 1.5g of catalyst is filled in a quartz reaction tube, a mixed solution of toluene and tertiary butanol is pumped into an evaporator through a micro plunger pump, reactants are gasified and enter the quartz reaction tube, the reaction temperature is 180 ℃, the mass ratio of raw materials toluene and tertiary butanol is 2:1, the feeding volume airspeed is 4.2 mL/(g.h), after the reaction is finished, the mixture is cooled and collected, and the mixture is analyzed by gas chromatography (Agilent 5820) provided with a FID detector.
[ example 14 ]
10 grams of MOR molecular sieve and 1.177 grams of ordered mesoporous directing agent (wherein R 1 ，R 3 ，R 5 Is hydrogen; r is R 2 ,R 3 Ethyl) to obtain a mixed solution A, stirring the mixed solution A at 50 ℃ for 60min, adding 300 g of 0.3M sodium hydroxide solution into the mixed solution A to obtain a mixed solution C, stirring the mixed solution C at 60 ℃ for 30min, centrifuging, washing and drying to obtain the mesoporous MOR molecular sieve. Wherein, the ordered mesoporous guiding agent and SiO in MOR molecular sieve 2 The molar ratio of sodium hydroxide solution to SiO in MOR molecular sieve is 0.05:1 2 The mass ratio of (2) is 30:1. The XRD spectrum of the obtained mesoporous MOR molecular sieve is shown in figure 5, and shows stronger diffraction peaks which are attributed to BEA topological structures. The isothermal curve of nitrogen adsorption and desorption is shown in figure 6, and is a mixed nitrogen adsorption curve of type I and type IV, and the high specific pressure area in 0.4-0.99 is multi-layer adsorption, which shows that the sample after alkali treatment contains abundant mesopores, and the mesopore volume is 0.50cm 3 And/g. The calculated yield of the mesoporous MOR molecular sieve is 84% and the crystallinity is 90%. TEM pictures show in figure 7 that mesoporous channels are uniform and orderly, the mesoporous channels are cylindrical, and the mesoporous channels are distributed in a divergent manner from the center to the periphery of the crystal, so that the three-dimensional space connectivity is good. The mesoporous MOR molecular sieve has the toluene conversion rate of 33% and the selectivity of 84% in the reaction of catalyzing the synthesis of toluene and tert-butyl alcohol gas phase into p-tert-butyl toluene. The specific reaction conditions are as follows: filling 1.5g of catalyst into a quartz reaction tube, pumping the mixed solution of toluene and tertiary butanol into an evaporator by a micro plunger pump, gasifying the reactant, and then introducing the gasified reactant into the quartz reaction tube for reactionThe reaction temperature was 180℃and the ratio of toluene to t-butanol was 2:1, the feed volume space velocity was 4.2 mL/(g.h), and after the completion of the reaction, the reaction mixture was cooled and collected and analyzed by gas chromatography (Agilent 5820) equipped with an FID detector.
