CN109967120A - Zeolite molecular sieve supports the preparation method and applications of ferrum-based catalyst - Google Patents
Zeolite molecular sieve supports the preparation method and applications of ferrum-based catalyst Download PDFInfo
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- CN109967120A CN109967120A CN201910173800.6A CN201910173800A CN109967120A CN 109967120 A CN109967120 A CN 109967120A CN 201910173800 A CN201910173800 A CN 201910173800A CN 109967120 A CN109967120 A CN 109967120A
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- molecular sieve
- zeolite molecular
- iron
- ferrum
- catalyst
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 76
- 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 76
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 58
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000010457 zeolite Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 31
- 239000001301 oxygen Substances 0.000 claims abstract description 31
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 29
- 229910052742 iron Inorganic materials 0.000 claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 23
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 15
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 12
- 210000003850 cellular structure Anatomy 0.000 claims abstract description 4
- 238000005342 ion exchange Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 230000001699 photocatalysis Effects 0.000 claims description 17
- 238000007146 photocatalysis Methods 0.000 claims description 16
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 claims description 8
- -1 Acyl acetone iron Chemical compound 0.000 claims description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 3
- 150000002220 fluorenes Chemical class 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- NBIJDQIBCRZHFK-UHFFFAOYSA-N 1,3,5-trihydroxy-1,3,5-triazinane-2,4,6-trione Chemical compound ON1C(=O)N(O)C(=O)N(O)C1=O NBIJDQIBCRZHFK-UHFFFAOYSA-N 0.000 claims description 2
- 125000003047 N-acetyl group Chemical group 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellityc acid Natural products OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims 1
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims 1
- LHOWRPZTCLUDOI-UHFFFAOYSA-K iron(3+);triperchlorate Chemical compound [Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LHOWRPZTCLUDOI-UHFFFAOYSA-K 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 description 27
- 239000003795 chemical substances by application Substances 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- VBBUVIWLZBAEEF-UHFFFAOYSA-N 2,6-dihydroxypyrrolo[3,4-f]isoindole-1,3,5,7-tetrone Chemical compound C1=C2C(=O)N(O)C(=O)C2=CC2=C1C(=O)N(O)C2=O VBBUVIWLZBAEEF-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CNRMRKSNOUGQLV-UHFFFAOYSA-N 2-hydroxy-4,5,6,7-tetraphenylisoindole-1,3-dione Chemical compound O=C1N(O)C(=O)C(C(=C(C=2C=CC=CC=2)C=2C=3C=CC=CC=3)C=3C=CC=CC=3)=C1C=2C1=CC=CC=C1 CNRMRKSNOUGQLV-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- JRSGPUNYCADJCW-UHFFFAOYSA-K iron(3+);trichlorate Chemical compound [Fe+3].[O-]Cl(=O)=O.[O-]Cl(=O)=O.[O-]Cl(=O)=O JRSGPUNYCADJCW-UHFFFAOYSA-K 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- QUWBGQXYZZQGGY-UHFFFAOYSA-N 2-hydroxy-1,1-dioxo-1,2-benzothiazol-3-one Chemical compound C1=CC=C2S(=O)(=O)N(O)C(=O)C2=C1 QUWBGQXYZZQGGY-UHFFFAOYSA-N 0.000 description 1
- DTASWMPPCOEWOU-UHFFFAOYSA-N 2-hydroxy-4-(pyridin-2-ylmethyl)isoindole-1,3-dione Chemical compound N1=C(C=CC=C1)CC1=C2C(C(=O)N(C2=O)O)=CC=C1 DTASWMPPCOEWOU-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000006897 homolysis reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—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
- B01J29/42—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 containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
-
- 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
-
- 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
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to photochemical catalyst preparation and application fields, it is desirable to provide a kind of zeolite molecular sieve supports the preparation method and applications of ferrum-based catalyst.Include: to be dispersed in water zeolite molecular sieve, add source of iron, is carried out ion exchange 6~24 hours under 80 DEG C and stirring condition；Reaction product is taken out, washing, drying are placed in Muffle furnace, roast 4~10 hours under the conditions of 400~600 DEG C, obtain zeolite molecular sieve and support ferrum-based catalyst.The cost of material used in preparation process of the present invention is lower, preparation process is simple.In the immobilized photochemical catalyst of gained zeolite, iron particle is dispersed on zeolite molecular sieve, and the content of iron is controllable, and mass fraction is adjustable within the scope of 0.1-99%, and molecular sieve pore passage structure is also adjustable, can select suitable cellular structure according to intermediate.Gained catalyst hydrocarbon oxidation application in, to reaction condition require it is not stringent, only using oxygen as oxygen source room temperature under can realize reaction, also very high conversion ratio and selectivity.
