CN114477220B - CaZSM-5 molecular sieve and preparation method and application thereof - Google Patents
CaZSM-5 molecular sieve and preparation method and application thereof Download PDFInfo
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- 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 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 49
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011575 calcium Substances 0.000 claims abstract description 14
- 150000001768 cations Chemical class 0.000 claims abstract description 13
- 230000032683 aging Effects 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- RGKMZNDDOBAZGW-UHFFFAOYSA-N aluminum calcium Chemical compound [Al].[Ca] RGKMZNDDOBAZGW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 229910001415 sodium ion Inorganic materials 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical group [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 5
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- -1 amine compound Chemical class 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011734 sodium Substances 0.000 abstract description 7
- 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 abstract description 4
- 229910052708 sodium Inorganic materials 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000003054 catalyst Substances 0.000 description 21
- 238000005342 ion exchange Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000005899 aromatization reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005360 mashing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 125000000123 silicon containing inorganic group Chemical group 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2729—Changing the branching point of an open chain or the point of substitution on a ring
- C07C5/2732—Catalytic processes
- C07C5/2737—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
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- General Life Sciences & Earth Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a CaZSM-5 molecular sieve and a preparation method and application thereof. The CaZSM-5 molecular sieve is prepared from Ca 2+ The ions are used as ZSM-5 molecular sieve framework balancing cations. The preparation method of the CaZSM-5 molecular sieve comprises the following steps: dissolving a template agent in water to prepare a feed liquid A; adding an aluminum-calcium source into the feed liquid A to obtain feed liquid B; adding a silicon source into the feed liquid B to obtain feed liquid C; and (3) aging and crystallizing the feed liquid C to obtain the CaZSM-5 molecular sieve. The invention realizes the direct synthesis of the CaZSM-5 molecular sieve in the absence of sodium, has the performance different from that of the NaZSM-5 molecular sieve, and is particularly suitable for the application in the meta-xylene isomerization reaction.
Description
Technical Field
The invention relates to the field of molecular sieve catalyst preparation, in particular to a CaZSM-5 molecular sieve, a preparation method thereof and application thereof in xylene isomerization reaction.
Background
The ZSM-5 molecular sieve is a molecular sieve with an MFI structure, and has two sets of mutually crossed pore structures, wherein one set of pore structures is oval ten-membered ring straight pore channels, the size of the pore structures is about 0.54nm and 0.56nm, and the other set of pore structures is round ten-membered ring Z-shaped pore channels, and the size of the pore structures is about 0.52nm and 0.58nm. The special pore channel type can enable reactants and products to smoothly enter and exit, and accumulation of byproducts in the pore channel is reduced because of no cage structure, so that the selectivity and the stability are high. Since the synthetic discovery of Mobil company in 1972, the use of the catalyst in the fields of catalysis, chemical industry and the like has been very widely achieved.
The conventional preparation of ZSM-5 is to obtain sodium-type raw powder, and then to obtain hydrogen-type molecular sieve by means of ion exchange with acid solution.
One method of modulating the acidity of ZSM-5 is to treat the sodium or hydrogen form of the ZSM-5 molecular sieve with acid and base. The acid-base treatment removes part of framework aluminum, thereby reducing the acidity of the molecular sieve. However, this method causes a decrease in the crystallinity of the molecular sieve to various degrees, and the degree of removal of framework silica-alumina and the falling position of the removed silica-alumina are difficult to control.