[ example 15 ]
10 grams of MOR molecular sieve and 0.848 grams of ordered mesoporous directing agent (wherein R 1 ，R 2 ，R 4 ，R 5 Is hydrogen; r is R 3 Propyl) is uniformly mixed to obtain a mixed solution A, 300 g of 0.2M sodium hydroxide solution is added into the mixed solution A after stirring for 120min at 80 ℃ to obtain a mixed solution C, and the mixed solution C is centrifuged, washed and dried after stirring for 30min at 60 ℃ to obtain the mesoporous MOR molecular sieve. Wherein, the ordered mesoporous guiding agent and SiO in MOR molecular sieve 2 The molar ratio of sodium hydroxide solution to SiO in MOR molecular sieve is 0.04:1 2 The mass ratio of (2) is 30:1. The XRD spectrum of the obtained mesoporous MOR molecular sieve is shown in figure 5, and shows stronger diffraction peaks which are attributed to BEA topological structures. The isothermal curve of nitrogen adsorption and desorption is shown in figure 6, and is a mixed nitrogen adsorption curve of type I and type IV, and the high specific pressure area in 0.4-0.99 is multi-layer adsorption, which shows that the sample after alkali treatment contains abundant mesopores, and the mesopore volume is 0.46cm 3 And/g. The calculated yield of the mesoporous MOR molecular sieve is 84% and the crystallinity is 93%. TEM pictures show in figure 7 that mesoporous channels are uniform and orderly, the mesoporous channels are cylindrical, and the mesoporous channels are distributed in a divergent manner from the center to the periphery of the crystal, so that the three-dimensional space connectivity is good. The mesoporous MOR molecular sieve has the toluene conversion rate of 36% and the selectivity of 85% in the reaction of catalyzing the synthesis of toluene and tert-butyl alcohol gas phase into p-tert-butyl toluene. The specific reaction conditions are as follows: 1.5g of catalyst is filled in a quartz reaction tube, a mixed solution of toluene and tertiary butanol is pumped into an evaporator through a micro plunger pump, reactants are gasified and enter the quartz reaction tube, the reaction temperature is 180 ℃, the mass ratio of raw materials toluene and tertiary butanol is 2:1, the feeding volume airspeed is 4.2 mL/(g.h), after the reaction is finished, the mixture is cooled and collected, and the mixture is analyzed by gas chromatography (Agilent 5820) provided with a FID detector.
[ example 16 ]
10 grams of MOR molecular sieve and 0.568 grams of ordered mesoporous directing agent (wherein R 1 ，R 2 ，R 3 ，R 4 ，R 5 All of which are hydrogen) are uniformly mixed to obtain a mixed solution A, stirring the mixed solution A at 80 ℃ for 60min, adding 300 g of 0.2M sodium hydroxide solution into the mixed solution A to obtain a mixed solution C, stirring the mixed solution C at 60 ℃ for 30min, centrifuging, washing and drying to obtain the mesoporous MOR molecular sieve. Wherein, the ordered mesoporous guiding agent and SiO in MOR molecular sieve 2 The molar ratio of sodium hydroxide solution to SiO in MOR molecular sieve is 0.04:1 2 The mass ratio of (2) is 30:1. The XRD spectrum of the obtained mesoporous MOR molecular sieve is shown in figure 5, and shows stronger diffraction peaks which are attributed to BEA topological structures. The isothermal curve of nitrogen adsorption and desorption is shown in figure 6, and is a mixed nitrogen adsorption curve of type I and type IV, and the high specific pressure area in 0.4-0.99 is multi-layer adsorption, which shows that the sample after alkali treatment contains abundant mesopores, and the mesopore volume is 0.52cm 3 And/g. The calculated solid yield of the mesoporous MOR molecular sieve is 86 percent, and the crystallinity is 91 percent. TEM pictures show in figure 7 that mesoporous channels are uniform and orderly, the mesoporous channels are cylindrical, and the mesoporous channels are distributed in a divergent manner from the center to the periphery of the crystal, so that the three-dimensional space connectivity is good. The mesoporous MOR molecular sieve has the toluene conversion rate of 32% and the selectivity of 85% in the reaction of catalyzing the synthesis of toluene and tert-butyl alcohol gas phase into p-tert-butyl toluene. The specific reaction conditions are as follows: 1.5g of catalyst is filled in a quartz reaction tube, a mixed solution of toluene and tertiary butanol is pumped into an evaporator through a micro plunger pump, reactants are gasified and enter the quartz reaction tube, the reaction temperature is 180 ℃, the mass ratio of raw materials toluene and tertiary butanol is 2:1, the feeding volume airspeed is 4.2 mL/(g.h), after the reaction is finished, the mixture is cooled and collected, and the mixture is analyzed by gas chromatography (Agilent 5820) provided with a FID detector.
