CN115806300B - Thin-sheet mordenite molecular sieve, and preparation method and application thereof - Google Patents
Thin-sheet mordenite molecular sieve, and preparation method and application thereof Download PDFInfo
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- 229910052680 mordenite Inorganic materials 0.000 title claims abstract description 93
- 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 89
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims abstract description 65
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 16
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 13
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 19
- 238000002425 crystallisation Methods 0.000 claims description 19
- 230000008025 crystallization Effects 0.000 claims description 19
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 18
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 238000005342 ion exchange Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 230000006315 carbonylation Effects 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- -1 aluminum alkoxide Chemical class 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 28
- 238000002441 X-ray diffraction Methods 0.000 description 18
- 239000007789 gas Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 7
- 238000013329 compounding Methods 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229910002796 Si–Al Inorganic materials 0.000 description 2
- QECJIGNJADOMIG-UHFFFAOYSA-N [C].COC Chemical compound [C].COC QECJIGNJADOMIG-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 229950006187 hexamethonium bromide Drugs 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- FAPSXSAPXXJTOU-UHFFFAOYSA-L trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;dibromide Chemical compound [Br-].[Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C FAPSXSAPXXJTOU-UHFFFAOYSA-L 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000009681 x-ray fluorescence measurement Methods 0.000 description 2
- 238000005004 MAS NMR spectroscopy Methods 0.000 description 1
- 101150113959 Magix gene Proteins 0.000 description 1
- FSTGPONFPZSUQS-UHFFFAOYSA-N [C].C(C)(=O)OC Chemical compound [C].C(C)(=O)OC FSTGPONFPZSUQS-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000005206 flow analysis Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
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- 238000000992 sputter etching Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a sheet mordenite molecular sieve, a preparation method and application thereof, wherein the mordenite molecular sieve has a chemical formula shown in a formula I: nR.mM (. Cndot.Si) x Al)O 2x+2 In the formula I, R represents a template agent, wherein the template agent is hexamethylammonium bromide; m represents alkali metal ions, and the template agent and the alkali metal ions are both positioned in the pore canal of the mordenite molecular sieve. The mordenite molecular sieve prepared by the method has a nano lamellar morphology, and shows excellent catalytic reaction performance in dimethyl ether carbonylation reaction.
Description
Technical Field
The application relates to a thin mordenite molecular sieve, a preparation method and application thereof, and belongs to the field of zeolite molecular sieve materials.
Background
Mordenite molecular sieves are a class of weightsThe required silicon-aluminum zeolite molecular sieve material is widely applied to the fields of petroleum processing and fine chemical engineering as an important adsorption and catalytic material. The mordenite molecular sieve skeleton structure belongs to an orthorhombic system and a Cmcm space group. The skeleton consists of 12-membered rings parallel to the c-axis directionAnd 8 membered ring->The pore canal is composed of two parts of the porous material through 8-membered ring in the direction of the b axis>The side pockets are connected. In fact, the MOR molecular sieve is characterized by a one-dimensional pore zeolite molecular sieve in an actual catalytic reaction because the 8-membered ring pore canal along the c-axis direction is too narrow to penetrate most molecules. The mordenite molecular sieve has unique pore canal structure and acid property, so that the mordenite molecular sieve can be widely applied to catalytic reaction processes of preparing dimethylbenzene by toluene disproportionation, preparing methylamine by methanol and ammonia, preparing methyl acetate by dimethyl ether carbonylation and the like.
However, the pore size of micropores of the mordenite molecular sieve is small, so that on one hand, reactant molecules with larger kinetic diameters are limited to enter the pore channels of the molecular sieve, and on the other hand, the diffusion resistance of the reactant molecules in the pore channels is increased, side reactions and carbon deposition are caused, and the service life of the molecular sieve is seriously shortened. Thus, research for preparing nano-sized molecular sieves to improve the diffusion properties of reactive molecules has received great attention.
