CN115353612B - Silver-loaded organic polymer porous material and preparation method and application thereof - Google Patents
Silver-loaded organic polymer porous material and preparation method and application thereof Download PDFInfo
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- CN115353612B CN115353612B CN202211136244.3A CN202211136244A CN115353612B CN 115353612 B CN115353612 B CN 115353612B CN 202211136244 A CN202211136244 A CN 202211136244A CN 115353612 B CN115353612 B CN 115353612B
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- porous material
- silver
- organic polymer
- polymer porous
- loaded
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- 239000011148 porous material Substances 0.000 title claims abstract description 107
- 229920000620 organic polymer Polymers 0.000 title claims abstract description 72
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 55
- 239000004332 silver Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 9
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 127
- 230000003197 catalytic effect Effects 0.000 claims abstract description 62
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 25
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 17
- 238000011068 loading method Methods 0.000 claims abstract description 15
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003446 ligand Substances 0.000 claims abstract description 10
- 230000007062 hydrolysis Effects 0.000 claims abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 8
- 238000005336 cracking Methods 0.000 claims abstract description 7
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 73
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 36
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- 238000003776 cleavage reaction Methods 0.000 claims description 10
- 230000007017 scission Effects 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 68
- 239000000463 material Substances 0.000 abstract description 30
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052751 metal Inorganic materials 0.000 abstract description 16
- 238000006555 catalytic reaction Methods 0.000 abstract description 15
- 238000006477 desulfuration reaction Methods 0.000 abstract description 15
- 230000023556 desulfurization Effects 0.000 abstract description 15
- 239000002184 metal Substances 0.000 abstract description 15
- 229910052763 palladium Inorganic materials 0.000 abstract description 12
- 238000001179 sorption measurement Methods 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 description 29
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 20
- 238000009826 distribution Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 238000002329 infrared spectrum Methods 0.000 description 12
- 239000001569 carbon dioxide Substances 0.000 description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 101710134784 Agnoprotein Proteins 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- JNWPRPLNUUMYCM-UHFFFAOYSA-N 5-bromo-2-(5-bromopyridin-2-yl)pyridine Chemical compound N1=CC(Br)=CC=C1C1=CC=C(Br)C=N1 JNWPRPLNUUMYCM-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 150000004763 sulfides Chemical class 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- SYHPANJAVIEQQL-UHFFFAOYSA-N dicarboxy carbonate Chemical compound OC(=O)OC(=O)OC(O)=O SYHPANJAVIEQQL-UHFFFAOYSA-N 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 125000001741 organic sulfur group Chemical group 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- FZTLLUYFWAOGGB-UHFFFAOYSA-N 1,4-dioxane dioxane Chemical compound C1COCCO1.C1COCCO1 FZTLLUYFWAOGGB-UHFFFAOYSA-N 0.000 description 1
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013310 covalent-organic framework Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- -1 hexaazabinaphthyl Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B01J35/61—
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/0644—Poly(1,3,5)triazines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/17—Silver
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/13—Morphological aspects
- C08G2261/135—Cross-linked structures
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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Abstract
The invention discloses a silver-loaded organic polymer porous material, and a preparation method and application thereof. The silver-loaded organic polymer porous material takes an organic polymer porous material with chelating ligand characteristic groups as a carrier, and silver is loaded on nitrogen-containing loading sites in pore channels of the organic polymer porous material. According to the invention, silver is adopted as a metal active center, meanwhile, the organic polymer porous material with a higher specific surface area and a larger pore diameter structure is selected and synthesized as a carrier, so that the adsorption performance of the material is improved, the advantage of the catalyst in a limited space catalytic reaction is reserved, and compared with the palladium active center material with the same structure, the catalyst has higher catalytic efficiency, the room-temperature normal-pressure hydrolysis desulfurization of carbon disulfide and carbonyl sulfide can be realized more efficiently, and the economic cost is reduced; the silver-loaded organic polymer porous material prepared by the method has great application potential in the field of hydrolyzing and cracking carbon disulfide and carbonyl sulfide at room temperature and normal pressure.
Description
Technical Field
The invention relates to the technical field of preparation of desulfurization catalysts, in particular to a silver-loaded organic polymer porous material, and a preparation method and application thereof.
Background
Carbon disulfide (CS) 2 ) And carbonyl sulfide (COS) occupies 80% of the total organic sulfide in crude oil and natural gas, and has extremely strong toxic action on metal catalysts used in petroleum rectification processes. Meanwhile, sulfur-containing components in blast furnace gas used in the steel industry also include hydrogen sulfide, carbonyl sulfide (COS) and carbon disulfide (CS) 2 ) Mainly, the chemically inert organic sulfur micromolecules are often discharged as industrial tail gas, so that not only are serious pollution and harm to the atmospheric environment and biological health caused, but also hydrogen sulfide generated by slow hydrolysis of the organic sulfur micromolecules can corrode production equipment. Degassing and desulfurizing are also essential steps and techniques in petroleum, natural gas and flue gas desulfurization processes.