Another method of modulating the acidity of ZSM-5 is to introduce other metal cations to neutralize some of the acidic sites. It is common practice to introduce other cations by impregnation, deposition or ion exchange. Gao Junhua et al (Gao Junhua, zhang Lidong, etc.), investigation and regeneration evaluation of benzene and ethanol alkylation reaction conditions on modified ZSM-5, chemical progress, 2008 27 (11): 1800) prepared a titanium modified ZSM-5 molecular sieve by ion exchange method, and the modified molecular sieve was applied to benzene and ethanol alkylation reaction. Wang Hengjiang et al (Wang Hengjiang, zhang Chenghua, etc., influence of Ga, zn modification methods on the aromatization performance of HZSM-5 catalyst, fuel chemistry report, 2010 38 (5): 576) modified ZSM-5 molecular sieve by impregnation and hydrothermal synthesis to obtain molecular sieve catalysts of different acidity, and examined the influence of different introduction methods on the aromatization catalytic performance of catalyst olefin. Zhang Shaolong et al (Zhang Shaolong, li, etc.), metal-modified P/HZSM-5 molecular sieves, physical chemistry report, 2011 27 (6): 1501) prepared Cr, co, cu, zn et al metal-modified M-P/HZSM-5 molecular sieves by impregnation, and examined the activity of catalyzing the aromatization of ethanol.
The post-treatment method is difficult to control the falling position and distribution of metal in the pore canal of the molecular sieve, and the stability of the metal position is poor. In addition, the method can cause the crystallinity of the molecular sieve to be reduced to different degrees like acid-base treatment, and has a plurality of process influencing factors which are difficult to repeat.
Another method of introducing metal cations is to add other metal cations directly into the synthesis of the molecular sieve raw powder. CN111056559a discloses a method for preparing flaky Zn/ZSM-5 for methanol aromatization, which is obtained by adding zinc nitrate or the like in preparing a molecular sieve. CN108554444a discloses a method for preparing hierarchical pore Ti-ZSM-5 for automobile exhaust, which is to directly add a titanium source into a mother solution synthesized by a molecular sieve. The hetero atom molecular sieve disclosed in CN110642265A is one prepared with iron metal and aluminum source as solution and through adding the solution into silicon source synthesized with molecular sieve, the hetero atom molecular sieve with skeleton and metal element is produced.
The prior art route is basically based on the introduction of hetero atoms based on the synthesis of sodium ZSM-5, but the prior art does not directly synthesize calcium ZSM-5 molecular sieves (namely CaZSM-5 molecular sieves).
Disclosure of Invention
The invention provides a CaZSM-5 molecular sieve, and a preparation method and application thereof. The method of the invention adopts the direct method to prepare the CaZSM-5 molecular sieve under the condition of no sodium ions, and introduces Ca into the molecular sieve mother liquor 2+ Ion substitution of conventional Na + The ions act as framework-balancing cations, thereby altering the performance of the molecular sieve.
The first aspect of the present invention provides a CaZSM-5 molecular sieve in which Ca 2+ As cations to balance the framework charge of the ZSM-5 molecular sieve.
In the technical scheme, the CaZSM-5 molecular sieve does not contain Ca 2+ External cations, such as sodium ions, that balance the charge of the ZSM-5 molecular sieve framework.
In the technical scheme, in the CaZSM-5 molecular sieve, siO 2 /Al 2 O 3 The molar ratio is 30-400.
In the technical scheme, in the CaZSM-5 molecular sieve, the mass content of Ca calculated by CaO is 0.2% -3.0%.
In the technical scheme, the relative crystallinity of the CaZSM-5 molecular sieve is 95-100%.
The second aspect of the invention provides a method for preparing a CaZSM-5 molecular sieve, comprising the steps of:
(1) Dissolving a template agent in water to prepare a feed liquid A;
(2) Adding an aluminum-calcium source into the feed liquid A to obtain feed liquid B;
(3) Adding a silicon source into the feed liquid B to obtain feed liquid C;
(4) And (3) aging and crystallizing the feed liquid C to obtain the CaZSM-5 molecular sieve.
In the technical proposal, the silicon source adopts SiO 2 Counting the amount of Al and Al-Ca source 2 O 3 The mol ratio of the raw materials of CaO meter, template agent (M) and water is SiO 2 ：Al 2 O 3 ：M：CaO：H 2 O=1: 0.002-0.03:0.1-0.5:0.002-0.03:10-50, M is template agent.
In the technical scheme, the raw materials used in the preparation method of the CaZSM-5 molecular sieve do not contain sodium ions.
