CN109647461A - The composite material of Keggin-type heteropoly acid or heteropolyacid salt and carbon molecular sieve, preparation method and application - Google Patents
The composite material of Keggin-type heteropoly acid or heteropolyacid salt and carbon molecular sieve, preparation method and application Download PDFInfo
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- CN109647461A CN109647461A CN201811518711.2A CN201811518711A CN109647461A CN 109647461 A CN109647461 A CN 109647461A CN 201811518711 A CN201811518711 A CN 201811518711A CN 109647461 A CN109647461 A CN 109647461A
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- molecular sieve
- carbon molecular
- keggin
- composite material
- heteropoly acid
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- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 141
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 134
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 120
- 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 120
- 239000002131 composite material Substances 0.000 title claims abstract description 79
- 150000003839 salts Chemical class 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 125000004429 atom Chemical group 0.000 claims abstract description 24
- 239000011148 porous material Substances 0.000 claims abstract description 23
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 22
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 16
- 239000013256 coordination polymer Substances 0.000 claims abstract description 16
- 229920001795 coordination polymer Polymers 0.000 claims abstract description 16
- 239000010457 zeolite Substances 0.000 claims abstract description 16
- -1 zeolite imidazoles esters Chemical class 0.000 claims abstract description 16
- 239000011261 inert gas Substances 0.000 claims abstract description 11
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 4
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 16
- 229910020881 PMo12O40 Inorganic materials 0.000 claims description 15
- 229910020628 SiW12O40 Inorganic materials 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 11
- 238000009938 salting Methods 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000007171 acid catalysis Methods 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000007146 photocatalysis Methods 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000003575 carbonaceous material Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 9
- 239000011630 iodine Substances 0.000 description 9
- 229910052740 iodine Inorganic materials 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 238000000926 separation method Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000010828 elution Methods 0.000 description 6
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052665 sodalite Inorganic materials 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 229910020347 Na2WO3 Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000003225 biodiesel Substances 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910005833 GeO4 Inorganic materials 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010903 husk Substances 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 238000003408 phase transfer catalysis Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- MYAQZIAVOLKEGW-UHFFFAOYSA-N DMDBT Natural products S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 1
- 229910020451 K2SiO3 Inorganic materials 0.000 description 1
- 239000007836 KH2PO4 Substances 0.000 description 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910020489 SiO3 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 101150017073 cmk1 gene Proteins 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-O octylazanium Chemical compound CCCCCCCC[NH3+] IOQPZZOEVPZRBK-UHFFFAOYSA-O 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical group [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen 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
- B01J29/00—Catalysts comprising molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/33—Electric or magnetic properties
-
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
The present invention provides composite material, preparation method and the applications of a kind of Keggin-type heteropoly acid or heteropolyacid salt and carbon molecular sieve.In the composite material, Keggin-type heteropoly acid or heteropolyacid salt molecule growth in situ are inside the duct of carbon molecular sieve.Wherein, the general structure of the Keggin-type heteropoly acid or heteropolyacid salt is H (Na, K)n[XM12O40], X indicates that center hetero atom and X=P, Si, Ge, As, M indicate to match atom and M=Mo, W, and n is 3 or 4；The carbon molecular sieve is obtained by calcined zeolite imidazoles esters coordination polymer ZIF-8 under inert gas protection.The present invention makes Keggin-type heteropoly acid or heteropolyacid salt molecule growth in situ inside the duct of carbon molecular sieve using the carbon molecular sieve that directly calcined zeolite imidazoles esters coordination polymer ZIF-8 is obtained under inert gas protection as carrier, and also limits the loss of Keggin-type heteropoly acid or heteropolyacid salt molecule during the reaction using the pore size of carbon molecular sieve.
Description
Technical field
The present invention relates to catalysis technical field more particularly to a kind of Keggin-type heteropoly acids or heteropolyacid salt and carbon molecular sieve
Composite material, preparation method and application.
Background technique
Heteropoly acid (HPA) by center hetero atom and be made up of by certain structure oxygen atom ligand bridging with atom one
The oxygen-containing polyacid of class, possess Keggin-type, Dawson type, Anderson type, Waugh type, Silverton type and
Six kinds of basic structures of Lindqvist type.In addition to six kinds of basic heteropoly acid structures, due to being used to prepare the Element Species of heteropoly acid
Class is various, therefore there is also numerous other types of heteropoly acid structures.In numerous heteropoly acid structures, Keggin-type heteropoly acid
Attracted more concerns, this is not only in that extensive use of the Keggin-type heteropoly acid in terms of Industrial Catalysis, also reside in its
Some key areas have potential application value.Keggin-type heteropoly acid is in the form of homogeneous catalyst mostly for industrializing
Process, such as the hydration of propylene, n-butene, isobutene, the polymerization of THF, methacrolein are oxidized to methacrylic acid, bisphenol-A, double
The synthesis etc. of phenol S.Keggin-type heteropoly acid homogeneous catalysis efficiency is higher, but need to carry out catalyst after reaction separation and
Recycling, this will increase equipment energy consumption and cost, therefore limit its wider course of industrialization.