To date, tetraethylammonium hydroxide or its halogenated derivative salts remain the most common templating agent for the synthesis of high silicon mordenite. The template agent is selected to influence the morphology, structure, acid strength, acid distribution and other physical and chemical properties of the synthesized mordenite molecular sieve in a host-guest action mode, and further influence the performance of the corresponding mordenite product in catalysis and adsorption. The novel template agent and the novel synthesis method for developing the mordenite molecular sieve are effective ways for modulating the physicochemical properties and the catalytic properties of the mordenite molecular sieve product, and have important practical application significance.
Disclosure of Invention
According to one aspect of the present application there is provided a lamellar mordenite molecular sieve having a chemical composition as shown in formula I, the templating agent and alkali metal ions being located in the channels of the mordenite molecular sieve. The mordenite prepared by the method has a nano lamellar morphology, and shows excellent catalytic reaction performance in dimethyl ether carbonylation reaction.
A mordenite molecular sieve having the formula I:
nR·mM·(Si x Al)O 2x+2 i is a kind of
Wherein R is a template agent, and the template agent is hexamethylammonium bromide; n is more than or equal to 0.1 and less than or equal to 0.95;
m is at least one of alkali metal elements; m is more than or equal to 0.05 and less than or equal to 0.9;
the R and the M are positioned in pore channels of the mordenite molecular sieve;
x is more than or equal to 10 and less than or equal to 30.
In formula I, n is n (Si x Al)O 2x+2 The number of moles of R in (B); m is per mole (Si x Al)O 2x+2 The mole number x of M is the mole ratio of Si element and Al element in the mordenite molecular sieve framework.
Optionally, n is selected from any value or range of values between any two of 0.1, 0.15, 0.2, 0.3, 0.5, 0.7, 0.9, 0.95.
Alternatively, m is selected from any value or range of values between any two of 0.05, 0.1, 0.15, 0.2, 0.3, 0.5, 0.7, 0.85, 0.9.
Optionally, the value of x is selected from any value or range of values between any two of 10, 15, 20, 25, 30.
Optionally, the value range of x is more than or equal to 10 and less than or equal to 20.
Optionally, the mordenite molecular sieve has a lamellar morphology.
Optionally, the mordenite molecular sieve has a size and thickness on the order of nanometers.
The mordenite molecular sieve provided by the application has a nano lamellar morphology, and shows excellent catalytic reaction performance in dimethyl ether carbonylation reaction.
The structural formula of the hexammoniate template agent is as follows:
further preferably, the molar ratio of Si element to Al element in the mordenite molecular sieve skeleton is more than or equal to 10 and less than or equal to 20.
Optionally, the mordenite molecular sieve has a nano-lamellar morphology.
Optionally, the mordenite molecular sieve has a size and thickness of 50-150nm.
Optionally, the molecular sieve X-ray diffraction pattern has characteristic peaks at the following positions:
according to another aspect of the application, the preparation method of the mordenite molecular sieve is provided, hexamethylammonium bromide is directly used as a template agent, a silicon source, an aluminum source and an alkali source used for synthesizing a conventional mordenite molecular sieve are used as raw materials, the pure-phase mordenite molecular sieve is synthesized and prepared under the hydrothermal synthesis condition, and the synthesized mordenite molecular sieve has a nano lamellar morphology.
A process for preparing a mordenite molecular sieve, said process comprising:
a) Mixing raw materials containing a silicon source, an aluminum source, alkali metal M hydroxide, seed crystals, water and a template agent to obtain an initial gel mixture:
b) Crystallizing the initial gel mixture obtained in the step a) under a closed condition to obtain the mordenite molecular sieve.
Optionally, after crystallization is completed, the solid product is separated, washed and dried.
Optionally, in the initial gel mixture obtained in step a):
SiO 2 /Al 2 O 3 the molar ratio of (2) is 20-60;
M 2 O/SiO 2 the molar ratio of (2) is 0.01-0.30;
template/SiO 2 The molar ratio of (2) is 0.05-0.60;
H 2 O/SiO 2 the molar ratio of (2) is 7-50;
seed mass/feed SiO 2 Solid mass=0.2-8%;
alternatively, siO 2 /Al 2 O 3 The molar ratio of (2) is selected from any value or range of values between any two of 20, 28, 36, 45, 60.