[ example 17 ]
10 grams of MOR molecular sieve and 0.848 grams of ordered mesoporous directing agent (wherein R 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Propyl) to obtain a mixed solution A, stirring at 80deg.C for 120min, adding 300 g of 0.2M hydrogen oxideAnd (3) obtaining a mixed solution C from the sodium solution, stirring the mixed solution C at 60 ℃ for 30min, centrifuging, washing and drying to obtain the mesoporous MOR molecular sieve. Wherein, the ordered mesoporous guiding agent and SiO in MOR molecular sieve 2 The molar ratio of sodium hydroxide solution to SiO in MOR molecular sieve is 0.04:1 2 The mass ratio of (2) is 30:1. The XRD spectrum of the obtained mesoporous MOR molecular sieve is shown in figure 5, and shows stronger diffraction peaks which are attributed to BEA topological structures. The isothermal curve of nitrogen adsorption and desorption is shown in figure 6, and is a mixed nitrogen adsorption curve of type I and type IV, and the high specific pressure area in 0.4-0.99 is multi-layer adsorption, which shows that the sample after alkali treatment contains abundant mesopores, and the mesopore volume is 0.50cm 3 And/g. The calculated solid yield of the mesoporous MOR molecular sieve is 82 percent, and the crystallinity is 91 percent. TEM pictures show in figure 7 that mesoporous channels are uniform and orderly, the mesoporous channels are cylindrical, and the mesoporous channels are distributed in a divergent manner from the center to the periphery of the crystal, so that the three-dimensional space connectivity is good. The mesoporous MOR molecular sieve has the toluene conversion rate of 38% and the selectivity of 82% in the reaction of catalyzing the synthesis of toluene and tertiary butyl alcohol gas phase into tertiary butyl toluene. The specific reaction conditions are as follows: 1.5g of catalyst is filled in a quartz reaction tube, a mixed solution of toluene and tertiary butanol is pumped into an evaporator through a micro plunger pump, reactants are gasified and enter the quartz reaction tube, the reaction temperature is 180 ℃, the mass ratio of raw materials toluene and tertiary butanol is 2:1, the feeding volume airspeed is 4.2 mL/(g.h), after the reaction is finished, the mixture is cooled and collected, and the mixture is analyzed by gas chromatography (Agilent 5820) provided with a FID detector.
Example 18
10 g MOR molecular sieve, 0.377 g ordered mesoporous directing agent 1 (wherein R 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Ethyl) and 0.331 g of ordered mesoporous directing agent 1 (wherein R 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Methyl) to obtain a mixed solution A, stirring the mixed solution A at 80 ℃ for 120min, adding 400 g of 0.2M sodium hydroxide solution into the mixed solution A to obtain a mixed solution C, stirring the mixed solution C at 60 ℃ for 60min, centrifuging, washing and drying to obtain the mesoporous MOR molecular sieve. Wherein, ordered mesoporous mediationSiO in the molecular sieve of the directing agent 1 and MOR 2 The mol ratio of (2) is 0.02:1, and the ordered mesoporous guiding agent is 2 and SiO in the MOR molecular sieve is the same as that of the molecular sieve 2 The molar ratio of sodium hydroxide solution to SiO in MOR molecular sieve is 0.02:1 2 The mass ratio of (2) is 40:1. The XRD spectrum of the obtained mesoporous MOR molecular sieve is shown in figure 5, and shows stronger diffraction peaks which are attributed to BEA topological structures. The isothermal curve of nitrogen adsorption and desorption is shown in figure 6, and is a mixed nitrogen adsorption curve of type I and type IV, and the high specific pressure area in 0.4-0.99 is multi-layer adsorption, which shows that the sample after alkali treatment contains a large amount of rich mesopores, and the mesopore volume is 0.50cm 3 And/g. Calculated, the solid yield of the mesoporous MOR molecular sieve is 85%, and the crystallinity is 90%. TEM pictures show in figure 7 that mesoporous channels are uniform and orderly, the mesoporous channels are cylindrical, and the mesoporous channels are distributed in a divergent manner from the center to the periphery of the crystal, so that the three-dimensional space connectivity is good. The mesoporous MOR molecular sieve has the toluene conversion rate of 34% and the selectivity of 83% in the reaction of catalyzing the synthesis of toluene and tertiary butyl alcohol gas phase into tertiary butyl toluene. The specific reaction conditions are as follows: 1.5g of catalyst is filled in a quartz reaction tube, a mixed solution of toluene and tertiary butanol is pumped into an evaporator through a micro plunger pump, reactants are gasified and enter the quartz reaction tube, the reaction temperature is 180 ℃, the mass ratio of raw materials toluene and tertiary butanol is 2:1, the feeding volume airspeed is 4.2 mL/(g.h), after the reaction is finished, the mixture is cooled and collected, and the mixture is analyzed by gas chromatography (Agilent 5820) provided with a FID detector.
