CN115818662A - Mordenite molecular sieve, and preparation method and application thereof - Google Patents
Mordenite molecular sieve, and preparation method and application thereof Download PDFInfo
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- CN115818662A CN115818662A CN202111087210.5A CN202111087210A CN115818662A CN 115818662 A CN115818662 A CN 115818662A CN 202111087210 A CN202111087210 A CN 202111087210A CN 115818662 A CN115818662 A CN 115818662A
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- mordenite
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- 229910052680 mordenite Inorganic materials 0.000 title claims abstract description 135
- 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 104
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 57
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 24
- GNUJKXOGRSTACR-UHFFFAOYSA-M 1-adamantyl(trimethyl)azanium;hydroxide Chemical group [OH-].C1C(C2)CC3CC2CC1([N+](C)(C)C)C3 GNUJKXOGRSTACR-UHFFFAOYSA-M 0.000 claims abstract description 19
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 10
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 97
- 238000002425 crystallisation Methods 0.000 claims description 49
- 230000008025 crystallization Effects 0.000 claims description 49
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 37
- 239000013078 crystal Substances 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 35
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 26
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 26
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 26
- 238000005810 carbonylation reaction Methods 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 25
- 229910052782 aluminium Inorganic materials 0.000 claims description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 20
- 230000006315 carbonylation Effects 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 238000005342 ion exchange Methods 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 238000000992 sputter etching Methods 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 239000002061 nanopillar Substances 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000007789 gas Substances 0.000 description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 238000002441 X-ray diffraction Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- -1 aluminum alkoxide Chemical class 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 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 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 239000005995 Aluminium silicate Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-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
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 159000000013 aluminium salts Chemical class 0.000 description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 3
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- 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
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000005004 MAS NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
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- 229910001657 ferrierite group Inorganic materials 0.000 description 1
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- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002188 infrared transmission spectroscopy Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 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
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The application discloses a mordenite molecular sieve, a preparation method and application thereof. The anhydrous chemical composition of the mordenite molecular sieve is represented as follows: nR mM (Si) x Al)O 2x+2 Formula I; wherein R represents a template agent, and the template agent is N, N, N-trimethyl-1-adamantyl ammonium hydroxide; the value range of n is more than or equal to 0.05 and less than or equal to 0.85; m represents an alkali metal ion(ii) a The value range of m is more than or equal to 0.15 and less than or equal to 0.95; the value range of x is more than or equal to 10 and less than or equal to 30. The mordenite molecular sieve takes N, N, N-trimethyl-1-adamantyl ammonium hydroxide as a template agent, and the prepared catalyst has high acid ratio of 8-membered ring channel B and better catalytic performance.
Description
Technical Field
The application relates to a mordenite molecular sieve, a preparation method and application thereof, belonging to the technical field of zeolite molecular sieve materials.
Background
Mordenite molecular sieves are an important class of silicoaluminophosphate molecular sieve materials and are widely applied to the fields of petroleum processing and fine chemical engineering as important adsorption and catalysis materials. The mordenite molecular sieve framework structure belongs to an orthorhombic system, ccm space group. The skeleton of which is composed of 12-membered rings parallel to the c-axis
And 8 membered ring
Channels formed by 8-membered rings along the b-axis
The side pockets are connected. In fact, the mordenite molecular sieve is characterized by one-dimensional channel zeolite molecular sieve in the actual catalytic reaction because the 8-membered ring channel along the c-axis direction is too narrow to penetrate most molecules. The unique pore channel structure and acid property of mordenite molecular sieve can make it be extensively used in the catalytic reaction processes of preparing xylene by utilizing toluene disproportionation, preparing methylamine by using methyl alcohol and ammonia and preparing methyl acetate by using dimethyl ether carbonylation.
Mordenite has proven to be an effective molecular sieve catalyst for the carbonylation of dimethyl ether. In particular mordenite shows high carbonylation activity of dimethyl ether and selectivity of methyl acetate. Previous work has demonstrated that the carbonylation mechanism of dimethyl ether on acidic zeolites involves the adsorption of dimethyl ether at the B acid site to form a methoxy group, which is then reacted with CO to form an acetyl intermediate, which in turn is reacted with dimethyl ether to form methyl acetate. Among them, the formation of acetyl group is the rate-determining step of the whole reaction. In addition, it was found that the active center of carbonylation is located in the side pocket of 8-membered ring, while the acid site of the main channel of 12-membered ring causes side reaction, resulting in carbon deposition deactivation of the catalyst. Therefore, the method for preparing the mordenite with the high acid ratio of the 8-membered ring channel B is beneficial to improving the dimethyl ether carbonylation reaction performance of the catalyst, and can also reduce the occurrence of side reactions and improve the reaction stability. The existing synthesis technology is difficult to realize the regulation and control of aluminum distribution. Therefore, the preparation of the mordenite molecular sieve with high 8-membered ring channel acid content ratio has important significance.
Disclosure of Invention
According to one aspect of the application, the mordenite molecular sieve is provided, and N, N, N-trimethyl-1-adamantyl ammonium hydroxide is used as a template agent, so that the prepared catalyst has high proportion of 8-membered ring channel B acid and better catalytic performance.
A mordenite molecular sieve, the mordenite molecular sieve having an anhydrous chemical composition represented by:
nR·mM·(Si x Al)O 2x+2 formula I;
wherein R represents a template agent, and the template agent is N, N, N-trimethyl-1-adamantyl ammonium hydroxide;
n represents (Si) per mole x Al)O 2x+2 The mole number of the middle template agent R, the value range of n is more than or equal to 0.05 and less than or equal to 0.85;
m represents an alkali metal ion;
m represents (Si) per mole x Al)O 2x+2 The mole number of the medium alkali metal ions M is that the value range of M is more than or equal to 0.15 and less than or equal to 0.95;
x represents the mole ratio of Si element and Al element in the mordenite molecular sieve framework, and the value range of x is more than or equal to 10 and less than or equal to 30.
Optionally, the value range of x is 10 ≦ x ≦ 24.
Optionally, the mordenite molecular sieve has a morphology that is agglomerated by circular nano-columns.
Optionally, the diameter of the circular nanopillar is about 200-300 nm.
According to one aspect of the present application, there is provided a process for the preparation of a mordenite molecular sieve as described in any preceding claim, wherein the process comprises the steps of:
crystallizing an initial gel mixture containing a silicon source, an aluminum source, an M source, a seed crystal, water and a template agent to obtain the mordenite molecular sieve.
Optionally, the silicon source comprises at least one of silica sol, silica white, active silica, orthosilicate, water glass, metakaolin, and kaolin.