The organic polymer porous material is used as a multifunctional solid material with designability and modifier, and is widely applied to the aspects of gas adsorption, separation, heterogeneous catalysis and the like. A large number of existing research results fully show that the dimension, the size, the shape, the size of an internal cavity, the hydrophilicity and the hydrophobicity and the like of a hole of an organic polymer material can be accurately regulated and controlled by selecting or designing a specific assembly module through a chemical synthesis method, and then the organic polymer porous material with a specific catalytic function can be obtained by loading the organic polymer material with metal with a high active center. In our earlier studies, as in patent CN110343240a and patent CN114181379a, both using palladium-containing organic polymer porous materials successfully and efficiently performed on carbon disulphide (CS 2 ) And carbonyl sulfide (COS) are subjected to room temperature and normal pressure activation hydrolysis. However, the use of noble metal palladium significantly increases the cost of the catalyst.
Thus, a low cost and high efficiency room temperature and pressure activated hydrolyzed carbon disulfide (CS) 2 ) And sulfur removal catalysts for organic sulfides such as carbonyl sulfide (COS) are of great significance.
Disclosure of Invention
The invention aims to overcome the technical defects, and provides a silver-loaded organic polymer porous material, a preparation method and application thereof, and solves the technical problem that a desulfurization catalyst in the prior art cannot achieve both low cost and high desulfurization effect.
According to a first aspect of the invention, there is provided a silver-loaded organic polymer porous material, which uses an organic polymer porous material having chelating ligand characteristic groups as a carrier, wherein silver is loaded on nitrogen-containing loading sites in pore channels of the organic polymer porous material.
In a second aspect, the present invention provides a method for preparing a silver-loaded organic polymer porous material, comprising the steps of:
the organic polymer porous material with chelating ligand characteristic groups is used as a carrier, and silver is loaded on nitrogen-containing loading sites in pore channels of the organic polymer porous material.
In a third aspect the present invention provides the use of a silver loaded organic polymer porous material for catalytic hydrolytic cleavage of organic sulfides.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, silver is adopted as a metal active center, meanwhile, the organic polymer porous material with higher specific surface area and larger pore diameter structure is selected and synthesized as the carrier, so that the adsorption performance of the material is improved, the advantage of the catalyst in a limited space catalytic reaction is maintained, and compared with the palladium active center material with the same structure, the catalyst has higher catalytic efficiency, and carbon disulfide (CS) 2 ) And room temperature and normal pressure hydrolytic desulfurization of carbonyl sulfide (COS), and reduces economic cost; the silver-loaded organic polymer porous material prepared by the invention hydrolyzes and cracks carbon disulfide (CS) at room temperature and normal pressure 2 ) And carbonyl sulfide (COS) fields have great application potential.
Drawings
FIG. 1 is an infrared spectrum of the raw material and the prepared BPY-POP in example 1;
FIG. 2 is an infrared spectrum of the starting material and Hatn-PIM prepared in example 2;
FIG. 3 is an infrared spectrum of the starting material and Hatn-CTF prepared in example 3;
FIG. 4 is a solid of BPY-POP prepared in example 1 13 C NMR chart;
FIG. 5 is a solid of Hatn-PIM prepared in example 2 13 C NMR chart;
FIG. 6 is a solid of Hatn-CTF prepared in example 3 13 C NMR chart;
FIG. 7 is N of BPY-POP prepared in example 1 2 Adsorption and desorption curves and pore size distribution curves;
FIG. 8 is N of Hatn-PIM prepared in example 2 2 Adsorption and desorption curves and pore size distribution curves;
FIG. 9 is N of Hatn-CYF prepared in example 3 2 Adsorption and desorption curves and pore size distribution curves;
FIG. 10 is an SEM image of BPY-POP, hatn-PIM and Hatn-CTF prepared in examples 1-3;
FIG. 11 is XPS patterns of Ag-BPY-POP, ag-Hatn-PIM and Ag-Hatn-CTF prepared in examples 4 to 6;
FIG. 12 is a schematic diagram of BPY-POP, silver nitrate (AgNO 3 ) The infrared spectrum corresponding to the catalyst Ag-BPY-POP and the Ag-BPY-POP-S after catalytic desulfurization;
FIG. 13 shows Hatn-PIM, silver nitrate (AgNO) 3 ) The infrared spectrum corresponding to the Ag-Hatn-PIM-S after catalytic desulfurization;
FIG. 14 is a schematic diagram of Hatn-CTF, silver nitrate (AgNO) 3 ) The infrared spectrum corresponding to the catalyst Ag-Hatn-CTF and the catalytic desulfurized Ag-Hatn-CTF-S;
FIG. 15 shows the results of the respective comparison of Ag-BPY-POP, ag-Hatn-PIM and Ag-Hatn-CTF with the control group on carbon disulfide (CS) 2 ) Is a comparison of catalytic efficiency;
FIG. 16 is a graph showing the comparison of Ag-BPY-POP catalytic efficiency and silver nitrate catalytic efficiency;
FIG. 17 is a chart of a gas phase mass spectrometry (GC-MS) test of an Ag-BPY-POP isotope tracking test;
FIG. 18 is a graph of results of cyclic catalytic performance studies for Ag-BPY-POP, ag-Hatn-PIM, and Ag-Hatn-CTF;
FIG. 19 shows the Ag-BPY-POP, ag-Hatn-PIM and Ag-Hatn-CTF and the corresponding structures of Pd-BPY-POP, pd-Hatn-PIM and Pd-Hatn-CTF vs. carbon disulfide (CS) 2 ) Is to be compared with the hydrolytic cleavage catalytic efficiencyA figure;
FIG. 20 is a graph of a 2-fold silver nitrate molecule versus palladium nitrate catalysis.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
According to a first aspect of the invention, there is provided a silver-loaded organic polymer porous material, which uses an organic polymer porous material having chelating ligand characteristic groups as a carrier, wherein silver is loaded on nitrogen-containing loading sites in pore channels of the organic polymer porous material.