Using its expansible industrial applications after the immobilized Keggin-type heteropoly acid composition heterogeneous reaction catalyst of carrier, still
Keggin-type heteropoly acid is easily soluble in water, and since structural stability height causes its active force between carrier small, is reacting
It is easy to be lost in the process.For carbon material is as carrier, the porous carbon bigger than Keggin-type heteropoly acid molecular dimension is utilized
Material is easy to be lost during the reaction as carrier, Keggin-type heteropoly acid molecule, and with than Keggin-type heteropoly acid molecule
As carrier, Keggin-type heteropoly acid molecule is difficult immobilized on carbon material the small porous carbon materials of size, restricts in view of current
The widely applied key of Keggin-type heteropoly acid solid catalyst is that suitable carrier avoids active component Keggin-type miscellaneous more
Acid is lost during the reaction.
Currently, can the carrier of immobilized Keggin-type heteropoly acid mainly include silica, metal oxide (such as TiO2、
NbOx、ZrO2) and carbon material.Active component is immobilized to being mainly the following mode on carrier: (1) active component and carrier
Chemical action occurs to be fixed on carrier；It (2) will be in the structure of active component insertion carrier；(3) cage structure of carrier is utilized
It will be in the cage of active component implantation carrier.
Wherein, size 1.0nm~1.3nm Keggin-type heteropoly acid stable structure and be easily soluble in water, can be with gold
Belong to oxide carrier and chemical action occurs, wherein in all poly-metal deoxides, Keggin-type heteropoly acid and NbOxIt acts on most strong.
Since Keggin-type heteropoly acid has highly acid, the carrier S iO stable as acid2It is studied most, but amorphous knot
The SiO of structure2It is weaker with the chemical action of Keggin-type heteropoly acid, while SiO2Cellular structure in macropore range, be much larger than
The molecular dimension of Keggin-type heteropoly acid causes Keggin-type heteropoly acid molecule to be very easy to fall off.
Carbon material is also a kind of carrier being widely noticed, this is not only in that carbon material to the stabilization of acid, alkali, solvent and heat
Property (especially can be resistant to the highly acid of heteropoly acid), also reside in carbon material with high-specific surface area.Traditional activated carbon is to pass through
Biological material (such as sawdust, rice husk, coconut husk and petroleum coke) activates micro-pore carbon material obtained, and feature is that raw material is easy
, processing it is convenient, the disadvantage is that specific surface area is small, pore-size distribution is wide, and due to the stability of carbon material height, substantially not with
Chemical action occurs for Keggin-type heteropoly acid, this limits application of the traditional active carbon as carrier to a certain extent.
Carbon molecular sieve (Carbon Molecular Sieves, CMS) is the uniform carbon material in a kind of aperture, and a kind of
Excellent carrier, pore size size depend on the activator used, such as military field 3KT-172 carbon molecular sieve and rock paddy GN-
UC-H carbon molecular sieve is to be prepared by chlorine as activator, but its pore size is smaller, about 0.28nm~0.36nm.
It is meso-porous carbon molecular sieve there are also one kind, is obtained by mesoporous material MCM-48, SBA-1, SBA-15 as template duplicating
CMK-1, CMK-2, CMK-3, the pore size of this kind of meso-porous carbon molecular sieve is in 3nm or more.However, being carbon molecular sieve or Jie
Hole carbon molecular sieve, pore size or the molecular dimension less than Keggin-type heteropoly acid lead to Keggin-type heteropoly acid molecule
It is difficult immobilized on carbon material, or greater than the molecular dimension of Keggin-type heteropoly acid, Keggin-type heteropoly acid molecule is caused to exist
It is easy to be lost in reaction process, therefore effectively Keggin-type heteropoly acid molecule cannot be implanted into its duct and do not flowed
It loses.
Summary of the invention
In view of the problems in the background art, the purpose of the present invention is to provide a kind of Keggin-type heteropoly acids or miscellaneous more
The composite material of hydrochlorate and carbon molecular sieve, preparation method and application utilize direct calcined zeolite under inert gas protection
The carbon molecular sieve that imidazoles esters coordination polymer ZIF-8 is obtained makes Keggin-type heteropoly acid or heteropolyacid salt molecule as carrier
Growth in situ limits Keggin-type heteropoly acid or miscellaneous inside the duct of carbon molecular sieve, and using the pore size of carbon molecular sieve
The loss of polyacid molecules of salt during the reaction.
In order to achieve the above object, in the first aspect of the present invention, the present invention provides a kind of Keggin type heteropoly acid or
The composite material of heteropolyacid salt and carbon molecular sieve, in the composite material, Keggin-type heteropoly acid or heteropolyacid salt molecule are former
Position is grown on inside the duct of carbon molecular sieve.Wherein, the general structure of the Keggin type heteropoly acid or heteropolyacid salt is H
(Na,K)n[XM12O40], X indicates that center hetero atom and X=P, Si, Ge, As, M indicate to match atom and M=Mo, W, and n is 3 or 4；Institute
Carbon molecular sieve is stated to obtain by calcined zeolite imidazoles esters coordination polymer ZIF-8 under inert gas protection.