Optionally, the aluminum source comprises at least one of sodium metaaluminate, aluminum alkoxide, aluminum salt, metakaolin, kaolin.
Optionally, the M source is a hydroxide of M.
Optionally, the hydroxide of M comprises at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide.
Optionally, the seed crystal comprises at least one of mordenite raw powder or mordenite obtained after the mordenite raw powder is treated.
The treatment comprises at least one of roasting, ball milling treatment, alkali treatment and fluorine ion etching treatment.
Optionally, the initial gel mixture comprises the following components in a molar ratio:
SiO 2 /Al 2 O 3 ＝20-60；
M 2 O/Al 2 O 3 =1-20, wherein M is an alkali metal ion;
R/Al 2 O 3 ＝1-25；
H 2 O/Al 2 O 3 ＝130-2000；
seed crystal quality/charge SiO 2 Solid mass = 0.1-7%.
Optionally, the molar ratio of each component in the initial gel mixture is:
SiO 2 /Al 2 O 3 ＝20-48；
M 2 O/Al 2 O 3 ＝4-12；
R/Al 2 O 3 ＝4-16；
H 2 O/Al 2 O 3 ＝150-1600；
seed quality/charge SiO 2 Solid mass =0.5-7%.
Alternatively, siO 2 /Al 2 O 3 The lower limit of the molar ratio of (a) is selected from any one of 20, 28, 36 and 45; siO 2 2 /Al 2 O 3 The upper limit of the molar ratio of (b) is selected from any one of values of 28, 36, 45 and 60.
Alternatively, M 2 O/Al 2 O 3 The lower limit of the molar ratio of (a) is selected from any one of 1.1, 2.1, 2.3, 2.4, 2.8, 3, 3.2, 3.6, 4, 4.4, 4.5, 5.5, 6, 7, 7.8, 8.5, 10, 12, 15, 18; m 2 O/Al 2 O 3 The upper limit of the molar ratio of (b) is selected from any one of values of 2.1, 2.3, 2.4, 2.8, 3, 3.2, 3.6, 4, 4.4, 4.5, 5.5, 6, 7, 7.8, 8.5, 10, 12, and 20.
Alternatively, R/Al 2 O 3 The lower limit of the molar ratio of (a) is selected from any one of 1.2, 1.6, 2.4, 3.5, 4, 4.3, 4.6, 4.9, 5.3, 5.8, 6.2, 6.7, 7.2, 7.6, 7.9, 8.3, 8.8, 11.5, 13, 14.5, 16.0, 17.5, 19, 20.5, 22, 23.5.
Alternatively, R/Al 2 O 3 The upper limit of the molar ratio of (a) is selected from any one of 1.6, 2.4, 3.5, 4, 4.3, 4.6, 4.9, 5.3, 5.8, 6.2, 6.7, 7.2, 7.6, 7.9, 8.3, 8.8, 11.5, 13, 14.5, 16, 17.5, 19, 20.5, 22, 23.5, and 24.
Alternatively, H 2 O/Al 2 O 3 The lower limit of the molar ratio of (b) is selected from any one of values 140, 180, 224, 250, 390, 450, 490, 620, 700, 730, 750, 760, 810, 850, 880, 900, 920, 936 and 1200.
Alternatively, H 2 O/Al 2 O 3 The upper limit of the molar ratio of (a) is selected from any one of 180, 224, 250, 390, 450, 490, 620, 700, 730, 750, 760, 810, 850, 880, 900, 920, 936, 1200, 1950.
Optionally, seed mass/charge SiO 2 The lower limit of the solid mass percentage is selected from 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%6 wt%; seed crystal quality/charge SiO 2 The upper limit of the percentage of the solid mass is selected from any one of 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7 wt%.
Optionally, the initial gel mixture is obtained by:
mixing an aluminum source, an M source and deionized water, then sequentially adding a silicon source, a seed crystal and a template agent, and stirring to obtain an initial gel mixture;
optionally, the crystallization conditions include:
the crystallization temperature is 120-220 ℃;
the crystallization time is 0.5-168 hours.
Optionally, the crystallization conditions include:
the crystallization temperature is 140-180 ℃;
the crystallization time is 0.5-168 hours.
Optionally, the crystallization is dynamic crystallization or static crystallization.
Optionally, the lower limit of the crystallization temperature is independently selected from any one of 120 ℃, 130 ℃, 135 ℃, 145 ℃, 150 ℃, 165 ℃, 175 ℃, 180 ℃, 190 ℃ and 200 ℃; the upper limit of the crystallization temperature is independently selected from any one of 130 ℃, 135 ℃, 145 ℃, 150 ℃, 165 ℃, 175 ℃, 180 ℃, 190 ℃, 200 ℃ and 220 ℃.
Optionally, the lower limit of the crystallization time is independently selected from any one of 0.5h, 16h, 24h, 32h, 41h, 45h, 49h, 52h, 58h, 66h, 70h, 78h, 90h, 105h, 110 h; the upper limit of the crystallization time is independently selected from any one of values of 16h, 24h, 32h, 41h, 45h, 49h, 52h, 58h, 66h, 70h, 78h, 90h, 105h, 110h, 168 h.
According to another aspect of the present application, there is provided a catalyst obtained by ion-exchanging mordenite molecular sieve and calcining;
the mordenite molecular sieve comprises at least one of the mordenite molecular sieve disclosed in any one of the above and the mordenite molecular sieve obtained by the preparation method disclosed in any one of the above.
Optionally, the ion exchange is ammonium ion exchange.
The roasting temperature is 400-700 ℃.
Optionally, the temperature of the calcination is selected from 400 ℃,450 ℃,500 ℃,550 ℃, 600 ℃, 650 ℃ or 700 ℃ at the upper limit and 400 ℃,450 ℃,500 ℃,550 ℃, 600 ℃ or 650 ℃ at the lower limit.
Optionally, the ratio of the number of B acid centers in the 8-membered ring channels of the catalyst to the total number of B acid centers is 80-92%.
The mordenite molecular sieve synthesized by using N, N, N-trimethyl-1-adamantyl ammonium hydroxide as a template agent is obtained, and the molar ratio of Si element to Al element in a framework is 10-30. The catalyst prepared by the method has good catalyst performance.
The catalyst prepared by the method is a pure-phase mordenite molecular sieve crystal with a high 8-membered ring channel B acid ratio, and the proportion of the B acid center number in the 8-membered ring channel of the molecular sieve in the total B acid center number of the mordenite molecular sieve is 80-92%.