[ example 19 ]
10 g MOR molecular sieve, 0.165 g ordered mesoporous directing agent 1 (wherein R 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Methyl), 0.189 grams of ordered mesoporous directing agent 2 (where R is 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Ethyl) and 0.212 gram of ordered mesoporous directing agent 3 (wherein R 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Propyl) to obtain a mixed solution A, stirring at 80deg.C for 120min, adding 300 g of 0.2M potassium hydroxide solution to the mixed solution A to obtain a mixed solution C, stirring at 60deg.C for 30min, and separatingAnd (5) performing heart and washing and drying to obtain the mesoporous MOR molecular sieve. Wherein, the ordered mesoporous guiding agent 1 and SiO in the MOR molecular sieve 2 The mol ratio of (2) is 0.01:1, and the ordered mesoporous guiding agent is 2 and SiO in the MOR molecular sieve is the same as that of the molecular sieve 2 The mol ratio of the ordered mesoporous guide agent 3 to the SiO in the MOR molecular sieve is 0.01:1 2 The molar ratio of sodium hydroxide solution to SiO in MOR molecular sieve is 0.01:1 2 The mass ratio of (2) is 30:1. The XRD spectrum of the obtained mesoporous MOR molecular sieve is shown in figure 5, and shows stronger diffraction peaks which are attributed to BEA topological structures. The isothermal curve of nitrogen adsorption and desorption is shown in figure 6, and is a mixed nitrogen adsorption curve of type I and type IV, and the high specific pressure area in 0.4-0.99 is multi-layer adsorption, which shows that the sample after alkali treatment contains abundant mesopores, and the mesopore volume is 0.52cm 3 And/g. The calculated yield of the mesoporous MOR molecular sieve is 88 percent, and the crystallinity is 90 percent. TEM pictures show in figure 7 that mesoporous channels are uniform and orderly, the mesoporous channels are cylindrical, and the mesoporous channels are distributed in a divergent manner from the center to the periphery of the crystal, so that the three-dimensional space connectivity is good. The mesoporous MOR molecular sieve has the toluene conversion rate of 37% and the selectivity of 86% in the reaction of catalyzing the synthesis of toluene and tertiary butyl alcohol gas phase into tertiary butyl toluene. The specific reaction conditions are as follows: 1.5g of catalyst is filled in a quartz reaction tube, a mixed solution of toluene and tertiary butanol is pumped into an evaporator through a micro plunger pump, reactants are gasified and enter the quartz reaction tube, the reaction temperature is 180 ℃, the mass ratio of raw materials toluene and tertiary butanol is 2:1, the feeding volume airspeed is 4.2 mL/(g.h), after the reaction is finished, the mixture is cooled and collected, and the mixture is analyzed by gas chromatography (Agilent 5820) provided with a FID detector.