In the present invention, the chelating ligand characteristic group includes, but is not limited to, common bipyridine, phenanthroline, hexaazabinaphthyl, etc. For example, the organic polymeric porous material may be a BPY-POP material, a Hatn-PIM material, or a Hatn-CTF material. Wherein, the BPY-POP material is synthesized by reacting 5,5 '-dibromo-2, 2' -bipyridine with 1,3, 5-benzene tricarbonic acid trippinacol ester, hatn-PIM is synthesized by reacting 2,3,8,9,14,15-hexafluoro-5,6,11,12,17,18-hexaazabinaphthyl or 2,3,8,9,14,15-hexachloro-5,6,11,12,17,18-hexaazabinaphthyl with 5,5', 6' -tetrahydroxy-3, 3 '-tetramethyl-1, 1' -spirobiindane, and Hatn-CTF is synthesized by reacting diquinoxalino [2,3-A:2',3' -C ] phenazine-2,8,14-trimethylnitrile by an ion thermal method.
In the invention, silver is loaded on the nitrogen-containing loading sites in the pore channels of the organic polymer porous material in the form of silver nitrate.
In some embodiments of the present invention, the silver-loaded organic polymeric porous material described above has the following structural formula:
Ag-BPY-POP：
Ag-Hatn-PIM：
Ag-Hatn-CTF：
in the invention, the three organic polymer porous materials with the similar 2,2' -bipyridine characteristic groups have rich micropore and mesoporous pore structures, a large amount of pyridine nitrogen exists in the limiting pore canal formed by the covalent organic framework, rich silver active load sites are provided, the catalytic efficiency is improved while the adsorption performance of the catalyst is improved, the raw materials are easy to obtain, and the preparation process is simple. The catalyst can realize carbon disulfide (CS) under mild conditions, namely room temperature and normal pressure 2 ) Compared with the hydrolytic cracking of carbonyl sulfide (COS), the catalyst with the palladium metal active center with the same structure has higher catalytic efficiency and economic application value.
In a second aspect, the present invention provides a method for preparing a silver-loaded organic polymer porous material, comprising the steps of:
the organic polymer porous material with chelating ligand characteristic groups is used as a carrier, and silver is loaded on nitrogen-containing loading sites in pore channels of the organic polymer porous material.
In the invention, the preparation method of the organic polymer porous material comprises the following steps:
(a1) Under the protection of nitrogen, 5 '-dibromo-2, 2' -bipyridine and 1,3, 5-benzene tricarbonyl trippinacol ester are subjected to Suzuki coupling reaction in a first base and a first organic solvent under the catalysis of a tetraphenylphosphine palladium catalyst to obtain an organic polymer porous material BPY-POP; or alternatively, the first and second heat exchangers may be,
(a2) 2,3,8,9,14,15-hexafluoro-5,6,11,12,17,18-hexaazabinaphthyl or 2,3,8,9,14,15-hexachloro-5,6,11,12,17,18-hexaazabinaphthyl and 5,5', 6' -tetrahydroxy-3, 3 '-tetramethyl-1, 1' -spirobiindane react in a second base and a second organic solvent under the protection of nitrogen to obtain an organic polymer porous material Hatn-PIM; or alternatively, the first and second heat exchangers may be,
(a3) The di-quinoxalino [2,3-A:2',3' -C ] phenazine-2,8,14-trimethylnitrile is subjected to high-temperature firing reaction in a tube furnace under the protection of nitrogen under the action of a dry zinc chloride catalyst to obtain the organic polymer porous material Hatn-CTF.
Further, the molar ratio of the 5,5 '-dibromo-2, 2' -bipyridine to the 1,3, 5-trimellitic acid trippinacol ester in the step (a 1) is (1.5-2): 1, preferably 3:2; the molar ratio of the tetraphenylphosphine palladium catalyst to the 1,3, 5-benzene tricarbonate trippinacol ester is (0.2-1): 1, preferably (0.3-0.5): 1.
Further, a first base and a first organic solvent are added in the Suzuki coupling reaction in the step (a 1); the first base is one or more of potassium carbonate, cesium carbonate, sodium hydroxide and sodium carbonate, preferably potassium carbonate; the first alkali is added into the reaction system in the form of an aqueous solution, and the concentration of the aqueous solution is 1-3 mol/L, preferably 2mol/L; the molar amount of the first base is 20-40 times, preferably 25-30 times, that of the 1,3, 5-benzene tricarbonyl tripicolinate; the first organic solvent is one or more of N, N' -dimethyl-formamide, dioxane, tetrahydrofuran and toluene, preferably dioxane; the dosage ratio of the first organic solvent to the 1,3, 5-benzene tricarbonyl tripicolinate is 1ml (10-20 mg), preferably 1ml (11-12 mg).
Further, the temperature of the Suzuki coupling reaction in the step (a 1) is 80-120 ℃, preferably 100 ℃, and the reaction time is 1-3 days, preferably 2 days.
Further, the reaction product in step (a 1) is dried in vacuum at 60 to 150℃after washing, preferably at a drying temperature of 100 to 120 ℃. In this process, the washing solvent may be water, N' -dimethyl-formamide, dichloromethane, ethanol, tetrahydrofuran, acetone, etc.