In the above technical scheme, the aluminum-calcium source is calcium aluminate, preferably high-purity calcium aluminate which does not contain sodium ions and other metal cations.
In the above technical scheme, the template agent is an organic amine compound, and can be at least one selected from ethylamine, ethylenediamine, triethylamine, n-butylamine, tetrapropylammonium hydroxide and the like.
In the above technical solution, the silicon source is a silicon-containing inorganic or organic compound that does not contain sodium and other metal cations, and may be at least one selected from white carbon black, silica sol, silica gel, methyl orthosilicate, ethyl orthosilicate, and the like.
In the above technical solution, the aging conditions in step (4) are as follows: the aging temperature is 20-100deg.C, and the aging time is 0.5-12 hr, preferably 1-6 hr.
In the above technical solution, the crystallization conditions in the step (4) are as follows: the crystallization temperature is 110-200 ℃, preferably 120-180 ℃, and the crystallization time is 1-96 hours, preferably 1-72 hours.
The third aspect of the invention provides the use of the CaZSM-5 molecular sieve described above in a meta-xylene isomerisation reaction.
In the technical scheme, the meta-xylene isomerization reaction conditions are as follows: the reaction temperature is 320-450 deg.c and the reaction pressure is 0.1-1.0MPa.
The CaZSM-5 molecular sieve of the invention has the following advantages:
1. the method can directly synthesize the CaZSM-5 molecular sieve under the condition of no sodium ion, and changes the performance of the ZSM-5 molecular sieve, in particular to the acid center distribution different from the NaZSM-5 molecular sieve by using calcium ion to replace sodium ion as a molecular sieve framework balancing cation. The CaZSM-5 molecular sieve of the invention can directly carry out ion exchange (such as ammonium exchange) with an acidic solution, not only can the acid quantity be adjusted in a wide range, but also the distribution of acid centers after exchange can be obviously changed compared with the NaZSM-5 molecular sieve due to the bivalent property of calcium ions.
2. The CaZSM-5 molecular sieve can be directly subjected to ion exchange with an acidic solution, so that the prepared catalyst is used in a meta-xylene isomerization reaction, and has higher meta-xylene conversion rate and higher para-xylene selectivity.
Drawings
FIG. 1 is an XRD pattern of the CaZSM-5 molecular sieve obtained in example 1;
FIG. 2 is an XRD pattern of the CaZSM-5 molecular sieve obtained in example 2;
FIG. 3 is an XRD pattern of the NaZSM-5 molecular sieve obtained in comparative example 1;
FIG. 4 is a representation of NH of the CaZSM-5 molecular sieve obtained in example 1 and the NaZSM-5 molecular sieve obtained in comparative example 1 3 -TPD profile.
Detailed Description
The technical scheme of the present invention will be described in more detail by means of specific examples, but the scope of the present invention is not limited thereto. Similar technical effects can be achieved by various modifications or combinations of the embodiments of the present invention, and other embodiments of the present invention can be obtained without departing from the scope of protection defined by the claims of the present invention.
In the invention, the characterization and identification of the crystalline phase structure of the sample are carried out by adopting an X-ray powder diffractometer type IV of Rigaku Ultima of Japanese science. CuK alpha ray sourceThe nickel filter has a 2 theta scanning range of 5-50 degrees, an operating voltage of 35KV, a current of 25mA and a scanning speed of 10 degrees/min. The relative crystallinity of each sample was calculated as the ratio of the sum of the diffraction peak intensities at each sample grade 2θ=22.8°, 23.1 °, 23.5 °, 23.7 °, 24.2 °, where the diffraction peak intensity of the sample of the synthesized NaZSM-5 molecular sieve was 100% in comparative example 1.