In the second aspect of the present invention, the present invention provides a kind of Keggin-type heteropoly acid or heteropolyacid salts and carbon molecular sieve
Composite material preparation method, be used to prepare Keggin type heteropoly acid or heteropolyacid salt described in first aspect present invention and
The composite material of carbon molecular sieve, comprising steps of (1) is under inert gas protection, by zeolite imidazole esters coordination polymer ZIF-8
Calcining obtains carbon molecular sieve；(2) at normal temperatures and pressures, it will be distributed to inside carbon molecular sieve in equal volume with atom salting liquid, then
Excessive center hetero atom salt is added in the case where heating stirring, wherein isometric dispersion refers to described with atom salt
The total volume of solution can adsorb equal with the volume of solvent of atom salt for dissolving with the carbon molecular sieve；(3) to
Concentrated hydrochloric acid is added dropwise in reaction system, the reaction was continued a period of time；(4) to be centrifugated collection solid after reaction, then will
Solid pickling, washing are dried to get the composite material of Keggin-type heteropoly acid and carbon molecular sieve is arrived, and are being used to prepare
When the composite material of Keggin-type heteropolyacid salt and carbon molecular sieve, step (3) is omitted.
In the third aspect of the present invention, the present invention provides a kind of Keggin-type heteropoly acid or heteropolyacid salts and carbon molecular sieve
Application of the composite material in acid catalysis, redox catalysis, photocatalysis, proton membrane field.
Compared with the existing technology, the present invention include at least it is as described below the utility model has the advantages that
(1) in the composite material of Keggin-type heteropoly acid of the invention or heteropolyacid salt and carbon molecular sieve, the carbon that uses
Molecular sieve is obtained by calcined zeolite imidazoles esters coordination polymer ZIF-8 under inert gas protection, has specific surface area
Greatly, the uniform feature of pore size, and its pore size is close with the molecular dimension of Keggin type heteropoly acid or heteropolyacid salt,
Therefore the molecule of Keggin-type heteropoly acid or heteropolyacid salt can be implanted into inside its duct, and utilizes the cage mouth ruler of carbon molecular sieve
The very little loss that can also limit Keggin type heteropoly acid or heteropolyacid salt molecule in catalytic reaction process, and then can improve
The service life of Keggin-type heteropoly acid or heteropolyacid salt, while expanding the application model of Keggin-type heteropoly acid or heteropolyacid salt
It encloses；
(2) preparation method of the composite material of Keggin-type heteropoly acid of the invention or heteropolyacid salt and carbon molecular sieve has
The feature that raw material availability is high, simple process is controllable is suitble to large-scale production.
Detailed description of the invention
Fig. 1 is Keggin-H prepared by embodiment 13PW12O40The TEM of@CMS composite material schemes；
Fig. 2 is Keggin-H prepared by embodiment 13PW12O40The infrared figure of FTIR of@CMS composite material；
Fig. 3 is Keggin-H prepared by embodiment 13PW12O40The TG of@CMS composite material schemes.
Specific embodiment
The following detailed description of the composite material of Keggin-type heteropoly acid according to the present invention or heteropolyacid salt and carbon molecular sieve,
Preparation method and application.
Illustrate the compound of Keggin-type heteropoly acid according to a first aspect of the present invention or heteropolyacid salt and carbon molecular sieve first
Material.
In composite material of the invention, Keggin-type heteropoly acid or heteropolyacid salt molecule growth in situ are in carbon molecular sieve
Inside duct.Wherein, the general structure of the Keggin-type heteropoly acid or heteropolyacid salt is H (Na, K)n[XM12O40], X is indicated
Center hetero atom and X=P, Si, Ge, As, M indicate that with atom and M=Mo, W, n be 3 or 4；The carbon molecular sieve passes through in inertia
Calcined zeolite imidazoles esters coordination polymer ZIF-8 is obtained under gas shield.
In composite material of the invention, the carbon molecular sieve used is by calcined zeolite imidazoles under inert gas protection
Esters coordination polymer ZIF-8 is obtained.ZIF-8 is by Zn2+With 2-methylimidazole (C4N2H6) constitute have sodalite (SOD)
The zeolite imidazole esters coordination polymer of structure, crystallinity is very high, and each unit structure cell includes 2 SOD cages, the ruler of SOD cage
Very little is 1.18nm, and each SOD cage is connected by the former molecular hexatomic ring cage mouths of 6 Zn, hexatomic ring cage mouth having a size of 0.34nm,
The SOD cage type shape of ZIF-8 is held essentially constant after high-temperature calcination.Therefore had by the carbon molecular sieve of ZIF-8 preparation than table
The feature that area is big, pore size is uniform, and its pore size (~1.2nm) and Keggin type heteropoly acid or heteropolyacid salt
Molecular dimension (1.0nm~1.3nm) is close, the molecule of Keggin-type heteropoly acid or heteropolyacid salt can be implanted to carbon molecular sieve
In duct, and Keggin-type heteropoly acid or heteropolyacid salt molecule can also be limited using the cage mouth size of carbon molecular sieve and is being catalyzed instead
Loss during answering, and then the service life of Keggin-type heteropoly acid or heteropolyacid salt can be improved, while expanding Keggin-type
The application range of heteropoly acid.