Alternatively, M 2 O/Al 2 O 3 The molar ratio of (3) is selected from any value or range of values between any two of 0.01, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3.
Alternatively, R/Al 2 O 3 The molar ratio of (c) is selected from any value or range of values between any two of 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6.
Alternatively, H 2 O/Al 2 O 3 The molar ratio of (2) is selected from any value or range of values between any two of 7, 10, 20, 30, 40, 50.
Optionally seed mass/charge SiO 2 The solid mass is selected from any value in 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt% or a range between any two.
Optionally, in the initial gel mixture:
SiO 2 /Al 2 O 3 the molar ratio of (2) is 20-40;
M 2 O/SiO 2 the molar ratio of (2) is 0.06-0.25;
template/SiO 2 The molar ratio of (2) is 0.05-0.3;
H 2 O/SiO 2 the molar ratio of (2) is 7-40;
seed mass/feed SiO 2 Solid mass=0.5 to 7%.
Optionally, in the step a), the solid of the aluminum source and the hydroxide of the alkali metal M are dissolved in deionized water, after the solution is uniformly mixed, the solution of the silicon source is slowly dripped into the solution, then seed crystal and template agent hexamethylammonium bromide are added into the mixture, and stirring is continued at room temperature until an initial gel mixture is uniformly formed.
Optionally, the silicon source comprises at least one of silica sol, active silica, orthosilicate, water glass, metakaolin and white carbon black;
the aluminum source comprises at least one of sodium metaaluminate, aluminum alkoxide, aluminum salt and metakaolin;
the hydroxide of the alkali metal M is at least one selected from lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide.
Optionally, the silicon source is at least one of silica sol, white carbon black and active silicon dioxide.
Optionally, the aluminum source is sodium metaaluminate or an aluminum salt.
Optionally, the hydroxide of an alkali metal is at least one of sodium hydroxide and potassium hydroxide.
Optionally, the seed crystals are unfired mordenite raw powder and/or calcined mordenite.
Optionally, the seed crystal is at least one of ball-milled mordenite, alkali-treated mordenite and fluorine ion etching-treated mordenite.
Optionally, the seed crystal is at least one of a raw uncalcined mordenite powder and an alkali-treated mordenite.
Optionally, the crystallization conditions are: the temperature is 120-225 ℃ and the time is 0.5-144 hours;
optionally, the crystallization conditions are: the temperature is 120-190 ℃ and the time is 4-96 hours;
optionally, the crystallization conditions are: the temperature is 150-180 ℃ and the time is 4-96 hours.
Alternatively, the crystallization process is performed in a static or dynamic state.
According to yet another aspect of the present application, there is provided a catalyst obtained from mordenite molecular sieves after ion exchange and calcination;
the mordenite molecular sieve is at least one selected from the mordenite molecular sieves and the mordenite molecular sieves prepared according to the method.
Optionally, the catalyst is mordenite molecular sieve for ammonium ion exchange;
alternatively, the NH used for the ammonium ion exchange 4 NO 3 The solution was stirred at 80℃for 1h for ion exchange.
Optionally, roasting in air at 400-700 ℃ for 0.5-24 hours.
According to a further aspect of the application, the catalyst and the application of the catalyst prepared by the method in the catalytic reaction of preparing methyl acetate by dimethyl ether carbonylation are also provided.
The catalytic reaction for preparing methyl acetate by dimethyl ether carbonylation comprises the following steps: reacting raw material gas containing dimethyl ether and carbon monoxide in the presence of a catalyst to obtain methyl acetate;
optionally, in the raw material gas, the volume ratio of the dimethyl ether to the carbon monoxide is 1:5 to 10;
the airspeed of the mixed gas is 500-6000 ml g -1 h -1 ；
The reaction conditions are as follows: the temperature is 150-350 ℃; the pressure is 0.5-4 MPa.