The catalyst prepared by the method shows excellent catalytic performance in the catalytic reaction of preparing methyl acetate by carbonylation of dimethyl ether, the conversion rate of dimethyl ether can reach more than 92%, and the selectivity of methyl acetate can reach more than 99%.
According to another aspect of the present application there is provided a process for the carbonylation of dimethyl ether to methyl acetate comprising the steps of:
the mixed gas containing dimethyl ether and carbon monoxide is contacted with a catalyst and reacts to obtain methyl acetate;
the catalyst comprises at least one of the catalysts described in any of the above.
Optionally, the volume ratio of dimethyl ether to carbon monoxide in the mixed gas is 1:5 to 9.
Optionally, the conditions of the reaction include:
the space velocity of the mixed gas is 500-7500 ml g -1 h -1 。
The reaction temperature is 150-300 ℃.
The reaction pressure is 0.5-5 MPa.
Optionally, the catalyst is treated with a pyridine-containing gas stream prior to contacting with the gas mixture.
Alternatively, the space velocity of the gas mixture is selected from 500ml g -1 h -1 、1000ml g -1 h -1 、2000ml g -1 h -1 、3000ml g -1 h -1 、4000ml g -1 h -1 、5000ml g -1 h -1 、6000ml g -1 h -1 、7500ml g -1 h -1 Or a range of values between any two values.
Optionally, the reaction temperature is any one of 150 ℃, 200 ℃, 250 ℃, or 300 ℃, or a range of values between any two values.
Optionally, the reaction pressure is any one of 0.5MPa, 2MPa, 4MPa, 5MPa, or a range of values between any two values.
As an embodiment, the application provides a mordenite molecular sieve which is a pure-phase mordenite molecular sieve (the mol ratio of Si element to Al element in a framework is 10-30), and N, N, N-trimethyl-1-adamantyl ammonium hydroxide is used as a template agent, so that the mordenite molecular sieve has excellent dimethyl ether carbonylation reaction performance.
The anhydrous chemical composition of the mordenite molecular sieve is represented as follows:
nR·mM·(Si x Al)O 2x+2 formula I
Wherein, in the formula I, R represents a template agent, and the template agent is N, N, N-trimethyl-1-adamantyl ammonium hydroxide;
n represents (Si) per mole x Al)O 2x+2 The value range of n is more than or equal to 0.05 and less than or equal to 0.85;
m represents an alkali metal ion;
m represents (Si) per mole x Al)O 2x+2 The mole number of the medium alkali metal ions, wherein the value range of m is more than or equal to 0.15 and less than or equal to 0.95;
x is the molar ratio of Si element to Al element in the mordenite molecular sieve framework, and the value range of x is more than or equal to 10 and less than or equal to 30.
The method can obtain the mordenite molecular sieve with high acid ratio of the 8-membered ring channel B, and has the effects of high conversion rate and high methyl acetate selectivity in the dimethyl ether carbonylation reaction.
The template agent is N, N, N-trimethyl-1-adamantyl ammonium hydroxide.
The structural formula of the template agent N, N, N-trimethyl-1-adamantyl ammonium hydroxide is as follows:
optionally, the value range of the molar ratio x of the Si element to the Al element in the mordenite molecular sieve framework is 10-24.
When the ratio of silicon to aluminum is 10-24, the high-silicon mordenite molecular sieve has better thermal stability and the acid ratio of the 8-membered ring channel B is high.
Further preferably, the value range of the molar ratio x of the Si element to the Al element in the mordenite molecular sieve framework is 11-18.
When the ratio of silicon to aluminum is 11-18, the high-silicon mordenite molecular sieve has the effects of high conversion rate and high methyl acetate selectivity in the dimethyl ether carbonylation reaction.
Optionally, the mordenite molecular sieve has a structure in which circular nano-columns are aggregated into clusters.
Optionally, the mordenite molecular sieve X-ray diffraction pattern has characteristic peaks at the following positions:
as another embodiment, the present application also provides a method of preparing the mordenite molecular sieve described in any preceding claim, comprising the steps of:
crystallizing an initial gel mixture containing a silicon source, an aluminum source, an M source, a seed crystal, deionized water and a template agent to obtain the mordenite molecular sieve; wherein the template agent is N, N, N-trimethyl-1-adamantyl ammonium hydroxide.
Optionally, the method of preparing the initial gel mixture comprises: mixing an aluminum source, an M source and deionized water, then sequentially adding a silicon source, a seed crystal and a template agent, and stirring to obtain the initial gel mixture. By adopting the sequential feeding, the pure phase mordenite molecular sieve can be obtained.
Optionally, the molar ratio of each component in the initial gel mixture is:
SiO 2 /Al 2 O 3 ＝20-60；
M 2 O/Al 2 O 3 =1-20, wherein M is an alkali metal ion;
R/Al 2 O 3 ＝1-25；
H 2 O/Al 2 O 3 ＝130-2000；
seed crystal quality/charge SiO 2 Solid mass = 0.1-7%.
Specifically, in the initial gel mixture, siO 2 /Al 2 O 3 The lower limit of the molar ratio of (a) is selected from any one of 20, 28, 36 and 45; siO 2 2 /Al 2 O 3 The upper limit of the molar ratio of (b) is selected from any one of values of 28, 36, 45 and 60.
M 2 O/Al 2 O 3 The lower limit of the molar ratio of (a) is selected from any one of 1.1, 2.1, 2.3, 2.4, 2.8, 3, 3.2, 3.6, 4, 4.4, 4.5, 5.5, 6, 7, 7.8, 8.5, 10, 12, 15, 18; m 2 O/Al 2 O 3 The upper limit of the molar ratio of (b) is selected from any one of values of 2.1, 2.3, 2.4, 2.8, 3, 3.2, 3.6, 4, 4.4, 4.5, 5.5, 6, 7, 7.8, 8.5, 10, 12, 20.
R/Al 2 O 3 The lower limit of the molar ratio of (a) is selected from 1.2, 1.6, 2.4, 3.5, 4, 4.3, 4.6, 4.9, 5.3, 5.8, 6.2, 6.7, 7.2, 7.6, 7.9, 8.3, 8Any one of values 8, 11.5, 13, 14.5, 16.0, 17.5, 19, 20.5, 22, 23.5; R/Al 2 O 3 The upper limit of the molar ratio of (a) is selected from any one of 1.6, 2.4, 3.5, 4, 4.3, 4.6, 4.9, 5.3, 5.8, 6.2, 6.7, 7.2, 7.6, 7.9, 8.3, 8.8, 11.5, 13, 14.5, 16, 17.5, 19, 20.5, 22, 23.5, and 24.