In composite material of the invention, N element, and carbon molecular sieve skeleton are contained in the skeleton structure of the carbon molecular sieve
N in structure can also play the role of immobilized Keggin-type heteropoly acid or heteropolyacid salt, the N member in carbon molecular sieve skeleton structure
It is also less for the supported quantity of Keggin-type heteropoly acid or heteropolyacid salt when cellulose content is less.
Preferably, the content of the N element in the skeleton structure of the carbon molecular sieve is the quality of the carbon molecular sieve
0.7%~2%；It is highly preferred that the content of the N element in the skeleton structure of the carbon molecular sieve is the quality of the carbon molecular sieve
0.7%~1.2%.
In composite material of the invention, it is preferable that the pore size of the carbon molecular sieve is 1.15nm~1.25nm；
It is highly preferred that the pore size of the carbon molecular sieve is 1.20nm.
In composite material of the invention, it is preferable that the BET specific surface area of the carbon molecular sieve is 1500m2/ g~
1650m2/g；It is highly preferred that the BET specific surface area of the carbon molecular sieve is 1500m2/ g~1580m2/g。
In composite material of the invention, carbon molecular sieve is obtained in calcined zeolite imidazoles esters coordination polymer ZIF-8
In the process, inert gas is selected from nitrogen or argon gas.
In composite material of the invention, carbon molecular sieve is obtained in calcined zeolite imidazoles esters coordination polymer ZIF-8
In the process, calcination temperature is 800 DEG C~1000 DEG C；Preferably, calcination temperature is 920 DEG C~1000 DEG C.In calcined zeolite imidazoles
During esters coordination polymer ZIF-8 obtains carbon molecular sieve, calcination time is 3h~6h.
The specific surface area and pore size size of the carbon molecular sieve are related with calcination temperature, with the liter of calcination temperature
The specific surface area of height, carbon molecular sieve is bigger, but the pore size of carbon molecular sieve also becomes larger simultaneously.The boiling point of metal Zn is 907 DEG C,
Calcination temperature lower than 907 DEG C needs with acid dissolution and removes metal Zn, increases technology difficulty and complexity；It is lower
Calcination temperature, such as < 650 DEG C, N element is difficult to enter into the skeleton structure of carbon molecular sieve, to Keggin-type heteropoly acid or miscellaneous
The immobilized ability of multi-acid salt is poor；When higher than 1000 DEG C of calcinings, N element is easily deviate from from the skeleton structure of carbon molecular sieve again,
Although the specific surface area of carbon molecular sieve increases, the pore size of carbon molecular sieve also becomes larger and the N in carbon molecular sieve skeleton structure
Content decline, it is also poor to the immobilized ability of Keggin-type heteropoly acid or heteropolyacid salt.
Simultaneously in calcination process, calcination temperature and calcination time need rationally setting, such as when calcination temperature is higher,
Calcination time tends to more slightly shorter, and N element is avoided largely to deviate from from the skeleton structure of carbon molecular sieve and reduce carbon molecular sieve
To the immobilized ability of Keggin-type heteropoly acid or heteropolyacid salt.
In composite material of the invention, it is preferable that the Keggin-type heteropoly acid or heteropolyacid salt are selected from H3PMo12O40、
H3PW12O40、H4SiMo12O40、H4GeMo12O40、H4AsMo12O40、 H4SiW12O40、H4GeW12O40、H4AsW12O40、
Na3PMo12O40、Na3PW12O40、 Na4SiMo12O40、Na4GeMo12O40、Na4AsMo12O40、Na4SiW12O40、Na4GeW12O40、
Na4AsW12O40、K3PMo12O40、K3PW12O40、K4SiMo12O40、K4GeMo12O40、 K4AsMo12O40、K4SiW12O40、
K4GeW12O40、K4AsW12O40One or more of.
In composite material of the invention, the iodine number of the carbon molecular sieve is 600mg/g~1000mg/g；Preferably, institute
The iodine number for stating carbon molecular sieve is 700mg/g~800mg/g.Iodine number can characterize the adsorption capacity of the carbon molecular sieve, and iodine number can
To use 0.1mol/L (1/2I2) measurement.
In composite material of the invention, every 1g carbon molecular sieve highest immobilized 1.5 × 10-4The Keggin type heteropoly acid of mol
Or heteropolyacid salt.
Secondly explanation Keggin-type heteropoly acid according to a second aspect of the present invention or heteropolyacid salt and carbon molecular sieve is compound
The preparation method of material is used to prepare Keggin-type heteropoly acid or heteropolyacid salt and carbon molecular sieve described in first aspect present invention
Composite material, comprising steps of
(1) under inert gas protection, it calcines zeolite imidazole esters coordination polymer ZIF-8 to obtain carbon molecular sieve；(2)
At normal temperatures and pressures, it will be distributed to inside carbon molecular sieve with atom salting liquid, then add in the case where heating stirring in equal volume
Enter excessive center hetero atom salt, wherein isometric dispersion refers to the total volume and the carbon with atom salting liquid
The volume for dissolving the solvent with atom salt that molecular sieve can adsorb is equal；(3) concentrated hydrochloric acid is added dropwise into reaction system,
The reaction was continued a period of time；(4) to be centrifugated collection solid after reaction, then by solid pickling, washing, drying, i.e.,
The composite material of Keggin-type heteropoly acid and carbon molecular sieve is obtained, and is being used to prepare Keggin type heteropolyacid salt and carbon molecules
When the composite material of sieve, step (3) is omitted.