[ example 20 ]
10 g MOR molecular sieve, 0.165 g ordered mesoporous directing agent 1 (wherein R 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Methyl), 0.189 grams of ordered mesoporous directing agent 2 (where R is 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Ethyl) and 0.424 gram of ordered mesoporous directing agent 3 (wherein R 3 ，R 4 ，R 5 Is hydrogen; r is R 1 Is methyl, R 2 Ethyl) mixtureMixing uniformly to obtain a mixed solution A, stirring at 80 ℃ for 120min, adding 300 g of 0.5M ammonium hydroxide solution into the mixed solution A to obtain a mixed solution C, stirring at 60 ℃ for 30min, centrifuging, washing and drying to obtain the mesoporous MOR molecular sieve. Wherein, the ordered mesoporous guiding agent 1 and SiO in the MOR molecular sieve 2 The mol ratio of (2) is 0.01:1, and the ordered mesoporous guiding agent is 2 and SiO in the MOR molecular sieve is the same as that of the molecular sieve 2 The mol ratio of the ordered mesoporous guide agent 3 to the SiO in the MOR molecular sieve is 0.01:1 2 The molar ratio of sodium hydroxide solution to SiO in MOR molecular sieve is 0.02:1 2 The mass ratio of (2) is 30:1. The XRD spectrum of the obtained mesoporous MOR molecular sieve is shown in figure 5, and shows stronger diffraction peaks which are attributed to BEA topological structures. The isothermal curve of nitrogen adsorption and desorption is shown in figure 6, and is a mixed nitrogen adsorption curve of type I and type IV, and the high specific pressure area in 0.4-0.99 is multi-layer adsorption, which shows that the sample after alkali treatment contains abundant mesopores, and the mesopore volume is 0.50cm 3 And/g. The calculated yield of the mesoporous MOR molecular sieve is 88 percent, and the crystallinity is 94 percent. TEM pictures show in figure 7 that mesoporous channels are uniform and orderly, the mesoporous channels are cylindrical, and the mesoporous channels are distributed in a divergent manner from the center to the periphery of the crystal, so that the three-dimensional space connectivity is good. The mesoporous MOR molecular sieve has the toluene conversion rate of 39% and the selectivity of 85% in the reaction of catalyzing the synthesis of toluene and tert-butyl alcohol gas phase into p-tert-butyl toluene. The specific reaction conditions are as follows: 1.5g of catalyst is filled in a quartz reaction tube, a mixed solution of toluene and tertiary butanol is pumped into an evaporator through a micro plunger pump, reactants are gasified and enter the quartz reaction tube, the reaction temperature is 180 ℃, the mass ratio of raw materials toluene and tertiary butanol is 2:1, the feeding volume airspeed is 4.2 mL/(g.h), after the reaction is finished, the mixture is cooled and collected, and the mixture is analyzed by gas chromatography (Agilent 5820) provided with a FID detector.
[ example 21 ]
10 g MOR molecular sieve, 0.165 g ordered mesoporous directing agent 1 (wherein R 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Methyl), 0.189 grams of ordered mesoporous directing agent 2 (where R is 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Ethyl), 0.212 grams of ordered mesoporous directing agent 3 (wherein R 3 ，R 4 ，R 5 Is hydrogen; r is R 1 Is methyl, R 2 Ethyl) and 0.189 grams of ordered mesoporous directing agent 4 (wherein R 3 ，R 4 ，R 5 Is hydrogen; r is R 1 Is methyl, R 2 Methyl) to obtain a mixed solution A, stirring the mixed solution A at 80 ℃ for 120min, adding 300 g of 0.5M sodium carbonate solution into the mixed solution A to obtain a mixed solution C, stirring the mixed solution C at 80 ℃ for 60min, centrifuging, washing and drying to obtain the mesoporous MOR molecular sieve. Wherein, the ordered mesoporous guiding agent 1 and SiO in the MOR molecular sieve 2 The mol ratio of (2) is 0.01:1, and the ordered mesoporous guiding agent is 2 and SiO in the MOR molecular sieve is the same as that of the molecular sieve 2 The mol ratio of the ordered mesoporous guide agent 3 to the SiO in the MOR molecular sieve is 0.01:1 2 The mol ratio of (2) is 0.01:1, and the ordered mesoporous guiding agent 4 and SiO in the MOR molecular sieve are as follows 2 The molar ratio of sodium hydroxide solution to SiO in MOR molecular sieve is 0.01:1 2 The mass ratio of (2) is 30:1. The XRD spectrum of the obtained mesoporous