In the invention, molecular sieve acidity desorbs (NH) through ammonia gas-temperature programming 3 TPD) analytical method determination, specific operations are: tabletting, mashing and screening the molecular sieve sample, and drying particles with 20-40 meshes for later use to obtain a sample to be tested. In the experiment, 150 mg of dry sample to be measured is accurately weighed and filled into a quartz tube. The sample is heated to 550 ℃ for activation for 2 hours under helium atmosphere, cooled to room temperature, adsorbed with 10% ammonia for 30 minutes, then heated to 100 ℃ for constant, heated to 650 ℃ at a heating rate of 10 ℃/minute until the baseline is stable, and collected ammonia desorption signals.
Example 1
The raw material slurry is prepared according to the following molar ratio: siO (SiO) 2 ：Al 2 O 3 ：M：CaO：H 2 O=1: 0.005:0.40:0.005:30. 80 g of tetrapropylammonium hydroxide (25 wt%) is weighed and dissolved in 30 ml of deionized water to form a feed liquid A, then 0.3 g of calcium aluminate is added into the feed liquid A, and the mixture is uniformly mixed and stirred to prepare a feed liquid B; then, 50 g of ethyl orthosilicate is weighed and added into the feed liquid B to be stirred and mixed uniformly, and the mixture is marked as feed liquid C. The material liquid C is stirred and aged for 1.5 hours at room temperature, then the material is transferred into a stainless steel reaction kettle, the reaction kettle is sealed and heated to 150 ℃, and crystallization is carried out for 72 hours under the hydrothermal condition. Centrifuging the product, washing with water to pH of the supernatant<8, transferring the product into an oven, and treating at 120deg.C for 6 hours to dryThen the sample is transferred into a muffle furnace and baked for 12 hours in an air atmosphere at 550 ℃ to obtain the CaZSM-5 molecular sieve, the SiO of which is 2 /Al 2 O 3 The molar ratio was 183 and the mass content of Ca as CaO was 0.5%. As can be seen from the XRD pattern of fig. 1, 2θ=7.6°, 8.5 °, 22.8 °, 23.1 °, 23.5 °, 23.7 ° 24.2 ° have distinct ZSM-5 characteristic peaks, and the relative crystallinity of the sample is 98%.
Mixing 10 g of CaZSM-5 molecular sieve with 50 g of 0.5mol/L ammonium chloride solution (solid-liquid volume ratio is 1:5), placing in a water bath for ion exchange, wherein the ion exchange temperature is 80 ℃, washing a sample after 2 hours of exchange, performing solid-liquid separation, exchanging for 2 times again according to the steps, and drying the sample at 120 ℃ for 4 hours and roasting at 550 ℃ for 6 hours to obtain the product catalyst.
Example 2
The raw material slurry is prepared according to the following molar ratio: siO (SiO) 2 ：Al 2 O 3 ：M：CaO：H 2 O=1: 0.006:0.40:0.006:20. weighing 10 g of n-butylamine, dissolving the n-butylamine in 30 ml of deionized water to form a feed liquid A, adding 0.5 g of calcium aluminate into the feed liquid A, and uniformly mixing and stirring to prepare a feed liquid B; then weighing 20 g of white carbon black, adding the white carbon black into the feed liquid B, stirring and mixing uniformly, and marking as feed liquid C. The material liquid C is stirred and aged for 1.5 hours at room temperature, then the material is transferred into a stainless steel reaction kettle, the reaction kettle is sealed and heated to 160 ℃, and crystallization is carried out for 60 hours under the hydrothermal condition. Centrifuging the product, washing with water to pH of the supernatant<8, transferring the product into a baking oven, treating at 120 ℃ for 6 hours to dry the product, transferring the sample into a muffle furnace, and roasting for 12 hours in an air atmosphere at 550 ℃ to obtain the CaZSM-5 molecular sieve, wherein SiO 2 /Al 2 O 3 The molar ratio was 153 and the mass content of Ca calculated as CaO was 0.7%. As can be seen from the XRD pattern of fig. 2, 2θ=7.6°, 8.5 °, 22.8 °, 23.1 °, 23.5 °, 23.7 ° 24.2 ° have distinct ZSM-5 characteristic peaks, and the relative crystallinity of the sample is 96%.