Description
Technical field
The present invention relates to photochemical catalyst preparations and application field, in particular to zeolite molecular sieve to support ferrum-based catalyst
Preparation method and its application in photocatalysis hydrocarbon oxidation.
Background technique
Hydrocarbon catalyticing oxidation has important researching value and status in petroleum, chemical field, and hydro carbons methylene aoxidizes
Research is used as its important component, has important science and application value.Traditional oxidation technology usually requires more severe
The reaction condition at quarter and a degree of pollution is brought to environment, design efficient photochemical catalyst system, realizes temperate condition
Direct oxidation of the lower molecular oxygen to hydro carbons is very significant and challenge a problem.
With the progress of human society, fossil fuel is largely burnt, and energy problem is more and more severeer.Therefore, the mankind compel
That cuts needs to solve energy crisis using new energy, realizes sustainable development.Sunlight is reproducible new energy, sufficiently
It can solve the following energy crisis that may be present using sunlight.A variety of effective photochemical catalysts are had developed,
They have that stability is good, photocatalytic activity is high, organic matter can at normal temperatures and pressures decomposed completely, thorough mineralising the features such as,
Therefore the attention of researcher is received.
Inorganic oxide (the oxygen of such as value Mn and chromium that this kind of reaction usually requires equivalent is completed with traditional method
Compound, selenium dioxide etc.), inorganic acid (such as nitric acid), halogen simple substance (such as bromine), it is not only expensive, but also environment is made
At very big pollution.Organic free radical has widely been used as the catalysis in oxidation reaction as a kind of higher substance of activity
Agent, the easy H that captures from the c h bond in organic reaction substrate (such as hydrocarbon compound) of free radical make substrate homolysis generate carbon freedom
Base, to cause free chain reaction.
But there are poor selectivities for conventional photochemical catalyst, can obtain product or its mixture that degree of oxidation does not wait；
Low to the utilization rate of intermediate, catalytic efficiency cannot be promoted.This method, which is used, is supported on zeolite molecular sieve for activated centre iron
On, using the duct of molecular sieve, intermediate is enriched with, realizes efficient hydrocarbon oxidation process, and have very high turn
Rate and selectivity.
Summary of the invention
The technical problem to be solved by the present invention is to overcome deficiency in the prior art, provide a kind of zeolite molecular sieve and support
The preparation method of ferrum-based catalyst and its application in photocatalysis hydrocarbon oxidation.
In order to solve the above technical problems, solution of the invention is:
The preparation method that a kind of zeolite molecular sieve supports ferrum-based catalyst is provided, comprising the following steps:
Zeolite molecular sieve is dispersed in water, source of iron is added, ion exchange 6~24 is carried out under 80 DEG C and stirring condition
Hour, the mass ratio of source of iron and zeolite molecular sieve is 0.001~1: 1；Reaction product is taken out, washing, drying are placed on Muffle furnace
In, it is roasted 4~10 hours under the conditions of 400~600 DEG C, obtains zeolite molecular sieve and support ferrum-based catalyst.
It in the present invention, is supported in ferrum-based catalyst final products in zeolite molecular sieve, iron accounts for the quality point of zeolite molecular sieve
Number is 0.1~99%.
In the present invention, the zeolite molecular sieve is the Si-Al molecular sieve of regular cellular structure or appointing in phosphate aluminium molecular sieve
One kind of meaning.
In the present invention, the source of iron is any one following: ferric nitrate, iron chloride, ferrous sulfate, frerrous chloride, height
Ferric chlorate, ferric oxalate, ironic citrate, ferric sulfate, ferric acetate, acetylacetone,2,4-pentanedione ferrous iron or ferric acetyl acetonade.