Further, the molar ratio of 2,3,8,9,14,15-hexafluoro-5,6,11,12,17,18-hexaazabinaphthyl or 2,3,8,9,14,15-hexachloro-5,6,11,12,17,18-hexaazabinaphthyl to 5,5', 6' -tetrahydroxy-3, 3 '-tetramethyl-1, 1' -spirobiindane in step (a 2) is 1 (1.5-2), preferably 2:3; the molar ratio of the second base to the 5,5', 6' -tetrahydroxy-3, 3 '-tetramethyl-1, 1' -spirobiindane is (10-30): 1, preferably (25-30): 1.
Further, the second base in step (a 2) is one or more of anhydrous potassium carbonate, cesium carbonate, sodium hydroxide, sodium carbonate, preferably anhydrous potassium carbonate and anhydrous cesium carbonate; the second organic solvent is one or more of N, N ' -dimethyl-formamide, N ' -dimethyl-acetamide, N ' -dimethyl-propionamide, N ' -diethyl-acetamide and N, N-dimethylacetamide, preferably N, N ' -dimethyl-formamide; the dosage ratio of the second organic solvent to the 5,5', 6' -tetrahydroxy-3, 3 '-tetramethyl-1, 1' -spirobiindane is 1ml (10-20 mg), preferably 1ml (10-12 mg).
Further, the reaction temperature in the step (a 2) is 80 to 200 ℃, preferably 150 to 170 ℃, and the reaction time is 2 to 7 days, preferably 3 to 5 days.
Further, the reaction product in step (a 2) is dried in vacuum at 60 to 150℃after washing, preferably at a drying temperature of 100 to 120 ℃. In the process, the washing solvent is water, ethanol, tetrahydrofuran, acetone and the like.
Further, the molar ratio of zinc chloride to the di-quinoxalino [2,3-A:2',3' -C ] phenazine-2,8,14-trimethylnitrile in step (a 3) is (4 to 15): 1, preferably (6 to 10): 1.
Further, the reaction temperature in the step (a 3) is 400-600 ℃, preferably 400 ℃, and the reaction time is 2-5 days, preferably 2-3 days.
Further, the reaction product in the step (a 3) is washed with 1-2 mol/L of dilute hydrochloric acid for 12-24 hours after being crushed, filtered and washed with a large amount of deionized water, and then washed with ethanol and acetone, and then vacuum-dried at 60-150 ℃, preferably at 100-120 ℃.
Further, in the step (a 3), the tube furnace is composed of a hearth, a furnace lining and a furnace tube, the furnace tube is placed in the hearth for heating, the furnace tube is matched with a ceramic boat for use, the ceramic boat is placed in the central position in the furnace tube for use, the furnace tube is matched with nitrogen for use, and the use process is carried out by heating under the protection of the nitrogen.
In the present invention, the step of loading silver on the nitrogen-containing loading sites in the pore channels of the organic polymer porous material comprises:
adding the organic polymer porous material into a silver nitrate-containing solution, stirring and reacting for 2-12 h under the conditions of darkness and nitrogen protection, and obtaining the silver-loaded organic polymer porous material.
Further, the silver nitrate is used in an amount of 0.1 to 2 times the mass of the organic polymer porous material, preferably in an amount of 0.5 to 1.5 times; in the silver nitrate-containing solution, the adopted solvent is one or more of water, acetonitrile, ethanol and acetone, preferably acetonitrile; the dosage ratio of the solvent to the silver nitrate is 1ml: (10-50) mg, preferably 1ml: (10-30) mg; the room temperature is 5-40 ℃, preferably 20-30 ℃; the catalyst is required to be washed after the reaction is finished and then is dried in vacuum at 60-150 ℃. In the process, the washing solvent is acetonitrile or acetone.
In a third aspect the present invention provides the use of a silver loaded organic polymer porous material for catalytic hydrolytic cleavage of organic sulfides.
In the invention, the reaction system for catalytically hydrolyzing and cracking the organic sulfide comprises: silver-loaded organic polymer porous material, water and organic sulfide.
In the present invention, the above organic sulfides include, but are not limited to, hydrogen sulfide (H) 2 S), carbon disulfide (CS) 2 ) Carbonyl sulfide (COS).
In the present invention, the above-mentioned catalytic hydrolysis process for cracking organic sulfide is carried out at room temperature and normal pressure.
In the invention, the reaction system for catalytically hydrolyzing and cracking the organic sulfide further comprises: a sacrificial agent. The silver-loaded organic polymer porous material can be recycled under the action of a sacrificial agent. Further, the sacrificial agent is one or more of nitric acid, acetic acid and hydrogen peroxide.
The three supported organic polymer porous material catalysts of silver nitrate produced by the method of the present invention are designated in the specification as: ag-BPY-POP, ag-Hatn-PIM, and Ag-Hatn-CTF.
Example 1
5,5 '-dibromo-2, 2' -bipyridine (471 mg,1.50 mmol), 1,3, 5-trimellitic acid trippinacol ester (450 mg,1.00 mmol), and catalyst tetrakis triphenylphosphine palladium (500 mg,0.44 mmol) were placed in a 100mL sealed tube, 40mL Dioxane (Dioxane) and 15mL 2M K were added 2 CO 3 The aqueous solution is used as a solvent, vacuum pumping and nitrogen protection are carried out, the temperature of the mixed solution is slowly raised to 100 ℃, and the reaction is continuously stirred for 24 hours. Stopping the reaction, cooling to room temperature, centrifugally separating the reaction liquid, and removing supernatant to obtain yellow precipitate; then repeatedly cleaning the yellow precipitate for 3-4 times by using N, N' -dimethyl-formamide, water and ethanol; finally, the yellow product BPY-POP is obtained after drying in vacuum at 100 ℃ for 24 hours.