Mixing 10 g of CaZSM-5 molecular sieve with 50 g of 0.5mol/L ammonium chloride solution (solid-liquid volume ratio is 1:5), placing in a water bath for ion exchange, wherein the ion exchange temperature is 80 ℃, washing a sample after 2 hours of exchange, performing solid-liquid separation, exchanging for 2 times again according to the steps, and drying the sample at 120 ℃ for 4 hours and roasting at 550 ℃ for 6 hours to obtain the product catalyst. .
Example 3
The raw material slurry is prepared according to the following molar ratio: siO (SiO) 2 ：Al 2 O 3 ：M：CaO：H 2 O=1: 0.003:0.30:0.003:20. 7.5 g of n-butylamine is weighed and dissolved in 30 ml of deionized water to form a feed liquid A, and then 0.3 g of calcium aluminate is added into the feed liquid A, and the feed liquid A and the feed liquid B are prepared by uniformly mixing and stirring. Then weighing 20 g of white carbon black, adding the white carbon black into the feed liquid B, stirring and mixing uniformly, and marking as feed liquid C. The material liquid C is stirred and aged for 1.5 hours at room temperature, then the material is transferred into a stainless steel reaction kettle, the reaction kettle is sealed and heated to 160 ℃, and crystallization is carried out for 72 hours under the hydrothermal condition. Centrifuging the product, washing with water to pH of the supernatant<8, transferring the product into a baking oven, treating at 120 ℃ for 6 hours to dry the product, transferring the sample into a muffle furnace, and roasting for 12 hours in an air atmosphere at 550 ℃ to obtain the CaZSM-5 molecular sieve, wherein SiO 2 /Al 2 O 3 The molar ratio was 302 and the mass content of Ca as CaO was 0.4%. The XRD pattern of the resulting CaZSM-5 molecular sieve was similar to that of FIG. 1.
Mixing 10 g of CaZSM-5 molecular sieve with 50 g of 0.5mol/L ammonium chloride solution (solid-liquid volume ratio is 1:5), placing in a water bath for ion exchange, wherein the ion exchange temperature is 80 ℃, washing a sample after 2 hours of exchange, performing solid-liquid separation, exchanging for 2 times again according to the steps, and drying the sample at 120 ℃ for 4 hours and roasting at 550 ℃ for 6 hours to obtain the product catalyst.
Example 4
The catalyst prepared in example 1 was charged into a pulse reactor to carry out meta-xylene isomerization reaction. The specific reaction conditions are as follows: raw materials: meta-xylene, reaction temperature 400 ℃, sample injection amount: 0.1 μl, catalyst loading: 0.1g. The chromatogram adopts FFAP capillary column analysis and FID detection.
Example 5
The catalyst of example 2 was charged to a pulse reactor to effect meta-xylene isomerization. The specific reaction conditions are as follows: raw materials: meta-xylene, reaction temperature 400 ℃, sample injection amount: 0.1 μl, catalyst loading: 0.1g. The chromatogram adopts FFAP capillary column analysis and FID detection.
Comparative example 1
The raw material slurry is prepared according to the following molar ratio: siO (SiO) 2 ：Al 2 O 3 ：M：Na 2 O：H 2 O=1: 0.005:0.40:0.2:30. 1.1 g of aluminum sulfate and 3.7 g of sodium hydroxide are weighed and dissolved in 60 ml of deionized water to form a solution, so as to obtain a feed liquid A, and then 80 g of tetrapropylammonium hydroxide (25 wt%) is added into the feed liquid A, and the mixture is uniformly mixed and stirred to prepare a feed liquid B; then, 50 g of ethyl orthosilicate is weighed and added into the feed liquid B to be stirred and mixed uniformly, and the mixture is marked as feed liquid C. The material liquid C is stirred and aged for 1.5 hours at room temperature, then the material is transferred into a stainless steel reaction kettle, the reaction kettle is sealed and heated to 150 ℃, and crystallization is carried out for 72 hours under the hydrothermal condition. Centrifuging the product, washing with water to pH of the supernatant<8, transferring the product into a baking oven, treating at 120 ℃ for 6 hours to dry the product, transferring the sample into a muffle furnace, and roasting for 12 hours in an air atmosphere at 550 ℃ to obtain NaZSM-5 molecular sieve, wherein SiO 2 /Al 2 O 3 Molar ratio of 191, na to Na 2 The mass content of O is 0.5%. As can be seen from the XRD pattern of fig. 3, 2θ=7.6°, 8.5 °, 22.8 °, 23.1 °, 23.5 °, 23.7 ° 24.2 ° have distinct ZSM-5 characteristic peaks, and the relative crystallinity of the sample is 100%.