Invention further provides zeolite molecular sieves to support application side of the ferrum-based catalyst in photocatalysis hydrocarbon oxidation
Method, be by mass ratio be 0.001~1: 0.001~1: 0.001~1 catalyst, intermediate and containing the hydro carbons of alpha position C-H
It closes object to be placed in reactor, using oxygen as oxygen source, photocatalysis hydrocarbon oxidization is carried out under the conditions of UV, visible light wave band.Light
The reaction condition for being catalyzed hydrocarbon oxidization can routinely photocatalysis hydrocarbon oxidization in the prior art execute (for example, often
Any light source of UV, visible light wave band can be used in normal temperature and pressure condition or high-temperature and high-pressure conditions).
In the present invention, the intermediate be it is following any one: n-Hydroxyphthalimide (N-
Hydroxyphthalimide, NHPI) or derivatives thereof, N, N '-dihydroxy pyromellitic acid imines (N, N '-
Dihydroxypyromellitimide, NDHPI), N- hydroxysaccharine (Nhydroxsaccharin, NHS),
N- acetyl group phthalimide (Nacetoxyphthalimide, NAPI), N, N ', N "-trihydroxy isocyanuric acid (N, N ',
N "-trihydroxyisocianuric acid, THICA), N- hydroxyl -3,4,5,6- tetraphenyl phthalimide (N-
Hydroxyl-3,4,5,6-tetraphenylphthalimide, NHTPPI), 3- picolyl-N- hydroxyl phthalyl it is sub-
Amine (3-pyridinylmethyl-N-hydroxyphthalimide, Py-NHPI) or dialkyl nitroxyl are (such as
TEMPO)。
In the present invention, the hydrocarbon compound containing alpha position C-H be it is following any one: ethylbenzene, hexamethylene, toluene, four
Hydrogen naphthalene, indane, methane, dimethylbenzene, diphenyl methane, fluorenes, cyclohexene or ethane.
Compared with prior art, the beneficial effects of the present invention are:
1, the cost of material used in preparation process of the present invention is lower, preparation process is simple.
3, in the present invention gained immobilized photochemical catalyst of zeolite, iron particle is dispersed on zeolite molecular sieve, and the content of iron can
Control, mass fraction is adjustable within the scope of 0.1-99%, and molecular sieve pore passage structure is also adjustable, and it is suitable to be selected according to intermediate
Cellular structure.
2, the immobilized photochemical catalyst of zeolite of the invention is not stringent to reaction condition requirement in the application of hydrocarbon oxidation, only
Using oxygen as oxygen source, under room temperature, so that it may realize reaction；And it due to the duct of molecular sieve, greatly improves to centre
The utilization rate of body, being also able to maintain while having saved reaction cost has very high conversion ratio and selectivity to alkane.
Detailed description of the invention
Fig. 1 is Fe/ZSM-5SEM figure；
Fig. 2 is Fe/SSZ-13SEM figure；
Fig. 3 is Fe/Beta SEM figure；
Fig. 4 is Fe/ZSM-5TEM figure；
Fig. 5 is the uv atlas of catalyst in embodiment 1,3,4,5.
Specific embodiment
Present invention is further described in detail With reference to embodiment, and each embodiment can make the special of this profession
The present invention, but do not limit the invention in any way is more fully understood in industry technical staff.
Embodiment 1
It disperses 0.1g ZSM-5 in the deionized water of 50ml, adds the ferric nitrate of 0.001 times of molecular sieve quality,
80 DEG C of stirrings lower exchange 6 hours；It takes out reaction product and washs drying, roasted 4 hours at 400 DEG C in Muffle furnace, obtain zeolite
Molecular sieve supported ferrum-based catalyst, in catalyst prod, the mass fraction that iron accounts for zeolite molecular sieve is 0.1%.