Example 2
2,3,8,9,14,15-hexachloro-5,6,11,12,17,18-hexaazabinaphthyl (591 mg,1 mmol) and 5,5', 6' -tetrahydroxy-3, 3' -tetramethyl-1, 1' -spirobiindane (510 mg,1.5 mmol) are placed in a 100mL sealed tube, 50mL of N, N ' -dimethyl-formamide and 6.2g (45 mmols) of anhydrous potassium carbonate are added, vacuum is applied and nitrogen protection is applied, and the mixture is slowly warmed to 150℃and stirred for 3 days. Stopping the reaction, cooling to room temperature, filtering and repeatedly washing with water, ethanol, tetrahydrofuran and acetone, and vacuum drying at 100 ℃ for 24 hours to obtain a dark red product Hatn-PIM.
Example 3
Diquinoxalino [2,3-A:2',3' -C ] phenazine-2,8,14-trimethylnitrile (459 mg,1 mmol) and 1.36g (10 mmol) of dried zinc chloride were mixed uniformly and then added into a clean ceramic boat, and the ceramic boat was placed in the central portion of a tube furnace tube and subjected to a high-temperature firing reaction at 400 ℃ under nitrogen protection for 2 days. Stopping the reaction, cooling to room temperature, grinding, stirring and washing with 1 mol/L50 mL of dilute hydrochloric acid for 12 hours, washing with a large amount of deionized water, washing with ethanol and acetone, and vacuum drying at 100 ℃ for 24 hours to obtain a black product Hatn-CTF.
Example 4
100mg of prepared BPY-POP was added to 5mL of acetonitrile solution containing 83mg of silver nitrate, and the mixture was reacted under stirring at room temperature under the dark condition and nitrogen protection for 12 hours, and the obtained powder was collected by centrifugation to remove the supernatant, and washed with acetonitrile and acetone 1 time each, and vacuum-dried at 60℃for 24 hours to obtain Ag-BPY-POP.
Example 5
100mg of Hatn-PIM prepared was added to 5mL of acetonitrile solution containing 56mg of silver nitrate, and the mixture was reacted under stirring at room temperature under the dark condition and nitrogen protection for 12 hours, and the obtained powder was collected by centrifugation to remove the supernatant, and washed with acetonitrile and acetone 1 time each, and vacuum-dried at 60℃for 24 hours to obtain Ag-Hatn-PIM.
Example 6
100mg of Hatn-CTF thus prepared was added to 5mL of acetonitrile solution containing 111mg of silver nitrate, and reacted under stirring at room temperature under the dark condition and nitrogen protection for 12 hours, the obtained powder was collected by centrifugation to remove the supernatant, and washed with acetonitrile and acetone 1 time each, and vacuum-dried at 60℃for 24 hours to obtain Ag-Hatn-CTF.
FIG. 1 is an infrared spectrum of the raw material and the prepared BPY-POP in example 1. Wherein BPY is 5,5 '-dibromo-2, 2' bipyridine; a is 1,3, 5-benzene three boric acid three pinacol ester. At 1452cm -1 There is a C=N characteristic peak of the telescopic vibration signal at 1596cm -1 The result proves the synthesis of the catalyst, wherein the characteristic peak of C=C stretching vibration signal on the benzene ring exists, and the characteristic peak of C-H stretching vibration on methyl in the raw material 1,3, 5-benzene tricarbonyl trippinacol ester is obviously disappeared.
FIG. 2 is an infrared spectrum of the starting material and Hatn-PIM prepared in example 2. Wherein Hatn-6Cl is 2,3,8,9,14,15-hexachloro-5,6,11,12,17,18-hexaazabinaphthyl; b is 5,5', 6' -tetrahydroxy-3, 3 '-tetramethyl-1, 1' -spirobiindane. At 3230cm -1 The characteristic peak of the extensional vibration signal at which-OH is present disappears at 2945cm -1 2860cm -1 There is a characteristic peak of methyl stretching vibration signal on the structure of the raw material B, and the peak is 1231cm -1 The new C-O-C stretching vibration signal characteristic peak appears, and the result proves the synthesis of the catalyst.
FIG. 3 is an infrared spectrum of the starting material and Hatn-CTF prepared in example 3. Wherein Hatn-3CN is a di-quinoxalino [2,3-A:2',3' -C]Phenazine-2,8,14-trimethylnitrile. At 2237cm -1 The characteristic peak of the C.ident.N stretching vibration signal existing at the position disappears, and the peak is 1655cm -1 The C=N stretching vibration signal characteristic peak exists at the position of 1460-1620 cm -1 The result shows that a new C-N stretching vibration signal characteristic peak appears on the triazine ring, and the synthesis of the catalyst is proved.
FIG. 4 is a solid of BPY-POP prepared in example 1 13 C NMR chart. From the figure, it can be observed that the interval of 120-160 ppm shows strong resonance signals, but no C-C characteristic signal in 84ppm quaternary carbon structure is found, and the disappearance of the methyl special signal of the raw material 1,3, 5-benzene tricarbonyl tripicolinate can be used for describing the synthesis of the catalyst in combination with infrared analysis.