Benefits that can be produced by the present application include, but are not limited to:
1) The mordenite molecular sieve using the hexamethonium bromide as the template agent is obtained, and the molar ratio of Si element to Al element in the framework is 10-30.
2) The mordenite prepared by the method has a nanometer lamellar morphology.
3) The mordenite molecular sieve prepared by the method has excellent catalytic performance in the catalytic reaction of preparing methyl acetate by dimethyl ether carbonylation.
Drawings
FIG. 1 is an X-ray diffraction pattern of the sample in example 1;
FIG. 2 is a scanning electron microscope image at a magnification of 1.5 ten thousand times for the sample in example 1;
FIG. 3 is a scanning electron microscope image at a magnification of 6 ten thousand times for the sample in example 1;
FIG. 4 is a thermogram of the sample of example 1;
FIG. 5 is an X-ray diffraction pattern of the product of comparative example 1;
FIG. 6 is an X-ray diffraction pattern of the product of comparative example 2;
FIG. 7 is a scanning electron microscope image of the product of comparative example 3;
FIG. 8 is an X-ray diffraction pattern of the product of comparative example 4;
FIG. 9 is a graph showing the catalytic performance of the catalyst of example 26 in the carbonylation of dimethyl ether.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
The application discloses a mordenite molecular sieve, the anhydrous chemical composition of which can be expressed as: nR.mM (. Cndot.Si) x Al)O 2x+2 Wherein R is hexamethylammonium bromide and is distributed in a twelve-membered ring pore canal of the mordenite molecular sieve; n is n per mole (Si x Al)O 2x+2 The number of moles of hexamethonium bromide; n is more than or equal to 0.1 and less than or equal to 0.95; m is alkali metal ion and is distributed in pore canal of mordenite molecular sieve; m is per mole (Si x Al)O 2x+2 The number of moles of the alkali metal ions in the catalyst is more than or equal to 0.05 and less than or equal to 0.9; x is the molar ratio of Si element and Al element in the mordenite molecular sieve skeleton, and the value range of x is more than or equal to 10 and less than or equal to 30. The molecular sieve has the shape of nano flake, and the invention also discloses the mordenite molecular sieveThe synthesis and preparation method and the catalytic application thereof in acid catalytic reaction, especially in methyl acetate preparation reaction by dimethyl ether carbonylation. The molecular sieve shows good catalytic performance in the reaction.
The analytical method in the examples of the present application is as follows:
x-ray powder diffraction phase analysis (XRD) test was performed using an X' Pert PRO X-ray diffractometer, cu target, ka radiation source (λ=0.15418 nm), voltage 40KV, current 40mA, company pamanaceae, pamalytical, netherlands.
Bulk elemental composition measurements in the examples were determined using a Magix 2424X-ray fluorescence analyser (XRF) from Philips. The surface element group measurements in the examples were performed using an X-ray photoelectron spectrometer ThermoESCALAB 250 Xi.
The Scanning Electron Microscope (SEM) test uses Hitachi SU8020 field emission scanning electron microscope with acceleration voltage of 2kV.
The samples were subjected to weight change and heat flow analysis under temperature programmed conditions using an SDT Q600 thermal analyzer from TA company in the united states. An air atmosphere was used at a flow rate of 100ml/min.
The gas sample analysis was performed on-line using a gas chromatograph from Agilent (America) 6890GC, and the column was a capillary column from Agilent (Agilent) PoraPLOT Q.