Aforementioned catalytic agent is added in reactor, NHPI is added as intermediate, is passed through sufficient amount of oxygen as oxygen source, urges
The mass ratio of agent, intermediate and hydrocarbon compound is 0.001: 1: 1.Mercury lamp is used at normal temperatures and pressures, and photocatalysis may be implemented
Ethylbenzene oxidation, conversion ratio is up to 50%, and selectivity is up to 90%.
Embodiment 2
It disperses 1g S-1 molecular sieve in the deionized water of 50ml, adds the iron chloride of 0.1 times of molecular sieve quality,
80 DEG C of stirrings lower exchange 24 hours；It takes out reaction product and washs drying, roast 10 hours, boiled at 600 DEG C in Muffle furnace
The molecular sieve supported ferrum-based catalyst of stone, in catalyst prod, the mass fraction that iron accounts for zeolite molecular sieve is 10%
Aforementioned catalytic agent is added in reactor, adds THICA as intermediate, and using oxygen as the condition of oxygen source
Under, the mass ratio of catalyst, intermediate and hydrocarbon compound is 0.001: 0.001: 0.5.Xenon is used under 2 atmospheric pressure of room temperature
Photocatalysis cyclohexane oxidation may be implemented in lamp, and conversion ratio is up to 50%, and selectivity is up to 100%.
Embodiment 3
It disperses 0.5g SSZ-13 in the deionized water of 50ml, the sulfuric acid for adding 0.05 times of molecular sieve quality is sub-
Iron, 80 DEG C of stirrings lower exchange 15 hours；It takes out reaction product and washs drying, roast 7 hours, obtain at 500 DEG C in Muffle furnace
Zeolite molecular sieve supports ferrum-based catalyst, and in catalyst prod, the mass fraction that iron accounts for zeolite molecular sieve is 5%.
Aforementioned catalytic agent is added in reactor, adds NDHPI as intermediate, and using oxygen as the condition of oxygen source
Under, the mass ratio of catalyst, intermediate and hydrocarbon compound is 1: 0.5: 0.001.Xenon lamp is used under 80 DEG C of normal pressures, may be implemented
Photocatalysis toluene oxidation, conversion ratio is up to 50%, and selectivity is up to 95%.
Embodiment 4
It disperses 1g Beta zeolite molecular sieve in the deionized water of 50ml, adds 0.07 times of molecular sieve quality
Frerrous chloride, 80 DEG C of stirrings lower exchange 10 hours；It takes out reaction product and washs drying, roasting 5 is small at 550 DEG C in Muffle furnace
When, it obtains zeolite molecular sieve and supports ferrum-based catalyst, in catalyst prod, the mass fraction that iron accounts for zeolite molecular sieve is 7%.
Aforementioned catalytic agent is added in reactor, adds NHS as intermediate, and using oxygen as the condition of oxygen source
Under, the mass ratio of catalyst, intermediate and hydrocarbon compound is 0.5: 1: 0.5.Metal halogen lamp is used under 70 DEG C of normal pressures, may be implemented
Photocatalysis tetrahydro Fluidized bed, conversion ratio is up to 90%, and selectivity is up to 95%.
Embodiment 5
It disperses 0.6g Y zeolite molecular sieve in the deionized water of 50ml, adds the height of 0.03 times of molecular sieve quality
Ferric chlorate, 80 DEG C of stirrings lower exchange 6 hours；It takes out reaction product and washs drying, roast 4 hours, obtain at 600 DEG C in Muffle furnace
Ferrum-based catalyst is supported to zeolite molecular sieve, and in catalyst prod, the mass fraction that iron accounts for zeolite molecular sieve is 3%.
Aforementioned catalytic agent is added in reactor, adds NHTPPI as intermediate, and using oxygen as the item of oxygen source
Under part, the mass ratio of catalyst, intermediate and hydrocarbon compound is 0.05: 1: 0.1.Metal halogen lamp is used under 50 DEG C of 4 atmospheric pressure,
The oxidation of photocatalysis indane may be implemented, conversion ratio is up to 80%, and selectivity is up to 95%.
Embodiment 6
It disperses 0.5g SAPO-5 zeolite molecular sieve in the deionized water of 50ml, adds 0.02 times of molecular sieve matter
The ferric oxalate of amount, 80 DEG C of stirrings lower exchange 8 hours；It takes out reaction product and washs drying, roasting 6 is small at 550 DEG C in Muffle furnace
When, it obtains zeolite molecular sieve and supports ferrum-based catalyst, in catalyst prod, the mass fraction that iron accounts for zeolite molecular sieve is 2%.