H 2 O/Al 2 O 3 The lower limit of the molar ratio of (a) is selected from any one of 140, 180, 224, 250, 390, 450, 490, 620, 700, 730, 750, 760, 810, 850, 880, 900, 920, 936, 1200; h 2 O/Al 2 O 3 The upper limit of the molar ratio of (a) is selected from any one of 180, 224, 250, 390, 450, 490, 620, 700, 730, 750, 760, 810, 850, 880, 900, 920, 936, 1200, 1950.
Seed crystal quality/charge SiO 2 The lower limit of the percentage of the solid mass is selected from any one of 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6 wt%; seed crystal quality/charge SiO 2 The upper limit of the percentage of solids by mass is selected from any of 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7 wt%.
Preferably, in the initial gel mixture, the molar ratio of each component is:
SiO 2 /Al 2 O 3 ＝20-48；
M 2 O/Al 2 O 3 ＝4-12；
R/Al 2 O 3 ＝4-16；
H 2 O/Al 2 O 3 ＝150-1600；
seed crystal quality/charge SiO 2 Solid mass =0.5-7%.
The molar ratio can ensure that the value range of the molar ratio x of Si element to Al element in the mordenite molecular sieve framework is more than or equal to 10 and less than or equal to 24.
Further preferably, in the initial gel mixture, the molar ratio of each component is:
SiO 2 /Al 2 O 3 ＝24-40；
M 2 O/Al 2 O 3 ＝5-12；
R/Al 2 O 3 ＝4-12；
H 2 O/Al 2 O 3 ＝160-1500；
seed crystal quality/charge SiO 2 Solid mass = 0.5-6%.
The molar ratio can ensure that the value range of the molar ratio x of Si element to Al element in the mordenite molecular sieve framework is more than or equal to 11 and less than or equal to 18.
Optionally, the silicon source includes one or a mixture of any several of silica sol, silica white, active silica, orthosilicate ester, water glass, metakaolin and kaolin.
Preferably, the silicon source is at least one of silica sol, white carbon black and active silica.
Optionally, the aluminum source comprises one or a mixture of any of sodium metaaluminate, aluminum alkoxide, aluminum salt, metakaolin and kaolin.
Preferably, the aluminium source is sodium metaaluminate or aluminium salt.
Alternatively, the source of M is a hydroxide of M;
the hydroxide of M is at least one selected from lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide.
Preferably, the hydroxide of M is at least one of sodium hydroxide and/or potassium hydroxide.
Optionally, the seed crystals are selected from at least one of raw powder of unfired mordenite, calcined mordenite, ball-milled mordenite, alkali treated mordenite, fluoride ion etched mordenite.
The preparation method of the unbaked mordenite raw powder is not strictly limited, and the unbaked mordenite raw powder can be purchased from commercial mordenite molecular sieves, or can be prepared by related documents in the prior art, or the mordenite molecular sieves synthesized according to the method can also be used as seed crystals required by the synthesis of the method.
The process for the preparation of the calcined mordenite is not critical and possible methods of preparation are described below: calcining the raw powder of the non-calcined mordenite in a muffle furnace or a tubular furnace at the temperature of 450-600 ℃ for 2-24 h in an air atmosphere (GHSV =1500-12000ml of air/g of molecular sieve/h).
The preparation method of the ball-milled mordenite is not strictly limited in the present application, and possible preparation methods are introduced below: and (3) performing ball milling treatment on the unbaked mordenite raw powder for 1-10h by using a planetary ball mill.
The process for the preparation of the alkali-treated mordenite is not critical in the present application and the possible preparation processes are described below: treating the raw powder of the non-calcined mordenite for 1-24h at the temperature of 80 ℃ by using 0.2-1 mol/L sodium hydroxide aqueous solution.
The method for preparing mordenite subjected to fluoride ion etching treatment is not strictly limited, and the following possible preparation methods are introduced: treating the non-calcined mordenite raw powder for 1-24h at 60 ℃ by using 0.1-0.5 mol/L ammonium fluoride aqueous solution.
Optionally, the crystallization conditions are: the crystallization temperature is 120-220 ℃;0.5 to 168 hours.
Optionally, the lower limit of the crystallization temperature is independently selected from any one of 120 ℃, 130 ℃, 135 ℃, 145 ℃, 150 ℃, 165 ℃, 175 ℃, 180 ℃, 190 ℃ and 200 ℃; the upper limit of the crystallization temperature is independently selected from any one of 130 ℃, 135 ℃, 145 ℃, 150 ℃, 165 ℃, 175 ℃, 180 ℃, 190 ℃, 200 ℃ and 220 ℃.
The lower limit of the crystallization time is independently selected from any one of 0.5h, 16h, 24h, 32h, 41h, 45h, 49h, 52h, 58h, 66h, 70h, 78h, 90h, 105h, 110 h; the upper limit of the crystallization time is independently selected from any one of 16h, 24h, 32h, 41h, 45h, 49h, 52h, 58h, 66h, 70h, 78h, 90h, 105h, 110h, 168 h.
Preferably, the crystallization temperature is preferably in the range of 120 to 200 ℃, and more preferably in the range of 150 to 180 ℃.
The crystallization time is preferably in the range of 10 to 96 hours.
Optionally, the crystallization is dynamic crystallization or static crystallization.
In another embodiment, the present application also provides a catalyst prepared from at least one of the mordenite molecular sieve described in any preceding claim, or a mordenite molecular sieve obtained by a preparation process described in any preceding claim.
Optionally, the mordenite molecular sieve is subjected to ammonium ion exchange and then is calcined in air at 400-700 ℃, so that the catalyst can be obtained.
As another embodiment, the application also provides the application of the catalyst in the catalytic reaction of preparing methyl acetate by carbonylation of dimethyl ether.
The catalyst is prepared by carrying out ammonium ion exchange on the mordenite molecular sieve and then roasting the mordenite molecular sieve in air at 400-700 ℃.
The catalytic reaction for preparing the methyl acetate by the carbonylation of the dimethyl ether comprises the following steps:
the mixed gas containing dimethyl ether and carbon monoxide contacts and reacts with the catalyst to obtain methyl acetate;
the reaction conditions are as follows: the volume ratio of dimethyl ether to carbon monoxide is 1:5 to 9;
the airspeed of the mixed gas is 500-7500 ml g -1 h -1 ；
The reaction temperature is 170-300 ℃,
the reaction pressure is 0.5-5 MPa.
In the present application, the template agent is added in the form of an aqueous solution of N, N-trimethyl-1-adamantyl ammonium hydroxide in a mass fraction of 25%.