In the embodiment of the application, conversion rate and selectivity are calculated as follows:
in the examples herein, the dimethyl ether conversion and methyl acetate selectivity are calculated on a carbon mole basis:
conversion of dimethyl ether = [ (moles of dimethyl ether in mixture) - (moles of dimethyl ether in product) ]/(moles of dimethyl ether in mixture) ×100%
Selectivity of methyl acetate= (2/3) (moles of methyl acetate carbon in product)/(moles of dimethyl ether carbon in mixture) - (moles of dimethyl ether carbon in product) ] × 100%
Example 1
Firstly, 0.54g of sodium metaaluminate and 0.8g of sodium hydroxide solid are dissolved in 4.9g of deionized water, and 16.46g of silica sol (27 wt%) is slowly added dropwise to the solution under stirring after the solution is uniformly mixed. To this mixture, 0.27g of unfired mordenite raw powder seed crystals and 2.77g of hexamethylammonium bromide were added continuously at one time, after which the initial gel formed was continuously stirred continuously at room temperature until homogeneous. And (3) transferring the gel into a stainless steel reaction kettle with a polytetrafluoroethylene lining, heating to 170 ℃ and crystallizing for 48 hours under dynamic conditions, centrifugally separating the obtained solid product, washing the solid product with deionized water to be neutral, and drying the solid product in air at 110 ℃ to obtain raw powder. XRD analysis is carried out on the product, the XRD spectrum is shown in figure 1, characteristic peaks of the X-ray diffraction spectrum are shown in table 1, and as can be seen from the XRD spectrum and table 1, the synthesized product has the characteristics of mordenite molecular sieve, and the mordenite molecular sieve is a pure-phase mordenite molecular sieve, wherein sharp and clear diffraction peaks indicate that the molecular sieve has high crystallinity. The sample obtained in example 1 was subjected to scanning electron microscope characterization. Scanning electron microscopy images of different magnifications of the sample are shown in fig. 2 and 3, the sample has a lamellar morphology with a dimensional thickness of the order of nanometers, about 50-100nm.
The bulk silica alumina composition of the molecular sieve crystals was analyzed by XRF and the results are set forth in table 1. The bulk Si/Al molar ratio of the sample of example 1 was 14.8.
Analysis of the raw powder sample of example 1 for CHN showed a C/N molar ratio of 6.01. Thermogravimetric analysis (thermogram see fig. 4) of the raw powder sample of example 1 showed that the organic weight loss was 8% of the dry basis mass of the molecular sieve. The inorganic elemental composition of the CHN elemental analysis, thermogravimetric analysis and XRF measurements were normalized to give the mordenite molecular sieve of example 1 a dry chemical composition of 0.57 R.0.43 Na (Si 14.8 Al)O 31.6 。
Sample mordenite raw powder of example 1 13 C MAS NMR analysis only found characteristic carbon formants attributed to hexamethylammonium bromide, indicating that hexamethylammonium bromide remained structurally intact during crystallization and was encapsulated as a templating agent within the channels of the resulting mordenite molecular sieve.
TABLE 1 characteristic peaks of X ray diffraction patterns
Examples 2 to 23
The specific blending ratios and crystallization conditions of examples 2 to 23 are shown in Table 2, and the specific blending process is the same as that of example 1. XRD analysis is carried out on the raw powder samples obtained by synthesis in examples 2-23, and the X-ray diffraction spectrogram of the product has the characteristics of figure 1, namely the peak positions and the shapes are basically the same, the relative peak intensity pairs of diffraction peaks fluctuate within +/-10% according to the change of synthesis conditions, and the synthetic products are proved to be mordenite molecular sieves. The elemental silicon-aluminum compositions of the bulk and surface phases of the molecular sieves of examples 2-23 were analyzed by XRF and XPS, and the ratios of the bulk silicon-aluminum ratios to the surface silicon-aluminum ratios are shown in Table 2. The raw powder samples of examples 2-23 were subjected to CHN elemental analysis, thermogravimetric analysis and XRF measurement, and the resulting elemental compositions were normalized to give the anhydrous chemical compositions (formula I) of the mordenite molecular sieves of examples 2-23 as set forth in table 2.
Example 24
3g of the synthesized samples of examples 1-23 were placed in a plastic beaker, 3mL of 40% hydrofluoric acid solution was added under ice water bath to dissolve the molecular sieve skeleton, and then 15mL of chloroform was added to dissolve the organic matters. The composition of the organics was analyzed by GC-MS to show that the organics contained therein were all hexamethylammonium bromide.