MOR molecular sieve is shown in figure 5, and shows stronger diffraction peaks which are attributed to BEA topological structures. The isothermal curve of nitrogen adsorption and desorption is shown in figure 6, and is a mixed nitrogen adsorption curve of type I and type IV, and the high specific pressure area in 0.4-0.99 is multi-layer adsorption, which shows that the sample after alkali treatment contains abundant mesopores, and the mesopore volume is 0.52cm 3 And/g. The calculated yield of the mesoporous MOR molecular sieve is 84% and the crystallinity is 95%. TEM pictures show in figure 7 that mesoporous channels are uniform and orderly, the mesoporous channels are cylindrical, and the mesoporous channels are distributed in a divergent manner from the center to the periphery of the crystal, so that the three-dimensional space connectivity is good. The mesoporous MOR molecular sieve has the toluene conversion rate of 34% and the selectivity of 81% in the reaction of catalyzing the synthesis of toluene and tert-butyl alcohol gas phase into p-tert-butyl toluene. The specific reaction conditions are as follows: filling 1.5g of catalyst in a quartz reaction tube, pumping a toluene and tertiary butanol mixed solution into an evaporator through a micro plunger pump, gasifying reactants, then entering the quartz reaction tube, wherein the reaction temperature is 180 ℃, the mass ratio of raw materials toluene and tertiary butanol is 2:1, the feeding volume airspeed is 4.2 mL/(g.h), cooling and collecting a reaction solution mixture after the reaction is finished, and using gas chromatography (Agil) with a FID detector to obtain the reaction solution mixtureent 5820) analysis.
[ example 22 ]
10 g MOR molecular sieve, 0.377 g ordered mesoporous directing agent 1 (wherein R 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Ethyl) and 0.377 g of ordered mesoporous directing agent 2 (wherein R 1 ，R 3 ，R 5 Is hydrogen; r is R 2 ，R 4 Methyl) to obtain a mixed solution A, stirring the mixed solution A at 80 ℃ for 120min, adding 300 g of 0.2M sodium hydroxide solution into the mixed solution A to obtain a mixed solution C, stirring the mixed solution C at 60 ℃ for 30min, centrifuging, washing and drying to obtain the mesoporous MOR molecular sieve. Wherein, the ordered mesoporous guiding agent 1 and SiO in the MOR molecular sieve 2 The mol ratio of (2) is 0.02:1, and the ordered mesoporous guiding agent is 2 and SiO in the MOR molecular sieve is the same as that of the molecular sieve 2 The molar ratio of sodium hydroxide solution to SiO in MOR molecular sieve is 0.02:1 2 The mass ratio of (2) is 30:1. The XRD spectrum of the obtained mesoporous MOR molecular sieve is shown in figure 5, and shows stronger diffraction peaks which are attributed to BEA topological structures. The isothermal curve of nitrogen adsorption and desorption is shown in figure 6, and is a mixed nitrogen adsorption curve of type I and type IV, and the high specific pressure area in 0.4-0.99 is multi-layer adsorption, which shows that the sample after alkali treatment contains abundant mesopores, and the mesopore volume is 0.54cm 3 And/g. Calculated, the solid yield of the mesoporous MOR molecular sieve is 85%, and the crystallinity is 96%. TEM pictures show in figure 7 that mesoporous channels are uniform and orderly, the mesoporous channels are cylindrical, and the mesoporous channels are distributed in a divergent manner from the center to the periphery of the crystal, so that the three-dimensional space connectivity is good. The mesoporous MOR molecular sieve has the toluene conversion rate of 38% and the selectivity of 85% in the reaction of catalyzing the synthesis of toluene and tert-butyl alcohol gas phase into p-tert-butyl toluene. The specific reaction conditions are as follows: 1.5g of catalyst is filled in a quartz reaction tube, a mixed solution of toluene and tertiary butanol is pumped into an evaporator through a micro plunger pump, reactants are gasified and enter the quartz reaction tube, the reaction temperature is 180 ℃, the mass ratio of raw materials toluene and tertiary butanol is 2:1, the feeding volume airspeed is 4.2 mL/(g.h), after the reaction is finished, the mixture is cooled and collected, and the mixture is analyzed by gas chromatography (Agilent 5820) provided with a FID detector.