FIG. 5 is a solid of Hatn-PIM prepared in example 2 13 C NMR chart. From the figure, it can be observed that the interval of 20-160 ppm shows strong resonance signals and is highly coincident with the resonance signals of the specific groups on the target structure, and the synthesis of the catalyst can be illustrated by the generation of new ether bonds (C-O-C) of the product in combination with infrared analysis.
FIG. 6 is a solid of Hatn-CTF prepared in example 3 13 C NMR chart. As can be seen from the graph, the region between 120 and 180ppm shows a strong resonance signal, no resonance signal of C.ident.N on the raw material is found at 118ppm, the resonance signal is consistent with infrared, the characteristic resonance signal of triazine group carbon appears at about 170ppm, 80ppm to 120ppm is spin sideband generated under test conditions, and the raw material is bisquinoxalino [2,3-A:2',3' -C]The disappearance of the cyano special signal on phenazine-2,8,14-trimethylnitrile indicates the synthesis of the catalyst.
FIG. 7 is N of BPY-POP prepared in example 1 2 Adsorption and desorption curves and pore size distribution curves. As shown in the figure, the BET specific surface area of BPY-POP is 31.5m 2 /g; the pore size distribution curve calculated by BJH reflects that the pore size distribution of the material is mainly concentrated at 1.5-30 nm, which indicates that the material has abundant micropore and mesopore structure and also indicates the successful synthesis of the organic polymer porous material.
FIG. 8 is N of Hatn-PIM prepared in example 2 2 Adsorption and desorption curves and pore size distribution curves. As shown, the BET specific surface area of Hatn-PIM is as high as 614.5m 2 /g; the pore size distribution curve calculated by BJH reflects that the pore size distribution of the material is mainly concentrated at 3-11 nm, which indicates that the material has rich mesoporous structure and also indicates the successful synthesis of the organic polymer porous material.
FIG. 9 is N of Hatn-CTF prepared in example 3 2 Adsorption and desorption curves and pore size distribution curves. As shown in the figure, the BET specific surface area of Hatn-CTF is as high as 609.3m 2 /g; the pore size distribution curve calculated by BJH reflects that the pore size distribution of the material is mainly concentrated at 3-12 nm, which indicates that the material has rich mesoporous structure and also indicates the successful synthesis of the organic polymer porous material.
FIG. 10 is an SEM image of BPY-POP, hatn-PIM and Hatn-CTF prepared in examples 1-3. As shown, BPY-POP presents a membranous powder structure, and both Hatn-PIM and Hatn-CTF present a bulk powder structure.
FIG. 11 is XPS spectra of Ag-BPY-POP, ag-Hatn-PIM and Ag-Hatn-CTF prepared in examples 4 to 6. From the figure, it can be seen that silver element has been successfully supported on three organic polymer porous materials. As can be seen from the infrared rays of fig. 12 to 14, the infrared vibration signal unique to nitrate was detected in each of the three catalysts prepared, and it was confirmed that silver was supported as silver nitrate.
Example 7
Into a 2.5mL sample bottle, 100. Mu.L of distilled water was added, and carbon disulfide (CS 2 ) 50 μl of catalyst Ag-BPY-POP, ag-Hatn-PIM or Ag-Hatn-CTF 10mg was added, and the mixture was sealed with a sample cap capable of being used for Gas Chromatography (GC) sampling, and stirred at room temperature to perform catalytic reaction. Four bottles were prepared simultaneously for the above samples, so that the reactions were carried out for 0 hour, 2 hours, 6 hours and 10.5 hours, respectively,the change in carbon dioxide content was tested by Gas Chromatography (GC) analysis using a gas chromatograph needle with a gas valve to take 500 μl of gas from the vial. The final results are shown in FIG. 15, which demonstrates that the silver-loaded organic polymeric porous materials prepared according to the present invention all have a high molecular weight distribution over carbon disulphide (CS 2 ) Is a hydrolytic cleavage of (a) a substrate.
FIG. 12 is a schematic diagram of BPY-POP, silver nitrate (AgNO 3 ) The infrared spectrum corresponding to the Ag-BPY-POP-S after catalytic desulfurization of the catalyst Ag-BPY-POP. As can be seen, nitrate leaves after catalysis.
FIG. 13 shows Hatn-PIM, silver nitrate (AgNO) 3 ) The infrared spectrum corresponding to the Ag-Hatn-PIM-S after catalytic desulfurization of the catalyst Ag-Hatn-PIM. As can be seen, nitrate leaves after catalysis.
FIG. 14 is a schematic diagram of Hatn-CTF, silver nitrate (AgNO) 3 ) The infrared spectrum corresponding to the Ag-Hatn-CTF-S after catalytic desulfurization of the catalyst Ag-Hatn-CTF. As can be seen, nitrate leaves after catalysis.
Table 1 shows the catalytic hydrolysis of carbon disulphide (CS 2 ) Variation of S content in front and rear XPS tested materials. The catalyst was further determined for carbon disulphide (CS 2 ) Is successfully hydrolyzed and cracked.
TABLE 1 comparison of S element content variation in materials before and after catalysis
Example 8
To exclude carbon disulphide (CS) 2 ) With the hydrolysis of water itself, a set of tests were carried out under the same conditions as in example 7, the only difference being that the process was carried out without catalyst, recorded as a blank catalytic control; to exclude the catalytic properties of the polymer itself, a set of tests were carried out under the same conditions as in example 7, the only difference being that the procedure was carried out with the addition of organic polymer porous with no silver nitrate loadingAnd (3) carrying out a catalytic comparison test by replacing the corresponding catalyst with the material. The end result is shown in FIG. 15, carbon disulfide (CS 2 ) The three organic polymer porous materials prepared by the method have no catalytic effect.