Example 25
The molar ratio of the preparation is 30SiO 2 :1Al 2 O 3 :3K 2 O:450H 2 O4.5R 4wt% seed initial gel. The procedure of example 1 was repeated except that the aluminum source was changed to anhydrous aluminum chloride, the alkali source was changed to 90wt% potassium hydroxide. The specific compounding process and crystallization conditions were the same as in example 1. XRD analysis is carried out on the product, and an X-ray diffraction spectrum of the product has the characteristics of the figure 1, namely, the peak positions and the shapes are basically the same, so that the synthesized product is proved to be the mordenite molecular sieve. The bulk Si/Al molar ratio of the sample of example 25 was 14.2 using XRF analysis of the bulk Si-Al composition of the molecular sieve crystals.
Table 2 molecular sieve initial gel formulation, crystallization conditions, product phase and surface elemental silicon-aluminum composition
Pouring * : silicon source: a silica sol, b Active silicon dioxide, c Orthosilicate ester, d Water glass, e Metakaolin.
Aluminum source: f sodium metaaluminate, g Aluminum alkoxide, h Aluminum salt, i Metakaolin.
Seed crystal: I unfired mordenite raw powder, II Calcined mordenite, III Ball-milled mordenite, IV Alkali treated mordenite, V Fluorine ion etched mordenite.
Crystallization conditions: α dynamic crystallization, β And (5) static crystallization.
Comparative example 1
Other compounding ratios and compounding procedures, and crystallization conditions were the same as in example 1 except that no organic template was added. The resulting product was identified by XRD as a mixture of mordenite and ZSM-5. The corresponding XRD pattern is shown in FIG. 5.
Comparative example 2
Other compounding ratios and compounding procedures, and crystallization conditions were the same as in example 25 except that no organic templating agent was added. The resulting product was identified by XRD as a mixture of mordenite and amorphous silicon. The corresponding XRD pattern is shown in FIG. 6.
Comparative example 3
The molar ratio of the preparation is 30SiO 2 :1Al 2 O 3 :3Na 2 O:450H 2 O4.5 TEAOH 4wt% seed initial gel. The template was changed to a 25wt% aqueous tetraethylammonium hydroxide (TEAOH) solution alone and the other materials were the same as in example 1. The specific compounding process and crystallization conditions were the same as in example 1. XRD analysis is carried out on the product, and an X-ray diffraction spectrum of the product has the characteristics of the figure 1, namely, the peak positions and the shapes are basically the same, so that the synthesized product is proved to be the mordenite molecular sieve.
The bulk Si/Al molar ratio of the sample of example 25 was 13.6 by XRF analysis of the bulk Si-Al composition of the molecular sieve crystals.
And carrying out scanning electron microscope characterization on the obtained sample. The scanning electron microscope image of the sample is shown in FIG. 7, and the morphology of the sample is a divergent cluster assembled from rod-like crystals with a length of about 1-5 μm.
Comparative example 4
The molar ratio of the preparation is 30SiO 2 :1Al 2 O 3 :3Na 2 O:450H 2 O4.5 initial gel of TIQ. The procedure of example 1 was followed except that no seed crystals were added. The specific compounding process and crystallization conditions were the same as in example 1. XRD analysis of the product was carried out, and the obtained product was a mixture of mordenite and EU-1 molecular sieve. The corresponding XRD pattern is shown in FIG. 8.