The beneficial effects that this application can produce include:
1) The mordenite molecular sieve provided by the application takes N, N, N-trimethyl-1-adamantyl ammonium hydroxide as a template agent, and the prepared catalyst has a high acid ratio of 8-membered ring channel B and better catalytic performance.
2) According to the catalyst provided by the application, the ratio of the number of B acid centers in 8-membered ring channels to the total number of B acid centers of the mordenite molecular sieve is 80-92%, and the catalyst shows excellent catalytic performance in a catalytic reaction for preparing methyl acetate by carbonylation of dimethyl ether.
3) According to the method for preparing methyl acetate by carbonylation of dimethyl ether, the conversion rate of dimethyl ether can reach more than 92%, and the selectivity of methyl acetate can reach more than 99%.
Drawings
FIG. 1 is an X-ray diffraction pattern of the sample in example 1;
FIG. 2 is a scanning electron microscope photograph of a sample in example 1;
FIG. 3 is a thermogravimetric plot of the sample of example 1;
FIG. 4 is an X-ray diffraction pattern of the product of comparative example 1;
FIG. 5 is an X-ray diffraction pattern of the product of comparative example 2;
FIG. 6 is a scanning electron microscope photograph of the product in comparative example 3;
FIG. 7 is an X-ray diffraction pattern of the product in comparative example 4;
FIG. 8 is an IR spectrum of a catalyst prepared in example 22;
FIG. 9 is a graph showing the catalytic performance of the catalyst prepared in example 22 in the carbonylation of dimethyl ether;
FIG. 10 is an IR spectrum of the catalyst prepared in comparative example 5;
FIG. 11 is an infrared spectrum of the catalyst prepared in comparative example 6.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
Possible embodiments are described below:
the application aims to provide a mordenite molecular sieve with a high ratio of 8-membered ring channel B acid, wherein the anhydrous chemical composition of the molecular sieve can be expressed as follows: nR mM (Si) x Al)O 2x+2 R is a template molecule, N, N, N-trimethyl-1-Adamantyl ammonium hydroxide. n is (Si) per mole x Al)O 2x+2 The mole number n of the template agent R =0.05-0.85; m is an alkali metal ion, M is per mole (Si) x Al)O 2x+2 The mole number of the medium alkali metal ions, m =0.15-0.95; x is the mole ratio of Si element and Al element in the mordenite molecular sieve framework, and x =10-30.
The X-ray diffraction pattern of the molecular sieve has characteristic peaks at the following positions:
the molar ratio x of silicon element to aluminum element in the molecular sieve skeleton is 10-30;
further, the molar ratio x of the silicon element to the aluminum element in the framework of the molecular sieve is preferably 10-24;
furthermore, the molar ratio x of silicon element to aluminum element in the framework of the molecular sieve is preferably 11-18.
Another object of the present application is to provide a method for synthesizing the mordenite molecular sieve.
The invention aims to solve the technical problem that a pure-phase mordenite molecular sieve is synthesized and prepared under the hydrothermal synthesis condition by directly taking an N, N, N-trimethyl-1-adamantyl ammonium hydroxide organic compound as a template agent and taking a silicon source, an aluminum source and an alkali source which are used for synthesizing the conventional mordenite molecular sieve as raw materials. The invention provides a hydrothermal synthesis method of the mordenite molecular sieve.
The synthesis method of the mordenite molecular sieve comprises the following steps:
a) Mixing a silicon source, an aluminum source, hydroxide of alkali metal M, seed crystal, deionized water and a template agent R to form an initial gel mixture with the following molar ratio:
SiO 2 /Al 2 O 3 ＝20-60；
M 2 O/SiO 2 =0.1-0.35, wherein M is an alkali metal;
R/SiO 2 ＝0.05-0.60；
H 2 O/SiO 2 ＝6-40；
seed crystal quality/charge SiO 2 Solid mass = 0.1-7%;
b) Putting the initial gel mixture obtained after the treatment in the step a) into a hydrothermal synthesis kettle, sealing, and heating to 120-220 ℃ for crystallization for 0.5-168 hours;
c) After the crystallization in the step b) is finished, separating, washing and drying the solid product to obtain the mordenite molecular sieve.
Wherein, the silicon source in the step a) is one or a mixture of any more of silica sol, active silica, orthosilicate ester, water glass and metakaolin; preferably, the silicon source is at least one of silica sol, white carbon black and active silica.
The aluminum source in the step a) is one or a mixture of any more of sodium metaaluminate, alkoxy aluminum, aluminum salt and metakaolin; preferably, the aluminium source is sodium metaaluminate or aluminium salt.
The hydroxide of the alkali metal M in the step a) is at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide; preferably, the hydroxide of an alkali metal is at least one of sodium hydroxide and potassium hydroxide.
The seed crystal in the step a) is at least one of unfired mordenite raw powder, calcined mordenite, ball-milled mordenite, alkali-treated mordenite and mordenite subjected to fluoride ion etching treatment. Preferably, the seed crystals are at least one of unfired mordenite raw powder and alkali-treated mordenite.
Said step a) SiO in the initial gel mixture 2 /Al 2 O 3 The molar ratio of (B) is preferably in the range of 20 to 48, more preferably in the range of 24 to 40.
Said step a) M in the initial gel mixture 2 O/SiO 2 The molar ratio of (B) is preferably in the range of 0.1 to 0.35, and more preferably in the range of 0.12 to 0.24.
Said step a) R/SiO in the initial gel mixture 2 The molar ratio of (A) is preferably in the range of 0.05 to 0.60.
H in the initial gel mixture of step a) 2 O/SiO 2 The molar ratio of (B) is preferably in the range of 6 to 40, and more preferably in the range of 8 to 20.
The crystallization temperature in the step b) is preferably in the range of 120 to 200 ℃, and more preferably in the range of 150 to 180 ℃.
The crystallization time in said step b) is preferably in the range of 10 to 96 hours.
The crystallization in step b) may be performed in a static state or in a dynamic state.
Still another object of the present invention is to provide a catalyst for preparing methyl acetate by dimethyl ether carbonylation, which can be applied to a catalytic reaction for preparing methyl acetate by dimethyl ether carbonylation and exhibits excellent catalytic performance.
The catalyst is obtained by ammonium ion exchange of at least one of the mordenite molecular sieve and the mordenite molecular sieve synthesized by any one of the methods and roasting in air at 400-700 ℃.
The analysis method in the examples of the present application is as follows:
x-ray powder diffractometer phase analysis (XRD) measurements an X' PertPROX X-ray diffractometer from pananace (PANalytical) of the netherlands, a Cu target, a ka radiation source (λ =0.15418 nm), a voltage of 40KV and a current of 40mA were used.