[ comparative example 4 ]
In contrast to example 22, the ordered mesoporous directing agent was not used, and the steps were performed as follows:
uniformly mixing 10 g of MOR molecular sieve and 300 g of 0.2M sodium hydroxide solution, stirring at 60 ℃ for 30min, centrifuging, washing and drying to obtain the mesoporous MOR molecular sieve. Wherein, the sodium hydroxide solution and SiO in the MOR molecular sieve 2 The mass ratio of (2) is 30:1. The calculated solid yield of the mesoporous MOR molecular sieve is 45 percent, and the crystallinity is 60 percent. As shown in FIG. 8, the TEM photograph shows that the mesoporous pores are disordered and irregular in shape and have a mesoporous volume of 0.24cm compared with the TEM photograph of the sample obtained in example 22 (FIG. 7) 3 And/g. The mesoporous MOR molecular sieve has 28 percent of toluene conversion rate and 73 percent of selectivity to the tert-butyltoluene in the reaction of catalyzing the synthesis of the toluene and the tert-butyl alcohol gas phase to the tert-butyltoluene. The specific reaction conditions are as follows: 1.5g of catalyst is filled in a quartz reaction tube, a mixed solution of toluene and tertiary butanol is pumped into an evaporator through a micro plunger pump, reactants are gasified and enter the quartz reaction tube, the reaction temperature is 180 ℃, the mass ratio of raw materials toluene and tertiary butanol is 2:1, the feeding volume airspeed is 4.2 mL/(g.h), after the reaction is finished, the mixture is cooled and collected, and the mixture is analyzed by gas chromatography (Agilent 5820) provided with a FID detector.
Comparative example 5
In contrast to example 22, instead of pre-contacting the MOR molecular sieve with the ordered mesoporous directing agent solution followed by alkali treatment, the MOR molecular sieve, ordered mesoporous directing agent solution and sodium hydroxide solution were directly and uniformly mixed to perform alkali treatment, and the specific implementation steps are as follows:
10 g MOR molecular sieve, 0.377 g ordered mesoporous directing agent 1 (wherein R 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Ethyl) and 0.377 g of ordered mesoporous directing agent 2 (wherein R 1 ，R 3 ，R 5 Is hydrogen; r is R 2 ，R 4 Methyl) is added into 300 g of 0.2M sodium hydroxide solution to obtain a mixed solution, and the mixed solution is stirred at 60 ℃ for 30min, and then is centrifuged, washed and dried to obtain the mesoporous MOR molecular sieve. Wherein, the order mediumPore directing agent 1 and SiO in MOR molecular sieves 2 The mol ratio of (2) is 0.02:1, and the ordered mesoporous guiding agent is 2 and SiO in the MOR molecular sieve is the same as that of the molecular sieve 2 The molar ratio of sodium hydroxide solution to SiO in MOR molecular sieve is 0.02:1 2 The mass ratio of (2) is 30:1. Calculated, the solid yield of the mesoporous MOR molecular sieve is 70%, the crystallinity is 72%, and the mesoporous volume is 0.28cm 3 And/g. The mesoporous MOR molecular sieve has the toluene conversion rate of 27% and the selectivity of 72% in the reaction of catalyzing the synthesis of toluene and tert-butyl alcohol gas phase into p-tert-butyl toluene. The specific reaction conditions are as follows: 1.5g of catalyst is filled in a quartz reaction tube, a mixed solution of toluene and tertiary butanol is pumped into an evaporator through a micro plunger pump, reactants are gasified and enter the quartz reaction tube, the reaction temperature is 180 ℃, the mass ratio of raw materials toluene and tertiary butanol is 2:1, the feeding volume airspeed is 4.2 mL/(g.h), after the reaction is finished, the mixture is cooled and collected, and the mixture is analyzed by gas chromatography (Agilent 5820) provided with a FID detector.