Example 26
The sample obtained in example 1 was calcined at 600℃for 4 hours by passing dry air through it, using 1mol/L NH 4 NO 3 The solution is stirred for 1h at 80 ℃ to remove sodium ions (solid-to-liquid ratio is 1:10), the process is repeated three times, and after washing and drying, the solution is roasted for 4h in air at 550 ℃, and then is tabletted and crushed into catalyst particles with the granularity of 40-60 meshes. 1.0g of the catalyst particles were weighed and charged into a fixed bed reactor for evaluation of the carbonylation reaction of dimethyl ether (abbreviated as DME). At the beginning of the reaction, nitrogen is introduced at 400 ℃ for activation for 1h, and then the temperature is reduced to 300 ℃. Pyridine was introduced into the reactor at a gas flow rate of 30ml/min, treated for 1 hour, and then purged with nitrogen for 1 hour (30 ml/min). Finally, the temperature is reduced to 200 ℃ for reaction. Mixed gas (DME/CO/N) 2 =2/14/84, volume ratio), gas space velocity of 3000ml g -1 h -1 (STP) the reaction pressure was 2.0MPa. After a 5h induction period, samples were taken to obtain the DME conversion and the methyl acetate selectivity of the product. The conversion rate of dimethyl ether is 86%, and the selectivity of methyl acetate is 99.9%. The corresponding dimethyl ether carbonylation reaction performance is shown in figure 9.
Comparative example 5
Commercial mordenite molecular sieves (from molecular sieves plant of university of south Kokai) were calcined at 600deg.C in dry air for 4h, NH 4 NO 3 Removing sodium ions by ion exchange, roasting in air at 550 ℃ for 4 hours, tabletting and crushing into catalyst with the granularity of 40-60 meshesAnd (3) a chemical agent particle. 1.0g of the catalyst particles were weighed and charged into a fixed bed reactor for evaluation of the carbonylation reaction of dimethyl ether (abbreviated as DME). At the beginning of the reaction, nitrogen is introduced at 400 ℃ for activation for 1h, and then the temperature is reduced to 300 ℃. Pyridine was introduced into the reactor at a gas flow rate of 30ml/min, treated for 1 hour, and then purged with nitrogen for 1 hour (30 ml/min). Finally, the temperature is reduced to 200 ℃ for reaction. Mixed gas (DME/CO/N) 2 =2/14/84, volume ratio), gas space velocity of 3000ml g -1 h -1 (STP) the reaction pressure was 2.0MPa. After 3h induction period, samples were taken to obtain the DME conversion and the methyl acetate selectivity of the product. The conversion rate of dimethyl ether is only 45%, and the selectivity of methyl acetate is also only 90%.
Comparative example 6
Calcining the mordenite molecular sieve product prepared in comparative example 3 at 600 ℃ in dry air for 4h, and NH 4 NO 3 Removing sodium ions by ion exchange, roasting in air at 550 ℃ for 4 hours, tabletting and crushing into catalyst particles with the granularity of 40-60 meshes. 1.0g of the catalyst particles were weighed and charged into a fixed bed reactor for evaluation of the carbonylation reaction of dimethyl ether (abbreviated as DME). At the beginning of the reaction, nitrogen is introduced at 400 ℃ for activation for 1h, and then the temperature is reduced to 300 ℃. Pyridine was introduced into the reactor at a gas flow rate of 30ml/min, treated for 1 hour, and then purged with nitrogen for 1 hour (30 ml/min). Finally, the temperature is reduced to 200 ℃ for reaction. Mixed gas (DME/CO/N) 2 =2/14/84, volume ratio), gas space velocity of 3000ml g -1 h -1 (STP) the reaction pressure was 2.0MPa. After 3h induction period, samples were taken to obtain the DME conversion and the methyl acetate selectivity of the product. The conversion of dimethyl ether was only 60%, the selectivity to methyl acetate was also only 88%, and the catalyst deactivation rate was significantly faster than in example 26.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (18)
1. The mordenite molecular sieve is characterized in that the chemical formula of the mordenite molecular sieve is shown in a formula I:
wherein R is a template agent, and the template agent is hexamethylammonium bromide; n is more than or equal to 0.1 and less than or equal to 0.95;
m is at least one of alkali metal elements; m is more than or equal to 0.05 and less than or equal to 0.9;
the R and the M are positioned in pore channels of the mordenite molecular sieve;
x is more than or equal to 10 and less than or equal to 30;
the mordenite molecular sieve has a nano lamellar morphology.