In the preparation process in accordance with the present invention, the composite material of Keggin-type heteropoly acid or heteropolyacid salt and carbon molecular sieve is benefit
It is obtained with in-situ synthesis, portion's fabricated in situ Keggin-type heteropoly acid or miscellaneous in the inner on the basis of the stability of carbon molecular sieve
Keggin-type heteropoly acid or heteropolyacid salt are implanted to inside the duct of carbon molecular sieve by multi-acid salt, and the preparation method has
The feature that raw material availability is high, simple process is controllable is suitble to large-scale production.
In the preparation process in accordance with the present invention, isometric dispersion refer to the total volume with atom salting liquid with it is described
The volume for dissolving the solvent with atom salt that carbon molecular sieve can adsorb is equal.Total volume with atom salting liquid is higher
When, excessive Keggin-type heteropoly acid or heteropolyacid salt can be grown in the outer surface of carbon molecular sieve, readily soluble in the process of washing
It is lost in Xie Yushui, increases production cost；When total volume with atom salting liquid is less than normal, some carbon molecular sieves do not have carrier
Effect, carbon molecular sieve utilization rate decline.
In the preparation process in accordance with the present invention, specifically, the total volume with atom salting liquid and the carbon molecular sieve
The ratio of quality is 2ml:1g.I.e. every 1g carbon molecular sieve itself can adsorb 2ml for dissolve solvent (such as the water with atom salt
Solvent etc.), therefore, every 1g carbon molecular sieve that is added needs corresponding addition total volume to match atom salting liquid for 2ml.
It is in the preparation process in accordance with the present invention, described with for dissolve the solvent with atom salt being water in atom salting liquid,
It can be organic solvent, preferably water.Water has the advantages that cheap and easy to get, non-environmental-pollution as solvent.
In the preparation process in accordance with the present invention, it is preferable that described to be selected from Na with atom salt2MoO3·2H2O、 Na2WO3·
2H2O、K2MoO3·2H2O、K2WO3·2H2O。
In the preparation process in accordance with the present invention, it is preferable that the center hetero atom salt is selected from NaH2PO4·12H2O、
Na2SiO3·5H2O、Na4GeO4、Na2HAsO4·12H2O、KH2PO4·12H2O、 K2SiO3·5H2O、K4GeO4、K2HAsO4·
12H2O。
In the preparation process in accordance with the present invention, it is preferable that collected using the hydrochloric acid solution washing centrifuge separation of pH=1~2
Solid.
In the preparation process in accordance with the present invention, it is preferable that pickling number is 2~3 times.
In the preparation process in accordance with the present invention, it is preferable that washing times are 2~3 times.
Illustrate the compound of Keggin-type heteropoly acid according to a third aspect of the present invention or heteropolyacid salt and carbon molecular sieve again
The application of material, composite material of the invention have the characteristics that long service life, and it is active through detection to place the several months in aqueous solution
Component Keggin-type heteropoly acid or heteropolyacid salt do not occur be lost and its activity also do not change, be highly suitable for acid catalysis,
Redox catalysis, photocatalysis, in proton membrane field.
Below with reference to embodiment, the application is further described.It should be understood that these embodiments be merely to illustrate the application without
For limiting scope of the present application.
Embodiment 1
Under nitrogen protection, ZIF-8 is calcined 4 hours at 920 DEG C, is then cooled down, collected black powder and obtain carbon point
Son sieve, the BET specific surface area of carbon molecular sieve are 1580m2/ g, pore size 1.20nm, N element content be 1.2%, iodine number
For 800mg/g.
It at normal temperatures and pressures, will include 0.22g Na2WO3·2H2The 0.8ml aqueous dispersion of O is to 0.4g carbon molecular sieve
In, 65 DEG C are then heated to, 0.24g NaH is added2PO4·12H2O, the reaction was continued 30 minutes, then heats to 95 DEG C, slowly
0.13ml concentrated hydrochloric acid is added dropwise, reaction terminates for 30 minutes, and solid is collected in centrifuge separation, by the salt acid elution 2 of solid pH=1~2
It~3 times, is washed with water and washs 2~3 times, obtain Keggin-H after dry3PW12O40@CMS composite material.
Fig. 1 gives the Keggin-H of preparation3PW12O40The TEM of@CMS composite material schemes.
Fig. 2 gives the Keggin-H of preparation3PW12O40The infrared figure of FTIR of@CMS composite material, FTIR IR Characterization are aobvious
Show Keggin-H3PW12O40H in@CMS composite structure3PW12O40Eigen vibration peak, wherein 1081cm-1It can be attributed to P-O
Vibration peak, 1000cm-1It is attributed to W=Od vibration peak, 888cm-1It is attributed to W-Ob-W vibration peak, 786cm-1It is attributed to W-Oc-W
Vibration peak.