Ion exchange is carried out on NaZSM-5 molecular sieve and ammonium chloride solution, the ion exchange conditions are the same as in example 1, and the catalyst is obtained after drying and roasting.
The catalyst of comparative example 1 was charged into a pulse reactor for meta-xylene isomerization under the following specific reaction conditions: raw materials: meta-xylene, reaction temperature 400 ℃, sample injection amount: 0.1 μl, catalyst loading: 0.1g. The chromatogram adopts FFAP capillary column analysis and FID detection.
Comparative example 2
The NaZSM-5 molecular sieve obtained in comparative example 1 was subjected to ion exchange with a 0.2mol/L calcium chloride solution to obtain a ZSM-5 molecular sieve having a mass content of 0.4% of Ca in terms of CaO. Then, ion exchange is carried out with 0.5mol/L ammonium chloride solution, and the catalyst is obtained after drying and roasting, wherein the processes and conditions of ion exchange, drying and roasting are the same as those of the example 1.
The catalyst of comparative example 2 was charged into a pulse reactor for meta-xylene isomerization under the following specific reaction conditions: raw materials: meta-xylene, reaction temperature 400 ℃, sample injection amount: 0.1 μl, catalyst loading: 0.1g. The chromatogram adopts FFAP capillary column analysis and FID detection.
Table 1 reaction results for each of examples and comparative examples
| Reaction temperature (. Degree. C.) | Conversion of meta-xylene (MX) (wt%) | Para-xylene (PX)/ortho-xylene (OX) | |
| Example 4 | 400 | 33.5 | 1.26 |
| Example 5 | 400 | 36.3 | 1.41 |
| Comparative example 1 | 400 | 25.1 | 0.97 |
| Comparative example 2 | 400 | 30.2 | 1.13 |
From NH of FIG. 4 3 As can be seen from the TPD spectrum, the molecular sieve of example 1 of the present invention has significantly changed acid center distribution and NH at low temperature region as compared with comparative example 1 3 The TPD desorption peak becomes significantly stronger, while the NH in the high temperature zone 3 The TPD desorption peak was significantly weaker.
As can be seen from Table 1, the selectivity for paraxylene was far higher for the catalyst prepared using the molecular sieve of example 1 of the present invention than for the catalyst prepared using the molecular sieve of comparative example 1.
The above describes in detail the specific embodiments of the present invention, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (11)
1. An application of CaZSM-5 molecular sieve in m-xylene isomerization reaction is characterized in that: ca in CaZSM-5 molecular sieve 2+ As cations for balancing the framework charge of the ZSM-5 molecular sieve; caZSM-5 molecular sieve contains no Ca 2+ External cations for balancing the framework charges of the ZSM-5 molecular sieve;
the preparation method of the CaZSM-5 molecular sieve comprises the following steps:
(1) Dissolving a template agent in water to prepare a feed liquid A;
(2) Adding an aluminum-calcium source into the feed liquid A to obtain feed liquid B;
(3) Adding a silicon source into the feed liquid B to obtain feed liquid C;
(4) Aging and crystallizing the feed liquid C to obtain a CaZSM-5 molecular sieve;
the raw materials used in the preparation method of the CaZSM-5 molecular sieve do not contain sodium ions.