2. The mordenite molecular sieve according to claim 1, wherein x has a value in the range of 10.ltoreq.x.ltoreq.20.
3. The mordenite molecular sieve according to claim 1, wherein said mordenite molecular sieve has a size and thickness of 50-150nm.
4. A process for preparing a mordenite molecular sieve according to any one of claims 1 to 3, said process comprising:
a) Mixing raw materials containing a silicon source, an aluminum source, hydroxide of alkali metal M, seed crystals, water and a template agent to obtain an initial gel mixture;
b) Crystallizing the initial gel mixture obtained in the step a) in a closed container to obtain the mordenite molecular sieve.
5. The method according to claim 4, wherein in the initial gel mixture obtained in step a):
SiO 2 /Al 2 O 3 the molar ratio of (2) is 20-60;
M 2 O/SiO 2 the molar ratio of (2) is 0.01-0.30;
template/SiO 2 The molar ratio of (2) is 0.05-0.60;
H 2 O/SiO 2 the molar ratio of (2) is 7-50;
seed mass/feed SiO 2 Solid mass=0.2 to 8%.
6. The method of claim 4, wherein in step a) the initial gel mixture:
SiO 2 /Al 2 O 3 the molar ratio of (2) is 20-40;
M 2 O/SiO 2 the molar ratio of (2) is 0.06-0.25;
template/SiO 2 The molar ratio of (2) is 0.05-0.3;
H 2 O/SiO 2 the molar ratio of (2) is 7-40;
seed mass/feed SiO 2 Solid mass=0.5 to 7%.
7. The method according to claim 4, wherein the silicon source comprises at least one of silica sol, activated silica, orthosilicate, water glass, metakaolin, and white carbon black.
8. The method according to claim 4, wherein the aluminum source comprises at least one of sodium metaaluminate, aluminum alkoxide, aluminum salt, and metakaolin.
9. The method according to claim 4, wherein the hydroxide of the alkali metal M is at least one selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide.
10. The method according to claim 4, wherein the seed crystal is a raw powder of uncalcined mordenite and/or calcined mordenite.
11. The method according to claim 4, wherein the crystallization conditions are: the temperature is 120-225 ℃ and the time is 0.5-144 hours.
12. The method according to claim 4, wherein the crystallization conditions are: the temperature is 120-190 ℃ and the time is 4-96 hours.
13. The method according to claim 4, wherein the crystallization conditions are: the temperature is 150-180 ℃ and the time is 4-96 hours.
14. The catalyst is characterized in that the catalyst is obtained by roasting and ion-exchanging mordenite molecular sieves;
the mordenite molecular sieve comprises at least one of the mordenite molecular sieve according to any one of claims 1 to 3 and the mordenite molecular sieve obtained by the preparation method according to any one of claims 4 to 13.
15. The catalyst of claim 14, wherein the ion exchange is ammonium ion exchange;
the mordenite molecular sieve is roasted before ion exchange, wherein the roasting temperature is 400-700 ℃ and the time is 0.5-24 hours;
the mordenite molecular sieve is roasted after ion exchange, and is roasted in air at 400-700 ℃ for 0.5-24 hours.
16. Use of a catalyst according to claim 14 or 15 in a catalytic reaction for the carbonylation of dimethyl ether to methyl acetate.
17. The use according to claim 16, wherein the catalytic reaction for the carbonylation of dimethyl ether to methyl acetate comprises:
and (3) contacting and reacting the mixed gas containing dimethyl ether and carbon monoxide with the catalyst to obtain methyl acetate.
18. The use according to claim 17, wherein the reaction conditions for the catalytic reaction of dimethyl ether carbonylation to methyl acetate are:
the volume ratio of dimethyl ether to carbon monoxide is 1: 5-10;
the airspeed of the mixed gas is 500-6000 ml g -1 h -1 ；
The reaction temperature is 150-350 ℃; the reaction pressure is 0.5-4 MPa.
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