FIG. 15 shows three catalysts prepared at room temperature and pressure for carbon disulfide (CS 2 ) And the results of the hydrolysis cracking test of (c) and the results of the test of the blank catalytic control group and the test of the organic polymer porous material catalytic control group. From the test results, it was found that the generated catalytic effect was derived from the catalytic action of the catalyst. As described in comparative example 1, the metal active center content of the three materials in the experiment is the same, and the comparison of the catalytic efficiency in the combined experimental results can also reflect that the catalytic efficiency of the materials is not only related to the active metal center load, but also related to the material carrier structure, such as the pore size, specific surface area, spatial ordering and the like, can directly or indirectly influence the catalytic efficiency.
Example 9
In order to compare the difference in catalytic efficiency between the catalytic effect of the catalyst and the catalytic efficiency of the active center metal salt thereof, a set of tests were performed under the same conditions as in example 7, except that the catalyst was replaced with the active center silver nitrate salt in the same molar amount in the process, and the final result is shown in fig. 16, wherein the comparison result of Ag-BPY-POP is taken as an example, and the other two catalysts have the same result, so that the catalytic efficiency of the prepared catalyst is far higher than that of the corresponding active metal salt.
Fig. 16 is a graph showing the comparison of the catalytic efficiency of Ag-BPY-POP with silver nitrate containing the same molar amount of the catalytic active center under the same conditions, and a group of blank controls, it can be seen from the graph that the silver nitrate itself has a catalytic effect by comparison with the blank controls, but the catalytic efficiency is greatly different from that of the prepared catalyst.
Example 10
To study whether the catalytic desulfurization process is hydrolytic cleavage desulfurization, an isotope tracking test was performed using Ag-BPY-POP as an example, namely, using 18 O-labelled H 2 18 O the catalytic test in example 7 was carried out, toAfter a sufficient period of time (over 12 hours) for the catalytic reaction to proceed to ensure that the catalytic product is detected, the gas in the vial is taken and subjected to a gas phase mass spectrometry (GC-MS) test, the test results of which are shown in fig. 17.
FIG. 17 is a chart showing the gas phase mass spectrum (GC-MS) test of the Ag-BPY-POP isotope tracking test. From the results of the gas phase mass spectrometry (GC-MS) test, the presence of the catalyst can be observed 18 O-labelled carbon dioxide (C) 18 O 2 ) And carbonyl sulfide (C) 18 OS) production, it is known from a great deal of research that carbonyl sulfide (COS) is liable to react with water under the action of a catalyst to form carbon dioxide (CO) 2 ). No hydrogen sulfide (H) was found in the gas mass spectrum 2 S), combined with XPS, it is known that the S element is captured by the catalyst. Thus, it can be judged that carbonyl sulfide (C) 18 OS) as an intermediate, carbon dioxide (C) 18 O 2 ) Such catalysts are also capable of catalyzing the hydrolytic cleavage of carbonyl sulfide (COS) as the final catalytic product.
Example 11
The reusability of the catalyst is one of important performances of the catalyst, and a catalyst activation catalysis test is designed for researching whether the prepared catalyst can be recycled, namely, the catalyst activation catalysis test is carried out by adopting materials Ag-BPY-POP-S, ag-Hatn-PIM-S and Ag-Hatn-CTF-S after complete catalytic deactivation. After the catalytic test has been carried out for a certain period of time, it is confirmed that the catalyst has been deactivated and then a sacrificial agent is added to give the catalyst catalytic performance again, and the test results are shown in fig. 18, taking nitric acid as an example. The catalytic system was subjected to a control test prior to the run, i.e. nitric acid with water and carbon disulphide (CS 2 ) Will not catalyze the generation of carbon dioxide (CO) 2 ) The method comprises the steps of carrying out a first treatment on the surface of the When there is no carbon disulphide (CS) 2 ) When the catalyst does not generate carbon dioxide (CO) with nitric acid and water 2 )。
FIG. 18 is a graph showing the results of the test of the activation of the catalyst by adding the sacrificial agent after deactivation of the three catalysts prepared, and the solid points in the graph represent the results of the test after adding the sacrificial agent. From the test results, it was confirmed that the prepared catalyst was able to recover the catalytic effect under the action of the sacrificial agent.
Comparative example 1
In order to compare the catalytic effects of the prepared catalyst and the palladium center catalyst with the same structure, the mass percentages of active metal centers contained in the palladium nitrate and silver nitrate supported catalyst are respectively analyzed and compared semi-quantitatively by XPS, and the prepared catalyst is found that the mass percentage content of palladium and silver is 18-21%, and the molecular weight of silver and palladium is 106.4 and 107.8 respectively, so that the error of metal atomic number caused by the metal mass difference can be ignored in the sampling of 10mg of trace materials. The amount of catalyst taken was 10mg, and it was considered that the number of metal active sites contained in each material taken in the experiment was approximately the same. Comparative experiments were performed using the same protocol as in example 7, except that the test time was taken to be 10.5 hours. The final results are shown in FIG. 19, in which Pd-BPY-POP, pd-Hatn-PIM and Pd-Hatn-CTF, which are materials carried out with the same preparation method, correspond to Ag-BPY-POP, ag-Hatn-PIM and Ag-Hatn-CTF, respectively, which are materials carried with the same structure.