In the examples, the measurement of the elemental composition of the bulk phase was carried out by means of a X-ray fluorescence analyzer (XRF) model Magix2424 from Philips.
The instrument used for the Scanning Electron Microscope (SEM) test is a Hitachi SU8020 field emission scanning electron microscope, and the accelerating voltage is 2kV.
Infrared Transmission Spectroscopy (FTIR) experiments were performed in a vacuum system with samples dehydrated at 450 ℃ and taken at room temperature.
The samples were analyzed for weight change and heat flow at programmed temperature using an SDTQ600 thermal analyzer from TA, USA. Air atmosphere, flow rate 100ml/min.
The gas sample analysis was performed on-line using an Agilent 6890GC gas chromatograph, agilent, USA, and the chromatographic column was a PoraPLOTQ capillary column.
Conversion of dimethyl ether = [ (carbon moles of dimethyl ether in gas mixture) - (carbon moles of dimethyl ether in product) ]/(carbon moles of dimethyl ether in gas mixture) × 100%
Selectivity for methyl acetate = (2/3) = (carbon mole methyl acetate in product)/[ (carbon mole dimethyl ether in gas mixture) - (carbon mole dimethyl ether in product) ] -100%
The preparation method of the unfired mordenite raw powder seed crystal comprises the following steps: see literature (ACS CATALYSIS, 2020,10,3372-3380).
The preparation method of the calcined mordenite seed crystal comprises the following steps: the mordenite raw powder molecular sieve prepared by the method of the literature is calcined in a muffle furnace or a tubular furnace for 12 hours at the temperature of 500 ℃ under the air atmosphere (GHSV =1500ml air/g molecular sieve/h).
The preparation method of the mordenite seed crystal subjected to ball milling treatment comprises the following steps: and (3) carrying out ball milling treatment on the unbaked mordenite raw powder for 5 hours by using a planetary ball mill.
The preparation method of the mordenite seed crystal treated by alkali comprises the following steps: the above-mentioned raw powder of unfired mordenite was treated with a 0.5mol/L aqueous solution of sodium hydroxide at a temperature of 80 ℃ for 12 hours.
The preparation method of the mordenite seed crystal subjected to fluoride ion etching treatment comprises the following steps: the unfired mordenite raw powder was treated with 0.3mol/L aqueous ammonium fluoride at 60 ℃ for 10 hours.
Example 1
The molar ratios of the starting materials in the initial gel and the crystallization conditions are shown in Table 2. First, 0.8g of sodium metaaluminate and 1.48g of sodium hydroxide solid were dissolved in 18.87g of deionized water and mixed uniformly, and then 32.92 g silica sol (27.3 wt%) was slowly added dropwise to the above solution under stirring. To this mixture was added 0.5g of the unfired mordenite raw powder seed crystals and 18.3939g of N, N-trimethyl-1-adamantylammonium hydroxide in one portion, after which the initial gel formed was stirred further at room temperature until homogeneous. And transferring the gel into a stainless steel reaction kettle with a polytetrafluoroethylene lining, heating to 185 ℃, crystallizing for 32 hours under a dynamic condition, centrifugally separating the obtained solid product, washing with deionized water to be neutral, and drying in the air at 110 ℃ to obtain raw powder (namely the mordenite molecular sieve in the application).
XRD analysis of the product of example 1 showed that the synthesized product has the characteristics of mordenite molecular sieve (XRD spectrum is shown in figure 1). The sample obtained in example 1 was characterized by scanning electron microscopy. Scanning electron microscopy of the sample as shown in fig. 2, the sample exhibited a structure in which circular nanopillars were aggregated into clusters, the diameter of the circular nanopillars being about 200 to 300nm.
The bulk silicon aluminum composition of the molecular sieve crystals was analyzed by XRF and the results are listed in table 2. The bulk Si/Al molar ratio of the sample of example 1 was 15.2.
Thermogravimetric analysis of the sample of the raw powder of example 1 (thermogravimetric spectrum see fig. 3) showed that the organic weight loss was 8% of the dry mass of the molecular sieve. The inorganic elemental composition by thermogravimetric analysis and XRF measurement was normalized to give the mordenite molecular sieve of example 1 having an anhydrous chemical composition of 0.61 R.multidot.0.39 Na. (Si) 15.2 Al)O 32.4 Wherein R is N, N, N-trimethyl-1-adamantyl ammonium hydroxide.
The mordenite crude powder sample of example 1 was subjected to 13 C MAS NMR analysis only finds the characteristic carbon resonance peak which is assigned to N, N, N-trimethyl-1-adamantyl ammonium hydroxide, and shows that the N, N, N-trimethyl-1-adamantyl ammonium hydroxide keeps the structure intact in the crystallization process and is used as a template agent to be wrapped in the pore channels of the obtained mordenite molecular sieve.
The characteristic peaks in figure 1 correspond to 2 theta values as shown in table 1, indicating that the synthesized product has the characteristics of mordenite molecular sieve.
TABLE 12 θ corresponding to characteristic peaks of FIG. 1
Examples 2 to 19
The specific compounding ratio and crystallization conditions of examples 2-19 are shown in Table 2, and the compounding process is the same as example 1. XRD analysis was performed on the raw powder samples synthesized in examples 2 to 19, and the X-ray diffraction pattern of the product had the characteristics of FIG. 1, that is, the peak positions and shapes were substantially the same, and the relative peak intensity of the diffraction peaks fluctuated within a range of. + -. 10% depending on the change of the synthesis conditions, which proves that the synthesized products were all mordenite molecular sieves.
The bulk silicon aluminum elemental composition of the molecular sieves of examples 2-19 were analyzed by XRF and the corresponding bulk silicon aluminum compositions are listed in table 2. The anhydrous chemical composition of the mordenite molecular sieve is shown in table 3.
Table 2 molecular sieve initial gel formulation, crystallization conditions and product bulk and surface silico-aluminous elemental composition
Note that * : silicon source: a silica sol, silica sol, b Active silicon dioxide, c Ortho silicate ester, d Water glass, e Metakaolin.
An aluminum source: f sodium metaaluminate, g An aluminum alkoxide, h Aluminium salt, i Metakaolin.
Template agent: n, N, N-trimethyl-1-adamantyl ammonium hydroxide.
Seed crystal: I raw powder of unfired mordenite, II Calcined mordenite, III Ball-milled mordenite, IV An alkali treated mordenite zeolite, V Fluorine ion etching of the treated mordenite.
Crystallization conditions are as follows: alpha dynamic crystallization and beta static crystallization.
The addition amount of the seed crystal is the mass of the seed crystal/feeding SiO 2 Mass of solids.