Aforementioned catalytic agent is added in reactor, adds TEMPO as intermediate, and using oxygen as the condition of oxygen source
Under, the mass ratio of catalyst, intermediate and hydrocarbon compound is 0.01: 0.1: 0.5.Metal halogen lamp is used under 3 atmospheric pressure of room temperature,
Photocatalysis methane oxidation may be implemented, conversion ratio is up to 50%, and selectivity is up to 95%.
Embodiment 7
It disperses 0.5g APO-5 zeolite molecular sieve in the deionized water of 50ml, adds 0.04 times of molecular sieve quality
Ironic citrate, the lower exchange of 80 DEG C of stirrings 6 hours；It takes out reaction product and washs drying, roasting 4 is small at 550 DEG C in Muffle furnace
When, it obtains zeolite molecular sieve and supports ferrum-based catalyst, in catalyst prod, the mass fraction that iron accounts for zeolite molecular sieve is 4%.
Aforementioned catalytic agent is added in reactor, adds NAPI as intermediate, and using oxygen as the condition of oxygen source
Under, the mass ratio of catalyst, intermediate and hydrocarbon compound is 1: 0.4: 0.8.Mercury lamp is used at normal temperatures and pressures, and light may be implemented
It is catalyzed p xylene oxidation, conversion ratio is up to 60%, and selectivity is up to 90%.
Embodiment 8
It disperses 0.8g SAPO-34 zeolite molecular sieve in the deionized water of 50ml, adds 0.03 times of molecular sieve matter
The ferric sulfate of amount, 80 DEG C of stirrings lower exchange 6 hours；It takes out reaction product and washs drying, roasting 4 is small at 550 DEG C in Muffle furnace
When, it obtains zeolite molecular sieve and supports ferrum-based catalyst, in catalyst prod, the mass fraction that iron accounts for zeolite molecular sieve is 3%.
Aforementioned catalytic agent is added in reactor, adds Py-NHPI as intermediate, and using oxygen as the item of oxygen source
Under part, the mass ratio of catalyst, intermediate and hydrocarbon compound is 1: 0.5: 0.01.Xenon lamp, Ke Yishi are used under 40 DEG C of normal pressures
Existing photocatalysis is to diphenylmethyl alkoxide, and conversion ratio is up to 60%, and selectivity is up to 100%.
Embodiment 9
It disperses 0.8g SAPO-34 zeolite molecular sieve in the deionized water of 50ml, adds 1 times of molecular sieve quality
Ferric acetate, the lower exchange of 80 DEG C of stirrings 6 hours；It takes out reaction product and washs drying, roasted 4 hours at 550 DEG C in Muffle furnace,
It obtains zeolite molecular sieve and supports ferrum-based catalyst, in catalyst prod, the mass fraction that iron accounts for zeolite molecular sieve is 99%.
Aforementioned catalytic agent is added in reactor, adds NHPI as intermediate, and using oxygen as the condition of oxygen source
Under, the mass ratio of catalyst, intermediate and hydrocarbon compound is 1: 0.05: 1.Xenon lamp, Ke Yishi are used under 2 atmospheric pressure of room temperature
Existing photocatalysis aoxidizes fluorenes, and conversion ratio is up to 80%, and selectivity is up to 100%.
Embodiment 10
It disperses 0.5g APO-11 zeolite molecular sieve in the deionized water of 50ml, adds 0.5 times of molecular sieve quality
Acetylacetone,2,4-pentanedione it is ferrous, the lower exchange of 80 DEG C of stirrings 6 hours；It takes out reaction product and washs drying, roasted at 550 DEG C in Muffle furnace
It 6 hours, obtains zeolite molecular sieve and supports ferrum-based catalyst, in catalyst prod, the mass fraction that iron accounts for zeolite molecular sieve is
50%.