H3PW12O40Content measured through ICP-AES, the results showed that, in Keggin-H3PW12O40In@CMS composite material
1g carbon molecular sieve can accommodate 0.42g H3PW12O40。
Fig. 3 gives the Keggin-H of preparation3PW12O40The TG of@CMS composite material schemes, and TG (thermogravimetric) figure shows Keggin-
H3PW12O40@CMS composite material is weightless in 450 DEG C of beginnings.
Conductivity test shows: Keggin-H3PW12O40The conductivity of@CMS composite material is 6.1 × 10-1S·cm-1,
Illustrate that composite material of the invention can be applied in proton membrane fuel battery.
With Keggin-H3PW12O40@CMS composite material is catalyst, and four octyl ammonium (TBAB) of bromination is phase transfer catalysis (PTC)
Agent, n (H2O2)/n (DBT/4-MDBT/4,6-DMDBT) > 6, at 50 DEG C, desulfurization degree reaches 99%, illustrates of the invention compound
Material has good redox catalysis ability.
Embodiment 2
Under nitrogen protection, ZIF-8 is calcined 4 hours at 920 DEG C, is then cooled down, collected black powder and obtain carbon point
Son sieve, the BET specific surface area of carbon molecular sieve are 1580m2/ g, pore size 1.20nm, N element content be 1.2%, iodine number
For 800mg/g.
It at normal temperatures and pressures, will include 0.364g Na2WO3·2H2The 0.8ml aqueous dispersion of O is to 0.4 g carbon molecular sieve
In, 65 DEG C are then heated to, 0.25g Na is added2SiO3·5H2O, the reaction was continued 30 minutes, then heats to 95 DEG C, slowly drips
Add 0.2ml concentrated hydrochloric acid, reaction terminates for 30 minutes, and solid is collected in centrifuge separation, by the salt acid elution 2~3 of solid pH=1~2
It is secondary, it is washed with water and washs 2~3 times, obtain Keggin-H after dry4SiW12O40@CMS composite material.
Keggin-H4SiW12O40The pattern of@CMS composite material is similar to Example 1.
FTIR IR Characterization shows Keggin-H4SiW12O40H in@CMS composite structure4SiW12O40Eigen vibration
Peak, wherein 1057cm-1It can be attributed to Si-O vibration peak, 1003cm-1It is attributed to W=Od vibration peak, 895cm-1It is attributed to W-Ob-W
Vibration peak, 896cm-1It is attributed to W-Oc-W vibration peak.
H4SiW12O40Content measured through ICP-AES, the results showed that, in Keggin-H4SiW12O40@CMS composite material
Middle 1g carbon molecular sieve can accommodate 0.43g H4SiW12O40。
Conductivity test shows: Keggin-H4SiW12O40The conductivity of@CMS composite material is 5.3 × 10-1S·cm-1,
Illustrate that composite material of the invention can be applied in proton membrane fuel battery.
1g soybean oil is added to the in the mixed solvent of 1.4ml methanol and 1ml tetrahydrofuran, 100mg preparation is then added
Keggin-H4SiW12O40@CMS composite material reacts the mixture 4 hours at 65 DEG C, high pressure liquid chromatography (HPLC) point
Analysis shows that conversion ratio of the soybean oil by transesterification preparation biodiesel is 95%, and the yield of biodiesel is 93%, illustrates this
The composite material of invention has good acid catalysis ability.
Embodiment 3
Under nitrogen protection, ZIF-8 is calcined 4 hours at 920 DEG C, is then cooled down, collected black powder and obtain carbon point
Son sieve, the BET specific surface area of carbon molecular sieve are 1580m2/ g, pore size 1.20nm, N element content be 1.2%, iodine number
For 800mg/g.
It at normal temperatures and pressures, will include 0.16g Na2MoO3·2H2The 1.6ml aqueous dispersion of O is to 0.81 g carbon molecules
In sieve, 65 DEG C are then heated to, 0.24g NaH is added2PO4·12H2O, the reaction was continued 30 minutes, then heats to 95 DEG C, delays
Slow that 0.13ml concentrated hydrochloric acid is added dropwise, reaction terminates for 30 minutes, and solid is collected in centrifuge separation, by the salt acid elution of solid pH=1~2
It 2~3 times, is washed with water and washs 2~3 times, obtain Keggin-H after dry3PMo12O40@CMS composite material.
Keggin-H3PMo12O40The pattern of@CMS composite material is similar to Example 1.
FTIR IR Characterization shows Keggin-H3PMo12O40H in@CMS composite structure3PMo12O40Eigen vibration
Peak, wherein 1080cm-1It can be attributed to P-O vibration peak, 1009cm-1It is attributed to Mo=Od vibration peak, 878cm-1It is attributed to Mo-Ob-
Mo vibration peak, 806cm-1It is attributed to Mo-Oc-Mo vibration peak.