TABLE 3 Anhydrous chemical composition of mordenite molecular sieves
| Examples | Chemical composition without water |
| 2 | 0.56R·0.44Na·(Si 19.8 Al)O 41.6 |
| 3 | 0.61R·0.39Na·(Si 11.2 Al)O 24.4 |
| 4 | 0.65R·0.35Na·(Si 12.5 Al)O 27 |
| 5 | 0.41R·0.59Na·(Si 13.1 Al)O 28.2 |
| 6 | 0.51R·0.49Na·(Si 21.3 Al)O 44.6 |
| 7 | 0.75R·0.25Na·(Si 26.8 Al)O 55.6 |
| 8 | 0.79R·0.21Na·(Si 16.3 Al)O 34.6 |
| 9 | 0.75R·0.25Na·(Si 15.2 Al) |
| 10 | 0.42R·0.58Na·(Si 14.7 Al)O 31.4 |
| 11 | 0.28R·0.72Na·(Si 14.8 Al)O 31.6 |
| 12 | 0.56R·0.44Na·(Si 11.9 Al)O 25.8 |
| 13 | 0.49R·0.51Na·(Si 12.6 Al)O 27.2 |
| 14 | 0.46R·0.54Na·(Si 11.8 Al) |
| 15 | 0.72R·0.28Na·(Si 13.2 Al)O 28.4 |
| 16 | 0.66R·0.34Na·(Si 14.1 Al)O 30.2 |
| 17 | 0.49R·0.51Na·(Si 14.8 Al)O 31.6 |
| 18 | 0.59R·0.41Na·(Si 13.3 Al)O 28.6 |
| 19 | 0.57R·0.43Na·(Si 12.8 Al)O 27.6 |
Example 20
3g of each of the synthesized samples of examples 1 to 19 was placed in a plastic beaker, and 3mL of a 40% hydrofluoric acid solution was added to dissolve the molecular sieve framework under ice-water bath conditions, and then 15mL of chloroform was added to dissolve the organic substances therein. The composition of the organic matters is analyzed by GC-MS, and the contained organic matters are all corresponding templates R adopted in the synthetic process.
Example 21
The molar ratio of the prepared material is 40SiO 2 :1Al 2 O 3 :6.2K 2 O:840H 2 5.8R 5.5wt% seed crystal starting gel, where R is N, N, N-trimethyl-1-adamantyl ammonium hydroxide. The aluminum source was changed to anhydrous aluminum chloride, the alkali source was changed to 90wt% potassium hydroxide, and the other raw materials were the same as in example 1. The specific material preparation process and crystallization conditions were the same as in example 1. XRD analysis is carried out on the product, and the X-ray diffraction spectrum of the product has the characteristics of figure 1, namely the peak position and the shape are basically the same, so that the synthesized product is proved to be the mordenite molecular sieve.
The bulk silicon aluminum composition of the molecular sieve crystals was analyzed by XRF and the bulk Si/Al molar ratio of the sample of example 21 was 14.5.
Comparative example 1
Except that no organic template agent is added, other blending proportions, blending processes and crystallization conditions are the same as those of example 1. The resulting product was identified by XRD as a mixture of mordenite and ZSM-5. The corresponding XRD pattern is shown in figure 4.
Comparative example 2
Except that no organic template agent is added, other blending proportions, blending processes and crystallization conditions are the same as those of example 21. The resulting product was identified by XRD as a mixture of mordenite and ferrierite. The corresponding XRD pattern is shown in FIG. 5.
Comparative example 3
The molar ratio of the preparation is 40SiO 2 :1Al 2 O 3 :6.2Na 2 O:840H 2 5.8TEAOH 5.5wt% seed initial gel. Only the templating agent was changed to a 25wt% aqueous solution of tetraethylammonium hydroxide (TEAOH) and the starting material was the same as in example 1. The specific material preparation process and crystallization conditions were the same as in example 1. XRD analysis is carried out on the product, and the X-ray diffraction spectrum of the product has the characteristics of figure 1, namely the peak positionThe arrangement and the shape are basically the same, and the synthesized product is proved to be the mordenite molecular sieve.
As shown in fig. 6, it can be seen from fig. 6 that when the template is changed to TEAOH, the synthesized molecular sieve has a bulk crystal with a size of 2-3 μm, and the difference from the molecular sieve is very large, and thus, the template provided by the present application is very important for forming the morphology of the structure in which the circular nano-pillars are aggregated.
Comparative example 4
The molar ratio of the prepared material is 40SiO 2 :1Al 2 O 3 :6.2Na 2 O:840H 2 5.8R, where R is N, N, N-trimethyl-1-adamantyl ammonium hydroxide. The procedure is as in example 1 except that no seed crystals are added. The specific material preparation process and crystallization conditions were the same as in example 1. XRD analysis is carried out on the product, and the obtained product is a mixture of mordenite and amorphous silica. The corresponding XRD pattern is shown in figure 7.
Example 22
The sample obtained in example 1 was calcined at 600 ℃ for 4h with dry air, using 1mol/L NH 4 NO 3 The solution is stirred for 1h at 80 ℃ to carry out ion exchange (the solid-to-liquid ratio is 1.
1.0g of catalyst # 1 was weighed out and subjected to dimethyl ether (abbreviated as DME) carbonylation in a fixed bed reactor for evaluation. When the reaction starts, nitrogen is introduced for activation for 1h at 400 ℃, and then the temperature is reduced to 300 ℃. The reactor was treated for 1h with pyridine at a gas flow rate of 30ml/min, followed by a nitrogen purge for 1h (30 ml/min). Finally, the temperature is reduced to 200 ℃ for reaction. Gas mixture (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. The conversion of DME after the reaction reached equilibrium (about 6 h) was 92% with methyl acetate selectivity greater than 99.9%. The performance diagram of the dimethyl ether carbonylation reaction is shown in figure 9.
Comparative example 5
The compounding ratio and compounding process and crystallization conditions were the same as in example 1 except that no organic template was added and crystallization was performed under static conditions. The resulting product was identified by XRD as MOR, product silicon to aluminum ratio (SiO) 2 /Al 2 O 3 ) Was 18.2.