Fig. 19 shows the three organic polymer porous materials prepared, after palladium nitrate and silver nitrate are respectively loaded, for carbon disulfide (CS 2 ) Is a comparison of the catalytic efficiency of the hydrolytic cleavage. As can be seen from the test comparison results, the silver nitrate supported catalyst material has more excellent catalytic effect.
Comparative example 2
To more recently demonstrate the advantages of the catalysts, we have conducted a comparison of catalytic efficiencies for the catalysis of metal active sites. The test protocol described in example 7 was used, with the only difference that the catalyst was replaced with 2mg palladium nitrate in comparison with 3mg silver nitrate. It is noted that the amount of silver nitrate (0.0177 mmol) used is 2 times that of palladium nitrate (0.0087 mmol), because the catalytic rate of the silver nitrate molecule alone is slow, and the catalytic performance of the silver nitrate molecule is shown in a short time for comparison, so that the amount of silver nitrate is doubled. The final results are shown in FIG. 20.
FIG. 20 is a graph of a 2-fold silver nitrate molecule versus palladium nitrate catalysis. From the results, the catalytic efficiency of the silver nitrate molecules alone is far lower than that of palladium nitrate molecules. The method is quite opposite to the result obtained in the polymer, and the advantages and application value of the silver-loaded organic polymer porous material in desulfurization catalysis are more highlighted.
In summary, the silver-loaded organic polymer porous material adopts the covalent organic polymer porous material as a carrier, and utilizes the covalent organic polymer porous material to introduce the silver serving as a metal active center into the framework of the material easily through the action of non-covalent bonds such as coordination bonds, hosts and the like, so that stable coordination synergistic catalytic sites are formed in pore channels of the material, and the stability, adsorption performance and confined space catalytic performance of the catalyst are improved. The silver-loaded organic polymer porous material can realize heterogeneous room-temperature normal-pressure activation hydrolytic pyrolysis of carbon disulfide (CS) under the action of silver in a metal active center 2 ) This is unprecedented and enables the recycling of the catalyst, which is also significantly more efficient than the supported palladium organic porous polymer catalysts previously developed by the applicant. Compared with the palladium-loaded organic porous polymer catalyst with the same structure, the silver-loaded organic porous polymer material prepared by the invention has lower production cost and higher catalytic efficiency, and can provide a new thought and possible way for green high-efficiency hydrolytic desulfurization of petroleum, natural gas and flue gas. The material synthesis method is simple and mature, the reaction condition is mild, the yield is high, and the material has high application value.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made in accordance with the technical idea of the present invention shall be included in the scope of the claims of the present invention.
Claims (7)
1. The silver-loaded organic polymer porous material is characterized in that the silver-loaded organic polymer porous material takes an organic polymer porous material with chelating ligand characteristic groups as a carrier, silver is loaded on nitrogen-containing loading sites in pore channels of the organic polymer porous material, and the chelating ligand characteristic groups are one or more of bipyridine, phenanthroline and hexaazatrinaphthalene; silver is loaded on nitrogen-containing loading sites in pore channels of the organic polymer porous material in the form of silver nitrate, and the silver-loaded organic polymer porous material has the following structural formula:
Ag-BPY-POP：；
Ag-Hatn-PIM：；
Ag-Hatn-CTF：。
2. a method for preparing a silver-loaded organic polymeric porous material as claimed in claim 1, comprising the steps of:
the method for preparing the organic polymer porous material with the chelating ligand characteristic group comprises the steps of taking the organic polymer porous material with the chelating ligand characteristic group as a carrier, loading silver on nitrogen-containing loading sites in pore channels of the organic polymer porous material, and loading silver on the nitrogen-containing loading sites in the pore channels of the organic polymer porous material, wherein the steps of:
adding the organic polymer porous material into a silver nitrate-containing solution, stirring and reacting for 2-12 h under the conditions of darkness and nitrogen protection, and obtaining the silver-loaded organic polymer porous material.
3. The method for preparing a silver-loaded organic polymer porous material according to claim 2, wherein the amount of silver nitrate is 0.1 to 10 times the mass of the organic polymer porous material; in the silver nitrate-containing solution, the adopted solvent is one or more of water, acetonitrile, ethanol and acetone; the dosage ratio of the solvent to the silver nitrate is 1ml: (10-50) mg.
4. Use of a silver-loaded organic polymeric porous material as claimed in claim 1, wherein the silver-loaded organic polymeric porous material is used for catalytic hydrolytic cleavage of organosulfides.
5. The use of a silver loaded organic polymeric porous material according to claim 4, wherein the organic sulphide comprises one or more of hydrogen sulphide, carbon disulphide, carbonyl sulphide.
6. The use of a silver loaded organic polymeric porous material according to claim 5, wherein the reaction system for catalytic hydrolytic cleavage of organosulfides comprises: silver-loaded organic polymer porous material, water and organic sulfide; the catalytic hydrolysis and cracking process of the organic sulfide is carried out at room temperature and normal pressure.
7. The use of a silver loaded organic polymeric porous material according to claim 6, wherein the reaction system for catalytic hydrolytic cleavage of organosulfides further comprises: a sacrificial agent; the sacrificial agent is one or more of nitric acid, acetic acid and hydrogen peroxide.
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