Aforementioned catalytic agent is added in reactor, adds NHPI as intermediate, and using oxygen as the condition of oxygen source
Under, the mass ratio of catalyst, intermediate and hydrocarbon compound is 0.8: 1: 0.01.Xenon lamp is used under 50 DEG C of 3 atmospheric pressure, it can be with
Photocatalysis is realized to cyclohexene oxide, conversion ratio is up to 70%, and selectivity is up to 90%.
Embodiment 11
It disperses 0.5g Y zeolite molecular sieve in the deionized water of 50ml, adds the second of 0.05 times of molecular sieve quality
Acyl acetone iron, 80 DEG C of stirrings lower exchange 6 hours；It takes out reaction product and washs drying, roasted 4 hours at 550 DEG C in Muffle furnace,
It obtains zeolite molecular sieve and supports ferrum-based catalyst, in catalyst prod, the mass fraction that iron accounts for zeolite molecular sieve is 5%.
Aforementioned catalytic agent is added in reactor, adds NHPI as intermediate, and using oxygen as the condition of oxygen source
Under, the mass ratio of catalyst, intermediate and hydrocarbon compound is 0.05: 0.01: 0.8.Xenon lamp is used under 60 DEG C of 4 atmospheric pressure,
Photocatalysis may be implemented to ethane oxidation, conversion ratio is up to 50%, and selectivity is up to 90%.
Finally it should be noted that the above enumerated are only specific embodiments of the present invention.It is clear that the invention is not restricted to
Above embodiments can also have many variations.Those skilled in the art can directly lead from present disclosure
Out or all deformations for associating, it is considered as protection scope of the present invention.
Claims (7)
1. the preparation method that a kind of zeolite molecular sieve supports ferrum-based catalyst, which comprises the following steps:
Zeolite molecular sieve is dispersed in water, source of iron is added, it is small that ion exchange 6~24 is carried out under 80 DEG C and stirring condition
When, the mass ratio of source of iron and zeolite molecular sieve is 0.001~1: 1；Reaction product is taken out, washing, drying are placed in Muffle furnace,
It is roasted 4~10 hours under the conditions of 400~600 DEG C, obtains zeolite molecular sieve and support ferrum-based catalyst.
2. the method according to claim 1, wherein supporting ferrum-based catalyst final products in zeolite molecular sieve
In, the mass fraction that iron accounts for zeolite molecular sieve is 0.1~99%.
3. the method according to claim 1, wherein the zeolite molecular sieve is the sial of regular cellular structure
Arbitrary one kind in molecular sieve or phosphate aluminium molecular sieve.
4. the method according to claim 1, wherein the source of iron is any one following: ferric nitrate, chlorination
Iron, ferrous sulfate, frerrous chloride, ferric perchlorate, ferric oxalate, ironic citrate, ferric sulfate, ferric acetate, acetylacetone,2,4-pentanedione ferrous iron or second
Acyl acetone iron.
5. the zeolite molecular sieve that claim 1 the method prepares supports ferrum-based catalyst in photocatalysis hydrocarbon oxidation
Application method, which is characterized in that be by mass ratio be 0.001~1: 0.001~1: 0.001~1 catalyst, intermediate and contain
There is the hydrocarbon compound of alpha position C-H to be placed in reactor, using oxygen as oxygen source, carries out light under the conditions of UV, visible light wave band and urge
Change hydrocarbon oxidization.
6. according to the method described in claim 5, it is characterized in that, the intermediate be it is following any one:
N-Hydroxyphthalimide or derivatives thereof, N, N '-dihydroxy pyromellitic acid imines, N- hydroxyl neighbour's sulfonyl-benzoyl
Imines, N- acetyl group phthalimide, N, N ', N "-trihydroxy isocyanuric acid, N- hydroxyl -3,4,5,6- tetraphenyl neighbour's benzene
Dicarboximide, 3- picolyl-n-Hydroxyphthalimide or dialkyl nitroxyl.
7. according to the method described in claim 5, it is characterized in that, the hydrocarbon compound containing alpha position C-H is following any
It is a kind of: ethylbenzene, hexamethylene, toluene, naphthane, indane, methane, dimethylbenzene, diphenyl methane, fluorenes, cyclohexene or ethane.
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