The sample of comparative example 5 was NH filtered 4 NO 3 Ion exchange to remove sodium ions (same as the treatment method in example 22), roasting in air at 550 ℃ for 4h, tabletting, crushing to 40-60 meshes, and recording as a 2# catalyst sample, wherein the proportion of 8-membered ring channel B acid in the total B acid is 52% (the infrared spectrum peak result is shown in figure 10). 1.0g of # 2 catalyst was weighed out and subjected to dimethyl ether (abbreviated as DME) carbonylation in a fixed bed reactor for evaluation. When the reaction starts, nitrogen is introduced at 400 ℃ to activate 1h, and then the temperature is reduced to 300 ℃. The reactor was treated for 1h with pyridine at a gas flow rate of 30ml/min, followed by a nitrogen purge for 1h (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 an induction period of 6h, samples were taken to obtain conversion of DME and selectivity to methyl acetate in the product. The conversion rate of dimethyl ether is 52 percent, the selectivity of methyl acetate is 99 percent, and the conversion rate of dimethyl ether is obviously lower than that of the example 22. Therefore, the template agent provided by the application is very important for synthesizing the mordenite sample with high 8-membered ring channel B acid ratio and excellent dimethyl ether carbonylation reaction activity.
Comparative example 6
The mordenite molecular sieve sample prepared in comparative example 3 was calcined at 600 deg.C for 4h by introducing dry air 4 NO 3 Removing sodium ions by ion exchange (same as the treatment method in the example 22), roasting in air at 550 ℃ for 4 hours, tabletting, crushing to 40-60 meshes, marking the obtained product as a 3# catalyst sample, and identifying the product as MOR by XRD, wherein the proportion of 8-membered ring channel B acid in the total B acid is 47% (the result of infrared spectrum peak separation is shown in figure 11).
1.0g of # 3 catalyst was weighed out and subjected to dimethyl ether (abbreviated as DME) carbonylation in a fixed bed reactor for evaluation. At the beginning of the reactionActivating for 1h at 400 ℃ by introducing nitrogen, and then cooling to 300 ℃. The reactor was treated for 1h with pyridine at a gas flow rate of 30ml/min, followed by a nitrogen purge for 1h (30 ml/min). Finally, the temperature is reduced to 200 ℃ for reaction. Gas mixture (DME/CO/N) 2 Volume ratio of 2/14/84), gas space velocity of 3000ml g -1 h -1 (STP), the reaction pressure was 2.0MPa. After an induction period of 6h, samples were taken to obtain conversion of DME and selectivity to methyl acetate in the product. The conversion rate of dimethyl ether is reduced to only 40 percent, the selectivity of methyl acetate is 99 percent, and the conversion rate of dimethyl ether is obviously lower than that of the example 22. Therefore, the template agent provided by the application is very important for synthesizing the mordenite sample with high 8-membered ring channel B acid ratio and excellent dimethyl ether carbonylation reaction activity.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A mordenite molecular sieve, characterized in that said mordenite molecular sieve has an anhydrous chemical composition represented by:
nR·mM·(Si x Al)O 2x+2 a formula I;
wherein R represents a template agent, and the template agent is N, N, N-trimethyl-1-adamantyl ammonium hydroxide;
n represents (Si) per mole x Al)O 2x+2 The mole number of the middle template agent R, the value range of n is more than or equal to 0.05 and less than or equal to 0.85;
m represents an alkali metal ion;
m represents (Si) per mole x Al)O 2x+2 The mole number of the medium alkali metal ions M is that the value range of M is more than or equal to 0.15 and less than or equal to 0.95;
x represents the mole ratio of Si element and Al element in the mordenite molecular sieve framework, and the value range of x is more than or equal to 10 and less than or equal to 30.
2. A mordenite zeolite molecular sieve as claimed in claim 1, wherein x is selected in the range 10 ≤ x ≤ 24;
preferably, the mordenite molecular sieve has a morphology structure agglomerated by circular nano-columns;
preferably, the diameter of the circular nano-pillar is 200 to 300nm.
3. A process for the preparation of a mordenite molecular sieve as claimed in any of claims 1 to 2, which process comprises the steps of:
crystallizing an initial gel mixture containing a silicon source, an aluminum source, an M source, a seed crystal, water and a template agent to obtain the mordenite molecular sieve.
4. The preparation method according to claim 3, characterized in that the seed crystal comprises at least one of mordenite raw powder or mordenite obtained after the mordenite raw powder is treated;
the treatment comprises at least one of roasting, ball milling treatment, alkali treatment and fluorine ion etching treatment.
5. The method according to claim 3, wherein the initial gel mixture comprises the following components in a molar ratio:
SiO 2 /Al 2 O 3 ＝20-60；
M 2 O/Al 2 O 3 =1-20, wherein M is an alkali metal ion;
R/Al 2 O 3 ＝1-25；
H 2 O/Al 2 O 3 ＝130-2000；
seed quality/charge SiO 2 Solid mass = 0.1-7%;
preferably, in the initial gel mixture, the molar ratio of each component is:
SiO 2 /Al 2 O 3 ＝20-48；
M 2 O/Al 2 O 3 ＝4-12；
R/Al 2 O 3 ＝4-16；
H 2 O/Al 2 O 3 ＝150-1600；
seed quality/charge SiO 2 Solid mass =0.5-7%.
6. The method of claim 3, wherein the initial gel mixture is obtained by:
mixing an aluminum source, an M source and deionized water, then sequentially adding a silicon source, a seed crystal and a template agent, and stirring to obtain an initial gel mixture;
preferably, the crystallization conditions include:
the crystallization temperature is 120-220 ℃;
the crystallization time is 0.5 to 168 hours;
preferably, the crystallization conditions include:
the crystallization temperature is 140-180 ℃;
the crystallization time is 0.5-168 hours.
7. The catalyst is characterized in that the catalyst is obtained by ion exchange and roasting of a mordenite molecular sieve;
the mordenite molecular sieve comprises at least one of the mordenite molecular sieve of any one of claims 1-2, the mordenite molecular sieve obtained by the preparation method of any one of claims 3-6.
8. The catalyst of claim 7, wherein the ion exchange is ammonium ion exchange;
the roasting temperature is 400-700 ℃;
preferably, the proportion of the number of B acid centers in the 8-membered ring channels of the catalyst in the total number of B acid centers is 80-92%.
9. A method for preparing methyl acetate by carbonylation of dimethyl ether is characterized by comprising the following steps:
the mixed gas containing dimethyl ether and carbon monoxide is contacted with a catalyst and reacts to obtain methyl acetate;
the catalyst comprises at least one of the catalysts of any one of claims 7-8.
10. The method of claim 9, wherein the volume ratio of dimethyl ether to carbon monoxide in the mixed gas is 1:5 to 9;
preferably, the conditions of the reaction include:
the space velocity of the mixed gas is 500-7500 ml g -1 h -1 ；
The reaction temperature is 150-300 ℃;
the reaction pressure is 0.5-5 MPa;
preferably, the catalyst is treated with a pyridine-containing gas stream prior to contacting with the gas mixture.
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