[ comparative example 6 ]
Compared with the embodiment 22, the treatment temperature and time of the mixed solution C are respectively changed to 170 ℃ and 30min, and the specific implementation steps are as follows:
10 g MOR molecular sieve, 0.377 g ordered mesoporous directing agent 1 (wherein R 1 ，R 3 ，R 4 ，R 5 Is hydrogen; r is R 2 Ethyl) and 0.377 g of ordered mesoporous directing agent 2 (wherein R 1 ，R 3 ，R 5 Is hydrogen; r is R 2 ，R 4 Methyl) to obtain a mixed solution A, stirring the mixed solution A at 80 ℃ for 120min, adding 300 g of 0.2M sodium hydroxide solution into the mixed solution A to obtain a mixed solution C, stirring the mixed solution C at 170 ℃ for 30min, centrifuging, washing and drying to obtain the mesoporous MOR molecular sieve. Wherein, the ordered mesoporous guiding agent 1 and SiO in the MOR molecular sieve 2 The mol ratio of (2) is 0.02:1, and the ordered mesoporous guiding agent is 2 and SiO in the MOR molecular sieve is the same as that of the molecular sieve 2 The molar ratio of sodium hydroxide solution to SiO in MOR molecular sieve is 0.02:1 2 The mass ratio of (2) is 30:1. Calculated, the yield of the mesoporous MOR molecular sieve is 15%, the crystallinity is 20%, the yield and crystallinity of the sample solid are very low, and the mesoporous volume is only 0.15cm 3 And/g. The mesoporous MOR molecular sieve has toluene conversion rate of 10% and selectivity of 55% in the reaction of catalyzing toluene and tertiary butyl alcohol gas phase to synthesize para-tertiary butyl toluene. The specific reaction conditions are as follows: 1.5g of catalyst is filled in a quartz reaction tube, a mixed solution of toluene and tertiary butanol is pumped into an evaporator through a micro plunger pump, reactants are gasified and enter the quartz reaction tube, the reaction temperature is 180 ℃, the mass ratio of raw materials toluene and tertiary butanol is 2:1, the feeding volume airspeed is 4.2 mL/(g.h), after the reaction is finished, the mixture is cooled and collected, and the mixture is analyzed by gas chromatography (Agilent 5820) provided with a FID detector.
Claims (6)
1. The preparation method of the mesoporous molecular sieve is characterized by comprising the steps of mixing and contacting the molecular sieve with an ordered mesoporous guiding agent to obtain a mixed solution A, adding an inorganic alkali solution B into the mixed solution A to obtain a mixed solution C, washing the mixed solution C, and drying to obtain the mesoporous molecular sieve, wherein the mesoporous molecular sieve is Beta molecular sieve or MOR molecular sieve, and the ordered mesoporous guiding agent has the structural formula:
wherein R is 1 Is one of hydrogen, methyl, ethyl, propyl or isopropyl, R 2 Is one of hydrogen, methyl, ethyl, propyl or isopropyl, R 3 Is one of hydrogen, methyl, ethyl, propyl or isopropyl, R 4 Is one of hydrogen, methyl, ethyl, propyl or isopropyl, R 5 The ordered mesoporous guiding agent is one of hydrogen, methyl, ethyl, propyl or isopropyl, and the ordered mesoporous guiding agent is one or a mixture of more of the following; siO in the ordered mesoporous guiding agent and the molecular sieve 2 The molar ratio of (2) is 0.02:1-0.15:1; wherein, after the mixed solution C is obtained, the mixed solution C is stirred for 5min-120min at 20-90 ℃.
2. The method for preparing the mesoporous molecular sieve according to claim 1, further comprising stirring the mixed solution A after the mixed solution A is obtained, wherein the stirring time is 5min-120min.
3. The method for preparing a mesoporous molecular sieve according to claim 1, further comprising stirring the mixed solution A at a stirring temperature of 20-100 ℃.
4. The method for preparing the mesoporous molecular sieve according to claim 1, wherein the inorganic base comprises at least one selected from the group consisting of sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, ammonium hydroxide, ammonium carbonate, and ammonium bicarbonate.
5. The method for preparing a mesoporous molecular sieve according to claim 1, wherein the molar concentration of the inorganic alkaline solution B is 0.15-1.0M.
6. The method for preparing mesoporous molecular sieve according to claim 1, wherein the inorganic alkali solution B and SiO in molecular sieve 2 The mass ratio of (2) is 5:1-40:1.
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