H3PMo12O40Content measured through ICP-AES, the results showed that, in Keggin-H3PMo12O40@CMS composite material
Middle 1g carbon molecular sieve can accommodate 0.18g H3PMo12O40。
Conductivity test shows: Keggin-H3PMo12O40The conductivity of@CMS composite material is 1.2 × 10-2S·cm-1,
Illustrate that composite material of the invention can be applied in proton membrane fuel battery.
1g oleic acid is added in 1.4ml methanol, the Keggin-H of 200mg preparation is then added3PMo12O40@CMS is compound
Material, by the mixture 65 DEG C react 4 hours, high pressure liquid chromatography (HPLC) analysis shows, oleic acid pass through transesterification preparation
The conversion ratio of biodiesel is 98%, and the yield of biodiesel is 95%, illustrates that composite material of the invention has good acid
Catalytic capability.
Embodiment 4
Under nitrogen protection, ZIF-8 is calcined 4 hours at 800 DEG C, is then cooled down, collected black powder, use salt later
Acid dissolves metal Zn therein, then is cleaned and dried to obtain carbon molecular sieve, and the BET specific surface area of carbon molecular sieve is 1500m2/
G, pore size is 1.15nm, N element content is 2.0%, iodine number 700mg/g.
It at normal temperatures and pressures, will include 0.22g Na2WO3·2H2The 0.8ml aqueous dispersion of O is to 0.4g carbon molecular sieve
In, 65 DEG C are then heated to, 0.25g KH is added2PO4·12H2O, the reaction was continued 30 minutes, then heats to 95 DEG C, slowly drips
Add 0.13ml concentrated hydrochloric acid, reaction terminates for 30 minutes, and solid is collected in centrifuge separation, by the salt acid elution 2~3 of solid pH=1~2
It is secondary, it is washed with water and washs 2~3 times, obtain Keggin-H after dry3PW12O40@CMS composite material.
H3PW12O40Content measured through ICP-AES, the results showed that, in Keggin-H3PW12O40In@CMS composite material
1g carbon molecular sieve can accommodate 0.31g H3PW12O40。
Embodiment 5
Under nitrogen protection, ZIF-8 is calcined 4 hours at 1000 DEG C, is then cooled down, collected black powder and obtain carbon point
Son sieve, the BET specific surface area of carbon molecular sieve are 1632m2/ g, pore size 1.25nm, N element content be 0.7%, iodine number
For 800mg/g.
It at normal temperatures and pressures, will include 0.22g Na2WO3·2H2The 0.8ml aqueous dispersion of O is to 0.4g carbon molecular sieve
In, 65 DEG C are then heated to, 0.24g NaH is added2PO4·12H2O, the reaction was continued 30 minutes, then heats to 95 DEG C, slowly
0.13ml concentrated hydrochloric acid is added dropwise, reaction terminates for 30 minutes, and solid is collected in centrifuge separation, by the salt acid elution 2 of solid pH=1~2
It~3 times, is washed with water and washs 2~3 times, obtain Keggin-H after dry3PW12O40@CMS composite material.
H3PW12O40Content measured through ICP-AES, the results showed that, in Keggin-H3PW12O40In@CMS composite material
1g carbon molecular sieve can accommodate 0.35g H3PW12O40。
Comparative example 1
By commercially available active carbon (AC, BET specific surface area 800m2/ g) it is activated 24 hours in 150 DEG C of baking ovens.Then normal
It will include 0.22g Na under normal temperature and pressure2WO3·2H2In commercially available active carbon after the 0.8ml aqueous dispersion of O to 0.4g activation,
65 DEG C are then heated to, 0.24g NaH is added2PO4·12H2O, the reaction was continued 30 minutes, then heats to 95 DEG C, is slowly added dropwise
0.13ml concentrated hydrochloric acid, reaction terminate for 30 minutes, and solid is collected in centrifuge separation, by the salt acid elution 2~3 of solid pH=1~2
It is secondary, it is washed with water and washs 2~3 times, obtain Keggin-H after dry3PW12O40@AC composite material.
H3PW12O40Content measured through ICP-AES, the results showed that, in Keggin-H3PW12O401g in@AC composite material
Carbon molecular sieve is substantially free of H3PW12O40.Reason is the pore size of commercially available active carbon or is greater than H3PW12O40Molecule
Size leads to H3PW12O40Molecule is easy to be lost during the reaction, or is less than H3PW12O40Molecular dimension, cause
H3PW12O40Molecule is difficult immobilized on commercially available active carbon；On the other hand, N member is substantially free of in commercially available active carbon skeleton structure
Element, therefore substantially cannot immobilized H3PW12O40。
Claims (10)
1. the composite material of a kind of Keggin-type heteropoly acid or heteropolyacid salt and carbon molecular sieve, which is characterized in that
Keggin-type heteropoly acid or heteropolyacid salt molecule growth in situ are inside the duct of carbon molecular sieve；
The general structure of the Keggin-type heteropoly acid or heteropolyacid salt is H (Na, K)n[XM12O40], X indicate center hetero atom and
X=P, Si, Ge, As, M indicate that with atom and M=Mo, W, n be 3 or 4；
The carbon molecular sieve is obtained by calcined zeolite imidazoles esters coordination polymer ZIF-8 under inert gas protection.