2. The use according to claim 1, characterized in that: in the CaZSM-5 molecular sieve, the mass content of Ca calculated by CaO is 0.2% -3.0%.
3. The use according to claim 1, characterized in that: siO of the CaZSM-5 molecular sieve 2 /Al 2 O 3 The molar ratio is 30-400.
4. The use according to claim 1, characterized in that: the relative crystallinity of the CaZSM-5 molecular sieve is 95% -100%.
5. The use according to claim 1, characterized in that: silicon source is SiO 2 Counting the amount of Al and Al-Ca source 2 O 3 The mol ratio of the raw materials of CaO meter, template agent and water is SiO 2 ：Al 2 O 3 ：M：CaO：H 2 O=1: 0.002-0.03:0.1-0.5:0.002-0.03:10-50, M is template agent.
6. The use according to claim 1, characterized in that: the aluminum calcium source is calcium aluminate.
7. The use according to claim 1, characterized in that: the template agent is an organic amine compound; and/or the silicon source is at least one of white carbon black, silica sol, silica gel, methyl orthosilicate and ethyl orthosilicate.
8. The use according to claim 7, characterized in that: the template agent is at least one of ethylamine, ethylenediamine, triethylamine, n-butylamine and tetrapropylammonium hydroxide.
9. The use according to claim 1, characterized in that: the aging conditions described in the step (4) are as follows: the aging temperature is 20-100 ℃ and the aging time is 0.5-12 hours; and/or the crystallization temperature is 110-200 ℃ and the crystallization time is 1-96 hours.
10. The use according to claim 9, characterized in that: the aging conditions described in the step (4) are as follows: the aging time is 1-6 hours.
11. The use according to claim 9, characterized in that: the crystallization temperature in the step (4) is 120-180 ℃ and the crystallization time is 1-72 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437605A (en) * | 2014-11-07 | 2015-03-25 | 中国石油天然气集团公司 | W-ZSM-5 molecular-sieve-based catalyst as well as preparation method and application of W-ZSM-5 molecular-sieve-based catalyst |
| CN104525246A (en) * | 2015-01-22 | 2015-04-22 | 厦门大学 | Preparation method and application of no-template-agent small-grain Zn-ZSM-5 catalyst |
| CN106698463A (en) * | 2015-11-12 | 2017-05-24 | 中国石油化工股份有限公司 | Synthesis method of nanosized ZSM-5 molecular sieve |
| CN108178164A (en) * | 2018-02-11 | 2018-06-19 | 四川润和催化新材料股份有限公司 | A kind of multi-stage porous ZSM-5 molecular sieve and preparation method thereof prepares the method for PX catalyst with it |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437605A (en) * | 2014-11-07 | 2015-03-25 | 中国石油天然气集团公司 | W-ZSM-5 molecular-sieve-based catalyst as well as preparation method and application of W-ZSM-5 molecular-sieve-based catalyst |
| CN104525246A (en) * | 2015-01-22 | 2015-04-22 | 厦门大学 | Preparation method and application of no-template-agent small-grain Zn-ZSM-5 catalyst |
| CN106698463A (en) * | 2015-11-12 | 2017-05-24 | 中国石油化工股份有限公司 | Synthesis method of nanosized ZSM-5 molecular sieve |
| CN108178164A (en) * | 2018-02-11 | 2018-06-19 | 四川润和催化新材料股份有限公司 | A kind of multi-stage porous ZSM-5 molecular sieve and preparation method thereof prepares the method for PX catalyst with it |
Non-Patent Citations (2)
| Title |
|---|
| 反应气氛对Ca/ZSM-5上二甲醚转化制丙烯反应的影响;满建明等;《燃烧化学学报》;第第39卷卷(第第1期期);42-43页1实验部分1.1催化剂的制备 * |
| 苯甲醇在Pt/Mg（Ca）-ZSM-5催化剂上的室温选择性氧化及其反应机理研究;洪叶江等;《第十七届全国分子筛学术大会会议论文集》;701-702 * |
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