2. composite material according to claim 1, which is characterized in that contain N member in the skeleton structure of the carbon molecular sieve
Element.
3. composite material according to claim 2, which is characterized in that the N element in the skeleton structure of the carbon molecular sieve
Content be the carbon molecular sieve quality 0.7%~2.0%, preferably 0.7%~1.2%.
4. composite material according to claim 1, which is characterized in that the pore size of the carbon molecular sieve be 1.15nm~
1.25nm, preferably 1.20nm.
5. composite material according to claim 1, which is characterized in that the BET specific surface area of the carbon molecular sieve is
1500m2/ g~1650m2/ g, preferably 1500m2/ g~1580m2/g。
6. composite material according to claim 1, which is characterized in that in calcined zeolite imidazoles esters coordination polymer ZIF-
During 8 obtain carbon molecular sieve: calcination temperature is 800 DEG C~1000 DEG C, and calcination time is 3h~6h.
7. composite material according to claim 1, which is characterized in that in the composite material, every 1g carbon molecular sieve is most
Height immobilized 1.5 × 10-4The Keggin-type heteropoly acid or heteropolyacid salt of mol.
8. composite material according to claim 1, which is characterized in that the Keggin-type heteropoly acid or heteropolyacid salt are selected from
H3PMo12O40、H3PW12O40、H4SiMo12O40、H4GeMo12O40、H4AsMo12O40、H4SiW12O40、H4GeW12O40、H4AsW12O40、
Na3PMo12O40、Na3PW12O40、Na4SiMo12O40、Na4GeMo12O40、Na4AsMo12O40、Na4SiW12O40、Na4GeW12O40、
Na4AsW12O40、K3PMo12O40、K3PW12O40、K4SiMo12O40、K4GeMo12O40、K4AsMo12O40、K4SiW12O40、
K4GeW12O40、K4AsW12O40One or more of.
9. a kind of preparation method of the composite material of Keggin-type heteropoly acid or heteropolyacid salt and carbon molecular sieve, is used to prepare right
It is required that the composite material of Keggin-type heteropoly acid or heteropolyacid salt and carbon molecular sieve described in any one of 1-8, which is characterized in that
Comprising steps of
(1) under inert gas protection, it calcines zeolite imidazole esters coordination polymer ZIF-8 to obtain carbon molecular sieve；
(2) at normal temperatures and pressures, it will be distributed to inside carbon molecular sieve in equal volume with atom salting liquid, then in the feelings of heating stirring
Excessive center hetero atom salt is added under condition, wherein isometric dispersion refer to the total volume with atom salting liquid with
The volume for dissolving the solvent with atom salt that the carbon molecular sieve can adsorb is equal；
(3) concentrated hydrochloric acid is added dropwise into reaction system, the reaction was continued a period of time；
(4) to be centrifugated collection solid after reaction, then by solid pickling, washing, drying to get miscellaneous to Keggin-type
The composite material of polyacid and carbon molecular sieve, and when being used to prepare the composite material of Keggin-type heteropolyacid salt and carbon molecular sieve,
Step (3) is omitted.
10. a kind of Keggin-type heteropoly acid according to claim 1 to 8 or heteropolyacid salt and carbon molecular sieve
Application of the composite material in acid catalysis, redox catalysis, photocatalysis, proton membrane field.
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| CN111693696A (en) * | 2020-06-28 | 2020-09-22 | 首都师范大学 | Conductive multifunctional nano probe and preparation method and application thereof |
| CN112126528A (en) * | 2020-09-23 | 2020-12-25 | 上海应用技术大学 | Preparation method of biodiesel |
| WO2021035266A1 (en) * | 2019-08-27 | 2021-03-04 | Omv Refining & Marketing Gmbh | Catalyst based on lacunar heteropolyacid supported in micropores, preparation process therefor and process for glycerol conversion therewith |
| CN112517077A (en) * | 2020-12-09 | 2021-03-19 | 三峡大学 | Preparation method and application of heteropolyacid-doped ZIF-67 catalyst |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021035266A1 (en) * | 2019-08-27 | 2021-03-04 | Omv Refining & Marketing Gmbh | Catalyst based on lacunar heteropolyacid supported in micropores, preparation process therefor and process for glycerol conversion therewith |
| AT522938A1 (en) * | 2019-08-27 | 2021-03-15 | OMV Downstream GmbH | catalyst |
| AT522938B1 (en) * | 2019-08-27 | 2021-06-15 | OMV Downstream GmbH | catalyst |
| CN111693696A (en) * | 2020-06-28 | 2020-09-22 | 首都师范大学 | Conductive multifunctional nano probe and preparation method and application thereof |
| CN111693696B (en) * | 2020-06-28 | 2022-08-09 | 首都师范大学 | Conductive multifunctional nano probe and preparation method and application thereof |
| CN112126528A (en) * | 2020-09-23 | 2020-12-25 | 上海应用技术大学 | Preparation method of biodiesel |
| CN112517077A (en) * | 2020-12-09 | 2021-03-19 | 三峡大学 | Preparation method and application of heteropolyacid-doped ZIF-67 catalyst |
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